CN108134035A - A kind of micropore complex lithium electric separator and preparation method thereof - Google Patents
A kind of micropore complex lithium electric separator and preparation method thereof Download PDFInfo
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- CN108134035A CN108134035A CN201711083085.4A CN201711083085A CN108134035A CN 108134035 A CN108134035 A CN 108134035A CN 201711083085 A CN201711083085 A CN 201711083085A CN 108134035 A CN108134035 A CN 108134035A
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- Prior art keywords
- lithium electric
- complex lithium
- electric separator
- micropore
- micropore complex
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 62
- 239000002121 nanofiber Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 241000196324 Embryophyta Species 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 16
- 239000011268 mixed slurry Substances 0.000 claims description 15
- 240000000907 Musa textilis Species 0.000 claims description 14
- 238000005119 centrifugation Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 239000013049 sediment Substances 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 244000060011 Cocos nucifera Species 0.000 claims description 11
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 238000007731 hot pressing Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920000742 Cotton Polymers 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000000713 high-energy ball milling Methods 0.000 claims description 5
- 229920003043 Cellulose fiber Polymers 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 101100112997 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MCM22 gene Proteins 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 241000269350 Anura Species 0.000 claims description 2
- 244000146553 Ceiba pentandra Species 0.000 claims description 2
- 235000003301 Ceiba pentandra Nutrition 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000012535 impurity 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
- 239000008104 plant cellulose Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 244000299507 Gossypium hirsutum Species 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 9
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000008602 contraction Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 20
- 241000219146 Gossypium Species 0.000 description 8
- 239000012528 membrane Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- SJRXVLUZMMDCNG-UHFFFAOYSA-N Gossypin Natural products OC1C(O)C(O)C(CO)OC1OC1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=C(O)C2=O SJRXVLUZMMDCNG-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- SJRXVLUZMMDCNG-KKPQBLLMSA-N gossypin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=C(O)C2=O SJRXVLUZMMDCNG-KKPQBLLMSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 206010000369 Accident Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002023 wood Substances 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
- H01M50/409—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
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a kind of micropore complex lithium electric separator and preparation method thereof, wherein, the plant fiber is by micrometer fibers and nanofiber with mass ratio 1:0.5‑1:The mass ratio of 5 compositions, micrometer fibers and inorganic particulate is 1:2‑1:10, the inorganic particulate is uniformly embedded between micrometer fibers and nanofiber.Micropore complex lithium electric separator provided by the invention is using plant fiber as skeleton, inorganic particulate is embedded between skeleton, make full use of the good chemical stability of inorganic particulate and thermal stability, so that prepared diaphragm is resistant to electrolytic corrosion, have good chemical stability, while the melting and thermal contraction of composite diaphragm at high temperature can be prevented, so that composite diaphragm has higher heat resistance and stability, under 200 DEG C of heat treatment, battery diaphragm is hardly shunk.
Description
Technical field
The invention belongs to battery diaphragm and its preparation fields, and in particular to a kind of micropore complex lithium electric separator and its preparation side
Method.
Background technology
Countries in the world all promote New Energy Industry to unprecedented strategic height, and motive force of development battery is by people's
Common concern.As the significant components of lithium ion battery, diaphragm be used to battery plus-negative plate be isolated, while conductive ion is allowed to lead to
It crosses.In addition, diaphragm material should also have following characteristic：1. with chemical stability, electrolytic corrosion, and and positive and negative anodes are can be resistant to
It does not react during contact；2. with certain aperture and porosity, ensure low resistance and high ionic conductivity, to lithium from
The preferable permeability of son；3. the thermal stability having had, positive and negative so as to avoid to improve its thermal shrinkage and melting temperature
Contact short circuit between pole promotes the security performance used；4. the electrolyte compatibility having had, to improve itself and electrolyte
Permeability and expand with the contact surface of electrolyte, so as to increase ionic conductivity, improve the cementability with electrode material, reduce every
The resistance of film and battery, so as to promote the cycle performance of battery and efficiency for charge-discharge.
