CN116565334A - Multilayer composite liquid absorption material and preparation method and application thereof - Google Patents
Multilayer composite liquid absorption material and preparation method and application thereof Download PDFInfo
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- CN116565334A CN116565334A CN202310669899.5A CN202310669899A CN116565334A CN 116565334 A CN116565334 A CN 116565334A CN 202310669899 A CN202310669899 A CN 202310669899A CN 116565334 A CN116565334 A CN 116565334A
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- 239000002131 composite material Substances 0.000 title claims abstract description 110
- 239000007788 liquid Substances 0.000 title claims abstract description 76
- 239000000463 material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 238000010521 absorption reaction Methods 0.000 title abstract description 15
- 239000006260 foam Substances 0.000 claims abstract description 57
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 52
- 239000011358 absorbing material Substances 0.000 claims abstract description 35
- 239000003792 electrolyte Substances 0.000 claims abstract description 35
- 239000003094 microcapsule Substances 0.000 claims abstract description 29
- 239000000919 ceramic Substances 0.000 claims abstract description 22
- 239000002086 nanomaterial Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 10
- 239000002861 polymer material Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 29
- 229910001416 lithium ion Inorganic materials 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 230000002745 absorbent Effects 0.000 claims description 24
- 239000002250 absorbent Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 18
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 18
- 239000004642 Polyimide Substances 0.000 claims description 17
- 229920001721 polyimide Polymers 0.000 claims description 17
- -1 polyethylene Polymers 0.000 claims description 10
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 9
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002775 capsule Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000004513 sizing Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 230000003139 buffering effect Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000007785 strong electrolyte Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008595 infiltration Effects 0.000 description 8
- 238000001764 infiltration Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004804 winding 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a multilayer composite liquid absorbing material and a preparation method and application thereof, wherein the multilayer composite liquid absorbing material comprises microporous foam, two sides of the microporous foam are respectively provided with a non-woven fabric composite layer, inorganic nano materials and microcapsules are filled in pores of the microporous foam, and electrolyte impregnating compound is filled in the microcapsules; the non-woven fabric composite layer consists of non-woven fabric and ceramic composite layers arranged on two sides of the non-woven fabric, and the materials of the ceramic composite layers comprise high polymer materials and nano ceramic materials; through the multilayer structural design and the filling of the electrolyte impregnating compound and the inorganic nano material in the microcapsules, the multilayer composite liquid absorbing material not only has strong electrolyte wettability, excellent liquid absorption and liquid retention, but also has good shockproof and buffering effects, and when the multilayer composite liquid absorbing material is applied to the inside of a battery shell, the electrolyte impregnating time can be effectively shortened, and the charge and discharge performance, the circulation performance and the safety of the battery are improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a multilayer composite liquid absorbing material, and a preparation method and application thereof.
Background
The lithium ion battery is rapidly developed in the fields of power batteries and energy storage batteries, and the requirements of the lithium ion battery on energy density and safety performance are also higher and higher, so that in order to improve the energy density of the lithium ion battery, the purposes of improving the energy density of the battery are generally realized by adopting a high-compaction electrode system, increasing the height and thickness of an electric core and the like. However, the high-compaction system has the problems of reduced electrolyte infiltration efficiency, increased infiltration difficulty and the like, the poor electrolyte infiltration can cause black spots on the surface of the pole piece after the battery is formed, the battery performance is deteriorated, lithium is separated out in the use process of the battery, and thermal runaway is caused when the battery is seriously used.
At present, two methods for improving the wettability of the electrolyte are adopted, namely, a high-pressure liquid injection machine is adopted, and negative pressure/normal pressure circulation is matched, so that the electrolyte is fully filled in the pores among the pole pieces, between the pole pieces and the diaphragm, and between the winding core/stacking core and the battery shell wall as much as possible; and secondly, before formation, the battery cell is allowed to stand at normal temperature or high temperature for a certain time, so that the electrolyte fully infiltrates the pole piece.
