CN107123766B - A kind of diaphragm for lithium ion battery and preparation method thereof - Google Patents
A kind of diaphragm for lithium ion battery and preparation method thereof Download PDFInfo
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- CN107123766B CN107123766B CN201710199531.1A CN201710199531A CN107123766B CN 107123766 B CN107123766 B CN 107123766B CN 201710199531 A CN201710199531 A CN 201710199531A CN 107123766 B CN107123766 B CN 107123766B
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- diaphragm
- lithium ion
- ion battery
- boehmite
- thin
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 35
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 33
- 239000000919 ceramic Substances 0.000 claims abstract description 27
- 239000002121 nanofiber Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 11
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 229910001868 water Inorganic materials 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 16
- 239000004698 Polyethylene Substances 0.000 claims description 15
- 229920000573 polyethylene Polymers 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000004743 Polypropylene Substances 0.000 claims description 11
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000002174 Styrene-butadiene Substances 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 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
- 239000004816 latex Substances 0.000 claims description 3
- 229920000126 latex Polymers 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 2
- 239000000835 fiber Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 40
- 229910052593 corundum Inorganic materials 0.000 description 25
- 229910001845 yogo sapphire Inorganic materials 0.000 description 25
- 239000010410 layer Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 210000002469 basement membrane Anatomy 0.000 description 6
- 210000004379 membrane Anatomy 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 230000010148 water-pollination Effects 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000005213 imbibition Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229960001422 aluminium chlorohydrate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- LVYZJEPLMYTTGH-UHFFFAOYSA-H dialuminum chloride pentahydroxide dihydrate Chemical compound [Cl-].[Al+3].[OH-].[OH-].[Al+3].[OH-].[OH-].[OH-].O.O LVYZJEPLMYTTGH-UHFFFAOYSA-H 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent 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
- 238000011056 performance test Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Cell Separators (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
It further include the ultra-thin porous soft ceramic layer for being compounded at least one surface of substrate the invention discloses a kind of diaphragm for lithium ion battery, including substrate；The ultra-thin porous soft ceramic layer includes the porous structure formed by the blend of the thin scale of boehmite nanometer or boehmite nanofiber and aluminium hydroxide through intersecting tiling, with a thickness of 0.5~1.0 μm.The present invention provides a kind of diaphragm for lithium ion battery, tensile strength and puncture strength are significantly improved, and significantly reduce the percent thermal shrinkage of diaphragm；The lithium ion battery being prepared with it has high security and excellent cyclical stability.
Description
Technical field
The present invention relates to lithium ion battery separator technical fields, and in particular to a kind of diaphragm for lithium ion battery and its preparation
Method.
Background technique
Lithium ion battery is mainly made of positive electrode, negative electrode material, diaphragm and electrolyte etc., and diaphragm is its core key
One of material.The performance of diaphragm determines the interfacial structure of battery, internal resistance etc., directly affects capacity, circulation and the safety of battery
Performance, the diaphragm haveing excellent performance play an important role the comprehensive performance for improving battery.The main function of diaphragm is to make battery
Positive and negative electrode separate, prevent the two poles of the earth contact and it is short-circuit, additionally have the function of electrolyte ion capable of being made to pass through.However,
While applying to fields such as energy storage, electric cars, the safety problem showed can not be ignored lithium ion battery.One side
Face, when battery is overcharging, can occur internal expansion under the states such as over-discharge and high temperature, porous poly- third used in usual lithium ion battery
Alkene (PP), polyethylene (PE) diaphragm retracts may cause Local Cracking, and certain thermal runaway points expand to form integral battery thermal runaway,
Safety problems extremely easy to cause fire etc..On the other hand, in high power charging-discharging overcharges, lithium ion shuttles battery in the electrolytic solution
Lithium easily is analysed in negative terminal surface in conductive process, analysis Li dendrite can penetrate diaphragm and cause battery plus-negative plate directly to contact to occur short
Road generates security risk.Therefore, the diaphragm pair of high mechanical strength and puncture strength, high ionic conductivity, high broken film temperature is studied
The safety for improving lithium ion battery is particularly important.
