CN108305977A - A kind of caking property polymer-coated lithium ion battery separator and preparation method thereof - Google Patents
A kind of caking property polymer-coated lithium ion battery separator and preparation method thereof Download PDFInfo
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- CN108305977A CN108305977A CN201810121110.1A CN201810121110A CN108305977A CN 108305977 A CN108305977 A CN 108305977A CN 201810121110 A CN201810121110 A CN 201810121110A CN 108305977 A CN108305977 A CN 108305977A
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- Prior art keywords
- caking property
- property polymer
- coating
- polymer powder
- particle
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- 229920000642 polymer Polymers 0.000 title claims abstract description 65
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 239000006185 dispersion Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 230000001070 adhesive effect Effects 0.000 claims abstract description 17
- 239000000853 adhesive Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 230000002776 aggregation Effects 0.000 claims description 9
- 238000004220 aggregation Methods 0.000 claims description 7
- 239000004816 latex Substances 0.000 claims description 7
- 229920000126 latex Polymers 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010020 roller printing Methods 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000004760 aramid Substances 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 230000002146 bilateral effect Effects 0.000 claims description 2
- 239000008199 coating composition Substances 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000120 polyethyl acrylate Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 claims 1
- 210000000481 breast Anatomy 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 239000002759 woven fabric Substances 0.000 claims 1
- 238000007731 hot pressing Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000029058 respiratory gaseous exchange Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- -1 alkene nitrile Chemical class 0.000 description 8
- 210000004379 membrane Anatomy 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 210000002469 basement membrane Anatomy 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000003384 imaging method Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 101150016402 fsn-1 gene Proteins 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical class CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying 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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- 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 present invention provides a kind of caking property polymer-coated lithium ion battery separators, including：Base material, the side of base material or both sides coat cementitious polymer coating, the coating is made of Aqueous Adhesives and caking property polymer powder, the random dispersion arrangement in the form of single of the particle of caking property polymer powder, or with more particle aggregate forms in random dispersion arrangement or proper alignment.The production process of the present invention is environmental-friendly, safe, production cost is low；Using micron-sized caking property polymer powder instead of nanoscale caking property polymer powder used in the prior art, reduce traditional nanoscale caking property polymeric powder particles and is formed by influence of the multilayer close-packed structure to value of breathing freely, meanwhile effectively avoid pole piece and during diaphragm hot-pressing cementitious material by the completely plugged battery core scrap problem formed caused by dead zone of diaphragm micro-hole.The present invention also provides a kind of preparation methods of caking property polymer-coated lithium ion battery separator.
Description
Technical field
The present invention relates to lithium ion battery separator fields, more particularly, to a kind of caking property polymer-coated lithium ion battery
The preparation method of diaphragm and this battery diaphragm.
Background technology
Lithium ion battery have the characteristics that energy density is high, operating voltage is high, memory-less effect and have extended cycle life and by
It is widely used as the power supply of various mobile devices.Lithium ion battery generally includes anode, cathode, diaphragm and electrolyte, diaphragm conduct
Barrier between positive and negative anodes play the role of to the performance of lithium ion battery it is vital, therefore pass through improve diaphragm performance
Come improve the safety of lithium ion battery, the research of usability, craftsmanship receives more and more attention.
Country requires to be continuously improved to lithium ion battery energy density, to improve battery energy density, selects ternary nickelic
Positive electrode is inexorable trend, and corresponding high-energy negative material must be matched using high energy positive electrode, electric in this system
Core easily deforms in charge and discharge process, at the same cathode pole piece rebound it is larger and with cycle-index it is continuous accumulation have by
Increase tendency is walked, to solve the problems, such as this, industry technical field proposes sticky diaphragm concept, and positive/negative plate is passed through certain condition
It bonds together, purpose is exactly to effectively control battery core deformation and inhibit cathode pole piece rebound, do not influencing battery performance
Under the premise of play bonding positive/negative plate function.