CN104868079a discloses a preparation method of a high wettability lithium ion battery diaphragm, which comprises the following specific steps: soaking a lithium ion battery diaphragm in a mixed solution formed by nitric acid and hydrogen peroxide, potassium persulfate or potassium permanganate, sealing, placing in a constant-temperature water bath at 25-60 ℃ for reaction for 24-72 h, then cleaning with a cleaning agent, naturally airing, trimming, and vacuum drying at 30-60 ℃ for 12-72 h to obtain the high-wettability lithium ion battery diaphragm; the high-wettability lithium ion battery diaphragm prepared by the method has uniform aperture, good wettability and high ion conductivity, improves the hydrophilicity and the electrophilicity of the lithium ion battery diaphragm, resists electrolyte corrosion, and has the advantages of simple process, strong stability and easy industrial application.
However, as the specific energy of the lithium ion battery is gradually increased, the compaction density of the pole piece is continuously increased, a conventional liquid injection process is adopted, an unimpregnated area is always arranged in the middle of the pole piece, the infiltration uniformity is poor, the infiltration rate is low, and lithium is separated from the corresponding position of the pole piece which is insufficiently infiltrated with the electrolyte, so that the charge and discharge performance, the cycle life and the safety of the battery are seriously affected.
Therefore, developing a multilayer composite liquid-absorbing material with stronger electrolyte wettability and excellent liquid-absorbing performance and liquid-retaining performance is a technical problem which needs to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a multilayer composite liquid absorbing material, a preparation method and application thereof, wherein the multilayer composite liquid absorbing material is characterized in that non-woven fabric composite layers are arranged at two sides of microporous foam, inorganic nano materials and microcapsules are filled in pores of the microporous foam, and electrolyte impregnating compound is filled in the microcapsules, so that the multilayer composite liquid absorbing material has good wettability to electrolyte, and simultaneously has excellent liquid absorbing performance and liquid retaining performance, and can effectively improve the cycle performance and safety performance of a battery when being applied to a lithium ion battery.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the invention provides a multilayer composite liquid absorbent material, which comprises microporous foam, wherein non-woven fabric composite layers are arranged on two sides of the microporous foam;
the pores of the microporous foam are filled with inorganic nano materials and microcapsules, and the microcapsules are filled with electrolyte impregnating compound;
the non-woven fabric composite layer consists of non-woven fabric and ceramic composite layers arranged on two sides of the non-woven fabric, and the materials of the ceramic composite layers comprise high polymer materials and nano ceramic materials.
The multi-layer composite liquid absorbing material provided by the invention comprises microporous foam, wherein non-woven fabric composite layers are arranged at two sides of the microporous foam, inorganic nano materials and microcapsules are filled in pores of the microporous foam, electrolyte impregnating compound is contained in the microcapsules, the non-woven fabric composite layers consist of non-woven fabrics and ceramic composite layers arranged at two sides of the non-woven fabrics, and materials for limiting the ceramic composite layers comprise high polymer materials and nano ceramic materials;
firstly, matching is carried out by adopting non-woven fabrics and ceramic composite layers, on one hand, the non-woven fabrics have good wettability to electrolyte for lithium ion batteries, and on the other hand, the large specific surface area of nano ceramic materials in the ceramic composite layers is utilized, and the matching of high polymer materials can overcome the defects of large aperture and uneven distribution of the non-woven fabrics, so that the liquid absorption performance of the obtained non-woven fabrics composite layers is further improved;
secondly, inorganic nano materials and microcapsules are filled in the pores of the microporous foam, on one hand, when the multi-layer composite liquid absorbing material is used in the battery, the volume expansion of the battery core can cause the microporous foam to be pressed, and the microcapsules are pressed and broken along with the pressing of the microporous foam, so that electrolyte impregnating compound in the microcapsules flows out of the pores and enters the battery, and electrolyte continuously consumed in the battery can be supplemented, so that the cycle life of the battery is prolonged; on the other hand, the microporous foam also has the advantages of high rebound resilience and high tensile resistance, has good shockproof and buffering performances, has a certain supporting effect on the volume expansion of the battery inner cell, effectively reduces the damage to the battery inner structure caused by external impact and the like, and effectively improves the safety performance of the battery;
finally, the microporous capsule is arranged on the outer surface of the battery core in the battery shell, so that the cycle life of the battery can be prolonged on the basis of not reducing the energy density of the battery core, and the manufacturing cost is lower.
