CN109037553A - A kind of preparation method of inorganic-organic hybridization composite diaphragm - Google Patents
A kind of preparation method of inorganic-organic hybridization composite diaphragm Download PDFInfo
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- CN109037553A CN109037553A CN201811136774.1A CN201811136774A CN109037553A CN 109037553 A CN109037553 A CN 109037553A CN 201811136774 A CN201811136774 A CN 201811136774A CN 109037553 A CN109037553 A CN 109037553A
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- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000009396 hybridization Methods 0.000 title claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 37
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 37
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 7
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 9
- 238000003837 high-temperature calcination Methods 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 229910017435 S2 In Inorganic materials 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 4
- 210000004379 membrane Anatomy 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 229910000901 LiFePO4/C Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 238000011017 operating method Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- 239000010954 inorganic particle Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a kind of preparation methods of inorganic-organic hybridization composite diaphragm, which comprises the following steps: S1: preparation La2O3‑Al2O3White powdery solids；S2: by La obtained2O3‑Al2O3Powder and Kynoar-hexafluoropropene are added to aprotic solvents by a certain percentage, prepare mixed liquor；The mixed liquor: being coated in the PP basement membrane upper surface of blank by S3, prepares La2O3‑Al2O3/ PVDF-HFP@PP inorganic-organic hybrid diaphragm.Inorganic-organic hybridization composite diaphragm prepared by the present invention, inorganic part add La2O3‑Al2O3Mixture, La2O3Al2O3 in slurry is helped avoid to reunite, Al2O3 is set to be better dispersed in membrane surface, organic moiety uses Kynoar-hexafluoropropene polymer, Kynoar-hexafluoropropene has preferable corrosion resistance, it can effectively prevent coating shedding, there is fold after preventing diaphragm long-time use and falls off, improves performance of lithium ion battery in inorganic-organic part collective effect.
Description
Technical field
The invention belongs to the preparation fields of lithium ion battery separator, and in particular to a kind of inorganic-organic hybridization it is compound every
The preparation method of film.
Background technique
Increasingly depleted with fossil energy, greenhouse effects constantly aggravate, and forcing people to constantly look for one kind can slow down
Energy crisis, and it is avoided that the novel environment friendly new energy of environmental pollution, therefore power of the lithium ion battery as electric car
Extensive concern of the energy by researcher.Present commercialized diaphragm is by poly- in polyolefin and colloidal sol type electrolyte mostly
Object is closed as diaphragm, but these diaphragm mechanical performances, wellability and high temperature resistance are all poor, and peace is easily caused under emergency case
Full hidden danger.
And inorganic material is due to having the research of good thermal stability and electrolyte wellability by research staff, and general
Its surface for being coated to organic micro film improves membrane properties with this.Organic micro-pore septum after being modified by inorganic matter is presented
The wetting property of better thermal stability out, electrolyte also gets a promotion.Miao etc. (J.Power.sources, 2008,184:
420-426) three-layer composite microporous membrane is handled by coating PVDF, the Modified Membrane formed on surface is made to be combined into one,
Battery volume is also reduced while reducing film thickness and enhances battery strength.Usually inorganic ceramic is glued with a certain amount of
Knot agent is mixed with slurry coated on MIcroporous polyolefin film, not only reduces the hot shortness of diaphragm in this way, and enhance electricity
The high temperature safe performance and cycle performance of battery in pond, but in practical commercial diaphragm, hydrophilic particles of inorganic material connects with air
Touching is easy the moisture in absorption air, has large effect to the safe cycle performance of further battery.
