CN112821008A - Fiber diaphragm, preparation method and application thereof, and lithium ion battery diaphragm - Google Patents
Fiber diaphragm, preparation method and application thereof, and lithium ion battery diaphragm Download PDFInfo
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- CN112821008A CN112821008A CN201911046828.XA CN201911046828A CN112821008A CN 112821008 A CN112821008 A CN 112821008A CN 201911046828 A CN201911046828 A CN 201911046828A CN 112821008 A CN112821008 A CN 112821008A
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- diaphragm
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- 239000000835 fiber Substances 0.000 title claims abstract description 64
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000010954 inorganic particle Substances 0.000 claims abstract description 33
- 239000006185 dispersion Substances 0.000 claims description 91
- 229920000642 polymer Polymers 0.000 claims description 64
- 239000007788 liquid Substances 0.000 claims description 56
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- -1 polypropylene Polymers 0.000 claims description 31
- 239000011258 core-shell material Substances 0.000 claims description 30
- 238000007731 hot pressing Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000010041 electrostatic spinning Methods 0.000 claims description 15
- 150000002576 ketones Chemical class 0.000 claims description 14
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 claims description 14
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 14
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 14
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 13
- 238000009987 spinning Methods 0.000 claims description 12
- 239000012792 core layer Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001523 electrospinning Methods 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 3
- 150000004706 metal oxides Chemical class 0.000 claims 3
- 229910000000 metal hydroxide Inorganic materials 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 239000012046 mixed solvent Substances 0.000 description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 238000005303 weighing Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000011257 shell material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 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 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 229910004764 HSV900 Inorganic materials 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- ZMZINYUKVRMNTG-UHFFFAOYSA-N acetic acid;formic acid Chemical compound OC=O.CC(O)=O ZMZINYUKVRMNTG-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010998 test method 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
- H01M10/052—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
Abstract
The invention relates to the field of lithium ion batteries, and discloses a fiber diaphragm, a preparation method and application thereof, and a lithium ion battery diaphragm. The fiber diaphragm can achieve the effect that inorganic particles do not fall off during high-rate charge and discharge, and has good heat resistance and porosity.
Description
Technical Field
The invention relates to the field of fiber diaphragms, in particular to a fiber diaphragm, a method for preparing the fiber diaphragm, a fiber diaphragm prepared by the method, application of the fiber diaphragm in preparing lithium ion battery diaphragms, and a lithium ion battery diaphragm containing the fiber diaphragm.
Background
Under the condition of large current, the lithium ion battery is easy to cause a large amount of lithium dendrites to pierce a battery diaphragm, so that the internal short circuit of the battery causes potential safety hazards.
The power battery has higher working temperature and more complex dynamic environment, and can explode, burn and the like under unconventional states, namely an abnormal charging and discharging state, abnormal heating and abuse of mechanical conditions, so the thermal safety performance of the power lithium ion battery is particularly important.
The safety performance of the lithium ion battery diaphragm is that the diaphragm is required to have good thermal dimensional stability and has no obvious deformation under a certain high-temperature environment; the flame-retardant material has good flame-retardant performance, can resist flame before short circuit of the battery, has no obvious loss of mechanical strength, and has high thermal safety temperature.
The lithium ion battery diaphragm which is commercially applied at present is a polypropylene (PP) diaphragm and a Polyethylene (PE) diaphragm, and the diaphragm cannot completely meet the requirements of the increasingly developed power battery market.
The new technology and the new material are used for preparing the new diaphragm, the electrostatic spinning method is an effective technology, and the inorganic material is doped into the spinning solution for electrospinning, so that the use of a binder can be avoided. The surface of the fiber diaphragm prepared by the method is loaded with inorganic particles, but the inorganic particles cannot be prevented from falling off during high-rate charge and discharge.
Disclosure of Invention
The invention aims to overcome the defects of potential safety hazards caused by easy falling of inorganic particles and poor heat resistance in high-rate charge and discharge when a diaphragm in the prior art is used in a lithium ion battery.
