CN106876634A - Composite diaphragm and preparation method thereof, and lithium ion battery - Google Patents
Composite diaphragm and preparation method thereof, and lithium ion battery Download PDFInfo
- Publication number
- CN106876634A CN106876634A CN201710137732.9A CN201710137732A CN106876634A CN 106876634 A CN106876634 A CN 106876634A CN 201710137732 A CN201710137732 A CN 201710137732A CN 106876634 A CN106876634 A CN 106876634A
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- conductive fiber
- layer
- nano
- fiber layer
- composite diaphragm
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Links
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 121
- 239000002121 nanofiber Substances 0.000 claims abstract description 114
- 238000009413 insulation Methods 0.000 claims abstract description 71
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 53
- 229920000642 polymer Polymers 0.000 claims description 48
- 239000002052 molecular layer Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 35
- 239000012528 membrane Substances 0.000 claims description 34
- 239000000919 ceramic Substances 0.000 claims description 30
- 239000004642 Polyimide Substances 0.000 claims description 24
- 229920001721 polyimide Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 19
- 238000010041 electrostatic spinning Methods 0.000 claims description 18
- 230000005611 electricity Effects 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 229920005575 poly(amic acid) Polymers 0.000 description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 29
- 238000009987 spinning Methods 0.000 description 24
- 239000002134 carbon nanofiber Substances 0.000 description 20
- 210000001787 dendrite Anatomy 0.000 description 20
- 239000002904 solvent Substances 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000010276 construction Methods 0.000 description 10
- 229920000049 Carbon (fiber) Polymers 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 9
- 239000004917 carbon fiber Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229910021392 nanocarbon Inorganic materials 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 7
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- -1 alkene nitrile Chemical class 0.000 description 6
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000005255 carburizing Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920002627 poly(phosphazenes) Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- 241000826860 Trapezium Species 0.000 description 3
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000013081 microcrystal Substances 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
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- 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)
- Nonwoven Fabrics (AREA)
- Cell Separators (AREA)
Abstract
The present invention relates to a kind of composite diaphragm, including the conductive fiber layer and electric insulation layers of nanofibers that are stacked, the conductive fiber layer includes multiple nano-conductive fibers, the multiple nano-conductive fiber intersects to form network structure, and the conductive fiber layer has multiple micropores formed by the nano-conductive fiber.A kind of lithium ion battery, including composite diaphragm, positive pole and negative pole, the conductive fiber layer are arranged on the negative pole side, and are electrically connected with the negative pole.The invention further relates to a kind of preparation method of composite diaphragm.
Description
Technical field
The present invention relates to field of batteries, more particularly to composite diaphragm and preparation method thereof, and apply the composite diaphragm
Lithium ion battery.
Background technology
Lithium ion battery have energy density high, output power, small self discharge, memory-less effect, have extended cycle life, ring
The features such as border is friendly, is widely used in power and energy storage aspect.And barrier film is the important component of lithium ion battery, for hindering
Every both positive and negative polarity, prevent the two poles of the earth directly contact and be short-circuited.Barrier film allows lithium ion to pass through, and prevents electronics from flowing through, and completes
Transmission of the lithium ion between both positive and negative polarity in charge and discharge process.Barrier film determines interfacial structure, internal resistance, the battery of lithium ion battery
Capacity etc., its performance can influence charge-discharge performance, service life and security performance of battery etc..
Additionally, due to the uneven abjection in cyclic process of lithium ion and deposition so that lithium an- ode surface has one
The phenomenon of preferential growth is planted, so as to produce dendritic metal Li dendrite.Lithium ion battery with graphite as negative pole in low temperature or
In the case of filling soon, also easily there is Li dendrite on graphite cathode surface.In cyclic process, the Li dendrite meeting of negative pole continued propagation
Pierce through barrier film arrival positive pole and cause the short circuit of inside battery both positive and negative polarity, cause hot-spot to cause fire even to explode, so as to have
Very big potential safety hazard.
The content of the invention
Based on this, it is necessary to provide a kind of composite diaphragm that can suppress negative pole lithium dendrite growth and preparation method thereof, and
A kind of lithium ion battery of the application composite diaphragm is provided.
A kind of composite diaphragm, including the conductive fiber layer and electric insulation layers of nanofibers being stacked, the conductive fiber
Layer includes multiple nano-conductive fibers, and the multiple nano-conductive fiber intersects to form network structure, the conductive fiber
Layer has multiple micropores formed by the nano-conductive fiber.
Wherein in one embodiment, the electric insulation layers of nanofibers includes nanofiber, and the nanofiber is mutual
Network structure is intersected to form, the electric insulation layers of nanofibers has multiple micropores formed by the nanofiber.
Wherein in one embodiment, the material of the nano-conductive fiber is poly- the third of the polyimides and carbonization being carbonized
At least one in alkene nitrile.
Wherein in one embodiment, the material of the nanofiber is polyimides, polyvinylidene fluoride and polypropylene
At least one in nitrile.
Wherein in one embodiment, the inorganic nano layer being stacked, the electric insulation nanofiber are further included
Layer is located between inorganic nano layer and the conductive fiber layer.
Wherein in one embodiment, two-layer inorganic nano layer is further included, the electric insulation layers of nanofibers is located at
Between the two-layer inorganic nano layer, the conductive fiber layer is laminated in the opposite side of any one layer inorganic nano layer.