Preferably, the microporous foam comprises ethylene-vinyl acetate copolymer (EVA) microporous foam or Polyurethane (PU) microporous foam.
As a preferable technical scheme of the invention, the EVA microporous foam has the advantages of high density, strong liquid absorption, corrosion resistance, no pollution, excellent heat preservation performance, rebound resilience and high tension resistance, and also has the advantage of excellent heat preservation and cold protection performance, so that the use environment temperature range of the battery can be widened.
As a preferable technical scheme of the invention, the PU microporous foam has larger specific surface area, good elasticity, good electrochemical corrosion resistance and light weight.
Preferably, the microporous foam has a porosity of 25 to 60%, such as 30%, 35%, 40%, 45%, 50% or 55%, etc.
Preferably, the thickness of the microporous foam is 1 to 6mm, for example 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm, 5mm or 5.5mm, etc.
Preferably, the inorganic nanomaterial is a porous inorganic nanomaterial.
As a preferable technical scheme of the invention, the microporous inorganic nano material is selected to be filled in the pores of the microporous foam, and the porous foam has a relatively large specific surface area and relatively strong adsorption capacity, so that the liquid absorption capacity of the microporous foam is improved.
Preferably, the microporous inorganic nanomaterial comprises any one or a combination of at least two of microporous nano-silica, microporous nano-titania or microporous nano-alumina.
Preferably, the electrolyte sizing agent comprises any one or a combination of at least two of vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate or ethylene sulfite.
Preferably, the material of the capsule wall of the microcapsule comprises any one or a combination of at least two of epoxy resin, polyethylene, polypropylene or polyurethane.
Preferably, the mass ratio of the microporous inorganic nanomaterial to the microcapsule is (5-15): 1, e.g., 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, etc.
Preferably, the nonwoven fabric is polyphenylene sulfide (PPS) nonwoven fabric having excellent acid and alkali resistance, high temperature resistance, and good wettability to lithium ion battery electrolyte.
Preferably, the nonwoven fabric has a thickness of 0.1 to 1mm, for example, 0.2mm, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, or the like.
Preferably, the ceramic composite layer has a thickness of 60 to 300 μm, for example 100 μm, 150 μm, 200 μm or 250 μm, etc.
Preferably, the mass ratio of the polymer material to the nano ceramic material is (20-25): 1, for example, 20.5:1, 21:1, 21.5:1, 22:1, 22.5:1, 23:1, 23.5:1, 24:1 or 24.5:1, etc.
Preferably, the nano ceramic material comprises any one or a combination of at least two of nano silica, nano alumina, nano silica, nano boehmite, nano titania or nano zirconia.
Preferably, the polymer material includes any one or a combination of at least two of Polyimide (PI), polyvinylidene fluoride (PVDF) or Styrene Butadiene Rubber (SBR), and more preferably Polyimide (PI).
As the preferable technical scheme of the invention, the PI has outstanding high temperature resistance, the long-term use temperature can reach 300 ℃, and the PI also has good thermal dimensional stability, thus improving the high-temperature use safety of the battery; secondly, the molecular structure of the PI material contains rich polar groups, so that the wetting property to electrolyte is better; finally, the PI material is flame-retardant and self-extinguished, and a more powerful safety guarantee is provided for the lithium ion battery.
In a second aspect, the present invention provides a method for preparing a multilayer composite liquid absorbent material according to the first aspect, the method comprising the steps of:
(1) Coating the material of the ceramic composite layer on two sides of the non-woven fabric to obtain a composite non-woven fabric;
(2) And (3) compositing the composite non-woven fabric obtained in the step (1) on two sides of the microporous foam to obtain the multilayer composite liquid absorbing material.
Preferably, the method of compounding in step (2) comprises bonding or thermocompression compounding.