Chinese patent (CN105390643A) discloses a kind of preparation method of composite diaphragm for lithium ion battery, it is compound every
Film includes porous substrate with hole and organic/inorganic composite layer, and the organic/inorganic composite layer is with including inorganic particle and one
Kind or it is a variety of selected from polyetherimide, the polymeric binder of poly(aryl ether ketone) and poly and optional
The mixture of high temperature closed-cell materials coats at least one surface of porous substrate or the portion surface area of porous substrate and is formed,
Wherein inorganic particle is connected with each other and is fixed by the polymeric binder, and the gap between inorganic particle forms hole,
The inorganic particle is one of to be selected from the group or a variety of: aluminium oxide, silica, zirconium dioxide, lanthana, titanium dioxide
Titanium, barium sulfate and calcium carbonate.Although can solve the high temperature resistance of lithium ion battery separator, polyetherimide, polyarylether
The organic matters corrosion resistance such as ketone and poly is lower, and lithium ion battery separator connects for a long time with electrolyte
Touching easily causes picking and crumples, causes safety problem.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of inorganic-organic hybridization composite diaphragm, solve above-mentioned background
The problem of middle proposition.
To achieve the above object, the invention provides the following technical scheme:
A kind of preparation method of inorganic-organic hybridization composite diaphragm, comprising the following steps:
S1: by La (NO3)3·6H2O and Al2O3Hot submersion in deionized water 100ml is added and stirs to moisture and steams completely
Gained mixture is dried in 60 DEG C of insulating boxs 12h, then is placed in box Muffle furnace high-temperature calcination by hair, is obtained after cooling
La2O3-Al2O3White powdery solids；
S2: by La obtained2O3-Al2O3White powder is added by a certain percentage with Kynoar-hexafluoropropene solution
To aprotic solvents, additive is added, quickly stirs 3h at a certain temperature, is cooled to room temperature, obtains mixed liquor；
S3: the mixed liquor is coated in the PP basement membrane upper surface of blank, nothing in homogeneous thickness is coated into using coating device
Machine-organic composite diaphragm is dried in vacuo 6h after drying 30min at room temperature at 70 DEG C, finally by diaphragm hot-pressing, can obtain
La2O3-Al2O3/ PVDF-HFP@PP inorganic-organic hybrid diaphragm.
Further, the La (NO3)3·6H2O and Al2O3Mass ratio be 0.084~1.5:1.
Further, in step S1,45~60 DEG C of dipping temperature, dip time 12h.
Further, in step S1, Muffle furnace high-temperature calcination is to be warming up to 600~700 with 1~3 DEG C/min heating rate
DEG C, and 3~5h is kept at such a temperature.
Further, in step S2, the La2O3-Al2O3White powder and Kynoar-hexafluoropropene mass ratio
For 0.625~1.875:1.
Further, in step S2, the aprotic solvents are one or more of acetone, DMF, DMAc.
Further, the Kynoar-hexafluoropropene solution mass fraction is 7%~15%.
Further, in step S3, the temperature of the diaphragm hot-pressing is 70~100 DEG C, and pressure is 0.6~1MPa, hot pressing
Time is 80~120s.
Compared with prior art, the beneficial effects of the present invention are:
Inorganic-organic hybridization composite diaphragm prepared by the present invention, inorganic part add La2O3-Al2O3Mixture, La2O3Have
Help avoid in slurry Al2O3 to reunite, Al2O3 made to be better dispersed in membrane surface, can be enhanced electrolyte wetting property and
The electric conductivity of battery；Organic moiety uses Kynoar-hexafluoropropene polymer, and Kynoar-hexafluoropropene has
Preferable corrosion resistance, can effectively prevent coating shedding, and inorganic-organic part collective effect prevents diaphragm from making for a long time
Occur fold after and fall off, improves lithium ion battery electric conductivity.