Microporous barrier using polyethylene and polypropylene as representative becomes the commercialization lithium electric separator of current main-stream, due to material
The limitation of matter, the heat-resisting quantity and electrolyte compatibility of this kind of microporous barrier are difficult to the requirement for meeting power battery development, prepare
Method is comparatively laborious, poor to electrolyte absorbability, thus limits the service life of lithium ion battery.Along with lithium is electric in recent years
The increase of pond power output demand and size causes high-power battery that can generate a large amount of heat when operating, it is easy to diaphragm occur
Melt and form short circuit, cause battery catches fire, explosion accident, such as in recent years Samsung mobile phone explode, tesla's electric vehicle it is on fire
Accident.
In view of the above-mentioned problems, application for a patent for invention (publication number CN106784545A) is by plant fiber skeleton and organic micro-spheres
Slurry is mixed into, fiber/microballoon lithium electricity composite diaphragm is obtained by wet method and aftertreatment technology.The diaphragm using plant fiber with
H-bonding capability between organic micro-spheres assigns diaphragm higher heat resistance.The hot melting cohesion of organic micro-spheres is utilized simultaneously
Property and plant fiber skeleton structure, assign the preferable mechanical performance of diaphragm and porosity.Using the diaphragm assembling button lithium from
Sub- battery is tested, and test result is 25~38 μm of membrane thicknesses, 0.5h processing at 54~64%, 150~180 DEG C of porosity
Afterwards, battery diaphragm does not occur significantly to shrink.Although the composite diaphragm is carried in terms of heat resistance, mechanical performance and porosity
It rises.But organic micro-spheres such as polyethylene microballoon, polypropylene microballoon etc. used by the composite diaphragm, due to its own material
The defects of matter, leads to it at high temperature, and this diaphragm still can be melted or be shunk, and causes dangerous accident.Organic micro-spheres simultaneously
Hydrophily it is bad, low to the wellability of electrolyte, the conductivity for leading to ion is low, and the internal resistance of diaphragm and battery is high, so as to hinder
The migration of lithium ion is hindered to be unfavorable for the charge and discharge of high current.
Therefore, high-performance composite diaphragm is further explored, thermal stability and the electrolyte for especially improving diaphragm are affine
Property becomes the important research direction of current lithium ion battery separator technology.
Invention content
In order to overcome prior art lithium battery diaphragm that cannot take into account lacking for thermal stability, porosity and electrolyte compatibility
It falls into, the purpose of the invention is to provide a kind of micropore complex lithium electric separators and preparation method thereof, which makes full use of
The skeleton structure and inorganic particulate of the plant fiber characteristic of itself such as chemical stability, high-temperature stability, hydrophily etc., can be notable
Porosity, chemical stability, thermal stability and electrolyte compatibility are improved, ensures the safety in utilization of lithium ion battery.
Purpose to realize the present invention, the technical solution used in the present invention are：
A kind of micropore complex lithium electric separator, the micropore complex lithium electric separator include plant fiber and inorganic particulate,
In, the plant fiber is by micrometer fibers and nanofiber with mass ratio 1:0.5-1:5 compositions, micrometer fibers and inorganic particulate
Mass ratio is 1:2-1:10, the inorganic particulate is uniformly embedded between micrometer fibers and nanofiber.
Wherein, the micron fiber diameter is 1 μm -5 μm, draw ratio 5-30, nanofiber diameter 3-5nm, long
Diameter ratio is 20-100.
Preferably, the source of the plant fiber includes cotton, kapok, abaca or cocoanut fiber.Preferably, the nothing
Machine particle for iron oxide, zinc oxide, calcium oxide, aluminium oxide, zirconium oxide, silica, titanium dioxide and MFI type, MOR types,
One or more of FAU types, CHA types, SAPO types, MCM22 type zeolites, particle size range are 0.05~5.0 μm.