In a third aspect, the present invention provides the use of a multilayer composite liquid absorbent material according to the first aspect in a battery.
In a fourth aspect, the present invention provides a lithium ion battery comprising a battery housing, an electrical core, and a multilayer composite liquid absorbent material according to the first aspect;
the multilayer composite liquid absorbing material is arranged inside the battery shell and is coated outside the battery core.
When the multilayer composite liquid absorbing material is used, the multilayer composite liquid absorbing material is adhered to the inner side surface of the battery shell and coats the battery core, so that electrolyte deposited at the bottom of the battery shell can be infiltrated into the middle upper part of the battery shell through the multilayer composite liquid absorbing material, the infiltration time of the electrolyte is greatly shortened, and the production efficiency of the battery is improved; meanwhile, when the volume of the battery expands, the stored electrolyte can be released, so that the cycle life of the battery cell is effectively prolonged, the problem of lithium precipitation caused by electrolyte drying is reduced, and further the charge and discharge performance and safety of the battery are effectively improved.
Preferably, the battery cell is a laminated battery cell or a wound battery cell.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a multilayer composite liquid absorbing material and a preparation method and application thereof, wherein the multilayer composite liquid absorbing material comprises microporous foam, two sides of the microporous foam are respectively provided with a non-woven fabric composite layer, inorganic nano materials and microcapsules are filled in pores of the microporous foam, and electrolyte impregnating compound is filled in the microcapsules; the non-woven fabric composite layer consists of non-woven fabric and ceramic composite layers arranged on two sides of the non-woven fabric, and the materials of the ceramic composite layers comprise high polymer materials and nano ceramic materials; through the structural design of the multilayer composite and the filling of the electrolyte impregnating compound in the microcapsules, the multilayer composite liquid absorbing material not only has strong electrolyte impregnating property, excellent liquid absorption and liquid retention, but also has good shockproof and buffering effects, and when the multilayer composite liquid absorbing material is applied to the inside of a battery shell, the impregnating time of the electrolyte can be effectively shortened, and the charge and discharge performance, the circulation performance and the safety of the battery are improved.
Drawings
Fig. 1 is a schematic cross-sectional view of a multilayer composite liquid absorbent material according to the present invention;
fig. 2 is a schematic structural diagram of the rectangular battery in the length-width direction of the lithium ion inner part;
fig. 3 is a schematic structural diagram of the rectangular battery in the width-thickness direction of lithium ions;
wherein, 1-microporous foam, 2-non-woven fabric composite layer, 2-1-non-woven fabric, 2-2-ceramic composite layer, 3-cell and 4-multilayer composite liquid absorbing material.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Preparation example 1
A microcapsule, the method of preparation comprising: at room temperature, firstly mixing toluene solution of epoxy resin with vinylene carbonate to obtain a mixed solution with epoxy resin as a continuous phase and vinylene carbonate as a disperse phase; and then adding acetone into the mixed solution, gradually gathering epoxy resin dissolved in toluene on the surface of vinylene carbonate, coating the vinylene carbonate, depositing the epoxy resin around the vinylene carbonate to form a continuous coating film, and finally curing to obtain the microcapsule with the capsule wall of the epoxy resin and the vinylene carbonate filled.
The specific preparation method of the microcapsule provided in the preparation example can be referred to CN113036218A.