In order to achieve the above object, a first aspect of the present invention provides a fiber separator, which is formed by core-shell structure fibers, wherein a middle core layer material of the core-shell structure fibers is an inorganic particle-high molecular polymer I composite formed by compounding inorganic particles and a high molecular polymer I, and a shell layer material of the core-shell structure fibers is a high molecular polymer II, the high molecular polymer I and the high molecular polymer II are different, and the high molecular polymer I and the high molecular polymer II are each independently selected from at least one of polypropylene, polyethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyamide, polyacrylonitrile, polyarylethersulfone ketone, polyethylene terephthalate, and polybutylene terephthalate.
A second aspect of the present invention provides a method of making a fibrous separator, the method comprising:
(1) mixing a dispersion liquid I containing inorganic particles and a dispersion liquid II containing a high molecular polymer I to obtain a dispersion liquid III;
(2) respectively introducing a dispersion liquid IV containing a high molecular polymer II and the dispersion liquid III into a storage with an outer needle head and a storage with an inner needle head of a coaxial electrostatic spinning device for electrostatic spinning to obtain core-shell structure fibers;
(3) carrying out hot pressing on the core-shell structure fiber to obtain the diaphragm,
the high molecular polymer I and the high molecular polymer II are different, and are respectively and independently selected from at least one of polypropylene, polyethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyamide, polyacrylonitrile, polyarylethersulfone ketone, polyethylene terephthalate and polybutylene terephthalate.
A third aspect of the present invention provides a fibrous separator prepared by the foregoing method.
A fourth aspect of the invention provides the use of the aforementioned fibrous membranes in the manufacture of fibrous membranes.
The fifth aspect of the invention provides a lithium ion battery separator containing the fiber separator.
The fiber diaphragm can achieve the effect that inorganic particles cannot fall off during high-rate charge and discharge when the fiber diaphragm is used in a lithium ion battery, and meanwhile, the diaphragm can have good heat resistance and higher safety at high temperature under the optimal condition.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a fibrous membrane, the fibrous membrane is formed by core-shell structure fibers, the middle core layer material of the core-shell structure fibers is an inorganic particle-high molecular polymer I composite formed by compounding inorganic particles and high molecular polymer I, and the shell layer material of the core-shell structure fibers is high molecular polymer II, the high molecular polymer I and the high molecular polymer II are different, and the high molecular polymer I and the high molecular polymer II are each independently selected from at least one of polypropylene, polyethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyamide, polyacrylonitrile, polyarylethersulfone ketone, polyethylene terephthalate, and polybutylene terephthalate.
Preferably, in the inorganic particle-high molecular polymer I composite, the weight content of the inorganic particles is 1% to 40%.
According to a preferred embodiment, the high molecular polymer I is at least one selected from polyacrylonitrile and polyarylethersulfone ketone; the high molecular polymer II is at least one selected from polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene and polymethyl methacrylate.
Preferably, the inorganic particles are selected from at least one of oxides of group IIA metals, sulfates of group IIA metals, hydroxides of group IIA metals, oxides of group IVB metals, oxides of group IIIA metals and silica.
Preferably, the inorganic particles are selected from at least one of hydrated alumina, magnesia, silica, zirconia, titania, boehmite, barium sulfate, and magnesium hydroxide.
More preferably, the inorganic particles have an average particle diameter of 10 to 200 nm.
Preferably, the diameter of the middle core layer of the core-shell structure fiber is 100-400nm, and the diameter of the core-shell structure fiber is 0.5-2 μm.
Preferably, the thickness of the separator is 20 to 50 μm.
Preferably, the core-shell structure fiber is prepared by a coaxial electrospinning method.
As previously mentioned, a second aspect of the present invention provides a method of making a fibrous membrane, the method comprising:
(1) mixing a dispersion liquid I containing inorganic particles and a dispersion liquid II containing a high molecular polymer I to obtain a dispersion liquid III;
(2) respectively introducing a dispersion liquid IV containing a high molecular polymer II and the dispersion liquid III into a storage with an outer needle head and a storage with an inner needle head of a coaxial electrostatic spinning device for electrostatic spinning to obtain core-shell structure fibers;
(3) carrying out hot pressing on the core-shell structure fiber to obtain the diaphragm,
the high molecular polymer I and the high molecular polymer II are different, and are respectively and independently selected from at least one of polypropylene, polyethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyamide, polyacrylonitrile, polyarylethersulfone ketone, polyethylene terephthalate and polybutylene terephthalate.