In addition, the preparation method of the micropore complex lithium electric separator is also claimed in the present invention, specifically comprise the following steps：
S1, plant fiber powder is immersed in acid solution that mass fraction is 80-95% or mass fraction is 20%-
In 40% alkaline solution, handled 2-6 hours using high energy ball milling after impregnating 1-5h, by treated, plant cellulose carried out
Filter is washed to neutrality；
S2, step S1 treated plant fibers are subjected to fractional centrifugation separation, first carry out first-stage centrifugal be separated off it is miscellaneous
Matter, the cellulose precipitated；The cellulose of precipitation absolute ethyl alcohol is diluted into simultaneously ultrasonic disperse 20min again, gained is mixed
Liquid carries out two-stage centrifugal separation again, and supernatant liquor and lower sediment thing are separated, and gained supernatant is molten for nano-cellulose alcohol
Glue, lower sediment thing are micrometer fibers cellulose fiber；
S3, micrometer fibers cellulose fiber, nano-cellulose alcosol and inorganic particulate are mixed, is 100-600r/ in rotating speed
Dry grind 0.5-1.5h in the ball mill of min, and 60min- is stirred by ultrasonic after adding in the deionized water of 10-50 parts by weight later
Mixed slurry is prepared in 120min；
S4, mixed slurry made from step S3 is slowly poured on film plate, and is gently moved back and forth with glass bar, make slurry
Liquid is paved on film plate, obtains wet film using vacuum dehydration method removing moisture, the vacuum degree of the vacuum dehydration is 50-
100Kpa；
S5, wet film made from step S4 is peeled from film plate, carrying out hot pressing after dry obtains having special three-dimensional apertures
The micropore complex lithium electric separator of road structure；Wherein, the temperature of the drying is 80-180 DEG C, drying time 2-10h, hot pressing temperature
It is 150-200 DEG C, pressure 5-40MPa.
Preferably, the acid described in the step S1 is H2SO4、HCl、HBr、H3PO4One or more of；Alkali is
NaoH、Na2O、Na2O2、K2O, one or more of KOH.
Preferably, the plant fiber described in the step S1 and the mass ratio of acid solution or lye are 1:1-1:5.
Preferably, the rotating speed of high energy ball milling described in the step S1 is 200-600r/min, and ball milling temperature is 60-100
℃。
Preferably, the centrifugal rotational speed of the separation of first-stage centrifugal described in the step S2 is 5000-8000r/min, during centrifugation
Between for 5-10min, the centrifugal rotational speed of two-stage centrifugal separation is 2000-3000r/min, centrifugation time 10-15min.
Preferably, the supersonic frequency being stirred by ultrasonic described in the step S3 is 10kHz-90kHz, ultrasound intensity 1w/
cm2-5w/cm2, ultrasonic temperature is 30 DEG C -50 DEG C.
Preferably, the mixed slurry in the step S3 be thick white slurry, solid content 60%-85%.
Preferably, the thickness of the micropore complex lithium electric separator in the step S5 be 10-40 μm, porosity reach 75% with
On, average pore size is distributed between 120nm-350nm.
Relative to the prior art, micropore complex lithium electric separator of the present invention has the beneficial effect that：
(1) raw material sources of micropore complex lithium electric separator of the present invention enrich, are cheap, and preparation method letter
List, process cycle are short, energy conservation and environmental protection；
(2) " hole " that nanofiber-filled micrometer fibers gap of the invention is formed is to reduce opening size；By inorganic grain
Son is embedded between plant fiber, improves interfibrous bond strength, adjusts the pore passage structure of fiber, assigns the good machine of diaphragm
Tool performance and porosity.Diaphragm is averaged obtained by being adjusted as changing the ratio of micrometer fibers, nanofiber and inorganic particulate
Aperture, to obtain required porosity, porosity can reach 75%, and average pore size is distributed between 120~350nm；
(3) using plant fiber as skeleton, inorganic particulate is embedded between skeleton the present invention, makes full use of inorganic particulate good
Chemical stability and thermal stability so that prepared diaphragm is resistant to electrolytic corrosion, has good chemical stability, together
When can prevent the melting and thermal contraction of composite diaphragm at high temperature so that composite diaphragm has higher heat resistance and steady
Qualitative, under 200 DEG C of heat treatment, battery diaphragm is hardly shunk；
(4) lyophily of the inorganic particulate of the present invention due to itself and electric conductivity as semiconductor, can improve compound
The wellability of diaphragm and electrolyte so as to improve the electrolyte absorptivity of composite diaphragm and ionic conductivity, is conducive to carry
The cycle and high rate performance of high lithium battery；
(5) technical method that uses of the present invention, which solves the prior art and is difficult to be simple and efficient, utilizes plant fiber to prepare nanometer
The problem of fiber, for the nanofiber diameter obtained using the method for fractional centrifugation separation in 3-5nm, large specific surface area, machinery are strong
Degree is high.
