CN102516585B - Biomass cellulose porous composite diaphragm used for lithium ion secondary cell - Google Patents
Biomass cellulose porous composite diaphragm used for lithium ion secondary cell Download PDFInfo
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- CN102516585B CN102516585B CN201110434221.6A CN201110434221A CN102516585B CN 102516585 B CN102516585 B CN 102516585B CN 201110434221 A CN201110434221 A CN 201110434221A CN 102516585 B CN102516585 B CN 102516585B
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 53
- 239000001913 cellulose Substances 0.000 title claims abstract description 50
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000002028 Biomass Substances 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title claims description 8
- 235000010980 cellulose Nutrition 0.000 claims abstract description 52
- 239000012528 membrane Substances 0.000 claims abstract description 44
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 11
- 239000000661 sodium alginate Substances 0.000 claims abstract description 11
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 11
- 239000004642 Polyimide Substances 0.000 claims abstract description 10
- 229920006260 polyaryletherketone Polymers 0.000 claims abstract description 10
- 229920001721 polyimide Polymers 0.000 claims abstract description 10
- 229920000636 poly(norbornene) polymer Polymers 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 238000009987 spinning Methods 0.000 claims description 12
- 229920002313 fluoropolymer Polymers 0.000 claims description 10
- 239000004811 fluoropolymer Substances 0.000 claims description 10
- 238000010041 electrostatic spinning Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002121 nanofiber Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims 2
- 229920009441 perflouroethylene propylene Polymers 0.000 claims 2
- 240000000491 Corchorus aestuans Species 0.000 claims 1
- 235000011777 Corchorus aestuans Nutrition 0.000 claims 1
- 235000010862 Corchorus capsularis Nutrition 0.000 claims 1
- 229920000742 Cotton Polymers 0.000 claims 1
- 229920001780 ECTFE Polymers 0.000 claims 1
- 229920001131 Pulp (paper) Polymers 0.000 claims 1
- VSDXTXZEWUJDRP-UHFFFAOYSA-N [Cl].[Cl].[Cl].C=C Chemical compound [Cl].[Cl].[Cl].C=C VSDXTXZEWUJDRP-UHFFFAOYSA-N 0.000 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 239000002250 absorbent Substances 0.000 claims 1
- 230000005684 electric field Effects 0.000 claims 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000035699 permeability Effects 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 230000004888 barrier function Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 11
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical class CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920004747 ULTEM® 1000 Polymers 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- 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
- Cell Separators (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a cellulose porous membrane able to be used for a lithium ion secondary cell diaphragm. Two side surfaces of the membrane are coated with sodium alginate, a fluorine-containing polymer, polyaryletherketone, polyimide, polynorbornene or inorganic nanoparticles and other structure enhanced and interface stable components. The membrane has thickness of 15-100 micrometers, and air permeability of 2-500s. The upper and lower surfaces as well as inner pores of the membrane are symmetrically and uniformly distributed, with an average pore size of 20-200 nanometers and tensile strength of 50-250MPa. The invention also discloses a preparation method of the cellulose porous membrane. The membrane of the invention can be used as a lithium ion cell diaphragm and has good heat resistance, and even if at a temperature of 150DEG C, a cell short circuit phenomenon cannot occur. Therefore, the cell diaphragm provided in the invention is especially suitable for large capacity and power lithium ion cells. In addition, employment of biomass cellulose that has the largest output in the nature as the raw material for producing the lithium ion cell diaphragm has the advantages of low cost, sustainability and environmental protection.
Description
Technical field
The present invention relates to a kind of biomass cellulose porous-film.
The invention still further relates to the preparation method of above-mentioned fibrination pore membrane.
The invention still further relates to the application of above-mentioned fibrination pore membrane in lithium-ion secondary cell.