Invention content
For problems of the prior art, the primary purpose of the present invention is that providing a kind of caking property polymer-coated
Lithium ion battery separator has good caking property and ion permeability, effectively improves the security performance of lithium ion battery and makes
Use performance；The secondary objective of the present invention is to provide a kind of preparation method of caking property polymer-coated lithium ion battery separator.
In order to solve the above technical problems, a kind of caking property polymer-coated lithium ion battery separator provided by the invention, packet
It includes：Base material, the side of the base material or both sides coat cementitious polymer coating, and the coating is by Aqueous Adhesives and bonding
Property polymer powder composition, the random dispersion in the form of single of the particle of the caking property polymer powder arranges, or with more
Grain aggregate form is arranged in random dispersion or proper alignment.
Further, the base material is that polyolefin, the microporous barrier of aromatic polyamide or non-woven fabrics material and its coating are modified
Product.
Further, the Aqueous Adhesives are：Butadiene-styrene latex, styrene-acrylic latex, purified petroleum benzin latex, polymethyl methacrylate,
Polybutyl methacrylate, polyethyl acrylate, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polyvinyl acetate, poly- ammonia
The mixture of one or more of ester.
Further, the caking property polymer powder is：Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, poly- third
One or more of alkene nitrile, polymethylmethacrylate powder；Grain size is in 0.1-20 μ ms.
Further, the particle of caking property polymer powder is in the form of single when random dispersion arrangement in the coating, institute
The grain diameter for stating polymer powder is in 0.1-10 μ ms, and particle of the grain size more than 2 μm accounts for total particle quantity
60% or more.
Further, in the coating particle of sticky polymers powder with aggregate form random dispersion arrangement or neat
When arrangement, the aggregation is in the crateriform of the sunken surrounding protrusion in center, and it is low to be distributed in the crateriform aggregation center
The quantity of the caking property polymer powder of concave portion point is less than crateriform aggregation surrounding projection portion, and between existing between particle
Gap；The grain diameter of coated polymeric powder is in 0.1-20 μ ms, and particle of the grain size more than 5 μm accounts for total particle quantity
60% or more.
A kind of preparation method of above-mentioned caking property polymer-coated lithium ion battery separator, this method comprises the following steps：
Step 1: after Aqueous Adhesives and deionized water are stirred evenly, caking property polymer powder is added, is uniformly dispersed
After obtain dispersion liquid；
Step 2: the dispersion liquid is ground 10-30min, caking property polymer paste, slurry viscosity 5- are obtained
300mpa.s；
Step 3: the slurry to be coated on to the unilateral or bilateral of base material, caking property polymer-coated is obtained after drying
Lithium ion battery separator, drying temperature are 40-70 DEG C.
Further, in the step 2, the caking property polymer paste contains 1-15% according to mass percent calculating
The Aqueous Adhesives, 1-40% the caking property polymer powder, surplus is deionized water.
Further, it in the step 3, is coated with using gravure, narrow slit type coating or dip-coating formula, by the bonding
Property polymer powder particle random dispersion arrangement in the form of single.
Further, in the step 3, jet printing type is coated with or sputtered using roller printing formula and is coated with, the caking property is gathered
Object powder is closed with aggregate form in random dispersion arrangement or proper alignment.