Description of the drawings
The SEM figures of micropore complex lithium electric separator prepared by Fig. 1 positions embodiment of the present invention 1.
Specific embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
Following embodiment unless specific instructions, the commercially available chemical reagent of reagent or industrial products of use.
Embodiment 1
A kind of preparation method of micropore complex lithium electric separator, includes the following steps：
S1. 50 grams of natural abaca fibres are immersed in 100 gram 90% of HBr, impregnate 2h after under 300r/min high temperature
Ball-milling treatment 3 hours, by treated, abaca fibre element is filtered, washs to neutrality；
S2. step S1 treated abaca fibres are subjected to fractional centrifugation separation, first carry out first-stage centrifugal be separated off it is miscellaneous
Matter keeps rotating speed 6000r/min, centrifuges 8min, the abaca fibre element precipitated；Again by the abaca fibre element of precipitation with anhydrous
Gained mixed liquor is carried out two-stage centrifugal separation by ethyl alcohol dilution and ultrasonic disperse 20min again, keeps rotating speed 2500r/min, centrifugation
15min separates supernatant liquor and lower sediment thing, and gained supernatant is nanometer abaca fibre element colloidal sol, and diameter is about
3nm, length are 1 μm, and lower sediment thing is micron abaca fibre, and diameter is about 1.5 μm, length is 6 μm；
S3. by MFI type zeolite that 20 grams of micron abaca fibres and 10 grams of nanometer abaca fibres and 2.5 gram particle diameters are 0.2 μm
It dry grinds 1 hour in the ball mill under 100r/min after particle mixing, 60min is stirred after adding in 50 grams of deionized waters later, make
It is standby to obtain the mixed slurry that solid content is 70%；
S4. the mixed slurry obtained by step S2 is poured on film plate, slurries is made to be paved on film plate, utilize vacuum
Evaporation removing moisture obtains wet film, and the vacuum degree of the vacuum dehydration is 60Kpa；
S5. the serous coat obtained by step S3 is peeled from film plate, the dry 4h at 120 DEG C, finally 180 DEG C,
Hot pressing obtains micropore complex lithium electric separator under 20MPa.
Above-mentioned micropore complex lithium electric separator is tested：
Membrane structure test result：18 μm, average pore size 220nm of thickness, porosity 78%.
Film-strength test result：Cross directional stretch is slight 35MPa, longitudinal tensile strength 44MPa.
Battery high rate performance test result：45% when the discharge capacity of battery is 0.5C multiplying powers under 12C.
Heat resistance test result：It is 2.3% that 200 DEG C, 0.5 hour, which are heat-treated lower percentage reduction of area,.
Electrolyte wellability test result：Electrolyte (the dimethyl carbonate solution of 1MLiPF6) 6.5 ° of contact angle.
Conductivity test result：Conductivity is 3.1mS/cm under room temperature.
Embodiment 2
A kind of preparation method of micropore complex lithium electric separator, includes the following steps：
S1. 100 grams of natural cotton fibers are immersed in 150 gram 95% of the concentrated sulfuric acid, after dipping 1.5h under 200r/min
High energy ball milling is handled 2.5 hours, and by treated, gossypin is filtered, washs to neutrality；
S2. step S1 treated cotton fibers are subjected to fractional centrifugation separation, first carry out first-stage centrifugal and be separated off impurity,
Rotating speed 5500r/min is kept, centrifuges 10min, the gossypin precipitated；It is again that the gossypin absolute ethyl alcohol of precipitation is dilute
Simultaneously ultrasonic disperse 20min is released, gained mixed liquor is subjected to two-stage centrifugal separation again, keeps rotating speed 2000r/min, centrifuges 15min,
Supernatant liquor and lower sediment thing are separated, gained supernatant is nanometer gossypin colloidal sol, and diameter is about 4nm, length is
6.2 μm, lower sediment thing is micron cotton fiber, and diameter is about 3.5 μm, length is 40 μm.