Nanometer scale ceramics powder is coated uniformly in porous PP or PE diaphragm, effect mainly improves the heat-resisting receipts of diaphragm
Contracting prevents diaphragm retracts from causing large area short-circuit.In addition, ceramic pyroconductivity is low, it can prevent certain heat in battery from losing
Control point, which expands, forms whole thermal runaway.For PP or PE diaphragm after coated ceramic thin layer, the tensile strength of diaphragm and puncture are strong
Degree significantly improves.
Other than improving the security performance of battery, for the porous ceramics thin layer high for chemical stability, advantage is also
There is the following aspects:
(1) porous ceramics thin layer maintains higher ionic conductivity and high-lithium ion transport coefficient, there is no with it is organic
The chemical side reactions of electrolyte；
(2) porous ceramics thin layer has the function of good imbibition liquid storage, reduces interfacial reaction impedance, improves battery
Power density；
(3) application of porous ceramics thin layer can reduce the thickness of PP or PE basement membrane, reduce battery volume, improve battery
Energy density；
(4) porous ceramics thin layer improves the operating temperature of diaphragm, is applicable to the operating conditions such as high temperature.
As the Chinese patent literature of Publication No. CN105514328A disclose a kind of lithium ion battery ceramic diaphragm and
Preparation method, wherein comprising steps of a, using nanoporous SiO2, porous Al2O3Or mixtures thereof be used as ceramic raw material, with
Binder and solvent are mixed, and are prepared into uniform slurry using mechanical stirring mode；B, slurry is coated uniformly on diaphragm
On, then in 70~90 DEG C of dry 2h~for 24 hours, the ceramic diaphragm with a thickness of 1~10 μm can be obtained.
In the prior art, the higher oxide of hardness such as SiO is generallyd use2Or Al2O3, control granular materials size is such as
Nanosizing constructs porous structure by the plane accumulation of nano particle.However granular material will realize continuous porous knot
Structure needs more coated weight, thus can not prepare ultra-thin ceramic diaphragm.The higher oxide of hardness is easy in charge and discharge simultaneously
The damage of paired electrode is made in the process.
Summary of the invention
The present invention provides a kind of diaphragm for lithium ion battery, this is compounded with the diaphragm of ultra-thin porous soft ceramic layer, draw
It stretches intensity and puncture strength is significantly improved, and significantly reduce the percent thermal shrinkage of diaphragm；The lithium ion being prepared with it
Battery has high security and excellent cyclical stability.
Specific technical solution is as follows:
A kind of diaphragm for lithium ion battery, including substrate further include be compounded at least one surface of substrate ultra-thin
Porous soft ceramic layer；
The ultra-thin porous soft ceramic layer include by the thin scale of boehmite nanometer or boehmite nanofiber with
The porous structure that the blend of aluminium hydroxide is formed through intersecting tiling, with a thickness of 0.5~1.0 μm.
Boehmite (structural formula: AlO (OH), molecular formula: Al2O3·H2O) there is the small (3.01-3.06g/ of density
cm3), the features such as hardness is low (Mohs' hardness 3.6), nontoxic, not soluble in water and organic solvent, chemical stability is high, Al2O3·H2O
(480 DEG C of >) can be thermally decomposed at high temperature, generate strong endothermic thermal event, be conducive to improve the safety under battery thermal runaway
Performance, while the lower Al of hardness2O3·H2The O layers of damage probability reduced in charge and discharge process to electrode.
But since its hydrophily is bad, it can not be uniformly mixed the slurry to be formed for coating with binder, solvent, therefore,
Aluminium hydroxide is dispersed in the thin scale of boehmite nanometer or boehmite nanofiber surface by modification,
To significantly improve its surface hydrophilicity.Aluminium hydroxide itself is not soluble in water, is difficult to realize when addition to boehmite on a small quantity
Uniformly modified, the present invention, as modified raw material, is dissolved in water and generates aluminium hydroxide and hydrochloric acid, is produced from centre using Aluminium chloride hexahydrate
Object hydrochloric acid volatilizees removal in subsequent drying course.
Preferably, the quality of the aluminium hydroxide is 1~2wt.% of the blend gross mass.
Preferably, the thin scale of boehmite nanometer with a thickness of 10~40nm, length is 1~3 μm, and width is
0.4~1.0 μm；
The diameter of the boehmite nanofiber is 20~50nm, and length is 1~3 μm.