Example 1
A multi-layer composite liquid absorbing material has a schematic cross-sectional structure shown in figure 1, and comprises microporous foam 1, wherein non-woven fabric composite layers 2 are arranged on two sides of the microporous foam 1;
wherein, the microporous foam 1 is EVA microporous foam, the thickness is 3mm, the porosity is 55%, and the pores of the microporous foam 1 are filled with microcapsules (preparation example 1) and microporous nano silicon dioxide with the mass ratio of 1:10; the method comprises the steps of carrying out a first treatment on the surface of the
The non-woven fabric composite layer 2 consists of a PPS non-woven fabric 2-1 and ceramic composite layers 2-2 arranged on two sides of the PPS non-woven fabric 2-1; wherein the thickness of the PPS non-woven fabric 2-1 is 0.5mm, the thickness of the ceramic composite layer 2-2 is 100 mu m, and the material comprises nano silicon dioxide and PI with the mass ratio of 1:20;
the preparation method of the multilayer composite liquid absorbing material provided by the embodiment comprises the following steps:
(1) Uniformly mixing nano silicon dioxide and PI, coating the mixture on two sides of a PPS non-woven fabric, and drying to obtain a composite non-woven fabric;
(2) And (3) compositing the composite non-woven fabric obtained in the step (1) on two sides of the EVA microporous foam, and pressing to obtain the multilayer composite liquid absorbing material.
Example 2
A multilayer composite absorbent material differs from example 1 only in that PVDF is used in place of PI, and other structures, materials and methods of preparation are described in reference to example 1.
Example 3
A multilayer composite absorbent material differing from example 1 only in that SBR was used in place of PI, and other structures, materials and methods of preparation were as described in example 1.
Example 4
A multilayer composite absorbent material which differs from example 1 only in that PU foam is used instead of EVA foam, and other structures, materials and methods of preparation are described in example 1.
Example 5
A multilayer composite liquid absorbent material differs from example 1 in that PU foam is used for replacing EVA foam, PVDF is used for replacing PI, and other structures, materials and preparation methods refer to example 1.
Example 6
A multilayer composite liquid absorbing material is different from the embodiment 1 in that PU foam is adopted to replace EVA foam, SBR is adopted to replace PI, and other structures, materials and preparation methods refer to the embodiment 1.
Comparative example 1
A multilayer composite liquid absorbent material is different from example 1 in that pores of EVA microporous foam are filled with microporous silica only, microcapsules are not filled, and other structures, materials and preparation methods refer to example 1.
Comparative example 2
A multilayer composite liquid absorbent material differs from example 1 in that only microcapsules are in the pores of EVA microporous foam, no microporous silica is filled, and other structures, materials and methods of preparation are described in example 1.
Comparative example 3
A multilayer composite liquid absorbent material is different from example 1 in that nano silicon dioxide is not added into the material of the ceramic composite layer, the material is PI only, and other structures, materials and preparation methods refer to example 1.
Comparative example 4
A multilayer composite liquid absorbing material comprises EVA microporous foam, wherein non-woven fabric layers are arranged on two sides of the EVA microporous foam;
the thickness of the EVA microporous foam is 3mm, the porosity is 55%, and the pores of the EVA microporous foam are filled with microcapsules (preparation example 1) and microporous nano silicon dioxide in a mass ratio of 1:10;
the thickness of the non-woven fabric composite layer is 0.5mm, and the non-woven fabric composite layer is PPS non-woven fabric;
the preparation method of the multilayer composite liquid absorbing material provided by the comparative example comprises the following steps: and compounding two layers of PPS non-woven fabrics on two sides of the EVA microporous foam, and pressing to obtain the multilayer composite liquid absorbing material.
Application example 1
The rectangular lithium ion battery comprises a battery shell, a battery core 3 and a plurality of layers of composite liquid absorbing materials 4 (embodiment 1), wherein the structure schematic diagram of the inner part in the length-width direction and the structure schematic diagram in the width-thickness direction are respectively shown in fig. 2 and 3, and the plurality of layers of composite liquid absorbing materials 4 are adhered inside the battery shell and are coated outside the battery core 3;
wherein, the battery shell is made of aluminum alloy; the preparation process of the battery cell comprises the following steps: respectively homogenizing, coating, rolling, slitting and baking the anode slurry and the cathode slurry to respectively obtain an anode plate and a cathode plate; laminating the positive and negative plates to obtain an electric core;
the preparation method of the rectangular lithium ion battery provided by the application example comprises the following steps: the multilayer composite liquid absorbing material 4 is adhered outside the battery core 3, and is put into a battery shell together, and then the battery shell is subjected to spot welding, baking and injection of electrolyte (consisting of 14 mass percent of lithium hexafluorophosphate, 30 mass percent of ethylene carbonate, 36 mass percent of methyl ethyl carbonate, 15 mass percent of diethyl carbonate, 3 mass percent of ethylene carbonate and 2 mass percent of N, N-dimethylacrylamide), cap welding, cleaning, shell code spraying, formation and capacity division to obtain the rectangular lithium ion battery.