S3. 15 grams of micron cotton fibers and 4 grams of nanometer cotton fibers are mixed with the aluminium oxide particles that 1.5 gram particle diameters are 0.6 μm
Dry grinding 0.5 is small in the ball mill under 260r/min afterwards, stirs 60min after adding in 30 grams of deionized waters, solid content is prepared
For 65% mixed slurry；
S4. the mixed slurry obtained by step S2 is poured on film plate, slurries is made to be paved on film plate, utilize vacuum
Evaporation removing moisture obtains wet film, and the vacuum degree of the vacuum dehydration is 40Kpa；
S5. the serous coat obtained by step S3 is peeled from film plate, the dry 2h at 150 DEG C, finally 170 DEG C,
Hot pressing obtains micropore complex lithium electric separator under 60MPa.
Above-mentioned micropore lithium electric separator is tested：
Membrane structure test result：23 μm, average pore size 260nm of thickness, porosity 75%.
Film-strength test result：Cross directional stretch is slight 30MPa, longitudinal tensile strength 23MPa.
Battery high rate performance test result：55% when the discharge capacity of battery is 0.5C multiplying powers under 12C.
Heat resistance：It is 2.5% that 200 DEG C, 0.5 hour, which are heat-treated lower percentage reduction of area,.
Electrolyte wellability：Electrolyte (the dimethyl carbonate solution of 1M LiPF6) 7.5 ° of contact angle.
Conductivity test result：Conductivity is 3.4mS/cm under room temperature.
Embodiment 3
A kind of preparation method of micropore complex lithium electric separator, includes the following steps：
S1. 200 grams of natural kawo fibers are immersed in 250 gram 15% of KOH, impregnate 1h after under 500r/min high temperature
Ball-milling treatment 4h, by treated, bombax cotton element is filtered, washs to neutrality；
S2. step S1 treated bombax cottons are subjected to fractional centrifugation separation, first carry out first-stage centrifugal be separated off it is miscellaneous
Matter keeps rotating speed 7000r/min, centrifuges 5min, the bombax cotton element precipitated；Again by the bombax cotton element of precipitation with anhydrous
Gained mixed liquor is carried out two-stage centrifugal separation by ethyl alcohol dilution and ultrasonic disperse 20min again, keeps rotating speed 3000r/min, centrifugation
10min separates supernatant liquor and lower sediment thing, and gained supernatant is nano wood gossypin colloidal sol, and diameter is about
4.5nm, length are 2 μm, and lower sediment thing is micron bombax cotton, and diameter is about 4.5 μm, length is 100 μm；
S3. by Zirconia particles that 12 grams of micron bombax cottons and 20 grams of nanometer bombax cottons and 5.2 gram particle diameters are 1.5 μm
It dry grinds 1.5 hours in the ball mill under 150r/min after mixing, stirs 140min after adding in 60 grams of deionized waters, be prepared
Solid content is 80% mixed slurry；
S4. the mixed slurry obtained by step S2 is poured on film plate, slurries is made to be paved on film plate, utilize vacuum
Evaporation removing moisture obtains wet film, and the vacuum degree of the vacuum dehydration is 100Kpa；
S5. the serous coat obtained by step S3 is peeled from film plate, the dry 2h at 140 DEG C, finally 170 DEG C,
Hot pressing obtains micropore complex lithium electric separator under 60MPa.
Above-mentioned micropore lithium electric separator is tested：
Membrane structure test result：32 μm, average pore size 120nm of thickness, porosity 77%.
Film-strength test result：Cross directional stretch is slight 28MPa, longitudinal tensile strength 32MPa.
Battery high rate performance test result：67% when the discharge capacity of battery is 0.5C multiplying powers under 12C.