Preferably, the porosity of the ultra-thin porous soft ceramic layer is 40~55%.
Preferably, the substrate is selected from porous polyethylene membrane or porous polypropylene film；The porosity of the substrate is 40
~60%.
The invention also discloses the preparation methods of the diaphragm for lithium ion battery, comprising the following steps:
(1) the thin scale of boehmite nanometer or boehmite nanofiber are mixed with Aluminium chloride hexahydrate, is added
Deionized water obtains the thin scale of boehmite nanometer that surface is modified or the boehmite that surface is modified through mechanical ball mill
Nanofiber；
(2) surface of binder, solvent and step (1) the preparation modified thin scale of boehmite nanometer or surface are changed
Property boehmite nanofiber mixing, obtain slurry after mixing evenly；
(3) slurry described in step (2) is coated in at least one surface of the substrate, institute is obtained after continuous drying
The diaphragm for lithium ion battery stated.
Preferably, in step (1), with the thin scale of the boehmite nanometer or boehmite nanofiber and six
The gross mass meter of aluminium chlorohydrate, the additional amount of the Aluminium chloride hexahydrate are 3~6wt.%, the additional amount of the deionized water
For 5~10wt.%；
Preferably, the revolving speed of the mechanical ball mill is 370~510rpm, the time is 4~6 hours.Further preferably, turn
Speed is 450rpm, time 5h.
After mechanical ball mill, Aluminium chloride hexahydrate is reacted with water generates aluminium hydroxide, is dispersed in boehmite and receives
The thin scale of rice or boehmite nanofiber surface, the as the surface modified thin scale of boehmite nanometer or table
The modified boehmite nanofiber in face.The modified Al in surface2O3·H2O nanometers thin scale or nanofiber are in deionization
Favorable dispersibility in aqueous medium.
Preferably, the binder is mixed selected from sodium carboxymethylcellulose (CMC)/styrene-butadiene latex (SBR) in step (2)
Object is closed, the solvent is selected from water.Further preferably, the mass ratio of the sodium carboxymethylcellulose and styrene-butadiene latex is 2: 1.It is excellent again
It selects, the concentration of sodium carboxymethylcellulose is 10wt.% in the aqueous solution.
Preferably, in step (2), the surface Modification on Al2O3·H2O nanometers thin scale or Al2O3·H2O nanofiber
Solid content in the slurry is 55~65wt.%；
The whipping temp is 35~45 DEG C.
Preferably, the continuous drying temperature is 75~105 DEG C in step (3), speed is 15~50m/min.
The present invention is by wet ball grinding, using AlCl3·6H2O Modification on Al2O3·H2O nanometers thin scale or nanofiber, shape
At the oxide powder of surface hydrophilicity, there is good dispersing uniformity in CMC and SBR mixed aqueous solution.By continuously squeezing
Extrusion is covered and is dried, and forms the ultra-thin porous soft ceramics that thin scale or nanofiber are evenly distributed in porous PP or PE membrane surface
Layer maintains the venting quality of former base film and the high ionic conductivity and electrochemical stability of porosity and diaphragm substantially, but aobvious
The tensile strength and puncture strength for improving diaphragm are write, and significantly reduces the percent thermal shrinkage of diaphragm, is used to prepare lithium-ion electric
Pond, had not only improved the security performance and cycle performance of battery, but also battery energy density can be improved.
Compared with prior art, the present invention has the advantage that
(1)Al2O3·H2O is in the thin scale of nanometer or nanofibrous structures, intersects tiling, can be covered with less surface density
It covers in porous membrane surface, aluminium oxide, silica, the zirconia particles pottery of existing higher caliper is reached with thinner coating layer thickness
The protection effect of enamel coating significantly improves the tensile strength and puncture strength of diaphragm, reduces diaphragm percent thermal shrinkage, and can protect substantially
Hold the porosity and venting quality of former porous PP or PE basement membrane.
(2) the coating porous Al prepared by2O3·H2There is the diaphragm of O thin layer good electrochemical stability and imbibition to store up
Liquid ability, it is high with basement membrane binding force, meet battery assembly application.