Wherein in one embodiment, the inorganic nano layer includes high molecular polymer and inorganic nano ceramic particle,
The high molecular polymer is at least one in polyvinylidene fluoride and polyethylene glycol oxide, and the inorganic nano ceramic particle is
One or two in silica, titanium dioxide, zirconium dioxide, alundum (Al2O3) and magnesia.
Wherein in one embodiment, the porosity of composite diaphragm is 60% to 96%, and average pore size is 4.0 μm to 5.5 μ
m。
Wherein in one embodiment, the pick up of composite diaphragm is 400%~900%.
Wherein in one embodiment, the mass area ratio of composite diaphragm is 6g/m2To 20g/m2, thickness be 15 μm extremely
70μm。
A kind of lithium ion battery, including foregoing any one composite diaphragm, positive pole and negative pole, the composite diaphragm
Be arranged between the positive pole and the negative pole, the conductive fiber layer is arranged on the negative pole side, and with the negative electricity
Connection.
A kind of preparation method of composite diaphragm, including：
Conductive fiber layer is prepared, the conductive fiber layer includes multiple nano-conductive fibers, and the multiple conductive nano is fine
Dimension intersects to form network structure, and the conductive fiber layer has multiple micropores formed by the nano-conductive fiber；With
And
Electric insulation layers of nanofibers is formed in the conductive fiber layer.
Wherein in one embodiment, further include：
Inorganic nano layer is formed in the electric insulation layers of nanofibers.
Wherein in one embodiment, the preparation conductive fiber layer includes：
First polymer solution is provided；
The first polymer solution is made by nano fibrous membrane by method of electrostatic spinning；And
By nano fibrous membrane carbonization, the conductive fiber layer is obtained.
Wherein in one embodiment, the electric insulation layers of nanofibers that formed in the conductive fiber layer includes：
Second polymer solution is provided；And
The second polymer solution is made into the electric insulation in the conductive fiber layer by method of electrostatic spinning to receive
Rice fibrage.
Wherein in one embodiment, described by nano fibrous membrane carbonization, the step of the conductive fiber layer is obtained
It is rapid take a step forward including：The nano fibrous membrane is pre-processed, the nano fibrous membrane internal component is cyclized, institute is improved
State the stability of nano fibrous membrane.
Composite diaphragm of the invention and lithium ion battery include the conductive fiber layer being stacked and electric insulation nanofiber
Layer.Conductive fiber layer includes that multiple intersects to form the nano-conductive fiber of network structure, and fine by the conduction with multiple
Tie up the micropore for being formed.Conductive fiber layer is electrically connected with GND in the battery, serves as pseudo- collector, relative to negative pole have compared with
Current potential high.And dendrite preferred growth is on high potential, therefore dendrite can be with preferred growth in conductive fiber layer.Due to the conduction
Nano-conductive fiber intersects to form micropore in fibrage, so that conductive fiber layer has larger specific surface area, it is internal
With the interior surface for forming micropore.Dendrite can disperse to grow in conductive fiber layer interior surface, so as to eliminate GND
The growth of dendrite.Conductive fiber layer interior surface is available for the site of dendritic growth more, and then can make the length of the dendrite of generation
Degree relative reduction, is conducive to preventing generating dendrite more long and punctures barrier film.
Brief description of the drawings
Fig. 1 is the composite diaphragm schematic diagram of the embodiment of the present invention.
Wherein,
Composite diaphragm -10；
Conductive fiber layer -12；
Electric insulation layers of nanofibers -14；
Inorganic nano layer -16.
Specific embodiment
For a better understanding of the present invention, below with reference to the accompanying drawings and with reference to specific embodiment the present invention is carried out specifically
It is bright.
Refer to Fig. 1, the present invention provides a kind of composite diaphragm 10, including the conductive fiber layer 12 that is stacked and electric insulation
Layers of nanofibers 14.Electric insulation layers of nanofibers 14 can completely cut off electronics and allow lithium ion to pass through.Conductive fiber layer 12 can be with
Conductive and permission lithium ion passes through.The conductive fiber layer 12 includes multiple nano-conductive fibers, the plurality of nano-conductive fiber phase
Mutually intersect, be wound network structure, the conductive fiber layer 12 has multiple micropores formed by the nano-conductive fiber.Work
During conductive fiber layer 12 electrically connected with GND, serve as pseudo- collector, relative to negative pole have current potential higher.And branch
Brilliant preferred growth is on high potential, therefore dendrite can be with preferred growth in conductive fiber layer 12.Due in the conductive fiber layer 12
Nano-conductive fiber intersects to form micropore, so that conductive fiber layer 12 has larger specific surface area, inside has shape
Into the interior surface of micropore.Dendrite can disperse to grow in the interior surface of conductive fiber layer 12, so as to eliminate GND dendrite
Growth.The interior surface of conductive fiber layer 12 is available for the site of dendritic growth more, and then can make the length of the dendrite of generation
Relative reduction, is conducive to preventing generating dendrite more long and punctures barrier film.Preferably, the mass area ratio of composite diaphragm 10 is
6g/m2To 20g/m2, thickness is 15 μm to 70 μm.