Specific embodiment
Case study on implementation 1
La (NO3) 36H2O is mixed with the solid powder that the mass ratio of Al2O3 is 0.848, deionized water 100ml is added
In be heated to the stirring of 55 DEG C of dippings to moisture evaporating completely, by gained mixture in 60 DEG C of insulating boxs dry 12h, then be placed in case
Formula Muffle furnace is warming up to 650 DEG C of high-temperature calcination 4h with the heating rate of 2 DEG C/min, and La2O3-Al2O3 white is obtained after cooling
Pulverulent solids；It is in mass ratio by La2O3-Al2O3 white powder and Kynoar-hexafluoropropene solution (PVDF-HFP)
The ratio of 1.3:1 is added to acetone and the mixing aprotic solvents of DMF, and wherein the mass percent of PVDF-HFP solution is
12%, then addition a small amount of additive quickly stirs 3h at a certain temperature thereto, is cooled to room temperature to obtain the mixed of stable uniform
Close liquid；Mixed liquor is coated in the PP basement membrane upper surface of blank, inorganic-organic hybrid in homogeneous thickness is coated into using coating device
Diaphragm, at room temperature dry 30min after 6h is dried in vacuo at 70 DEG C, finally by diaphragm at 80 DEG C of 0.8MPa hot pressing 90s, i.e.,
La2O3-Al2O3/PVDF-HFP@PP inorganic-organic hybrid diaphragm can be obtained；Using inorganic-organic hybrid diaphragm as lithium-ion electric
Pond diaphragm be applied to LiFePO4/C battery, 0.1C charge and discharge, specific discharge capacity reach 146mAh/g, recycle 50 weeks, capacity substantially without
Decaying.
Case study on implementation 2
La (NO3) 36H2O is mixed with the solid powder that the mass ratio of Al2O3 is 0.1 and is added in deionized water 100ml
It is heated to 55 DEG C of dippings stirrings and gained mixture is dried into 12h in 60 DEG C of insulating boxs to moisture evaporating completely, then be placed in box
Muffle furnace is warming up to 650 DEG C of high-temperature calcination 4h with the heating rate of 2 DEG C/min, obtains La2O3-Al2O3 white powder after cooling
Last shape solid；It is in mass ratio 1.3:1's by La2O3-Al2O3 white powder and Kynoar-hexafluoropropene PVDF-HFP
Ratio is added to acetone and the mixing aprotic solvents solvent of DMF, and wherein the mass percent of PVDF-HFP solution is 12%,
Addition a small amount of additive quickly stirs 3h at a certain temperature thereto again, is cooled to room temperature to obtain the mixed liquor of stable uniform；
Mixed liquor is coated in the PP basement membrane upper surface of blank, inorganic-organic hybrid diaphragm in homogeneous thickness is coated into using coating device,
At room temperature dry 30min after 6h is dried in vacuo at 70 DEG C, finally by diaphragm at 80 DEG C of 0.8MPa hot pressing 90s, can obtain
La2O3-Al2O3/PVDF-HFP@PP inorganic-organic hybrid diaphragm；Using inorganic-organic hybrid diaphragm as lithium ion battery every
Film is applied to LiFePO4/C battery, 0.1C charge and discharge, and specific discharge capacity reaches 134mAh/g, recycles 50 weeks, and capacity is substantially without declining
Subtract.
Case study on implementation 3
La (NO3) 36H2O is mixed with the solid powder that the mass ratio of Al2O3 is 1.3 and is added in deionized water 100ml
It is heated to 55 DEG C of dippings stirrings and gained mixture is dried into 12h in 60 DEG C of insulating boxs to moisture evaporating completely, then be placed in box
Muffle furnace is warming up to 650 DEG C of high-temperature calcination 4h with the heating rate of 2 DEG C/min, obtains La2O3-Al2O3 white powder after cooling
Last shape solid；It is in mass ratio 1.3:1's by La2O3-Al2O3 white powder and Kynoar-hexafluoropropene PVDF-HFP
Ratio is added to acetone and the mixing aprotic solvents solvent of DMF, and wherein the mass percent of PVDF-HFP solution is 12%,
Addition a small amount of additive quickly stirs 3h at a certain temperature thereto again, is cooled to room temperature to obtain the mixed liquor of stable uniform；
Mixed liquor is coated in the PP basement membrane upper surface of blank, inorganic-organic hybrid diaphragm in homogeneous thickness is coated into using coating device,
At room temperature dry 30min after 6h is dried in vacuo at 70 DEG C, finally by diaphragm at 80 DEG C of 0.8MPa hot pressing 90s, can obtain
La2O3-Al2O3/PVDF-HFP@PP inorganic-organic hybrid diaphragm；Using inorganic-organic hybrid diaphragm as lithium ion battery every
Film is applied to LiFePO4/C battery, 0.1C charge and discharge, and specific discharge capacity reaches 138mAh/g, recycles 50 weeks, and capacity is substantially without declining
Subtract.