Preferably, the aperture of the inner needle is 0.3-0.5mm, and the aperture of the outer needle is 0.7-1.0 mm.
Preferably, the operating conditions of the electrospinning include: the spinning voltage is 15-30kV, the receiving distance is 10-30cm, the humidity is 20-50%, and the spinning temperature is 20-40 ℃.
According to a preferred embodiment, the hot pressing is carried out by a plate press, the operating conditions of the hot pressing comprising: the hot pressing temperature is 70-100 deg.C, pressure is 3-7MPa, and hot pressing time is 1-3 min.
Preferably, the mass concentration of the inorganic particles in the dispersion liquid I is 10% to 50%, and the mass concentration of the high molecular polymer I in the dispersion liquid II is 10% to 60%.
Preferably, the mixing volume ratio of the dispersion liquid I and the dispersion liquid II is 1:9 to 5: 5.
Preferably, the mass concentration of the dispersion IV is 10-60%.
Preferably, the solids content of the dispersion III is from 5% to 50%.
According to a preferred embodiment, in the method of the present invention, the high molecular polymer I is at least one selected from polyacrylonitrile and polyarylethersulfone ketone; the high molecular polymer II is at least one selected from polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene and polymethyl methacrylate.
Preferably, the solvent in the dispersion I, the dispersion II, the dispersion IV is each independently selected from at least one of dimethylformamide, acetone, tetrahydrofuran, chloroform, dichloromethane, dimethyl sulfoxide, N-methylpyrrolidone, trifluoroethanol, trifluoroacetic acid, dimethylacetamide, ethanol, and hexafluoroisopropanol.
According to a particularly preferred embodiment 1, the organic solvent in the dispersion IV is a DMF/acetone mixed solvent, the volume ratio of DMF to acetone is 5:5 to 9:1, and the high molecular polymer in the dispersion IV is polyvinylidene fluoride; the inorganic particles are Al2O3And the high molecular polymer in the dispersion liquid II is polyacrylonitrile.
According to another particularly preferred embodiment 2, the organic solvent in the dispersion IV is a DMF/acetone mixed solvent, the volume ratio of DMF to acetone is 5:5 to 9:1, and the high molecular polymer in the dispersion IV is polyvinylidene fluoride-hexafluoropropylene; the inorganic particles are MgO, and the high molecular polymer in the dispersion liquid II is polyarylethersulfone ketone; the organic solvent in the dispersion liquid II and the dispersion liquid I is a tetrahydrofuran/N-methyl pyrrolidone mixed solvent, and the volume ratio of tetrahydrofuran to N-methyl pyrrolidone is 1: 9-5: 5.
According to another particularly preferred embodiment 3, the high molecular weight polymer in the dispersion IV is polymethyl methacrylate, and the inorganic particles are SiO2The high molecular polymer in the dispersion liquid II is polyacrylonitrile, and the organic solvents in the dispersion liquid II and the dispersion liquid I are DMF.
The fiber membranes provided by the above preferred embodiments 1, 2 and 3 of the present invention have better high temperature resistance.
Preferably, in the method of the present invention, the inorganic particles are selected from at least one of an oxide of a group IIA metal, a sulfate of a group IIA metal, a hydroxide of a group IIA metal, an oxide of a group IVB metal, an oxide of a group IIIA metal and silica.
More preferably, in the method of the present invention, the inorganic particles are selected from at least one of hydrated alumina, magnesia, silica, zirconia, titania, boehmite, barium sulfate, and magnesium hydroxide.
Preferably, in the method of the present invention, the inorganic particles have an average particle diameter of 10 to 200 nm.
Preferably, the flow rates of the dispersion IV and the dispersion III in the coaxial electrospinning device are controlled so that the diameter of the intermediate core layer of the core-shell structure fiber is 100-400nm and the diameter of the core-shell structure fiber is 0.5-2 μm.
Preferably, the thickness of the separator is 20 to 50 μm.