Background technology
Lithium-ion secondary cell with its height ratio capacity, high-voltage, volume is little, lightweight, the advantage such as without memory, obtains huge development nearly ten years, but for using the lithium-ion secondary cell of liquid electrolyte, at some time, smoldering easily appears in lithium ion battery, catches fire, blast, even cause the potential safety hazards such as injury to personnel, make heavy body and power lithium-ion battery also there is no widespread use, thus improve the key that lithium ion battery safety performance is research and development lithium-ion secondary cell.Now conventional battery diaphragm is as polyethylene (PE), due to temperature of fusion, (the self-closing temperature as PE barrier film is 135-140 DEG C to polypropylene (PP) lower than 160 DEG C, the self-closing temperature of PP barrier film is about 160 DEG C), in some cases, such as outside temperature is too high, when thermal inertia in the excessive or electrolytic solution thermal histories of discharging current, even if electric current is interdicted, the temperature of battery also likely continues to raise, therefore barrier film may be destroyed completely and cause battery short circuit, thus causes battery explosion or catch fire.In addition, the PE barrier film of unilateral stretching and PP barrier film, tensile strength in the horizontal also goes up the far short of what is expected of tensile strength than longitudinal direction, at battery lamination or when being subject to accidental shock, there is the hidden danger of film rupture.Therefore, adopt the security of PE barrier film and PP barrier film lower.
The factor of heavy body and the increase of high-power battery internal heat and temperature rising is a lot, and the resistance to elevated temperatures therefore improving battery becomes and is even more important.Adopt the safety performance of PE barrier film and PP barrier film can not meet the need, thus need the better polymer separators material of resistance toheat.Natural cellulose is compared with PE with PP, there is higher heat resisting temperature and physical strength, thus, the present invention adopts the biomass cellulose of natural a large amount of low cost, in conjunction with advanced nano-fabrication technique, the resistant to elevated temperatures heavy-duty battery diaphragm material of preparation low cost, has low cost and eco-friendly advantage.
CN1215505A has set forth Mierocrystalline cellulose barrier film for alkaline cell after amine oxide solution spinning, JP10003898A, JP2005317495A, JP2005239028A etc. report the porous-film of Mierocrystalline cellulose and cellulose acetate etc. for lithium ion battery separator, and barrier film prepared by aforesaid method all belongs to asymmetric membrane.Fiber multihole film prepared by the present invention belongs to symmetric membrane, pore structure and being evenly distributed, and easy to prepare, is suitable for batch production, and resistance toheat is high simultaneously, is particularly useful for lithium-ion power battery dissepiment.
Summary of the invention
The object of the present invention is to provide a kind of biomass cellulose porous-film.
Another object of the present invention is to provide the method preparing Mierocrystalline cellulose composite porous film.
For achieving the above object, the cellulose nano-fibrous composite membrane of one provided by the invention, be that 20-500 nanofiber is formed by diameter, the both side surface of film is coated with sodium alginate, fluoropolymer, polyaryletherketone, polyimide, the structure such as polynorbornene or inorganic nano-particle strengthens, the component of stable interface, and film thickness is 15-100 micron, and film air penetrability is 2-500 second; Film surface and internal holes are distributed symmetrically and evenly, mean pore size is 20-200 nanometer, and tensile strength is 50-250 MPa.
The present invention also provides a kind of method preparing nano fibrous membrane, is characterised in that and adopts electrostatic spinning or wet-spinning to carry out spinning to cellulose solution, obtain cellulose non-woven film.
Wherein, the mass percent of cellulose solution is 1-20%, and solvent is N-tertiary amine oxide class or lithium chloride/DMAc system;
Wherein, the spinning syringe needle internal diameter of electrostatic spinning is 0.8-2.0 millimeter, and voltage is 100 volts-30 kilovolts, and syringe needle is 10-30 centimetre with the distance accepting electrode, and spinning solution flow is greater than 0.1 ml/hour.
The present invention also provides a kind of method preparing cellulose composite membrane, it is characterized in that being coated with sodium alginate, fluoropolymer, polyaryletherketone, polyimide in the both side surface of nano fibrous membrane, the component that polynorbornene or inorganic nano-particle etc. strengthen.
Wherein, sodium alginate, fluoropolymer, polyaryletherketone, polyimide, the solution of polynorbornene to be mass percent be 1-10%, solvent is water, acetone, tetrahydrofuran (THF), DMF, one or both among N,N-dimethylacetamide;
Wherein, inorganic nano-particle is nano silicon, zirconium dioxide, the inorganic nano-particle such as alchlor or lithium niobate, inorganic nano-particle and sodium alginate, fluoropolymer, and polyaryletherketone, the polymer quality per-cents such as polyimide are 0 ~ 9:10 ~ 1.
Fibrination pore membrane prepared by the present invention belongs to symmetric membrane, pore structure and being evenly distributed, and it is easy to prepare, be suitable for batch production, resistance toheat is high simultaneously, can be used as lithium ion battery separator, even if this barrier film is under 150 DEG C of high temperature, battery also can not be short-circuited, and thus fibrination pore membrane provided by the invention can be used in heavy body and power cell.