Electric insulation layers of nanofibers 14 includes nanofiber.Nanofiber is intersected, is wound network-like structure, and
Formed based on tortuous hole, interconnect open pore structure.Pore size is interconnected up to submicron order, hole, specific surface area
Greatly.The material of nanofiber is polymeric, preferably polar polymer.And the crystal region in polymer can not be electrolysed
Liquid is swelling, can play certain supporting role；Unformed area can by electrolyte it is swelling so that formed gel phase, so as to electricity
Solution liquid has preferable compatibility.There may be certain electrolyte with by swelling amorphous regions in the space of crystal region.Electricity
Insulating nanofibers layer 14 can be prepared using method of electrostatic spinning, so as to be easier to obtain the low electric insulation nanometer of fibre crystallinity
Fibrage 14, so as to get electric insulation layers of nanofibers 14 have good electrolyte compatibility, wellability and retentivity, can obtain
Ionic conductivity and interface compatibility higher is obtained, so as to be conducive to the discharge and recharge of high current.Polymer be preferably polyimides,
At least one in polyvinylidene fluoride and polyacrylonitrile.The thickness of the layers of nanofibers 14 that is electrically insulated is preferably 8 μm to 60 μm, receives
Rice fibre diameter is preferably 50nm to 800nm, and average pore size is preferably 5 μm to 6.5 μm.Wherein, polyimides thermal stable temperature
More than 300 DEG C, more than 150 DEG C, polyacrylonitrile thermal stable temperature is more than 270 DEG C for polyvinylidene fluoride thermal stable temperature.
Conductive fiber layer 12 includes the carbon nano-fiber for intersecting, winding, and is formed based on tortuous hole, possesses interconnection and opens
The network-like structure of discharge hole gap structure.Pore size is interconnected up to submicron order, hole, the specific surface area of conductive fiber layer 12
Greatly, and then more lithium ions growth sites can be provided.And conductive fiber layer 12 can reduce the polarization reaction of battery, improve
Electric property.Conductive fiber layer 12 can be the carbon nano-fiber layer obtained after polymeric fibrage is carbonized, so that
The properties such as the original fibre diameter of polymeric electric insulation layers of nanofibers, porosity are kept after carbonization.Led for being formed
The polymeric fibrage of electric fibrage 12 can also be prepared using method of electrostatic spinning.Polymeric is preferably
At least one in polyimides and polyacrylonitrile.The thickness of conductive fiber layer 12 is preferably 5 μm to 30 μm, conductive fiber diameter
50nm to 800nm is preferably sized to, average pore size is preferably 5 μm to 6.5 μm, and specific surface area is preferably 100-800m2/g。
The electric insulation layers of nanofibers 14 and conductive fiber layer 12 of composite diaphragm 10 are respectively provided with network-like structure, so as to have
Larger specific surface area and porosity, it is preferred that the porosity of composite diaphragm 10 is 60% to 96%, and average pore size is preferably
4.0 μm to 5.5 μm.
Preferably, composite diaphragm 10 further includes the inorganic nano layer 16 being stacked.Electric insulation layers of nanofibers 14
Between inorganic nano layer 16 and conductive fiber layer 12.In electric insulation layers of nanofibers 14 side, inorganic nano layer 16 is set,
The electrolyte being located in electric insulation layers of nanofibers 14 is difficult outflow, improve the water retainability of composite diaphragm 10.By
Electric insulation layers of nanofibers 14 side sets inorganic nano layer 16, and the pick up of composite diaphragm 10 can reach 400%~
900%.
It is furthermore preferred that further including two-layer inorganic nano layer 16.Electric insulation layers of nanofibers 14 is located at that two-layer is inorganic receives
Between rice layer 16.Conductive fiber layer 12 is laminated in any one layer of inorganic nano layer 16.In electric insulation layers of nanofibers 14 both sides point
Not She Zhi inorganic nano layer 16, the electrolyte in electric insulation layers of nanofibers 14 is protected from both sides, substantially increase multiple
Close the water retainability of barrier film 10.
Inorganic nano layer 16 includes mixed uniformly high molecular polymer and inorganic nano ceramic particle.High molecular polymer
Can be at least one in polyvinylidene fluoride and polyethylene glycol oxide for bonding inorganic nano ceramic particle.Inorganic nano
Ceramic particle can be one or two in silica, titanium dioxide, zirconium dioxide, alundum (Al2O3) and magnesia.Nothing
The thickness of machine nanometer layer 16 is preferably 2 μm to 10 μm, and the particle diameter of inorganic nano ceramic particle is preferably 20nm to 1000nm.It is inorganic
Nanometer layer 16 can improve interfacial characteristics, reduce interface impedance, strengthen the mechanical property at interface, ionic conductivity and thermally-stabilised
Property, wherein mechanical property is mainly reflected in the mechanical strength of increase composite diaphragm 10, makes barrier film be difficult to be pierced through by Li dendrite.
The present invention also provides a kind of lithium ion battery, and the lithium ion battery includes any composite diaphragm in the various embodiments described above
10th, positive pole and negative pole, conductive fiber layer 12 is arranged on negative pole side, and is electrically connected with negative pole.Specifically, conductive fiber layer 12 can
With setting of directly being fitted with negative pole.Relative to the barrier film without conductive fiber layer, composite diaphragm of the invention 10 can be significantly
The growth length of negative pole Li dendrite is reduced, and changes the growth position of Li dendrite.Found through experiment, under the same conditions, used
In the lithium ion battery of composite diaphragm of the invention 10, Li dendrite is mainly grown in inside conductive fiber layer 12, and growth length
Only use the 1/20 of the now Li dendrite length of septate lithium ion battery.