According to a particularly preferred embodiment, the method of the invention comprises:
(a) dissolving a high molecular polymer II in an organic solvent to form a dispersion IV with the mass concentration of 10-60%;
(b) dispersing inorganic particles in an organic solvent to form a dispersion I with the mass concentration of 10% -50%; dissolving a high molecular polymer I in an organic solvent to form a dispersion liquid II with the mass concentration of 10-60%; mixing the dispersion liquid I and the dispersion liquid II to obtain a dispersion liquid III;
(c) respectively introducing the dispersion liquid IV and the dispersion liquid III into an outer needle injector and an inner needle injector of a coaxial electrostatic spinning device, and carrying out electrostatic spinning to obtain core-shell structure fibers;
(d) and carrying out hot pressing on the core-shell structure fiber by using a plate type hot press, wherein the hot pressing temperature is 70-100 ℃, the pressure is 3-7MPa, and the hot pressing time is 1-3min, so as to obtain the diaphragm.
As previously mentioned, a third aspect of the present invention provides a fibrous separator produced by the foregoing method.
As previously mentioned, a fourth aspect of the invention provides the use of the aforementioned fibrous separator in the preparation of a lithium ion battery separator.
As described above, the fifth aspect of the present invention provides a lithium ion battery separator containing the aforementioned fibrous separator.
The fiber diaphragm provided by the invention has high porosity, high liquid absorption rate, high heat resistance and good ionic conductivity.
In addition, the "high molecular polymer" forming the shell layer of the fiber separator of the present invention covers the "inorganic particle-high molecular polymer composite" of the intermediate core layer therein, so that a series of problems caused by the shedding of inorganic particles such as ceramic nanoparticles can be avoided.
At high temperature, the diaphragm of the invention has good heat-resistant flame-retardant effect, prevents the thermal runaway of the battery, and simultaneously, the nuclear layer material can maintain the dimensional stability of the fiber diaphragm, and has small thermal shrinkage and high safety.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are all common commercial products unless otherwise specified.
The following coaxial spinning apparatus was purchased from Beijing Innovative science and technology, Inc.
Polyvinylidene fluoride (available from Achima, France under the trade designation HSV900)
Polyvinylidene fluoride-hexafluoropropylene (available from Arkema, France under the trade designation SL-023)
Polyarylethersulfone ketones (available from Dalibo Limo, Inc., Mw 1X 105)
Polyethylene (from Suzhou Suchang plastication Co., Ltd., trade mark DMDA-8008)
Polyamide (from China petrochemical company of ba ling, product number BL3280)
Polyacrylonitrile (available from carbofuran, Mw 1.5X 10)5)
Polymethyl methacrylate (Mw 11.7 ten thousand g/mol, Jiangsu Nantong Liyang chemical Co., Ltd.)
Polyethylene terephthalate (available from Whitman chemical Co., Ltd., N.K., Mw 2X 10)4)
Polycaprolactone (available from Jinan Dai handle band science and technology Co., Ltd., Mw 200000)
Polybutylene succinate (super grade, available from polyester GmbH, blue mountain of Xinjiang)
Example 1
(a) Weighing 15g of polyvinylidene fluoride, dissolving the polyvinylidene fluoride in 85g of DMF/acetone mixed solvent, wherein the volume ratio of DMF to acetone in the mixed solvent is 7: stirring for 12h at the temperature of 3 and 25 ℃ until the mixture is uniform and transparent, and obtaining a high molecular polymer solution (dispersion IV) with the mass fraction of 15%;
(b) weighing 4g of Al2O3Particles having an average particle diameter of 100nm were added to 10g of DMF solvent and dispersed for 30 minutes at 1200rpm using a stirrer to obtain a uniform dispersion (dispersion I); weighing 15g of polyacrylonitrile, dissolving in 71g of DMF solvent, stirring at 25 ℃ for 12h until the mixture is uniform and transparent to obtain uniform dispersion liquid (dispersion liquid II), and adding the dispersion liquid II into the dispersion liquid I to form Al2O3Particle-high molecular polymer complex "dispersion (dispersion III, solids content 19%);
(c) placing the dispersion IV prepared in the step (a) into an outer needle injector of a coaxial electrostatic spinning device, placing the dispersion III prepared in the step (b) into an inner needle injector of the coaxial spinning device, and carrying out electrostatic spinning to obtain the core-shell structure fiber, wherein the average diameter of a core layer is 300nm, and the average diameter of the fiber is 1.2 mu m; wherein the inner needle head aperture diameter is 0.3mm, the outer needle head aperture diameter is 0.7mm, the spinning voltage is 15kV, the receiving distance is 15cm, and the humidity is 30%; the temperature is 28 ℃;
(d) and (c) carrying out hot pressing on the fibers obtained in the step (c) by using a plate type hot press, wherein the hot pressing temperature is 70 ℃, the pressure is 3MPa, the hot pressing time is 1min, and the fiber diaphragm is obtained after hot pressing, and the thickness of the diaphragm is 25 microns.