The above-mentioned technical proposal of the present invention has the advantages that：The present invention has abandoned traditional use acetone or N- first
The intensive polar solvents such as base pyrrolidones, N ' N- dimethylacetylamides prepare the technique of oiliness PVDF coatings, production process environment friend
It is good, safe, production cost is low；On the other hand the present invention uses micron-sized caking property polymer powder instead of existing skill
Nanoscale caking property polymer powder employed in art reduces traditional nanoscale caking property polymeric powder particles institute shape
At influence of the multilayer close-packed structure to ventilative value, meanwhile, effectively avoid cementability during pole piece and diaphragm hot-pressing
Material by diaphragm micro-hole it is completely plugged formed dead zone caused by battery core scrap problem；
By the present invention in that with micron order caking property polymer powder improve in hot pressing adhesive material with it is positive and negative
Active force between the material of pole makes adhesive material be easier in the hole for being embedded into positive and negative electrode material surface, is formed stronger
Interlocking, and then the adhesive effect between diaphragm and pole piece is improved, battery core hardness is effectively improved, reduces battery core deformation, therefore
With higher security performance；
Caking property polymer material used herein has good imbibition, liquid-keeping property, can improve following for battery core
Ring performance, while the present invention can improve effective bonding point by the adjustment of caking property polymer powder grain size and the morphology of the aggregate
Ratio, reach the usage amount for reducing caking property polymer material, and reduce the purpose that tightness degree is accumulated between particle, can be with
More channels are provided for the conduction of lithium ion, especially after hot-pressing, breathing freely to increase is much smaller than conventional adhesive separator product,
Diaphragm impedance is reduced, the permeability of lithium ion is improved, makes battery that there is good high rate performance.
Description of the drawings
It below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art are briefly described, it should be apparent that, in being described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, other drawings may also be obtained based on these drawings.
Fig. 1 is caking property polymer powder of the present invention diaphragm apparent form electronics when random dispersion is arranged in the form of single
Scanning imaging figure (SEM figures)；
Fig. 2 is diaphragm table when caking property polymer powder of the present invention is arranged with the random dispersion of crateriform aggregate form
It sees one of pattern electron scanning imaging figure (SEM figures)；
Fig. 3 is diaphragm table when caking property polymer powder of the present invention is arranged with the random dispersion of crateriform aggregate form
See two (SEM figures) of pattern electron scanning imaging figure；
Fig. 4 is the single crateriform aggregation apparent form electron scanning imaging figure of caking property polymer powder of the present invention
(SEM figures)；
Specific implementation mode
Technical scheme of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
The every other embodiment that personnel are obtained without making creative work, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that term "center", "upper", "lower", "left", "right", "vertical",
The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" be based on the orientation or positional relationship shown in the drawings, merely to
Convenient for the description present invention and simplify description, do not indicate or imply the indicated device or element must have a particular orientation,
With specific azimuth configuration and operation, therefore it is not considered as limiting the invention.In addition, term " first ", " second ",
" third " is used for description purposes only, and is not understood to indicate or imply relative importance.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected；It can
Can also be electrical connection to be mechanical connection；It can be directly connected, can also indirectly connected through an intermediary, Ke Yishi
Connection inside two elements.For the ordinary skill in the art, above-mentioned term can be understood at this with concrete condition
Concrete meaning in invention.
Embodiment 1
Step 1: after the aqueous butadiene-styrene latex adhesives of 1kg and 98kg deionized waters are stirred evenly, the poly- methyl of 1kg is added
Methyl acrylate powder obtains dispersion liquid after being uniformly dispersed；
Step 2: above-mentioned dispersion liquid is ground 30min, caking property polymer paste, slurry viscosity 5.1mpa.s are obtained；
Step 3: choose overall thickness be 12 μm of ceramic coated modified poly ethylene microporous barriers as base material, wherein polyethylene is micro-
Hole film thickness is 9 μm, and porosity 38%, ceramic layer thickness is 3 μm, and above-mentioned slurry is coated on base material using plate gravure coating method
Both sides, application rate 55m/min dried using three-level baking oven, oven temperatures at different levels are respectively 50 DEG C, 60 DEG C, 55
DEG C, caking property polymer coating is obtained after dry, two-sided coatings surface density value added is 0.6g/m2.Poly- methyl in the coating
Methyl acrylate powder random dispersion arrangement, polymeric powder particles grain size in the form of single are in 0.1-10 μ ms,
And particle accounting of the grain size more than 2 μm be more than 70%, with reference to figure 1.