The present invention also provides a kind of preparation method of composite diaphragm 10, including：
S110, prepares conductive fiber layer 12；And
S120, forms electric insulation layers of nanofibers 14 in conductive fiber layer 12.
Preferably, further include：
S130, forms inorganic nano layer 16 in electric insulation layers of nanofibers 14.
Wherein in one embodiment, S110 is further included：
S112, there is provided first polymer solution；
S114, nano fibrous membrane is made by method of electrostatic spinning by first polymer solution；And
S116, nano fibrous membrane is carbonized, and obtains conductive fiber layer 12.
In step S112, first polymer solution is preferably at least in polyamic acid solution and polyacrylonitrile solution
Kind.Solvent in first polymer solution can for N, dinethylformamide, dimethylacetylamide, acetone, tetrahydrofuran, N-
At least one in methyl pyrrolidone and DMSO.If two kinds of solvent mixing, then the mixed proportion of two kinds of solvents is excellent
Elect 1 as:1 to 1:99.The mass percent of the solute in first polymer solution is preferably 6% to 15%.
In one embodiment, polyamic acid solution is synthesized in solvent and is obtained under cryogenic using dianhydride with diamines,
Reaction temperature is -5 DEG C to 15 DEG C, preferably 0 DEG C to 5 DEG C.Wherein dianhydride can be pyromellitic acid anhydride (PMDA), 3,3',
Any one in 4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and bibenzene tetracarboxylic dianhydride (BPDA)；Diamines can be p-phenylenediamine
(PPD), any one in diaminodiphenyl ether (ODA) and benzidine (BID).
Ambient humidity is controlled to be preferably 30% to 70% in step S114, in electrostatic spinning；Syringe pump and spinning syringe needle
By pipeline communication；Spinning syringe needle is preferably 10cm to 70cm with the spacing of reception device, and voltage between the two is preferably
12kV to 70kV；By pipeline from the polymer solution in syringe pump arrival spinning syringe needle preferably with 0.1mL/h's to 130mL/h
Flow sprays polymer nanofiber；Collected polymer nanofiber, forms nano fibrous membrane on the reception device.
By controlling the dense of voltage in electrostatic spinning between spinning syringe needle and reception device, spacing and polymer solution
Degree, the flow velocity for spraying, can obtain the fiber of different-diameter.And can be by controlling the time of electrostatic spinning and to fiber
The subsequent treatment of film controls to adjust the thickness of tunica fibrosa.
In step S116, high temperature cabonization treatment is carried out in atmosphere of inert gases, carburizing temperature can be 700 DEG C to 900
℃.Inert gas can be nitrogen, argon gas or the helium of high-purity, and purity is preferably above 99.999%.
Wherein in one embodiment, the step S116 take a step forward including：
S116a, pre-processes to nano fibrous membrane, is cyclized the nano fibrous membrane internal component, improves Nanowire
Tie up the stability of film.
In step S116a, if polyamic acid nano fibrous membrane obtained in polyamic acid solution then using hot imidization,
The mode that chemical imidization or both is combined obtains polyimide nanofiber membrane；If poly- third obtained in polyacrylonitrile solution
Alkene nitrile nanofibre film then carries out pre-oxidizing the polyacrylonitrile nano for obtaining network structure fibre at a temperature of 120 DEG C to 130 DEG C
Dimension film.The structural instability of polyamic acid, readily soluble, degradable, polyamic acid is understood cyclodehydration and then is obtained in imidization
Constitutionally stable polyimide structures.To there are a series of chemistry such as cyclisation, dehydrogenation in polyacrylonitrile fibre anti-in preoxidation process
Should, the chemical composition and structure of fiber is changed, and then internally form the original knot converted to graphite microcrystal during carbonization
Structure.Polyacrylonitrile fibre membrane changes into heat-resisting trapezium structure by the linearity molecular structure in polyacrylonitrile after pre-oxidation.
In trapezium structure polymer, a disconnection for key will not make whole molecular chain rupture, prevent polyacrylonitrile fibre in pyrocarbon
The fusion and decomposition in high-temperature heating process during change.In high temperature cabonization, not melting for this trapezium structure makes polyacrylonitrile heat
Good stability, and chemistry and mechanical performance can be kept before structural break, after making polyacrylonitrile fibre through pre-oxidation, can protect
Carbonization is made carbon fiber under holding the form of fiber.
Wherein in one embodiment, S120 is further included：
S122, there is provided second polymer solution；And
S124, makes second polymer solution that electric insulation nanofiber is formed in conductive fiber layer 12 by method of electrostatic spinning
Layer 14.
In step S122, second polymer solution can be polyamic acid solution, polyacrylonitrile solution and gather inclined difluoro
At least one in vinyl solution.Solvent in second polymer solution can be N, dinethylformamide, dimethylacetamide
At least one in amine, acetone, tetrahydrofuran, N-methyl pyrrolidone and DMSO.If the mixing of two kinds of solvents, then two
The mixed proportion for planting solvent is 1:1 to 1:99.The mass percent of the solute in second polymer solution is 6% to 15%.It is poly-
Acid amides acid solution synthesizes prepared in solvent under cryogenic using dianhydride with diamines, and reaction temperature is -5 DEG C to 15 DEG C, excellent
Elect 0 DEG C to 5 DEG C as.Wherein dianhydride can be pyromellitic acid anhydride (PMDA), 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides
(BTDA) any one and in bibenzene tetracarboxylic dianhydride (BPDA)；Diamines can be p-phenylenediamine (PPD), diaminodiphenyl ether
(ODA) any one and in benzidine (BID).