Example 2
(a) Weighing 10g of polyvinylidene fluoride-hexafluoropropylene, dissolving in 90g of DMF/acetone mixed solvent, wherein the volume ratio of DMF to acetone in the mixed solvent is 7: stirring for 12h at the temperature of 3 and 25 ℃ until the mixture is uniform and transparent, and obtaining a high molecular polymer solution (dispersion IV) with the mass fraction of 10%;
(b) weighing 4g of MgO particles with the average particle size of 50nm, adding the MgO particles into 10g of tetrahydrofuran/N-methylpyrrolidone mixed solvent, wherein the volume ratio of tetrahydrofuran to N-methylpyrrolidone in the mixed solvent is 3: dispersing for 60 minutes at 1000rpm using a stirrer to obtain a uniform dispersion (dispersion I); weighing 16g of polyarylethersulfone ketone, dissolving the polyarylethersulfone ketone in 70g of tetrahydrofuran/N-methylpyrrolidone mixed solvent, stirring for 12h at 25 ℃ until the mixed solvent is uniform and transparent, wherein the volume ratio of tetrahydrofuran to N-methylpyrrolidone in the mixed solvent is 3:7, obtaining a uniform dispersion liquid (dispersion liquid II), and adding the dispersion liquid II into the dispersion liquid I to form a dispersion liquid (dispersion liquid III, the solid content is 20%) of a 'MgO particle-high molecular polymer compound';
(c) placing the dispersion IV prepared in the step (a) into an outer needle injector of a coaxial electrostatic spinning device, placing the dispersion III prepared in the step (b) into an inner needle injector of the coaxial spinning device, and carrying out electrostatic spinning to obtain the core-shell structure fiber, wherein the average diameter of a core layer is 300nm, and the average diameter of the fiber is 1 mu m; wherein the inner needle head aperture is 0.3mm, the outer needle head aperture is 0.9mm, the spinning voltage is 20kV, the receiving distance is 20cm, and the humidity is 35%; the temperature is 30 ℃;
(d) and (c) hot-pressing the fibers obtained in the step (c) by using a plate type hot press, wherein the hot-pressing temperature is 80 ℃, the pressure is 4MPa, the hot-pressing time is 1min, and the fiber diaphragm is obtained after hot pressing, and the thickness of the diaphragm is 30 microns.
Example 3
(a) Weighing 25g of polymethyl methacrylate, dissolving the polymethyl methacrylate in 75g of DMF solvent, and stirring the solution at 25 ℃ for 12h until the solution is uniform and transparent to obtain a high molecular polymer solution (dispersion IV) with the mass fraction of 25%;
(b) 6g of SiO are weighed2Particles having an average particle diameter of 100nm were added to 12g of hexafluoroisopropanol solvent, and dispersed for 45 minutes at 1200rpm using a stirrer to obtain a uniform dispersion (dispersion I); weighing 16g of polyacrylonitrile, dissolving the polyacrylonitrile in 66g of DMF solvent, stirring for 12h at 25 ℃ until the mixture is uniform and transparent to obtain uniform dispersion liquid (dispersion liquid II), and adding the dispersion liquid II into the dispersion liquid I to form SiO2Particle-high molecular polymer complex "dispersion (dispersion III, solids content 22%);
(c) placing the dispersion IV prepared in the step (a) into an outer needle injector of a coaxial electrostatic spinning device, placing the dispersion III prepared in the step (b) into an inner needle injector of the coaxial spinning device, and carrying out electrostatic spinning to obtain the core-shell structure fiber, wherein the average diameter of a core layer is 340nm, and the average diameter of the fiber is 1.5 mu m; wherein the aperture of the inner needle is 0.5mm, the aperture of the outer needle is 1mm, the spinning voltage is 28kV, the receiving distance is 25cm, and the humidity is 30%; the temperature is 30 ℃;
(d) and (c) hot-pressing the fibers obtained in the step (c) by using a plate type hot press, wherein the hot-pressing temperature is 100 ℃, the pressure intensity is 5MPa, the hot-pressing time is 2min, and the fiber diaphragm is obtained after hot pressing, and the thickness of the diaphragm is 35 mu m.