Application examples 2 to 6
A rectangular lithium ion battery was different from application example 1 only in that the multilayer composite liquid absorbent materials obtained in example 1 were replaced with the multilayer composite liquid absorbent materials obtained in examples 2 to 6, respectively, and the other structures and materials were the same as application example 1.
Comparative application examples 1 to 4
A rectangular lithium ion battery was different from application example 1 only in that the multilayer composite liquid absorbent material obtained in example 1 was replaced with the multilayer composite liquid absorbent materials obtained in comparative examples 1 to 4, respectively, and the other structures and materials were the same as application example 1.
Performance test:
(1) Liquid injection amount: recording the mass of electrolyte injected into the rectangular lithium ion battery;
(2) Liquid absorption rate: the liquid absorption rate is calculated as Q= (m) 2 -m 1 )/m 1 Wherein Q represents the liquid absorption rate, m 1 Represents the net weight (g), m of the multilayer composite liquid absorbent material 2 Representing the weight (g) of the multi-layer composite absorbent material after absorption;
(3) Complete immersion time: the test was performed with reference to CN112084627a, a method among methods for qualitatively characterizing the wettability of an electrolyte.
Rectangular lithium ion batteries provided in application examples 1 to 7 and comparative application examples 1 to 4 were tested according to the above test methods, and the test results are shown in table 1:
TABLE 1
From the data in table 1, it can be seen that:
(1) The liquid injection amount of the rectangular lithium ion battery provided by application examples 1-6 is 722-780 g, the liquid absorption rate of the multilayer composite liquid absorption material in the rectangular lithium ion battery is as high as 143-288%, and the complete infiltration time of the electrolyte is only 380-464 min.
(2) As can be seen from the data of comparative application examples 1 and 1 to 4, the pores of the EVA microporous foam are filled with only microporous silica, the pores of the EVA microporous foam are filled with only microcapsule, the nano silica is not added to the material of the ceramic composite layer, and the ceramic composite layer is not arranged, so that the liquid injection amount of the finally obtained rectangular lithium ion battery is reduced, the liquid absorption rate of the multilayer composite liquid absorption material is also reduced, and the electrolyte infiltration time is prolonged.
The applicant states that the present invention has been described by way of the above examples as a multi-layered composite absorbent material, and methods of making and using the same, but the present invention is not limited to, i.e., it is not meant to be limited to, or to be practiced without resorting to, the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The multilayer composite liquid absorbing material is characterized by comprising microporous foam, wherein non-woven fabric composite layers are arranged on two sides of the microporous foam;
the pores of the microporous foam are filled with inorganic nano materials and microcapsules, and the microcapsules contain electrolyte impregnating compound;
the non-woven fabric composite layer consists of non-woven fabric and ceramic composite layers arranged on two sides of the non-woven fabric, and the materials of the ceramic composite layers comprise high polymer materials and nano ceramic materials.
2. The multilayer composite of claim 1, wherein the microporous foam comprises ethylene-vinyl acetate copolymer microporous foam or polyurethane microporous foam;
preferably, the porosity of the microporous foam is 25-60%;
preferably, the thickness of the microporous foam is 1-6 mm.
3. The multilayer composite liquid absorbent material according to claim 1 or 2, wherein the inorganic nanomaterial is a microporous inorganic nanomaterial;
preferably, the microporous inorganic nanomaterial comprises any one or a combination of at least two of microporous nano-silica, microporous nano-titania or microporous nano-alumina;
preferably, the electrolyte sizing agent comprises any one or a combination of at least two of vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate or ethylene sulfite;
preferably, the material of the capsule wall of the microcapsule comprises any one or a combination of at least two of epoxy resin, polyethylene, polypropylene or polyurethane;
preferably, the mass ratio of the inorganic nano material to the microcapsule is (5-15): 1.