Ambient humidity is controlled to be preferably 30% to 70% in step S124, in electrostatic spinning；Syringe pump and spinning syringe needle
By pipeline communication；Spinning syringe needle is preferably 10cm to 70cm with the spacing of reception device, and voltage between the two is preferred
12kV to 70kV；By pipeline from the polymer solution in syringe pump arrival spinning syringe needle preferably with 0.1mL/h's to 130mL/h
Flow sprays polymer nanofiber；Conductive fiber layer 12 is placed on the reception device and in the collection of the top of conductive fiber layer 12
Polymer nanofiber.
By controlling the dense of voltage in electrostatic spinning between spinning syringe needle and reception device, spacing and polymer solution
Degree, the flow velocity for spraying, can obtain the fiber of different-diameter.And can be by controlling the time of electrostatic spinning and to fiber
The subsequent treatment of film controls to adjust the thickness of fibrage.
Wherein in one embodiment, S124 is further included：
S124a, is processed nano fibrous membrane.
In step S124a, if polyamic acid nano fibrous membrane obtained in polyamic acid solution then using hot imidization,
The mode that chemical imidization or both is combined obtains polyimides electric insulation layers of nanofibers.
Wherein in one embodiment, S130 is further included：
S132, prepares inorganic nano ceramic particle solution；And
S134, the electric insulation nanofiber layer surface is coated in by inorganic nano ceramic particle solution, or by the electricity
Insulating nanofibers layer is immersed in the inorganic nano ceramic particle solution, so as to the shape in the electric insulation layers of nanofibers
Into inorganic nano layer.
In step S132, first by caking property high molecular polymer in a solvent machinery or magnetic agitation to completely it is molten
Solution, adds a certain amount of inorganic nano ceramic particle, ultrasonic disperse 30min to 120min.The solvent of selection can be N- first
Base pyrrolidones or water.The mass concentration of inorganic nano ceramic particle is preferably 0.1% to 5%, caking property high molecular polymer
Mass ratio with inorganic nano ceramic particle is preferably 1:0.5 to 1:2.
The present invention also provides a kind of preparation method of composite diaphragm 10, including：
S210, prepares conductive fiber layer 12；
S220, forms the first inorganic nano layer in conductive fiber layer 12；
S230, forms electric insulation layers of nanofibers 14 on the first inorganic nano layer；And
S240, forms the second inorganic nano layer in electric insulation layers of nanofibers 14.
Wherein, step S210 is identical with step S110.First and second is formed in step S220 and step S240 inorganic to receive
The step of rice layer, is essentially identical with step S130, and difference is placement conductive fiber layer 12 in reception device in step S220,
First inorganic nano is laminated on the top of conductive fiber layer 12 layer by layer；Conductive fiber layer 12/ the is placed in step S240 in reception device
One inorganic nano layer/electric insulation layers of nanofibers 14, the second inorganic nano is laminated on the top of electric insulation layers of nanofibers 14 layer by layer；Step
The electric insulation layers of nanofibers 14 of conductive fiber layer 12/ is placed in reception device in rapid S130, inorganic nano layer 16 is laminated in electricity
The top of insulating nanofibers layer 14.So the extension for step S130 is equally applicable to step S220 and step S240.
Embodiment 1
S110, prepares the carbon nano-fiber of conductive fiber layer 12 layer, including：
S112, using bibenzene tetracarboxylic dianhydride (BPDA) and p-phenylenediamine (PPD), in N, dinethylformamide solution
In, the polyamic acid solution that mass percent is 6% is synthesized under the conditions of -5 DEG C；
S114, polyamic acid nano fibrous membrane is prepared by method of electrostatic spinning.It is poly- specially by what is obtained in step S112
Acid amides acid solution adds syringe pump, and it is 30% to control ambient humidity；Syringe pump is connected with spinning syringe needle by pipeline；Syringe needle with
The spacing of reception device is 30cm, and the high-tension electricity of 25kV is applied between the two；Reached in spinning syringe needle from syringe pump by pipeline
Polymer solution polyamic acid nanofiber is sprayed with the flow of 1mL/h；Polyamic acid Nanowire is collected using reception device
Dimension, obtains the polyamic acid nano fibrous membrane that thickness is 10 μm；
S116a, hot imidization is carried out to polyamic acid nano fibrous membrane, obtains polyimide nanofiber membrane；
S116, polyimide nanofiber membrane is carbonized in the nitrogen atmosphere that purity is 99.999%, carbonization temperature
It is 900 DEG C to spend, and obtains carbon nano-fiber layer.
S120, forms electric insulation layers of nanofibers 14 in conductive fiber layer 12, specifically includes：
S122, prepares the polyvinylidene fluoride solution that mass percent is 15%.The solvent of selection is volume ratio 1:50
Acetone and N, the mixed liquor of dinethylformamide；
S124, carbon nano-fiber is placed in reception device；Polyvinylidene fluoride solution, control are added in syringe pump
Ambient humidity is 50%；Syringe pump is connected with spinning syringe needle by pipeline；The spacing of syringe needle and reception device is 15cm, both it
Between apply 18kV high-tension electricity；The polymer solution reached from syringe pump by pipeline in spinning syringe needle is sprayed with the flow of 4mL/h
Go out polyvinylidene fluoride nanofiber；Polyvinylidene fluoride nanofiber is collected, polyimide nano carbon fiber layer/poly- inclined is obtained
The composite construction of PVF electric insulation layers of nanofibers 14.
