CN112886133A - Coating diaphragm for eliminating proton hydrogen and preparation method thereof - Google Patents
Coating diaphragm for eliminating proton hydrogen and preparation method thereof Download PDFInfo
- Publication number
- CN112886133A CN112886133A CN202110005388.4A CN202110005388A CN112886133A CN 112886133 A CN112886133 A CN 112886133A CN 202110005388 A CN202110005388 A CN 202110005388A CN 112886133 A CN112886133 A CN 112886133A
- Authority
- CN
- China
- Prior art keywords
- coating
- slurry
- proton hydrogen
- coating material
- inorganic ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 59
- 238000000576 coating method Methods 0.000 title claims abstract description 59
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 24
- 239000001257 hydrogen Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000012528 membrane Substances 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 238000005524 ceramic coating Methods 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 13
- 239000006255 coating slurry Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 230000002000 scavenging effect Effects 0.000 claims abstract description 3
- -1 tetramethyl sulfoxide Chemical class 0.000 claims description 17
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000004745 nonwoven fabric Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920006122 polyamide resin Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- MOVRCMBPGBESLI-UHFFFAOYSA-N prop-2-enoyloxysilicon Chemical compound [Si]OC(=O)C=C MOVRCMBPGBESLI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 125000004442 acylamino group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 14
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011247 coating layer Substances 0.000 abstract description 5
- 238000000227 grinding Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000003335 steric effect Effects 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Cell Separators (AREA)
Abstract
The invention discloses a coating diaphragm for eliminating proton hydrogen and a preparation method thereof, which are used for eliminating or adsorbing proton hydrogen (H +), and reducing the amount of hydrofluoric acid (HF) or proton hydrogen (H +) generated by the decomposition of electrolyte in the use process of a battery. A coated diaphragm for eliminating proton hydrogen is composed of basic film and coating layer prepared through coating slurry on the surface of basic film, drying, mixing inorganic ceramic or organic paint with disperser, ball grinding or stirring, and adding resin containing electron-donating group. A method for preparing a proton hydrogen scavenging coated membrane comprising the steps of: (1) mixing an inorganic ceramic coating material or an organic coating with a dispersant, adding the mixture into a solvent, carrying out ball milling or stirring, then adding resin containing electron-donating groups, and stirring to obtain coating slurry; (2) and coating the obtained slurry on the surface of the base film, and drying to obtain the composite diaphragm.
Description
Technical Field
The invention relates to a coating diaphragm for eliminating proton hydrogen and a preparation method thereof, belonging to the technical field of lithium ion battery diaphragms.
Background
The diaphragm is used as a key main material in a lithium ion battery system, mainly plays a role in isolating a positive electrode and a negative electrode, preventing short circuit, simultaneously ensuring certain electrolyte wettability and liquid retention and providing a channel for lithium ion transmission. Various performances of the diaphragm directly determine the interface performance and the internal resistance of the battery, and further influence the charge-discharge performance and the cycle performance of the battery.
The lithium ion battery separator in the prior art mainly comprises a polyolefin porous separator, and the preparation method mainly comprises dry-method stretching and wet-method stretching, for example, a patent with publication number of CN100448922C and named as "microporous membrane made of polyolefin" discloses a method for preparing a microporous membrane made of polyolefin and related characteristics. Publication nos. CN107910476A, CN108565382A, CN109686900A and CN107275550A disclose that the heat resistance and wettability of the separator are mainly improved by inorganic or inorganic-organic mixed coating.
Although the existing polyolefin porous diaphragm can be applied to the lithium ion battery in a mature way, along with the wide application of the lithium ion battery in the aspects of high power, high energy density and long rate cycle, stricter requirements are put forward on the diaphragm. The conventional diaphragm and the coating diaphragm mainly play a role in physically isolating the positive electrode and the negative electrode in the battery, but hydrofluoric acid (HF) or proton hydrogen (H +) generated by decomposition of electrolyte corrodes or reacts on an electrode material, particularly the positive electrode material in the use process of the battery, and an electrode active site is damaged, so that the cycle performance and the capacity of the battery are attenuated. The prior art does not have a lithium battery diaphragm capable of eliminating or adsorbing proton hydrogen (H +), so that hydrofluoric acid (HF) or proton hydrogen (H +) generated by decomposition of electrolyte in the use process of the battery is avoided. In order to meet the development requirements of power batteries, it is important to develop a battery diaphragm capable of effectively eliminating or adsorbing proton hydrogen (H +).