Example 4
This example was carried out in a similar manner to example 1, except that the high-molecular polymer in the dispersion liquid IV in this example was polyethylene.
The rest is the same as in example 1.
Obtaining the fiber diaphragm.
Example 5
This example was carried out in a similar manner to example 2, except that the same mass of polyamide was used instead of polyvinylidene fluoride-hexafluoropropylene in example 2, and a formic acid-acetic acid (volume ratio 1:1) mixed solvent capable of dissolving polyamide well was used as a solvent to form a polymer solution (dispersion IV) having a mass fraction of 10%.
The rest is the same as in example 2.
Obtaining the fiber diaphragm.
Comparative example 1
The comparative example was conducted in a manner similar to that of example 1, except that polycaprolactone and polybutylene succinate of the same mass were used instead of polyvinylidene fluoride and polyacrylonitrile in example 1, respectively.
The rest is the same as in example 1.
Obtaining the fiber diaphragm.
Test example 1
The performance parameters of each separator were measured, and the specific test methods are shown below, and the test results are shown in table 1.
Thickness: measuring the thickness by a micrometer (the precision is 0.01 mm), randomly sampling 5 points on a sample, and averaging; the thicker the separator is, the lower the capacity of the battery, but the higher the safety;
porosity: the membrane was soaked in n-butanol for 2 hours and then the porosity (p) was calculated according to the formula:
where ρ is1And ρ2Is the density of n-butanol and the dry density of the separator, m1And m2The mass of n-butanol sucked by the diaphragm and the mass of the diaphragm per se; the porosity reflects the microstructure and the number of micropores of the membrane; the higher the porosity of the diaphragm is in a certain range, the more easily a lithium ion channel is formed in the lithium battery, so that the charging and discharging time can be reduced, and the internal resistance can be reduced; however, if the porosity is too high, the porosity is too highShort circuits in the battery are easy to occur, and the porosity is usually 40 to 70 percent.
Liquid absorption rate: the membrane was immersed in n-butanol for 12 hours, and then the liquid uptake (P) was calculated according to the formula:
wherein, W2And W1The mass of n-butanol sucked by the diaphragm and the mass of the diaphragm per se; the liquid absorption rate reflects the infiltration performance of the diaphragm and the electrolyte; the higher the liquid absorption rate of the diaphragm is, the better the affinity of the diaphragm and the electrolyte is, the ionic conductivity is increased, and the charge and discharge performance and capacity of the battery are improved.
Heat shrinkage ratio: the dimensional heat shrinkage was measured using an oven, the sample was heat treated at 200 ℃ for 2 hours, and then the heat shrinkage (δ) was calculated according to the formula:
wherein S is1And S2Is the area of the diaphragm before and after heat treatment; the thermal shrinkage rate reflects the dimensional stability of the separator when heated; the battery releases heat during charge and discharge, and the separator should maintain its original integrity, i.e., a thermal shrinkage rate as low as possible, when the temperature is increased.
Tensile strength: testing the tensile strength of the diaphragm by adopting a plastic tensile experiment method of GB 1040-79; the tensile strength reflects the mechanical strength and safety of the separator; the higher the tensile strength of the separator, the better, and if the separator breaks, a short circuit may occur.