S130, forms inorganic nano layer 16 in electric insulation layers of nanofibers 14, specifically includes：
S132, prepares inorganic nano ceramic particle solution, specifically includes and first caking property polyphosphazene polymer vinylidene fluoride exists
Mechanical agitation adds a certain amount of SiO 2-ceramic particle, ultrasonic disperse until being completely dissolved in N-methyl pyrrolidone
30min.Wherein the mass concentration of SiO 2-ceramic particle solution is 0.1%, and polyvinylidene fluoride used is made pottery with silica
The mass ratio of porcelain particle is 1:0.5；
S134, by SiO 2-ceramic particle solution, by paint-on technique in polyimide nano carbon fiber layer/poly- inclined fluorine
Inorganic nano layer is formed in the Kynoar electric insulation layers of nanofibers 14 of the ethene electric insulation composite construction of layers of nanofibers 14
16, obtain being received with polyimide nano carbon fiber layer, Kynoar electric insulation layers of nanofibers 14 and silica inorganic
The composite diaphragm for lithium ion battery 10 of the rice stacking of layer 16.
Embodiment 2
S110, prepares the carbon nano-fiber of conductive fiber layer 12 layer, including：
S112, prepare mass percent be 15% polyacrylonitrile solution, from for N, N-dimethylformamide be solvent；
S114, polyamic acid nano fibrous membrane is prepared by method of electrostatic spinning.Polyacrylonitrile solution is added to syringe pump
In, it is 50% to control ambient humidity；Syringe pump is connected with spinning syringe needle by pipeline；Syringe needle is with the spacing of reception device
20cm, applies the high-tension electricity of 35kV between the two；By pipeline from syringe pump reach spinning syringe needle in polymer solution with
The flow of 2mL/h sprays polyacrylonitrile nanofiber；Polyacrylonitrile nanofiber is collected using reception device, it is 20 to obtain thickness
μm polyacrylonitrile nanofiber film；
S116a, polyacrylonitrile nanofiber film is pre-oxidized, the polyacrylonitrile nanofiber film after being processed,
Pre oxidation is 120 DEG C；
S116, carbon is carried out by the polyacrylonitrile nanofiber film after treatment in the nitrogen atmosphere that purity is 99.999%
Change, carburizing temperature is 700 DEG C, obtain carbon nano-fiber layer.
S120, forms electric insulation layers of nanofibers 14 in conductive fiber layer 12, specifically includes：
S122, prepares the polyacrylonitrile solution that mass percent is 13%, and the solvent of selection is dimethylacetylamide；
S124, polyacrylonitrile-based carbon nanofibers are placed in reception device；Polyacrylonitrile solution is added in syringe pump,
It is 30% to control ambient humidity；Syringe pump is connected with spinning syringe needle by pipeline；Syringe needle is 10cm, two with the spacing of reception device
Apply a high-tension electricity of 18kV between person；By pipeline from the polymer solution in syringe pump arrival spinning syringe needle with 1mL/h
Flow spray polyacrylonitrile nanofiber；Polyacrylonitrile nanofiber is collected, polyacrylonitrile-based carbon nanofibers layer/poly- third is obtained
The composite construction of alkene nitrile electric insulation layers of nanofibers 14.
S130, forms inorganic nano layer 16 in electric insulation layers of nanofibers 14, specifically includes：
S132, prepares inorganic nano ceramic particle solution, specifically includes and first caking property polyphosphazene polymer vinylidene fluoride exists
Mechanical agitation adds a certain amount of aluminum oxide ceramic particle, ultrasound point until being completely dissolved in N-methyl pyrrolidone
Dissipate 30min.The mass concentration of SiO 2-ceramic particle solution is 0.2%, and polyvinylidene fluoride used is made pottery with alundum (Al2O3)
The mass ratio of porcelain particle is 1:0.5；
S134, by aluminum oxide ceramic particle solution, by paint-on technique in polyacrylonitrile-based carbon nanofibers layer/poly- third
Inorganic nano layer 16 is formed in the polyacrylonitrile electric insulation layers of nanofibers 14 of the alkene nitrile electric insulation composite construction of layers of nanofibers 14,
Obtain with polyacrylonitrile-based carbon nanofibers layer, polyacrylonitrile electric insulation layers of nanofibers 14 and alundum (Al2O3) inorganic nano layer
Three layers of composite diaphragm for lithium ion battery 10 of 16 stackings.