Disclosure of Invention
The invention aims to provide a coating membrane for eliminating proton hydrogen and a preparation method thereof, which are used for eliminating or adsorbing the proton hydrogen (H +), and reducing the amount of hydrofluoric acid (HF) or the proton hydrogen (H +) generated by the decomposition of an electrolyte in the use process of a battery.
The invention adopts the following technical scheme: a coating diaphragm for eliminating proton hydrogen comprises a base film and a coating layer, wherein the coating layer is formed by coating slurry on the surface of the base film and drying, the coating slurry is formed by mixing an inorganic ceramic coating material or an organic coating material with a dispersing agent, then adding the mixture into a solvent for ball milling or stirring, and then adding resin containing an electron-donating group.
A method for preparing a proton hydrogen scavenging coated membrane comprising the steps of: (1) mixing an inorganic ceramic coating material or an organic coating with a dispersant, adding the mixture into a solvent, carrying out ball milling or stirring, then adding resin containing electron-donating groups, and stirring to obtain coating slurry; (2) and coating the obtained slurry on the surface of the base film, and drying to obtain the composite diaphragm.
The slurry obtained in the step (1) comprises the following components in percentage by weight: the inorganic ceramic coating material is 0-50% of the slurry, the organic coating is 0-25% of the slurry, the dispersing agent is 0.02-0.45% of the inorganic ceramic coating material or the organic coating, and the resin containing the electron-donating group is 0.1-60% of the inorganic ceramic coating material or the organic coating or 0.02-30% of the slurry.
The inorganic ceramic coating material in the step (1) is Al2O3、SiO2、TiO2、MgO、Mg(OH)2Clay, ZrO2One or more than two of ceramic powder of SiC; the organic coating material is one or more than two of polyvinylidene fluoride, polymethyl methacrylate, polyethylene oxide, polyacrylonitrile and aramid fiber organic powder or suspension.
The dispersing agent in the step (1) is one or more than two mixed dispersing agents of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylate and sodium dodecyl benzene sulfonate.
The solvent in the step (1) is one or a mixed solution of more than two of water, acetone, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and tetramethyl sulfoxide.
The resin containing electron-donating groups in the step (1) is one or a mixture of more than two of polyvinyl pyridine, divinylbenzene crosslinked resin, polydialkylamino alkyl/methacrylamide, acryloxy silicon resin, hydroxy acrylic resin and polyamide resin.
The electron donating group containing group in the resin containing an electron donating group in the step (1) comprises: one or more of oxyanion, dialkylamino, alkylamino, amino, hydroxyl, alkoxy, acylamino and acyloxy.
In the step (2), the base membrane is a porous polyethylene membrane or a porous polypropylene membrane or a porous polyvinylidene fluoride membrane or a polyamide non-woven fabric or a polyester non-woven fabric or a polyolefin non-woven fabric or a mixed membrane, and the mixed membrane is a mixed membrane composed of two or more of polyethylene, polypropylene, polyvinylidene fluoride and polyamide.
The ball milling time in the step (1) is 0-6 h; adding resin containing electron-donating groups, and then mechanically stirring at 20-80 ℃ for 3-12 h; in the step (2), the drying temperature is 50-85 ℃, the drying temperature mainly controls the moisture content of the coating film and the stretching degree of the molecular chain of the binder to improve the binding force between the coating layer and the base film, the coating thickness of the slurry is 30nm-6 mu m, and the thickness mainly improves the heat resistance of the diaphragm.