Embodiment 2
Step 1: after 15kg aqueous polyacrylamide acetoacetic ester adhesives and 45kg deionized waters are stirred evenly, 40kg is added
Vinylidene fluoride-hexafluoropropylene copolymer powder obtains dispersion liquid after being uniformly dispersed；
Step 2: above-mentioned dispersion liquid is ground 10min, caking property polymer paste, slurry viscosity 296.8mpa.s are obtained；
Step 3: choose overall thickness be 20 μm of ceramic coated modified polypropene microporous barriers as base material, wherein polypropylene is micro-
Hole film thickness is 16 μm, and porosity 50%, ceramic layer thickness is 4 μm, is coated on above-mentioned slurry by the way of rotary spraying
The both sides of base material, application rate 35m/min, rotary speed 10000r/min, quantity for spray 4m1/m2 are carried out using three-level baking oven
Drying, oven temperatures at different levels are respectively 48 DEG C, 55 DEG C, 60 DEG C, obtain caking property polymer coating after dry, two-sided coatings face is close
Degree value added is 1.1g/m2.Vinylidene fluoride-hexafluoropropylene copolymer particle is in the form of crateriform aggregation in the coating
Random dispersion arrangement, polymeric powder particles grain size are in 0.1-20 μ ms, and particle accounting of the grain size more than 5 μm exists
More than 80%, referring to figs. 2 and 3.
Embodiment 3
Step 1: after the aqueous styrene-acrylic latex adhesives of 11.5kg and 68.5kg deionized waters are stirred evenly, 20kg is added
Kynoar, 3.5kg modified polyacrylonitrile powder, dispersion liquid is obtained after being uniformly dispersed；
Step 2: above-mentioned dispersion liquid is ground 20min, caking property polymer paste, slurry viscosity 181.6mpa.s are obtained；
Step 3: choosing the polyethylene micropore film base material of 12 μ m thicks, porosity 38% will using roller printing mode
Above-mentioned slurry is coated on the both sides of base material, and application rate 55m/min is dried using three-level baking oven, oven temperatures at different levels
Respectively 60 DEG C, 65 DEG C, 70 DEG C, caking property polymer-coated diaphragm is obtained after dry, two-sided coatings surface density value added is
1.0g/m2.It is neatly arranged in the form of crateriform aggregation in the caking property polymer coating, polymeric powder particles grain
Diameter is in 0.1-20 μ ms, and particle accounting of the grain size more than 5 μm is more than 60%.
Embodiment 4
Step 1: after 7kg Aqueous Polyurethane Adhesives and 88kg deionized waters are stirred evenly, 5kg polyvinylidene fluorides are added
Alkene powder obtains dispersion liquid after being uniformly dispersed；
Step 2: above-mentioned dispersion liquid is ground 15min, caking property polymer paste, slurry viscosity 92.4mpa.s are obtained；
Step 3: it is 16 μm to choose thickness, the microporous polypropylene membrane that porosity is 50% will be upper using slot coated mode
The both sides that slurry is coated on base material are stated, application rate 30m/min is dried using three-level baking oven, oven temperatures at different levels point
Wei not be 40 DEG C, 50 DEG C, 60 DEG C, caking property polymer-coated diaphragm is obtained after dry, two-sided coatings surface density value added is 0.8g/
m2.Vinylidene fluoride-hexafluoropropylene copolymer particle is by the random dispersion row in the form of single in the caking property polymer coating
Cloth, polymeric powder particles grain size are in 0.1-10 μ ms, and particle accounting of the grain size more than 2 μm is more than 60%.
Comparative example 1
The PVDF coatings diaphragm prepared according to conventional oil coating processes as a comparison case 1,1 membrane thicknesses of comparative example is taken to be
18 μm, two-sided coatings, 2 μm of coating layer thickness, basement membrane is microporous polypropylene membrane, 16 μm of basement membrane thickness, porosity 50%.