(3)Al2O3·H2O thin layer thermally decomposes at high temperature (480 DEG C of >), generates endothermic thermal event, is conducive to improve battery heat
Security performance under out of control.
(4) porous Al is coated by aqueous slurry2O3·H2The diaphragm of the soft thin layers of ceramic of O, the lower Al of hardness2O3·H2O
Layer, which reduces in charge and discharge process, overcomes existing coating high rigidity aluminium oxide, silica, zirconium oxide to the damage probability of electrode
The disadvantage of particulate ceramic layer easy damaged electrode plates in charge and discharge process improves the whole electrochemistry of lithium ion battery
Energy.
Detailed description of the invention
Fig. 1 is the ultra-thin Al of coating prepared by embodiment 12O3·H2The stereoscan photograph of O layers of diaphragm.
Specific embodiment
The present invention is made below by embodiment and further being illustrated, but the invention is not limited to following realities
Example.
Embodiment 1
(1) by 3wt.%AlCl3·6H2O and 97wt.%Al2O3·H2The mixing of O nanometers thin scale, be added 5wt.% go from
Sub- water, in the case where revolving speed is 450rpm mechanical ball mill 5 hours, to Al2O3·H2O nanometers thin scale carries out surface and is modified, and changes through surface
The Al of property2O3·H2O nanometers thin scale has good hydrophily, the favorable dispersibility in deionized water medium；
(2) by surface Modification on Al2O3·H2O nanometers thin scale is added to concentration 10wt.%CMC and 5wt.%SBR mixing water
In solution, surface Modification on Al2O3·H2Solid content is 55wt.% to O nanometers thin scale in the slurry, is stirred at 40 DEG C of temperature mixed
Synthesize uniform sizing material；
(3) by above-mentioned slurry it is continuously extruded be coated in porosity 51%, 16.2 μm of thickness of wet process PE basement membrane monoplanar surface,
The continuous drying at 75~105 DEG C of oven temperature, drying rate 40m/min, deionized water volatilize and form hole, change after drying
Property Al2O3·H2O nanometers thin scale bonds to form high bond strength, with a thickness of 0.8 μm of porous painting in porous PE membrane surface
Layer；
It is tested through elemental analysis, chlorine element is not detected in thin layers of ceramic, the Aluminium chloride hexahydrate of addition has been converted to hydrogen
Aluminium oxide, in the porous coating being prepared, the content of aluminium hydroxide is 1wt.%.
Fig. 1 is coating Al manufactured in the present embodiment2O3·H2The stereoscan photograph of O nanometers thin scale thin layer diaphragm.
Embodiment 2
(1) by 4wt.%AlCl3·6H2O and 96wt.%Al2O3·H2The mixing of O nanofiber, is added 8wt.% deionization
Water, in the case where revolving speed is 450rpm mechanical ball mill 5 hours, to Al2O3·H2It is modified that O nanofiber carries out surface.Surface-modified
Al2O3·H2O nanofiber has good hydrophily, the favorable dispersibility in deionized water medium；
(2) by surface Modification on Al2O3·H2It is water-soluble that O nanofiber is added to concentration 10wt.%CMC and 5wt.%SBR mixing
In liquid, surface Modification on Al2O3·H2Solid content is 60wt.% to O nanofiber in the slurry, is stirred at 40 DEG C of temperature
Uniform sizing material；
(3) by above-mentioned slurry it is continuously extruded be coated in porosity 46%, 16.1 μm of thickness of dry method PP basement membrane monoplanar surface,
The continuous drying at 75-105 DEG C of oven temperature, drying rate 40m/min, deionized water volatilize and form hole, change after drying
Property Al2O3·H2O nanofiber bonds in porous PP membrane surface and to form high bond strength, with a thickness of 0.6 μm of porous coating；
It is tested through elemental analysis, chlorine element is not detected in thin layers of ceramic, the Aluminium chloride hexahydrate of addition has been converted to hydrogen
Aluminium oxide, in the porous coating being prepared, the content of aluminium hydroxide is 1.3wt.%.