The invention has the beneficial effects that: according to the invention, the inorganic ceramic coating material is uniformly dispersed in the solution by using the dispersing agent, the inorganic ceramic coating material can obtain the required particle size by ball milling, and the inorganic ceramic coating material mainly plays a role in improving the puncture strength, heat resistance and wettability of the diaphragm; the organic coating is adopted, and the organic coating mainly improves the heat resistance, the adhesion and the wettability of the diaphragm; the dispersing agent can form a charge layer or high steric effect on the surface of the coating material, and uniform dispersion of the coating material is realized. The resin can eliminate or adsorb proton hydrogen generated by the battery system. Therefore, the diaphragm product produced by the method can effectively adsorb proton hydrogen (H +), reduce the amount of hydrofluoric acid (HF) or proton hydrogen (H +) generated by the decomposition of electrolyte in the use process of the battery, slow down the corrosion or reaction of the diaphragm product on electrode materials, particularly anode materials, damage electrode active sites, avoid reducing the cycle performance and capacity attenuation of the battery, be beneficial to improving the cycle stability of the lithium ion battery and the high-voltage battery, and be suitable for the power lithium ion battery.
The invention effectively overcomes the defect that the lithium ion battery generates hydrogen protons to corrode electrode materials in the recycling process, further reduces the cycle performance and the service life of the battery, has high industrial utilization value, is not only suitable for power lithium ion batteries, but also has wide application prospect in the fields of sodium ion batteries and potassium ion batteries.
Drawings
FIG. 1 is a flow chart of an exemplary method of making a coated proton hydrogen deficient membrane.
Detailed Description
The embodiments of the present invention are further described below with reference to specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the invention.
The coating slurry is formed by mixing an inorganic ceramic coating material or an organic coating material and a dispersing agent, adding the mixture into a solvent for ball milling or stirring, and adding a resin containing an electron-donating group.
The preparation method of the proton hydrogen eliminating coating membrane comprises the following steps: (1) mixing an inorganic ceramic coating material or an organic coating with a dispersant, adding the mixture into a solvent, carrying out ball milling or stirring, then adding resin containing electron-donating groups, and stirring to obtain coating slurry; (2) and coating the obtained slurry on the surface of the base film, and drying to obtain the composite diaphragm.
By way of example, the coating slurry obtained in step (1) comprises the following components in percentage by weight: the inorganic ceramic coating material is 0-50% of the slurry, the organic coating is 0-25% of the slurry, the dispersing agent is 0.02-0.45% of the inorganic ceramic coating material or the organic coating, and the resin containing the electron-donating group is 0.1-60% of the inorganic ceramic coating material or the organic coating or 0.02-30% of the slurry. Preferably, the inorganic ceramic coating material is 5-25% of the slurry, the organic coating material is 1-15% of the slurry, the dispersant is 0.05-0.30% of the inorganic ceramic coating material or the organic coating material, and the resin of the electron-donating group is 0.1-0.3% of the inorganic ceramic coating material or the organic coating material or 0.02-15% of the slurry.
As an example, the inorganic ceramic coating material in the step (1) is Al2O3、SiO2、TiO2、MgO、Mg(OH)2Clay (Clay), ZrO2One or more than two of ceramic powder of SiC; however, in practice it is not limited to the listed onesThe ceramic powder can be uniformly dispersed in the solution through the dispersing agent, and the required particle size can be obtained through ball milling. The ceramic powder mainly improves the puncture strength, heat resistance and wettability of the diaphragm.
In the step (1), an organic coating material may be further used, for example, the organic coating material is one or more of polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), polyethylene oxide (PEO), Polyacrylonitrile (PAN), and an organic powder or suspension of aramid, and the aramid may specifically be PPTA or PMIA. However, in practice, the organic coating material is not limited to the listed organic materials, and the organic coating material can be uniformly dispersed in the solution by the dispersant and can obtain a desired uniform solution by ball milling or stirring, and the organic coating material mainly plays a role in improving heat resistance, adhesiveness and wettability.
As an example, the dispersant in the step (1) is one or more of mixed dispersants of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylate and sodium dodecyl benzene sulfonate. The dispersing agent can form a charge layer or high steric effect on the surface of the coating material, and uniform dispersion of the coating material is realized.
The solvent in step (1) is, for example, one or a mixture of two or more of water, acetone, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, and tetramethylsulfoxide. The solvent may also be other suitable solvents, and is not listed here.
As an example, the resin containing an electron donating group in step (1) is one or a mixture of two or more of, for example, polyvinylpyridine (P (n-VP)) and a divinylbenzene-crosslinked resin, poly (dialkylaminoalkyl (meth) acrylamide)), acryloxysilicon resin, hydroxyacrylic resin, polyamide resin, and the like, and the resin can eliminate or adsorb proton hydrogen generated from the battery system.