Comparative example 2
The PVDF coatings diaphragm prepared according to standard aqueous coating processes as a comparison case 2,2 membrane thicknesses of comparative example is taken to be
18 μm, two-sided coatings, 2 μm of coating layer thickness, basement membrane is microporous polypropylene membrane, 16 μm of basement membrane thickness, porosity 50%, comparative example 2
Used in PVDF toners particle spherical in shape, grain diameter 150-200nm.
Diaphragm and comparative example 1-2 diaphragms prepared by Example 1-5, carries out surface density value added and permeability test, so
Afterwards heat is carried out with after the nickel-cobalt-manganese ternary material of preparation (523 type) anode pole piece and graphite (FSN-1) cathode pole piece winding respectively
Dry-pressing performance test.Specific test condition is to preheat 30min under the conditions of 80 DEG C first, then under the conditions of 80 DEG C, 0.8MPa
Hot pressing 60s.Diaphragm and pole piece adhesion strength contrast test are carried out after the completion of hot dry-pressing, and take the diaphragm testing air permeable after stripping
Property, the data obtained such as following table one：
The caking property polymer coating surface density from the diaphragm that one data of upper table can be seen that the embodiment of the present invention 1-4
The peel strength that value added is significantly less than between comparative example 1 and 2, with pole piece is positively retained at 10N/m or more, it can thus be appreciated that this hair
The diaphragm of bright making can play the role of good cohesive positive/negative plate, and battery is made to have more excellent security performance.
In addition, the gas permeability of diaphragm of the present invention is better than comparative example 1 and 2, after especially hot dry-pressing is completed, ventilative value added is significantly less than
Comparative example 1 and 2 improves the transmission ability of lithium ion, makes it can thus be appreciated that the diaphragm that the present invention makes advantageously reduces diaphragm impedance
Battery has good high rate performance and cycle performance, effectively avoids in pole piece and cementitious material will be every during diaphragm hot-pressing
The completely plugged battery core scrap problem formed caused by dead zone of membrane micropore.
Diaphragm prepared by Example 2 and comparative example 2, respectively with the positive pole of the nickel-cobalt-manganese ternary material of preparation (523 type)
Piece and graphite (FSN-1) cathode pole piece use winding process, and flexible packing lithium ion battery is made.Above two battery carries out
Inner walkway under the conditions of 3.85V, the capacity under the conditions of 0.5C constant-current constant-voltage chargings/1.0C constant-current discharges after 500 cycles are protected
Holdup, 4.2V, 168h is shelved under the conditions of 60 DEG C after battery core expansion rate test, acquired results are shown in Table two：
From two data of upper table can be seen that using diaphragm of the present invention preparation polymer Li-ion battery cycle performance,
Impedance, the performance for preventing battery core deformation etc. are better than comparative example diaphragm.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of caking property polymer-coated lithium ion battery separator, which is characterized in that including：Base material, the side of the base material
Or both sides coat cementitious polymer coating, which is made of Aqueous Adhesives and caking property polymer powder, described
The random dispersion arrangement in the form of single of the particle of caking property polymer powder, or with more particle aggregate forms in random point
Dissipate arrangement or proper alignment.
2. battery diaphragm as described in claim 1, which is characterized in that the base material is polyolefin, aromatic polyamide or nothing
The microporous barrier and its coating modified product of woven fabric material.
3. battery diaphragm as described in claim 1, which is characterized in that the Aqueous Adhesives are：Butadiene-styrene latex, phenylpropyl alcohol breast
Glue, purified petroleum benzin latex, polymethyl methacrylate, polybutyl methacrylate, polyethyl acrylate, polyvinyl alcohol, ethyl vinyl acetate
The mixture of one or more of ethylene copolymer, polyvinyl acetate, polyurethane.
4. battery diaphragm as described in claim 1, which is characterized in that the caking property polymer powder is：Kynoar,
One or more of vinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethylmethacrylate powder；Grain size is in
In 0.1-20 μ ms.