Embodiment 3
(1) by 6wt.%AlCl3·6H2O and 94wt.%Al2O3·H2The mixing of O nanometers thin scale, be added 10wt.% go from
Sub- water, in the case where revolving speed is 450rpm mechanical ball mill 5 hours, to Al2O3·H2It is modified that O nanometers thin scale carries out surface.Change through surface
The Al of property2O3·H2O nanometers thin scale has good hydrophily, the favorable dispersibility in deionized water medium；
(2) by surface Modification on Al2O3·H2O nanometers thin scale is added to concentration 10wt.%CMC and 5wt.%SBR mixing water
In solution, surface Modification on Al2O3·H2Solid content is 65wt.% to O nanometers thin scale in the slurry, is stirred at 40 DEG C of temperature mixed
Synthesize uniform sizing material；
(3) by above-mentioned slurry it is continuously extruded be coated in porosity 48%, 12.3 μm of thickness of wet process PE basement membrane monoplanar surface,
The continuous drying at 75-105 DEG C of oven temperature, drying rate 40m/min, deionized water volatilize and form hole, change after drying
Property Al2O3·H2O nanometers thin scale bonds to form high bond strength, with a thickness of 1.0 μm of porous paintings in porous PE membrane surface
Layer；
It is tested through elemental analysis, chlorine element is not detected in thin layers of ceramic, the Aluminium chloride hexahydrate of addition has been converted to hydrogen
Aluminium oxide, in the porous coating being prepared, the content of aluminium hydroxide is 2wt.%.
Comparative example 1: wet process PE porous septum；
Comparative example 2: wet process PP porous septum；
Comparative example 3: wet process PE porous septum.
Performance test
Above-described embodiment 1~3 and comparative example 1~3 are subjected to thickness, porosity, puncture strength, venting quality, stretched by force
Degree and percent thermal shrinkage test；And above-described embodiment 1~3 and comparative example 1~3 and positive and negative electrode are respectively assembled into 20 26650
Steel shell cylindrical battery (523 ternary materials anode) and 20 38120 aluminum shell column type batteries (iron phosphate lithium positive pole), are being full of
Pin prick test is carried out under electricity condition.
The physical index of Examples 1 to 3 and comparative example 1~3 is as shown in Table 1 and Table 2.
Examples 1 to 3 and comparative example 1~3 are assembled into 26650 steel shell cylindrical batteries (positive electrode: 523 ternary materials
Material) and 38120 aluminum shell column type batteries (positive electrode: LiFePO4) full of electricity condition carry out pin prick test, as a result such as table 3
With shown in table 4.
Table 1
Table 2
Table 3
| Battery | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| 26650 types | Pass through | Pass through | Pass through |
| 38120 types | Pass through | Pass through | Pass through |
* pass through: without explosion, without on fire
Table 4
| Battery | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| 26650 types | Pass through | 2 do not pass through | 1 does not pass through |
| 38120 types | 1 does not pass through | 3 do not pass through | 2 do not pass through |
* pass through: without explosion, without on fire.
Claims (9)
1. a kind of diaphragm for lithium ion battery, including substrate, which is characterized in that further include being compounded at least one table of the substrate
The ultra-thin porous soft ceramic layer in face；
The ultra-thin porous soft ceramic layer includes by the thin scale of boehmite nanometer or boehmite nanofiber and hydrogen-oxygen
Change the porous structure that the blend of aluminium is formed through intersecting tiling, with a thickness of 0.5~1.0 μm；
The preparation method of the diaphragm for lithium ion battery, comprising the following steps:
(1) the thin scale of boehmite nanometer or boehmite nanofiber are mixed with Aluminium chloride hexahydrate, addition go from
Sub- water obtains the thin scale of boehmite nanometer that surface is modified or the boehmite nanometer that surface is modified through mechanical ball mill
Fiber；
(2) surface of binder, solvent and step (1) the preparation modified thin scale of boehmite nanometer or surface are modified
The mixing of boehmite nanofiber, obtains slurry after mixing evenly；
(3) slurry described in step (2) is coated in at least one surface of the substrate, is obtained after continuous drying described
Diaphragm for lithium ion battery.
2. diaphragm for lithium ion battery according to claim 1, which is characterized in that the quality of the aluminium hydroxide is described
1~2wt.% of blend gross mass.