Case study on implementation 4
The mass ratio of La (NO3) 36H2O and Al2O3 is 1.6, by inorganic-organic by operating procedure such as case study on implementation 1
Composite diaphragm is applied to LiFePO4/C battery, 0.1C charge and discharge as lithium ion battery separator, and specific discharge capacity reaches 138mAh/
G is recycled 50 weeks, capacity slight fading, is the 91% of initial capacity.
Case study on implementation 5
Operating procedure such as case study on implementation 1, the mass percent of PVDF-HFP solution is 4%, by inorganic-organic hybrid diaphragm
It is applied to LiFePO4/C battery, 0.1C charge and discharge as lithium ion battery separator, specific discharge capacity reaches 136mAh/g, circulation 50
In week, discharge capacity is 88% initially, and dismantling battery core metacneme slightly loses powder and slight fold.
Case study on implementation 6
Operating procedure such as case study on implementation 1, the mass percent of PVDF-HFP solution are 17%, by inorganic-organic hybrid every
Film is applied to LiFePO4/C battery, 0.1C charge and discharge as lithium ion battery separator, and specific discharge capacity reaches 125mAh/g, circulation
50 weeks, discharge capacity was 90% initially.
Case study on implementation 7
Operating procedure such as case study on implementation 1 does not add La (NO3) 36H2O, using inorganic-organic hybrid diaphragm as lithium from
Sub- battery diaphragm is applied to LiFePO4/C battery, 0.1C charge and discharge, and specific discharge capacity reaches 128mAh/g, recycles 50 weeks, light capacity
Microwave attenuation is the 94% of initial capacity.
Case study on implementation 8
Operating procedure such as case study on implementation 1, does not add organic polymer P VDF-HFP, using inorganic-organic hybrid diaphragm as
Lithium ion battery separator is applied to LiFePO4/C battery, 0.1C charge and discharge, and specific discharge capacity reaches 120mAh/g, recycles 50 weeks, puts
Capacitance is initial capacity 80%, and dismantling battery core metacneme picking is serious.
Case study on implementation 9
Operating procedure such as case study on implementation 1, not adding organic polymer P VDF-HFP and inorganic salts La (NO3) 36H2O will
Inorganic-organic hybrid diaphragm is applied to LiFePO4/C battery, 0.1C charge and discharge, specific discharge capacity as lithium ion battery separator
It up to 117mAh/g, recycles 50 weeks, discharge capacity is 70% initially, and picking is serious after disassembling battery core.
Case study on implementation 10
Operating procedure such as case study on implementation 1, is reduced to 65 DEG C for hot temperature of colding pressing, and the time is reduced to 60s, by inorganic-organic hybrid
Diaphragm is applied to LiFePO4/C battery as lithium ion battery separator, and after fluid injection chemical conversion, diaphragm is slightly crumpled.
The preferred embodiment of the patent is described in detail above, but this patent is not limited to above-mentioned embodiment party
Formula within the knowledge of one of ordinary skill in the art can also be under the premise of not departing from this patent objective
It makes a variety of changes.