Heat resistance：It is 1.4% that 200 DEG C, 0.5 hour, which are heat-treated lower percentage reduction of area,.
Electrolyte wellability：Electrolyte (the dimethyl carbonate solution of 1M LiPF6) 4.2 ° of contact angle.
Conductivity test result：Conductivity is 3.5mS/cm under room temperature.
Embodiment 4
A kind of preparation method of micropore complex lithium electric separator, includes the following steps：
S1. 150 grams of natural coconut fibers are immersed in 300 gram 20% of NaOH, it is high under 600r/min after dipping 3h
Warm ball-milling treatment 4h, by treated, cocoanut fiber element is filtered, washs to neutrality；
S2. step S1 treated cocoanut fibers are subjected to fractional centrifugation separation, first carry out first-stage centrifugal be separated off it is miscellaneous
Matter keeps rotating speed 6500r/min, centrifuges 7min, the cocoanut fiber element precipitated；Again by the cocoanut fiber element of precipitation with anhydrous
Gained mixed liquor is carried out two-stage centrifugal separation, keeps rotating speed 26000r/min by ethyl alcohol dilution and ultrasonic disperse 20min again, from
Heart 12min, supernatant liquor and lower sediment thing are separated, and gained supernatant is nanometer cocoanut fiber element colloidal sol, and diameter is about
5nm, length are 1.5 μm, and lower sediment thing is micron cocoanut fiber, and diameter is about 2.5 μm, length is 32 μm.
S3. 15 grams of micron cocoanut fibers and 10 grams of nanometer cocoanut fibers and 2.2 gram particle diameters are boiled for 0.8 μm of MCM22 types
It dry grinds 0.5 hour in the ball mill under 500r/min after the mixing of stone grain, 110min is stirred after adding in 50 grams of deionized waters, make
It is standby to obtain the mixed slurry that solid content is 75%；
S4. the mixed slurry obtained by step S2 is poured on film plate, slurries is made to be paved on film plate, utilize vacuum
Evaporation removing moisture obtains wet film, and the vacuum degree of the vacuum dehydration is 90Kpa；
S5. the serous coat obtained by step S3 is peeled from film plate, the dry 4h at 100 DEG C, finally 150 DEG C,
Hot pressing obtains micropore complex lithium electric separator under 65MPa.
Above-mentioned micropore lithium electric separator is tested：
Membrane structure test result：19 μm, average pore size 340nm of thickness, porosity 76%.
Film-strength test result：Cross directional stretch is slight 25MPa, longitudinal tensile strength 42MPa.
Battery high rate performance test result：48% when the discharge capacity of battery is 0.5C multiplying powers under 12C.
Heat resistance：It is 3.5% that 200 DEG C, 0.5 hour, which are heat-treated lower percentage reduction of area,.
Electrolyte wellability：Electrolyte (the dimethyl carbonate solution of 1M LiPF6) 7.9 ° of contact angle.
Conductivity test result：Conductivity is 4mS/cm under room temperature.
Comparative example 1
A kind of preparation method of complex lithium electric separator, includes the following steps：
S1. 50 grams of natural abaca fibres are immersed in 100 gram 90% of HBr, impregnate 2h after under 300r/min high temperature
Ball-milling treatment 3 hours, by treated, abaca fibre element is filtered, washs to neutrality；
S2. in 100r/ after treated abaca fibre is mixed with the MFI type zeolite particle that 2.5 gram particle diameters are 0.2 μm
It dry grinds 1 hour in ball mill under min, 60min is stirred after adding in 50 grams of deionized waters later, it is 70% that solid content, which is prepared,
Mixed slurry；
S3. the mixed slurry obtained by step S2 is poured on film plate, slurries is made to be paved on film plate, utilize vacuum
Evaporation removing moisture obtains wet film, and the vacuum degree of the vacuum dehydration is 60Kpa；
S4. the serous coat obtained by step S3 is peeled from film plate, the dry 4h at 120 DEG C, finally 180 DEG C,
Hot pressing obtains micropore complex lithium electric separator under 20MPa.