Accompanying drawing explanation
Fig. 1 is the electron micrograph of fibrination pore membrane in embodiment 2.
Embodiment
The fibrination pore membrane of symmetry provided by the invention, be characterised in that this film upper and lower surface and internal holes are distributed symmetrically evenly, aperture is adjustable, tensile strength is high, the more important thing is that the resistance toheat of this film is good, as the barrier film of lithium-ion secondary cell, even if also battery short circuit phenomenon can not be there is at 150 DEG C.
The present invention prepares the method for fibrination pore membrane, first adopt electrostatic spinning to carry out nanometer spinning to cellulose solution, obtain cellulose nano-fibrous membrane, the both side surface of film is coated with sodium alginate, fluoropolymer, polyaryletherketone, polyimide, the component that polynorbornene or inorganic nano-particle etc. strengthen.
Fibrination pore membrane of the present invention can be used in lithium-ion secondary cell, this battery electrode group and nonaqueous electrolytic solution, electrode group and nonaqueous electrolytic solution are sealed in battery case, and electrode group comprises positive pole, negative pole and barrier film, and barrier film wherein used is fibrination pore membrane of the present invention.
Battery membranes provided by the invention, owing to adopting high temperature resistant good natural cellulose porous-film as base material, thus has excellent chemical stability, resistance to elevated temperatures, excellent permeability and high tensile strength.The battery diaphragm obtained in the embodiment of the present invention is heated to 150 DEG C of high temperature and also can not breaks; Battery diaphragm is less than 0.5% at the percent thermal shrinkage of 150 DEG C, in prior art 3% and 5% percent thermal shrinkage, that pierces through that intensity is greater than battery diaphragm in prior art pierces through intensity, film surface and internal holes are evenly distributed, aperture and porosity all meet the requirement of electric conductivity, have suitable excellent Gas permeability.Use the lithium-ion secondary cell of battery diaphragm provided by the invention, even if also can not be short-circuited phenomenon under 150 DEG C of high temperature, thus battery diaphragm provided by the invention can be used in heavy body and power cell.
Embodiment 1
3.0 grams of Mierocrystalline celluloses and 8.0 grams lithium chlorides are joined in 89.0 grams of N,N-dimethylacetamide to stir at 25 DEG C and slowly dissolve for 24 hours, obtain homogeneous cellulose solution (massfraction is 3%).Then cellulose solution is placed on 0-5 DEG C of preservation in refrigerator.Another taking-up 3.0 milliliters of cellulose solutions carry out electrostatic spinning, and needle diameter is 1.6 millimeters, and spinning voltage is 25 kilovolts, and needle point is 10 centimetres to the height of dash receiver, and Electrospun 4 hours obtains the cellulose nano-fibrous membrane that thickness is 85 microns.This film is immersed in the sodium alginate aqueous solution of 3% after 10 minutes, takes out, and after air drying, this film being placed on pressure is stop 2 minutes in the roll squeezer of 2 MPas, obtains the compound cellulose nano fibrous membrane of thickness 40 microns.
Embodiment 2
5.0 grams of Mierocrystalline celluloses are added in 95 grams of N-methylmorpholine-N-oxide compounds to stir at 25 DEG C and slowly dissolve for 3 hours, obtain homogeneous cellulose solution (massfraction is 5%).Then cellulose solution is placed on 0-5 DEG C of preservation in refrigerator.Another taking-up 3.0 milliliters of cellulose solutions carry out electrostatic spinning, and needle diameter is 1.6 millimeters, and spinning voltage is 25 kilovolts, and needle point is 10 centimetres to the height of dash receiver, and Electrospun 4 hours obtains the cellulose nano-fibrous membrane that thickness is 85 microns.This film be immersed in be dissolved with 2.7% Nano particles of silicon dioxide and 0.3% copolymer from vinylidene fluoride and hexafluoropropylene DMF solution in 10 minutes, take out, after drying, this film being placed on pressure is stop 2 minutes in the roll squeezer of 2 MPas, obtains the regenerated cellulose nano fibrous membrane of thickness 40 microns.