Heat resistance temperature: testing the melting point of the shell material by using a differential scanning calorimeter, and determining the approximate range of the heat-resistant temperature; then carrying out heat treatment at different temperatures for 30min, and then testing the porosity, wherein the temperature when the porosity is rapidly reduced is determined as the heat-resistant temperature; the heat-resistant temperature reflects the heat resistance and the thermal safety of the diaphragm, and when the heat-resistant temperature is reached, the diaphragm cannot work normally.
TABLE 1
From the above results, it can be seen that the separator of the present invention has a high porosity and good heat resistance. In addition, the fiber diaphragm of the invention does not have the phenomenon of inorganic particle falling off.
Further, it can be seen from the results of comparative example 1 and example 4 that the porosity, liquid absorption, heat shrinkage and heat resistant temperature can be further improved with the more preferable kind of the high molecular polymer of the present invention under the condition of the same thickness.
Comparing the results of example 2 and example 5, it can be seen that, although the heat resistant temperature and the porosity are lower than those of example 5 in example 2 using the polymer of the more preferred type of the present invention under the same thickness, the heat resistant temperature and the porosity of example 2 can be maintained within the range generally accepted by those skilled in the art, and example 2 can obtain significantly better liquid absorption and heat shrinkage.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (19)
1. A fiber diaphragm is characterized in that the diaphragm is formed by core-shell structure fibers, a middle core layer material of the core-shell structure fibers is an inorganic particle-high polymer I compound formed by compounding inorganic particles and high polymer I, a shell layer material of the core-shell structure fibers is high polymer II, the high polymer I is different from the high polymer II, and the high polymer I and the high polymer II are respectively and independently selected from at least one of polypropylene, polyethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyamide, polyacrylonitrile, polyarylethersulfone ketone, polyethylene terephthalate and polybutylene terephthalate.
2. The separator according to claim 1, wherein the inorganic particle is contained in an amount of 1 to 40% by weight in the inorganic particle-high molecular polymer I composite.
3. The diaphragm of claim 1 or 2, wherein the high molecular polymer I is selected from at least one of polyacrylonitrile and polyarylethersulfone ketone; the high molecular polymer II is at least one selected from polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene and polymethyl methacrylate.
4. The membrane of any one of claims 1-3, wherein the inorganic particles are selected from at least one of an oxide of a group IIA metal, a sulfate of a group IIA metal, a hydroxide of a group IIA metal, an oxide of a group IVB metal, an oxide of a group IIIA metal, and silica;
preferably, the inorganic particles are selected from at least one of hydrated alumina, magnesia, silica, zirconia, titania, boehmite, barium sulfate, and magnesium hydroxide;
preferably, the inorganic particles have an average particle diameter of 10 to 200 nm.
5. The separator according to any one of claims 1 to 4, wherein the diameter of the intermediate core layer of the core-shell structured fiber is 100-400nm, and the diameter of the core-shell structured fiber is 0.5-2 μm.
6. A membrane according to any one of claims 1 to 5, wherein the membrane has a thickness of 20-50 μm.
7. The separator according to any one of claims 1 to 6, wherein the core-shell structured fiber is a fiber prepared by a coaxial electrospinning method.
8. A method of making a fibrous membrane, the method comprising:
(1) mixing a dispersion liquid I containing inorganic particles and a dispersion liquid II containing a high molecular polymer I to obtain a dispersion liquid III;
(2) respectively introducing a dispersion liquid IV containing a high molecular polymer II and the dispersion liquid III into a storage with an outer needle head and a storage with an inner needle head of a coaxial electrostatic spinning device for electrostatic spinning to obtain core-shell structure fibers;
(3) carrying out hot pressing on the core-shell structure fiber to obtain the diaphragm,
the high molecular polymer I and the high molecular polymer II are different, and are respectively and independently selected from at least one of polypropylene, polyethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyamide, polyacrylonitrile, polyarylethersulfone ketone, polyethylene terephthalate and polybutylene terephthalate.
9. The method of claim 8, wherein the bore of the inner needle is 0.3-0.5mm and the bore of the outer needle is 0.7-1.0 mm;
preferably, the operating conditions of the electrospinning include: the spinning voltage is 15-30kV, the receiving distance is 10-30cm, the humidity is 20-50%, and the spinning temperature is 20-40 ℃.