Claims (9)
1. a kind of preparation method of inorganic-organic hybridization composite diaphragm, which comprises the following steps:
S1: preparation La2O3-Al2O3White powdery solids；
S2: by La obtained2O3-Al2O3It is molten that powder with Kynoar-hexafluoropropene is added to aprotic by a certain percentage
Agent prepares mixed liquor；
The mixed liquor: being coated in the PP basement membrane upper surface of blank by S3, prepares La2O3-Al2O3/ PVDF-HFP@PP is inorganic-has
Machine composite diaphragm.
2. the preparation method of inorganic-organic hybridization composite diaphragm according to claim 1, which is characterized in that including following
Step:
S1: by La (NO3)3·6H2O and Al2O3Hot submersion in deionized water 100ml is added to stir to moisture evaporating completely, it will
Gained mixture dry 12h in 60 DEG C of insulating boxs, then it is placed in box Muffle furnace high-temperature calcination, La is obtained after cooling2O3-
Al2O3White powdery solids；
S2: by La obtained2O3-Al2O3White powder and Kynoar-hexafluoropropene solution are added to non-matter by a certain percentage
Additive is added in subtype solvent, quickly stirs 3h at a certain temperature, is cooled to room temperature, obtains mixed liquor；
S3: by the mixed liquor be coated in blank PP basement membrane upper surface, using coating device be coated into it is in homogeneous thickness it is inorganic-have
Machine composite diaphragm is dried in vacuo 6h after drying 30min at room temperature at 70 DEG C, finally by diaphragm hot-pressing, can obtain La2O3-
Al2O3/ PVDF-HFP@PP inorganic-organic hybrid diaphragm.
3. the preparation method of inorganic-organic hybridization composite diaphragm according to claim 2, which is characterized in that the La
(NO3)3·6H2O and Al2O3Mass ratio be 0.084~1.5:1.
4. the preparation method of inorganic-organic hybridization composite diaphragm according to claim 2 or 3, which is characterized in that step S1
In, 45~60 DEG C of dipping temperature, dip time 12h.
5. the preparation method of inorganic-organic hybridization composite diaphragm according to claim 2 or 3, which is characterized in that step S1
In, Muffle furnace high-temperature calcination be warming up to 600~700 DEG C with 1~3 DEG C/min heating rate, and at such a temperature keep 3~
5h。
6. the preparation method of inorganic-organic hybridization composite diaphragm according to claim 1 or 2, which is characterized in that step S2
In, the La2O3-Al2O3White powder and Kynoar-hexafluoropropene mass ratio are 0.625~1.875:1.
7. the preparation method of inorganic-organic hybridization composite diaphragm according to claim 1 or 2, which is characterized in that step S2
In, the aprotic solvents are one or more of acetone, DMF, DMAc.
8. the preparation method of inorganic-organic hybridization composite diaphragm according to claim 2, which is characterized in that polyvinylidene fluoride
Alkene-hexafluoropropene solution mass fraction is 7%~15%.
9. the preparation method of inorganic-organic hybridization composite diaphragm according to claim 2, which is characterized in that in step S3,
The temperature of the diaphragm hot-pressing is 70~100 DEG C, and pressure is 0.6~1MPa, and hot pressing time is 80~120s.
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| CN201811136774.1A CN109037553A (en) | 2018-09-28 | 2018-09-28 | A kind of preparation method of inorganic-organic hybridization composite diaphragm |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112768835A (en) * | 2021-01-07 | 2021-05-07 | 陈云 | Cr (chromium)3AlC2Preparation method of/PVDF-PVA lithium ion battery diaphragm |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306726A (en) * | 2011-08-12 | 2012-01-04 | 沧州明珠塑料股份有限公司 | Compound modified polyolefin lithium ion battery separator and manufacturing method thereof |
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2018
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| CN112768835A (en) * | 2021-01-07 | 2021-05-07 | 陈云 | Cr (chromium)3AlC2Preparation method of/PVDF-PVA lithium ion battery diaphragm |
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