Embodiment 3
5.0 grams of Mierocrystalline celluloses are added in 95 grams of N-methylmorpholine-N-oxide compounds to stir at 25 DEG C and slowly dissolve for 3 hours, obtain homogeneous cellulose solution (massfraction is 5%).Then cellulose solution is placed on 0-5 DEG C of preservation in refrigerator.Another taking-up 3.0 milliliters of cellulose solutions carry out electrostatic spinning, and needle diameter is 1.6 millimeters, and spinning voltage is 25 kilovolts, and needle point is 10 centimetres to the height of dash receiver, and Electrospun 4 hours obtains the cellulose nano-fibrous membrane that thickness is 85 microns.This film to be immersed in the DMF solution being dissolved with the Nano particles of silicon dioxide of 2.4% and the polyetherimide (Ultem1000) of 0.6% 10 minutes, take out, after drying, this film being placed on pressure is stop 2 minutes in the roll squeezer of 2 MPas, obtains the regenerated cellulose nano fibrous membrane of thickness 40 microns.
Comparative example 1
Adopt business-like polyalkene diaphragm Celgard2400 as a comparison, to illustrate the advantage of the cellulose nano-fibrous barrier film described in the present invention further.
Membrane properties in above-described embodiment 1-3 and comparative example 1 is characterized:
Infrared spectra: the chemical structure carrying out characterization of membrane with Fourier transformation infrared spectrometer (Nicolet iN10).
Scanning electron microscope: observe the surface of film and the pattern in transverse section by cold field emission scanning electronic microscope (S-4800), the size of nanofiber and arrangement, and part aperture size.
Ventilation property: adopt Gurley 4110N Permeability gauge (USA) to measure the ventilation property of membrane sample.
Film thickness: the thickness adopting milscale (precision 0.01 millimeter) test cellulose nano-fibrous membrane, 5 points on any sample thief, and average.
Porosity: adopt following testing method, to be immersed in propyl carbinol 2 hours, then according to formulae discovery porosity cellulose nano-fibrous membrane:
Wherein, ρ
aand ρ
pthe density of propyl carbinol and the dry density of tunica fibrosa, m
aand m
pthe quality of propyl carbinol and the quality of tunica fibrosa self of film suction.
Tensile strength: adopt the plastic tensile laboratory method of GB1040-79 to test tensile strength and the elongation of cellulose nano-fibrous membrane.
Acquired results lists in table 1.From the results shown in Table 1, the cellulose nano-fibrous non-woven membrane adopting method provided by the invention to prepare has high porosity, ventilation property and physical strength, meet the requirement of lithium ion battery separator to aperture, as can be seen from the test result of embodiment 1-3 and comparative example 1, the resistance to shrinking percentage of business-like polyalkene diaphragm and transverse tensile strength all poor.
Test battery performance
1) preparation of positive pole
First by 5.75 grams of positive active material LiCoO
2, 0.31 gram of conductive agent acetylene black mixes, and then adds polyvinylidene difluoride (PVDF) (PVDF) solution (solvent is METHYLPYRROLIDONE) that 6.39 gram mass marks are 5% again, stirs and forms uniform positive pole slip.
This slip is coated on aluminium foil uniformly, then dries at 120 DEG C, roll-in, punching obtains radius to be 12 millimeters and thickness the be circular positive plate of 80 microns, wherein containing 17.6 milligrams of activeconstituents LiCO
2.
2) preparation of negative pole
By 4.74 grams of negative electrode active material natural graphites, 0.10 gram of conductive agent acetylene black mixes, then add polyvinylidene difluoride (PVDF) (PVDF) solution (solvent is METHYLPYRROLIDONE) that 2.55 gram mass marks are 10% again, stir and form uniform negative pole slip.
Cathode size is coated on Copper Foil equably, then dries at 120 DEG C, roll-in, punching obtains radius to be 14 millimeters and thickness the be circular negative plate of 70 microns, the natural graphite wherein containing 11.9 milligrams of activeconstituentss.
3) with film preparation battery of the present invention
By positive pole obtained above, negative pole and barrier film lamination load (battery size 2032) in button cell successively, described film is respectively the commercialization polyalkene diaphragm in embodiment 1-3 in cellulose nano-fibrous membrane and comparative example 1.
1 mole of lithium hexafluoro phosphate (LiPF is contained by mixed solvent (ethylene carbonate: the volume ratio of methyl ethyl carbonate (EC/EMC) is 1: 1)
6) electrolytic solution about 150 milligrams inject above-mentioned battery, and conventionally ageing, namely sealed cell aluminum hull obtains lithium-ion secondary cell.