Embodiment 3
S110, prepares the carbon nano-fiber of conductive fiber layer 12 layer, including：
S112, is monomer from pyromellitic acid anhydride (PMDA) and diaminodiphenyl ether (ODA), from being N, N diformazan
Base formamide is solvent with tetrahydrofuran, and tetrahydrofuran and N, the ratio of N-dimethylformamide are 1:20, synthesis at low temperature is matched somebody with somebody
Polyamic acid solution processed.The mass percent of polyamic acid solution is 8%；
S114, polyamic acid nano fibrous membrane is prepared by method of electrostatic spinning.Polyamic acid solution is added to syringe pump
In, it is 30% to control ambient humidity；Syringe pump is connected with spinning syringe needle by pipeline；Syringe needle is with the spacing of reception device
30cm, applies the high-tension electricity of 30kV between the two；By pipeline from syringe pump reach spinning syringe needle in polymer solution with
The flow of 1mL/h sprays polyamic acid nanofiber；Polyamic acid nanofiber is collected using reception device, polyamic acid is obtained
Nano fibrous membrane, thickness is 20 μm；
S116a, imines is carried out by polyamic acid nano fibrous membrane by way of hot imidization is combined with chemical imidization
Change, obtain polyimide nanofiber membrane；
S116, carbon is carried out by the polyimide nanofiber membrane in step 3 in the argon atmosphere that purity is 99.999%
Change, carburizing temperature is 800 DEG C, obtains polyimide nano carbon fiber layer.
S120, forms electric insulation layers of nanofibers 14 in conductive fiber layer 12, specifically includes：
S122, prepares the polyacrylonitrile solution that mass percent is 11%, and the solvent of selection is dimethylacetylamide；
S124, polyimide nano carbon fiber layer is placed in reception device；Polyacrylonitrile solution is added in syringe pump,
It is 30% to control ambient humidity；Syringe pump is connected with spinning syringe needle by pipeline；Syringe needle is 10cm, two with the spacing of reception device
Apply a high-tension electricity of 18kV between person；By pipeline from the polymer solution in syringe pump arrival spinning syringe needle with 1mL/h
Flow spray polyacrylonitrile nanofiber；Polyacrylonitrile nanofiber is collected, polyimide nano carbon fiber layer/poly- third is obtained
The composite construction of alkene nitrile electric insulation layers of nanofibers 14.
S130, forms inorganic nano layer 16 in electric insulation layers of nanofibers 14, specifically includes：
S132, prepares inorganic nano ceramic particle solution, specifically includes first by caking property polyphosphazene polymer ethylene oxide in water
Middle mechanical agitation adds a certain amount of zirconia ceramic particle, ultrasonic disperse 110min until being completely dissolved.Zirconium dioxide
The mass concentration of ceramic particle solution is 1.5%, and polyethylene glycol oxide used is 1 with the mass ratio of zirconia ceramic particle:1；
S134, by zirconia ceramic particle solution, by paint-on technique in polyimide nano carbon fiber layer/polypropylene
Inorganic nano layer 16 is formed in the polyacrylonitrile electric insulation layers of nanofibers 14 of the nitrile electric insulation composite construction of layers of nanofibers 14, is obtained
To with 16 layers of polyimide nano carbon fiber layer, polyacrylonitrile electric insulation layers of nanofibers 14 and zirconium dioxide inorganic nano layer
Three layers of folded composite diaphragm for lithium ion battery 10.
Embodiment 4
S110, prepares the carbon nano-fiber of conductive fiber layer 12 layer, including：
S112, prepares the polyacrylonitrile solution that mass percent is 15%, and the solvent of selection is N, N-dimethylformamide；
S114, polyamic acid nano fibrous membrane is prepared by method of electrostatic spinning.Polyacrylonitrile solution is added to syringe pump
In, it is 50% to control ambient humidity；Syringe pump is connected with spinning syringe needle by pipeline；Syringe needle is with the spacing of reception device
20cm, applies the high-tension electricity of 35kV between the two；By pipeline from syringe pump reach spinning syringe needle in polymer solution with
The flow of 2mL/h sprays polyacrylonitrile nanofiber；Polyacrylonitrile nanofiber is collected using reception device, polyacrylonitrile is obtained
Nano fibrous membrane, thickness is 10 μm；
S116a, polyacrylonitrile nanofiber film is pre-oxidized, the polyacrylonitrile nanofiber film after being processed,
Pre oxidation is 130 DEG C；
S116, carbon is carried out by the polyacrylonitrile nanofiber film after treatment in the helium atmosphere that purity is 99.999%
Change, carburizing temperature is 750 DEG C, obtain carbon nano-fiber layer.
S120, forms electric insulation layers of nanofibers 14 in conductive fiber layer 12, specifically includes：
S122, from 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides (PMDA) are monomer with benzidine (BID), from diformazan
Yl acetamide is solvent with acetone, and dimethylacetylamide is 1 with the volume ratio of acetone:1, synthesize at 5 DEG C and prepare polyamic acid
Solution.The mass percent of polyamic acid solution is 15%；
S124, polyacrylonitrile-based carbon nanofibers are placed in reception device；Polyamic acid solution is added in syringe pump,
It is 50% to control ambient humidity；Syringe pump is connected with spinning syringe needle by pipeline；Syringe needle is 50cm, two with the spacing of reception device
Apply a high-tension electricity of 70kV between person；By pipeline from the polymer solution in syringe pump arrival spinning syringe needle with 130mL/
The flow of h sprays polyamic acid nanofiber；Polyamic acid nanofiber is collected, polyacrylonitrile-based carbon nanofibers layer/poly- is obtained
The composite construction of amic acid electric insulation layers of nanofibers 14；
S124a, the composite construction to polyacrylonitrile-based carbon nanofibers layer/polyamic acid electric insulation layers of nanofibers 14 passes through
Chemical imidization treatment, obtains the composite construction of polyacrylonitrile-based carbon nanofibers layer/polyimides electric insulation layers of nanofibers 14.