As an example, the electron donating group containing group in the resin containing an electron donating group in step (1) includes: one OR more of oxyanion (-O-), dialkylamino (-NR 2), alkylamino (-NHR), amino (-NH 2), hydroxyl (-OH), alkoxy (-OR), amide (-NHCOR), and acyloxy (-OCOR). The electron donating group is a proton hydrogen host that eliminates or adsorbs from the cell system.
As an example, in the step (2), the base film is a porous polyethylene film or a porous polypropylene film or a porous polyvinylidene fluoride film or a polyamide nonwoven fabric or a polyester nonwoven fabric or a polyolefin nonwoven fabric or a mixed film, and the mixed film is a mixed film composed of two or more of polyethylene, polypropylene, polyvinylidene fluoride and polyamide.
As an example, an inorganic ceramic coating material or an organic coating material is mixed with a dispersant and added to a solvent, wherein the ball milling time is 2 to 6 hours in the case of including the inorganic ceramic coating material and 0 to 2 hours in the case of not including the inorganic ceramic coating material, after which a certain amount of resin containing an electron-donating group is added and mechanical stirring is performed at 20 to 80 ℃ for 3 to 12 hours, resulting in uniform coating slurry.
The obtained slurry is coated on the surface of a base film, the coating thickness is 30nm-6 mu m, the thickness of the organic coating is relatively lower than 30nm-3 mu m, and the thickness mainly improves the heat resistance, puncture strength, wettability, lotion retention rate, voltage resistance and safety of the diaphragm. And then drying to obtain the composite diaphragm, wherein the drying temperature is 50-85 ℃, and the drying temperature mainly controls the moisture content of the coating film and controls the stretching degree of a molecular chain of the binder to improve the binding force between the coating layer and the base film. The cycle capacity retention of the resulting coated separator 1C battery was 98%.
One specific experimental example: the base film adopted is a polyethylene diaphragm, and the coating slurry comprises the following experimental components: ceramic (Al)2O3) Polyvinylidene fluoride (PVdF-HFP), sodium carboxymethylcellulose (CMC), acrylic latex (solid content 40%), resin for electron-donating group (crosslinked poly-4-Vinylpyridine (4-Vinylpyridine-copolymer)), solvent (water, acetone) in a mass ratio of 36: 12.4: 0.3: 0.8: 0.5: 50.
the thickness of the prepared coating membrane is 1-3 mu m, the gram weight of the coating is 0.8-4.2 g/square meter, and the ventilation value of the coating membrane relative to the base membrane is increased by 10-100 sec/100 cc.
The cycle capacity retention rate of a soft package battery (a positive electrode NCM-622 and a negative electrode graphite) 1C battery assembled by the obtained coating diaphragm is 98%, the cycle capacity retention rate of a battery 1C battery assembled by resin without electron donating groups and other components with the same coating diaphragm is 92%, and the capacity retention rate is improved by 6.5%.
The prepared diaphragm product can effectively adsorb proton hydrogen (H +), reduce the amount of hydrofluoric acid (HF) or proton hydrogen (H +) generated by decomposition of electrolyte in the use process of the battery, slow down corrosion or reaction of the battery on electrode materials, particularly anode materials, damage electrode active sites, cause the cycle performance and capacity attenuation of the battery, and is beneficial to improving the cycle stability of the lithium ion battery and the high-voltage battery, and suitable for power lithium ion batteries. Therefore, the invention effectively overcomes the problem that the lithium ion battery generates hydrogen protons to corrode electrode materials in the recycling process, thereby reducing the cycle performance and the service life of the battery, and has high industrial utilization value.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A proton hydrogen scavenging coated membrane characterized by: the coating is formed by coating slurry on the surface of a base film and drying, wherein the coating slurry is formed by mixing an inorganic ceramic coating material or an organic coating and a dispersing agent, adding the mixture into a solvent, carrying out ball milling or stirring, and adding resin containing an electron-donating group.
2. A preparation method of a coating membrane for eliminating proton hydrogen is characterized by comprising the following steps: (1) mixing an inorganic ceramic coating material or an organic coating with a dispersant, adding the mixture into a solvent, carrying out ball milling or stirring, then adding resin containing electron-donating groups, and stirring to obtain coating slurry; (2) and coating the obtained slurry on the surface of the base film, and drying to obtain the composite diaphragm.