3. diaphragm for lithium ion battery according to claim 1, which is characterized in that the thin scale of boehmite nanometer
With a thickness of 10~40nm, length is 1~3 μm, and width is 0.4~1.0 μm；
The diameter of the boehmite nanofiber is 20~50nm, and length is 1~3 μm.
4. diaphragm for lithium ion battery according to claim 1, which is characterized in that the hole of the ultra-thin porous soft ceramic layer
Gap rate is 40~55%.
5. diaphragm for lithium ion battery according to claim 1, which is characterized in that the substrate is selected from porous polyethylene membrane
Or porous polypropylene film；
The porosity of the substrate is 40~60%.
6. diaphragm for lithium ion battery according to claim 1, which is characterized in that in step (1), with the soft aluminium of a water
The gross mass meter of the thin scale of stone nanometer or boehmite nanofiber and Aluminium chloride hexahydrate, the Aluminium chloride hexahydrate add
Entering amount is 3~6wt.%, and the additional amount of the deionized water is 5~10wt.%；
The revolving speed of the mechanical ball mill is 370~510rpm, and the time is 4~6 hours.
7. diaphragm for lithium ion battery according to claim 1, which is characterized in that in step (2), the binder is carboxylic
Sodium carboxymethylcellulose pyce/styrene-butadiene latex mixture, the solvent are water.
8. diaphragm for lithium ion battery according to claim 1, which is characterized in that in step (2), what the surface was modified
The solid content of the modified boehmite nanofiber in the thin scale of boehmite nanometer or surface in the slurry is 55~
65wt.%；
The whipping temp is 35~45 DEG C.
9. diaphragm for lithium ion battery according to claim 1, which is characterized in that in step (3), the continuous drying temperature
Degree is 75~105 DEG C, and speed is 15~50m/min.
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| EP4064446A1 (en) * | 2021-03-23 | 2022-09-28 | SK Innovation Co., Ltd. | Composite separator and electrochemical device using the same |
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| CN108428844A (en) * | 2018-03-22 | 2018-08-21 | 衢州学院 | A kind of new modified isolation film |
| WO2021087191A1 (en) * | 2019-10-31 | 2021-05-06 | Pacific Industrial Development Corporation | Inorganic materials for composite separator in electrochemical cells |
| CN114716234B (en) * | 2022-04-20 | 2023-02-24 | 武汉钢铁有限公司 | Nano composite thermal insulation material and preparation method thereof |
| CN116061510B (en) * | 2022-12-07 | 2023-12-05 | 南通大学 | Multilayer self-adjusting composite non-woven material, preparation method and application thereof |
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| CN103460443A (en) * | 2011-03-28 | 2013-12-18 | 丰田自动车株式会社 | Lithium ion secondary battery |
| CN103915591A (en) * | 2014-04-09 | 2014-07-09 | 深圳市星源材质科技股份有限公司 | Water-based ceramic coating lithium ion battery diaphragm and processing method thereof |
| CN105789539A (en) * | 2016-04-29 | 2016-07-20 | 沧州明珠隔膜科技有限公司 | Waterborne ceramic coated membrane for lithium ion battery and preparation method thereof |
| CN205406613U (en) * | 2016-01-18 | 2016-07-27 | 新乡市中科科技有限公司 | Soft ceramic lithium ion battery diaphragm |
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| US8313853B2 (en) * | 2002-06-06 | 2012-11-20 | Kaun Thomas D | Flexible, porous ceramic composite film |
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| CN103460443A (en) * | 2011-03-28 | 2013-12-18 | 丰田自动车株式会社 | Lithium ion secondary battery |
| CN103915591A (en) * | 2014-04-09 | 2014-07-09 | 深圳市星源材质科技股份有限公司 | Water-based ceramic coating lithium ion battery diaphragm and processing method thereof |
| CN205406613U (en) * | 2016-01-18 | 2016-07-27 | 新乡市中科科技有限公司 | Soft ceramic lithium ion battery diaphragm |
| CN105789539A (en) * | 2016-04-29 | 2016-07-20 | 沧州明珠隔膜科技有限公司 | Waterborne ceramic coated membrane for lithium ion battery and preparation method thereof |
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| EP4064446A1 (en) * | 2021-03-23 | 2022-09-28 | SK Innovation Co., Ltd. | Composite separator and electrochemical device using the same |
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