10. A method according to claim 8 or 9, wherein the hot pressing is performed by a plate press, the operating conditions of the hot pressing comprising: the hot pressing temperature is 70-100 deg.C, pressure is 3-7MPa, and hot pressing time is 1-3 min.
11. The method according to any one of claims 8 to 10, wherein the mass concentration of the inorganic particles in the dispersion I is 10% to 50%, and the mass concentration of the high molecular polymer I in the dispersion II is 10% to 60%;
preferably, the mixing volume ratio of the dispersion liquid I and the dispersion liquid II is 1:9 to 5: 5.
12. The method according to any one of claims 8 to 10, wherein the dispersion IV has a mass concentration of 10% to 60%.
13. The method according to any one of claims 8 to 10, wherein the high molecular polymer I is at least one selected from polyacrylonitrile and polyarylethersulfone ketone; the high molecular polymer II is at least one selected from polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene and polymethyl methacrylate.
14. The process according to any one of claims 8 to 10, wherein the solvent in the dispersion I, the dispersion II, the dispersion IV is each independently selected from at least one of dimethylformamide, acetone, tetrahydrofuran, chloroform, dichloromethane, dimethyl sulfoxide, N-methylpyrrolidone, trifluoroethanol, trifluoroacetic acid, dimethylacetamide, ethanol, and hexafluoroisopropanol.
15. The method of any of claims 8-10, wherein the inorganic particles are selected from at least one of group IIA metal oxides, group IIA metal sulfates, group IIA metal hydroxides, group IVB metal oxides, group IIIA metal oxides, and silica;
preferably, the inorganic particles are selected from at least one of hydrated alumina, magnesia, silica, zirconia, titania, boehmite, barium sulfate, and magnesium hydroxide;
preferably, the inorganic particles have an average particle diameter of 10 to 200 nm.
16. The method as claimed in any one of claims 8 to 15, wherein the flow rates of the dispersion IV and the dispersion III in the coaxial electrospinning device are controlled so that the diameter of the intermediate core layer of the core-shell structured fiber is 100-400nm and the diameter of the core-shell structured fiber is 0.5-2 μm;
preferably, the thickness of the separator is 20 to 50 μm.
17. A fibrous separator produced by the process of any one of claims 8 to 16.
18. Use of a fibrous separator according to any one of claims 1 to 7 and 17 in the preparation of a lithium ion battery separator.
19. A lithium ion battery separator comprising the fibrous separator of any of claims 1-7 and 17.
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| CN104022245A (en) * | 2014-06-24 | 2014-09-03 | 中国第一汽车股份有限公司 | High-safety lithium battery composite diaphragm and coaxial electrostatic spinning preparation method thereof |
| CN104022246A (en) * | 2014-06-24 | 2014-09-03 | 中国第一汽车股份有限公司 | High-performance lithium battery ceramic diaphragm and preparation method thereof |
| US20150287967A1 (en) * | 2012-10-23 | 2015-10-08 | Cornell University | Ceramic nanofiber separators |
| US20150333310A1 (en) * | 2012-12-21 | 2015-11-19 | Amogreentech Co., Ltd. | Porous separation membrane, secondary battery using same, and method for manufacturing said secondary battery |
| CN106450101A (en) * | 2016-08-29 | 2017-02-22 | 大连理工大学 | Method for preparing novel lithium battery diaphragm by coaxial electrostatic spinning |
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| US20150287967A1 (en) * | 2012-10-23 | 2015-10-08 | Cornell University | Ceramic nanofiber separators |
| US20150333310A1 (en) * | 2012-12-21 | 2015-11-19 | Amogreentech Co., Ltd. | Porous separation membrane, secondary battery using same, and method for manufacturing said secondary battery |
| CN104022245A (en) * | 2014-06-24 | 2014-09-03 | 中国第一汽车股份有限公司 | High-safety lithium battery composite diaphragm and coaxial electrostatic spinning preparation method thereof |
| CN104022246A (en) * | 2014-06-24 | 2014-09-03 | 中国第一汽车股份有限公司 | High-performance lithium battery ceramic diaphragm and preparation method thereof |
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