3. The method for producing a proton hydrogen eliminating coated membrane according to claim 2, characterized in that: the slurry obtained in the step (1) comprises the following components in percentage by weight: the inorganic ceramic coating material is 0-50% of the slurry, the organic coating is 0-25% of the slurry, the dispersing agent is 0.02-0.45% of the inorganic ceramic coating material or the organic coating, and the resin containing the electron-donating group is 0.1-60% of the inorganic ceramic coating material or the organic coating or 0.02-30% of the slurry.
4. The method for producing a proton hydrogen eliminating coated membrane according to claim 2, characterized in that: the inorganic ceramic coating material in the step (1) is Al2O3、SiO2、TiO2、MgO、Mg(OH)2Clay, ZrO2One or more than two of ceramic powder of SiC; the organic coating material is one or more than two of polyvinylidene fluoride, polymethyl methacrylate, polyethylene oxide, polyacrylonitrile and aramid fiber organic powder or suspension.
5. The method for producing a proton hydrogen eliminating coated membrane according to claim 2, characterized in that: the dispersing agent in the step (1) is one or more than two mixed dispersing agents of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylate and sodium dodecyl benzene sulfonate.
6. The method for producing a proton hydrogen eliminating coated membrane according to claim 2, characterized in that: the solvent in the step (1) is one or a mixed solution of more than two of water, acetone, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and tetramethyl sulfoxide.
7. The method for producing a proton hydrogen eliminating coated membrane according to claim 2, characterized in that: the resin containing electron-donating groups in the step (1) is one or a mixture of more than two of polyvinyl pyridine, divinylbenzene crosslinked resin, polydialkylamino alkyl/methacrylamide, acryloxy silicon resin, hydroxy acrylic resin and polyamide resin.
8. The method for producing a proton hydrogen eliminating coated membrane according to claim 2, characterized in that: the electron donating group containing group in the resin containing an electron donating group in the step (1) comprises: one or more of oxyanion, dialkylamino, alkylamino, amino, hydroxyl, alkoxy, acylamino and acyloxy.
9. The method for producing a proton hydrogen eliminating coated membrane according to claim 2, characterized in that: in the step (2), the base membrane is a porous polyethylene membrane or a porous polypropylene membrane or a porous polyvinylidene fluoride membrane or a polyamide non-woven fabric or a polyester non-woven fabric or a polyolefin non-woven fabric or a mixed membrane, and the mixed membrane is a mixed membrane composed of two or more of polyethylene, polypropylene, polyvinylidene fluoride and polyamide.
10. The method for producing a proton hydrogen eliminating coated membrane according to claim 2, characterized in that: the ball milling time in the step (1) is 0-6 h; adding resin containing electron-donating groups, and then mechanically stirring at 20-80 ℃ for 3-12 h; in the step (2), the drying temperature is 50-85 ℃, and the coating thickness of the slurry is 30nm-6 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110005388.4A CN112886133A (en) | 2021-01-05 | 2021-01-05 | Coating diaphragm for eliminating proton hydrogen and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110005388.4A CN112886133A (en) | 2021-01-05 | 2021-01-05 | Coating diaphragm for eliminating proton hydrogen and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112886133A true CN112886133A (en) | 2021-06-01 |
Family
ID=76046793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110005388.4A Pending CN112886133A (en) | 2021-01-05 | 2021-01-05 | Coating diaphragm for eliminating proton hydrogen and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112886133A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101356665A (en) * | 2006-04-28 | 2009-01-28 | 松下电器产业株式会社 | Separator for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| CN103022530A (en) * | 2012-12-14 | 2013-04-03 | 辽宁师范大学 | Porous membrane and preparation method as well as application thereof in fuel battery |
| CN106450105A (en) * | 2016-10-14 | 2017-02-22 | 中航锂电（洛阳）有限公司 | Porous composite material partition and preparation method thereof, composite-structure cell and lithium ion battery |