5. battery diaphragm as described in claim 1, which is characterized in that in the coating particle of caking property polymer powder with
When the single random dispersion of form is arranged, the grain diameter of the polymer powder is in 0.1-10 μ ms, and grain size is big
60% or more of total particle quantity is accounted in 2 μm of particles.
6. battery diaphragm as described in claim 1, which is characterized in that the particle of sticky polymers powder is with poly- in the coating
When the random dispersion arrangement of aggregate forms or proper alignment, the aggregation is in the crateriform of the sunken surrounding protrusion in center, and
The quantity for being distributed in the caking property polymer powder of the sunken part in crateriform aggregation center is less than crateriform aggregation
Surrounding projection portion, and there are gaps between particle；The grain diameter of coated polymeric powder is in 0.1-20 μ ms, and
Particle of the grain size more than 5 μm accounts for 60% or more of total particle quantity.
7. a kind of preparation method of the caking property polymer-coated lithium ion battery separator as described in any in 1-6 such as claim,
This method comprises the following steps：
Step 1: after Aqueous Adhesives and deionized water are stirred evenly, caking property polymer powder is added, is obtained after being uniformly dispersed
Obtain dispersion liquid；
Step 2: the dispersion liquid is ground 10-30min, caking property polymer paste, slurry viscosity 5-300mpa.s are obtained；
Step 3: the slurry to be coated on to the unilateral or bilateral of base material, obtained after drying caking property polymer-coated lithium from
Sub- battery diaphragm, drying temperature are 40-70 DEG C.
8. preparation method as claimed in claim 7, which is characterized in that in the step 2, the caking property polymer paste
The caking property polymer powder of the Aqueous Adhesives containing 1-15%, 1-40% are calculated according to mass percent, it is remaining
Amount is deionized water.
9. preparation method as claimed in claim 7, which is characterized in that in the step 3, utilize gravure, narrow slit type
Coating or the coating of dip-coating formula, by the particle of the caking property polymer powder, random dispersion is arranged in the form of single.
10. preparation method as claimed in claim 7, which is characterized in that in the step 3, using roller printing formula coating or
Jet printing type coating is sputtered, by the caking property polymer powder with aggregate form in random dispersion arrangement or proper alignment.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810121110.1A CN108305977B (en) | 2018-02-07 | 2018-02-07 | Adhesive polymer coated lithium ion battery diaphragm and preparation method thereof |
| PCT/CN2018/115521 WO2019153822A1 (en) | 2018-02-07 | 2018-11-15 | Adhesive polymer-coated lithium-ion battery separator and manufacturing method therefor |
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| CN201810121110.1A CN108305977B (en) | 2018-02-07 | 2018-02-07 | Adhesive polymer coated lithium ion battery diaphragm and preparation method thereof |
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| CN108305977B CN108305977B (en) | 2019-12-27 |
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Also Published As
| Publication number | Publication date |
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| CN108305977B (en) | 2019-12-27 |
| WO2019153822A1 (en) | 2019-08-15 |
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Effective date of registration: 20221101 Address after: 061000 West side of Jilin Avenue, north side of Changchun Road, Cangzhou Hi tech Industrial Development Zone, Hebei Province Patentee after: CANGZHOU MINGZHU LITHIUM-ION BATTERY SEPARATOR Co.,Ltd. Address before: 061,001 Zhangzhuangzi Industrial Park, Cangshi Road, Yunhe District, Cangzhou City, Hebei Province Patentee before: CANGZHOU MINGZHU PLASTIC Co.,Ltd. Patentee before: CANGZHOU MINGZHU LITHIUM-ION BATTERY SEPARATOR Co.,Ltd. |
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Denomination of invention: A bonding polymer coated lithium-ion battery separator and its preparation method Effective date of registration: 20231123 Granted publication date: 20191227 Pledgee: Cangzhou Branch of China Everbright Bank Co.,Ltd. Pledgor: CANGZHOU MINGZHU LITHIUM-ION BATTERY SEPARATOR Co.,Ltd. Registration number: Y2023980067250 |
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