4. A multilayer composite liquid absorbent material according to any one of claims 1 to 3, wherein the nonwoven fabric is a polyphenylene sulfide nonwoven fabric;
preferably, the thickness of the non-woven fabric is 0.1-1 mm.
5. The multilayer composite liquid absorbent material according to any one of claims 1 to 4, wherein the ceramic composite layer has a thickness of 60 to 300 μm;
preferably, the mass ratio of the polymer material to the nano ceramic material is (20-25): 1;
preferably, the nano ceramic material comprises any one or a combination of at least two of nano silicon dioxide, nano aluminum oxide, nano silicon oxide, nano boehmite, nano titanium oxide or nano zirconium oxide;
preferably, the polymer material includes any one or a combination of at least two of polyimide, polyvinylidene fluoride or styrene butadiene rubber, and more preferably polyimide.
6. A method of preparing a multilayer composite liquid absorbent material according to any one of claims 1 to 5, comprising the steps of:
(1) Coating the material of the ceramic composite layer on two sides of the non-woven fabric to obtain a composite non-woven fabric;
(2) And (3) compositing the composite non-woven fabric obtained in the step (1) on two sides of the microporous foam to obtain the multilayer composite liquid absorbing material.
7. The method of claim 6, wherein the method of compounding in step (2) comprises bonding or thermocompression compounding.
8. Use of a multilayer composite liquid absorbent material according to any one of claims 1 to 5 in a battery.
9. A lithium ion battery, characterized in that the lithium ion battery comprises a battery shell, an electric core and the multilayer composite liquid absorbing material as claimed in any one of claims 1 to 5;
the multilayer composite liquid absorbing material is arranged in the battery shell and is coated outside the battery core.
10. The lithium ion battery of claim 9, wherein the cells are laminated cells or wound cells.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN207082560U (en) * | 2017-08-23 | 2018-03-09 | 深圳市比克动力电池有限公司 | A kind of electrical core of power battery and the lithium battery comprising the battery core |
| CN114566745A (en) * | 2022-01-28 | 2022-05-31 | 上海兰钧新能源科技有限公司 | Roll up core and battery |
| CN115312890A (en) * | 2022-09-02 | 2022-11-08 | 宁夏宝丰昱能科技有限公司 | Battery and preparation method thereof |
| CN217903403U (en) * | 2022-07-15 | 2022-11-25 | 楚能新能源股份有限公司 | Lithium battery structure |
| US20230046770A1 (en) * | 2021-07-13 | 2023-02-16 | Contemporary Amperex Technology Co., Limited | Battery cell, battery and power consumption apparatus |
| CN115966789A (en) * | 2023-02-01 | 2023-04-14 | 天津市捷威动力工业有限公司 | Battery diaphragm, preparation method thereof, battery and vehicle |
-
2023
- 2023-06-07 CN CN202310669899.5A patent/CN116565334A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN207082560U (en) * | 2017-08-23 | 2018-03-09 | 深圳市比克动力电池有限公司 | A kind of electrical core of power battery and the lithium battery comprising the battery core |
| US20230046770A1 (en) * | 2021-07-13 | 2023-02-16 | Contemporary Amperex Technology Co., Limited | Battery cell, battery and power consumption apparatus |
| CN114566745A (en) * | 2022-01-28 | 2022-05-31 | 上海兰钧新能源科技有限公司 | Roll up core and battery |
| CN217903403U (en) * | 2022-07-15 | 2022-11-25 | 楚能新能源股份有限公司 | Lithium battery structure |
| CN115312890A (en) * | 2022-09-02 | 2022-11-08 | 宁夏宝丰昱能科技有限公司 | Battery and preparation method thereof |
| CN115966789A (en) * | 2023-02-01 | 2023-04-14 | 天津市捷威动力工业有限公司 | Battery diaphragm, preparation method thereof, battery and vehicle |
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Application publication date: 20230808 |