| CN109698300A (en) * | 2017-10-24 | 2019-04-30 | 住友化学株式会社 | Nonaqueous electrolytic solution secondary battery porous layer |
| CN110571393A (en) * | 2019-07-29 | 2019-12-13 | 河北金力新能源科技股份有限公司 | slurry for lithium battery diaphragm, preparation method of slurry, lithium battery diaphragm and lithium battery |
| CN111029514A (en) * | 2019-11-14 | 2020-04-17 | 珠海冠宇电池有限公司 | Diaphragm and high-voltage battery comprising same |
-
2021
- 2021-01-05 CN CN202110005388.4A patent/CN112886133A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101356665A (en) * | 2006-04-28 | 2009-01-28 | 松下电器产业株式会社 | Separator for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| CN103022530A (en) * | 2012-12-14 | 2013-04-03 | 辽宁师范大学 | Porous membrane and preparation method as well as application thereof in fuel battery |
| CN106450105A (en) * | 2016-10-14 | 2017-02-22 | 中航锂电（洛阳）有限公司 | Porous composite material partition and preparation method thereof, composite-structure cell and lithium ion battery |
| CN109698300A (en) * | 2017-10-24 | 2019-04-30 | 住友化学株式会社 | Nonaqueous electrolytic solution secondary battery porous layer |
| CN110571393A (en) * | 2019-07-29 | 2019-12-13 | 河北金力新能源科技股份有限公司 | slurry for lithium battery diaphragm, preparation method of slurry, lithium battery diaphragm and lithium battery |
| CN111029514A (en) * | 2019-11-14 | 2020-04-17 | 珠海冠宇电池有限公司 | Diaphragm and high-voltage battery comprising same |
Non-Patent Citations (1)
| Title |
|---|
| 王积涛等: "《有机化学》", 南开大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111653717B (en) | Preparation method of composite diaphragm, composite diaphragm and lithium ion battery | |
| CN107959049B (en) | Preparation method of gel electrolyte, gel electrolyte and lithium ion battery | |
| CN108963153B (en) | Lithium ion battery diaphragm and preparation method thereof | |
| CN107749464A (en) | A kind of energy density lithium ion power battery | |
| CN107732169B (en) | Silicon-based negative electrode material of lithium battery, preparation method of silicon-based negative electrode material, battery negative electrode and lithium battery | |
| CN111180641A (en) | Diaphragm with self-crosslinking function and preparation method thereof | |
| CN101814590A (en) | Porous solid membrane used for lithium ion battery and production method thereof | |
| CN113659104A (en) | Preparation method of battery active layer, battery pole piece and application | |
| CN107069008B (en) | Silicon-carbon negative electrode material and preparation method thereof | |
| CN108630869B (en) | Diaphragm, preparation method thereof and lithium battery | |
| CN110649313A (en) | Lithium ion battery without diaphragm and preparation method thereof | |
| CN109473664B (en) | Preparation method of silicon-carbon composite material | |
| CN113067100A (en) | Water-based PVDF (polyvinylidene fluoride) coated lithium ion battery diaphragm and preparation method thereof | |
| CN113270691A (en) | Pole piece/diaphragm integrated lithium ion battery and preparation method thereof | |
| CN111342120B (en) | Polymer solid electrolyte, nano composite diaphragm and preparation method thereof, and lithium metal battery | |
| CN112582611B (en) | Application of polyacid oxide NVO in positive electrode of lithium-sulfur battery | |
| CN112886133A (en) | Coating diaphragm for eliminating proton hydrogen and preparation method thereof | |
| CN115172865B (en) | Composite solid electrolyte membrane and preparation method and application thereof | |
| KR101470022B1 (en) | Particulate silicon-polymer composites for a negative electrode of lithium secondary batteries and the method of preparation of the same | |
| CN111244361A (en) | Modified polyolefin diaphragm and preparation method and application thereof | |
| CN114865226A (en) | Preparation method and application of MXene-based inorganic particle/PVDF-based polymer composite diaphragm | |
| CN114243209A (en) | Composite diaphragm material and preparation method and application thereof | |
| CN109037689B (en) | Preparation method of lithium ion silicon-based negative electrode material, battery negative electrode and lithium battery | |
| CN111916619A (en) | Lithium ion battery composite diaphragm containing modified inorganic particles and preparation method thereof | |
| CN112563669A (en) | High-wettability diaphragm and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210601 |