4) battery resistance to elevated temperatures test
Testing method is as follows: battery is carried out 1C and is charged to 100% Charging state, and place in an oven, oven temperature is elevated to 150 DEG C with 5 DEG C/min from room temperature, and wherein cell voltage falls and is greater than 0.2 volt and is considered as short circuit.
5) battery life test
Testing method is as follows: at 25 ± 5 DEG C, battery is carried out cycle charge-discharge 250 times, and record dump energy, dump energy is higher, and battery life is longer.
Battery will be made into commercialization barrier film in fibrination pore membrane obtained by embodiment 1-4 and comparative example 1, carry out battery resistance to elevated temperatures and life test according to above-mentioned testing method, obtain that the results are shown in Table 2.
From the results shown in Table 2, as lithium ion battery prepared by battery diaphragm, there is better safety performance and longer work-ing life with cellulose nano-fibrous membrane of the present invention.
Table 1
Table 2
Claims (3)
1. a biomass cellulose nanofibers composite membrane, it is characterized in that: base material is adopt electrostatic spinning law technology to carry out to biomass cellulose the Gradient distribution cellulose non-woven film that diameter that spinning obtains is 20 nanometer ~ 20 micron, the both side surface of film is coated with sodium alginate, fluoropolymer, polyaryletherketone, polyimide, polynorbornene and/or inorganic nano-particle, film thickness is 15 ~ 100 microns, and film air penetrability is 2 ~ 500 seconds; Film surface and internal holes are distributed symmetrically and evenly, mean pore size is 20 ~ 200 nanometers, and tensile strength is 50 ~ 250 MPas;
Wood pulp, jute pulp or cotton pulp are as the initial feed of biomass cellulose;
Adopt electrostatic spinning technique to carry out spinning to biomass fiber cellulose solution, obtain the Gradient distribution cellulose non-woven film that diameter is 20 nanometer ~ 20 micron, the large fiber of micron order is for improving physical strength, and nanofiber is used for uniform electric field intensity and improves absorbent;
Wherein, the mass percent of biomass fiber cellulose solution is 1-20%, and solvent is N-tertiary amine oxide class or lithium chloride/DMAc system,
Wherein, the spinning syringe needle internal diameter of electrostatic spinning is 0.8-2.0 millimeter, and voltage is 100 volts-30 kilovolts, and syringe needle is 10-30 centimetre with the distance accepting electrode, and spinning solution flow is greater than 0.1 ml/hour.
2. a kind of biomass cellulose nanofibers composite membrane according to claim 1, is characterized in that being coated with sodium alginate, fluoropolymer, polyaryletherketone, polyimide in the both side surface of cellulose membrane, polynorbornene and/or inorganic nano-particle;
Wherein, sodium alginate, fluoropolymer, polyaryletherketone, polyimide, the solution of polynorbornene to be mass percent be 1-10%, solvent is water, acetone, tetrahydrofuran (THF), DMF, one or both among N,N-dimethylacetamide;
Wherein, fluoropolymer is vinylidene fluoride-hexafluoropropylene copolymer (P (VDF-HFP)), vinylidene-chlorotrifluoroethylcopolymer copolymer (P (VDF-CTFE)) and vinylidene-trifluoro-ethylene copolymer P (VDF-TFE), fluorinated ethylene propylene (FEP), ethylene tetrafluoroethylene copolymer (ETFE), ethene trichlorine fluoride copolymers (ECTFE);
Wherein, inorganic nano-particle is nano silicon, zirconium dioxide, alchlor or lithium niobate inorganic nano-particle, inorganic nano-particle and sodium alginate, fluoropolymer, polyaryletherketone, and polyimide polymer mass ratio is 0 ~ 9: 10 ~ 1.
3. the application of biomass cellulose nanofibers composite membrane according to claim 1 in lithium-ion secondary cell.
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| CN109860478A (en) * | 2018-12-19 | 2019-06-07 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of organic-inorganic composite diaphragm material and products thereof and application |
| CN112952295B (en) * | 2019-11-26 | 2023-03-10 | 北京卫蓝新能源科技有限公司 | Polyolefin-cellulose composite diaphragm and preparation method thereof |
| CN113629228B (en) * | 2021-07-23 | 2022-07-22 | 江苏科技大学 | Silicon oxide/phosphide carbonized compound and preparation method and application thereof |
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