S130, forms inorganic nano layer 16 in electric insulation layers of nanofibers 14, specifically includes：
S132, prepares inorganic nano ceramic particle solution, specifically includes first by caking property polyphosphazene polymer ethylene oxide in water
Middle mechanical agitation adds a certain amount of zirconia ceramic particle, ultrasonic disperse 110min until being completely dissolved.Zirconium dioxide
The mass concentration of ceramic particle solution is 1.5%, and polyethylene glycol oxide used is 1 with the mass ratio of zirconia ceramic particle:2；
S134, by zirconia ceramic particle solution, by paint-on technique in polyacrylonitrile-based carbon nanofibers layer/polyamides Asia
Inorganic nano layer 16 is formed in the polyimides electric insulation layers of nanofibers 14 of the amine electric insulation composite construction of layers of nanofibers 14, is obtained
To with 16 layers of polyacrylonitrile-based carbon nanofibers layer, polyimides electric insulation layers of nanofibers 14 and zirconium dioxide inorganic nano layer
Three layers of folded composite diaphragm for lithium ion battery 10.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Shield scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (16)
1. a kind of composite diaphragm, it is characterised in that described including the conductive fiber layer and electric insulation layers of nanofibers that are stacked
Conductive fiber layer includes multiple nano-conductive fibers, and the multiple nano-conductive fiber intersects to form network structure, described
Conductive fiber layer has multiple micropores formed by the nano-conductive fiber.
2. composite diaphragm according to claim 1, it is characterised in that the electric insulation layers of nanofibers includes Nanowire
Dimension, the nanofiber intersects to form network structure, and the electric insulation layers of nanofibers has multiple by the Nanowire
Tie up the micropore for being formed.
3. composite diaphragm according to claim 1, it is characterised in that the material of the nano-conductive fiber is the poly- of carbonization
At least one in acid imide and the polyacrylonitrile of carbonization.
4. composite diaphragm according to claim 2, it is characterised in that the material of the nanofiber is polyimides, poly-
At least one in vinylidene fluoride and polyacrylonitrile.
5. composite diaphragm according to claim 1, it is characterised in that further include the inorganic nano layer being stacked,
The electric insulation layers of nanofibers is located between inorganic nano layer and the conductive fiber layer.
6. composite diaphragm according to claim 1, it is characterised in that further include two-layer inorganic nano layer, the electricity
Insulating nanofibers layer is located between two-layer inorganic nano layer, and it is described inorganic that the conductive fiber layer is laminated in any one layer
The opposite side of nanometer layer.
7. the composite diaphragm according to claim 5 or 6, it is characterised in that the inorganic nano layer includes high molecular polymerization
Thing and inorganic nano ceramic particle, the high molecular polymer are at least one in polyvinylidene fluoride and polyethylene glycol oxide,
The inorganic nano ceramic particle be silica, titanium dioxide, zirconium dioxide, alundum (Al2O3) and magnesia in one kind or
It is various.
8. composite diaphragm according to claim 1, it is characterised in that the porosity of composite diaphragm is 60% to 96%, is put down
Equal aperture is 4.0 μm to 5.5 μm.
9. composite diaphragm according to claim 5, it is characterised in that the pick up of composite diaphragm is 400%~900%.
10. composite diaphragm according to claim 1, it is characterised in that the mass area ratio of composite diaphragm is 6g/m2Extremely
20g/m2, thickness is 15 μm to 70 μm.
A kind of 11. lithium ion batteries, including composite diaphragm as described in any one in claim 1-10, positive pole and negative pole,
The composite diaphragm is arranged between the positive pole and the negative pole, and the conductive fiber layer is arranged on the negative pole side, and
Electrically connected with the negative pole.
A kind of 12. preparation methods of composite diaphragm, including：
Conductive fiber layer is prepared, the conductive fiber layer includes multiple nano-conductive fibers, the multiple nano-conductive fiber phase
Network structure is mutually intersected to form, the conductive fiber layer has multiple micropores formed by the nano-conductive fiber；And
Electric insulation layers of nanofibers is formed in the conductive fiber layer.
The preparation method of 13. composite diaphragms according to claim 12, it is characterised in that further include：
Inorganic nano layer is formed in the electric insulation layers of nanofibers.
The preparation method of 14. composite diaphragms according to claim 12, it is characterised in that the preparation conductive fiber layer bag
Include：
First polymer solution is provided；
The first polymer solution is made by nano fibrous membrane by method of electrostatic spinning；And
By nano fibrous membrane carbonization, the conductive fiber layer is obtained.
The preparation method of 15. composite diaphragms according to claim 12, it is characterised in that described in the conductive fiber layer
The upper electric insulation layers of nanofibers that formed includes：
Second polymer solution is provided；And
The second polymer solution is made by the electric insulation Nanowire in the conductive fiber layer by method of electrostatic spinning
Dimension layer.
The preparation method of 16. composite diaphragms according to claim 14, it is characterised in that by the nano fibrous membrane carbon
Change, take a step forward the step of obtain the conductive fiber layer including：The nano fibrous membrane is pre-processed, makes the nanometer
Tunica fibrosa internal component is cyclized, and improves the stability of the nano fibrous membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710137732.9A CN106876634B (en) | 2017-03-09 | 2017-03-09 | Composite diaphragm, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
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