Above-mentioned micropore complex lithium electric separator is tested：
Membrane structure test result：25 μm, average pore size 280nm of thickness, porosity 57%.
Film-strength test result：Cross directional stretch is slight 22MPa, longitudinal tensile strength 35MPa.
Battery high rate performance test result：40% when the discharge capacity of battery is 0.5C multiplying powers under 12C.
Heat resistance test result：It is 5.8% that 200 DEG C, 0.5 hour, which are heat-treated lower percentage reduction of area,.
Electrolyte wellability test result：Electrolyte (the dimethyl carbonate solution of 1MLiPF6) 7.7 ° of contact angle.
Conductivity test result：Conductivity is 1.7mS/cm under room temperature.
Embodiment the result shows that, between inorganic particulate is embedded in plant fiber by the present invention, it is strong to improve interfibrous combination
Degree, adjusts the pore passage structure of fiber, makes full use of the good chemical stability of inorganic particulate and thermal stability so that prepared
Diaphragm be resistant to electrolytic corrosion, have good chemical stability, at the same can prevent the melting of composite diaphragm at high temperature and
It is heat-shrinked, so that composite diaphragm has higher heat resistance and stability, under 200 DEG C of heat treatment, battery diaphragm is several
It does not shrink.Lyophily of the inorganic particulate due to itself and electric conductivity as semiconductor simultaneously, can improve composite diaphragm
With the wellability of electrolyte, so as to improve the electrolyte absorptivity of composite diaphragm and ionic conductivity, be conducive to improve lithium
The cycle and high rate performance of battery realize the resultant performance enhancements of lithium electric separator.Composite diaphragm preparation process is simple, cost
It is low, environmentally protective, it can be achieved that large-scale industrial production.
It is above-mentioned that exemplary embodiment is illustrated, it should not be construed as limiting the invention.For fields
Those of ordinary skill for, other different forms of changes or modifications may be made based on the above description.Here
There is no need to be enumerated to all embodiments.And the obvious changes or variations thus extended out still in
Among the protection domain of the invention.
Claims (10)
1. a kind of micropore complex lithium electric separator, it is characterised in that：The micropore complex lithium electric separator includes plant fiber and nothing
Machine particle, wherein, the plant fiber is by micrometer fibers and nanofiber with mass ratio 1:0.5-1:5 composition, micrometer fibers with
The mass ratio of inorganic particulate is 1:2-1:10, the inorganic particulate is uniformly embedded between micrometer fibers and nanofiber.
2. micropore complex lithium electric separator according to claim 1, which is characterized in that the micron fiber diameter for 1 μm-
5 μm, draw ratio 5-30, nanofiber diameter 3-5nm, draw ratio 20-100.
3. micropore complex lithium electric separator according to claim 1, which is characterized in that the source of the plant fiber includes
Cotton, kapok, abaca or cocoanut fiber.
4. micropore complex lithium electric separator according to claim 1, which is characterized in that the inorganic particulate for iron oxide,
Zinc oxide, calcium oxide, aluminium oxide, zirconium oxide, silica, titanium dioxide and MFI type, MOR types, FAU types, CHA types, SAPO
One or more of type, MCM22 type zeolites, particle size range are 0.05~5.0 μm.
5. the preparation method of any one of a kind of claim 1-4 micropore complex lithium electric separators, which is characterized in that including as follows
Step：
S1, plant fiber powder is immersed in acid solution that mass fraction is 80-95% or mass fraction is 20%-40%'s
In alkaline solution, handled 2-6 hours using high energy ball milling after impregnating 1-5h, by treated, plant cellulose is filtered, washes
It washs to neutrality；
S2, step S1 treated plant fibers are subjected to fractional centrifugation separation, first carry out first-stage centrifugal and be separated off impurity, obtain
To the cellulose of precipitation；Again by the cellulose of precipitation with absolute ethyl alcohol dilute and ultrasonic disperse 20min, by gained mixed liquor again into
Row two-stage centrifugal detach, supernatant liquor and lower sediment thing are separated, gained supernatant be nano-cellulose alcosol, lower floor
Sediment is micrometer fibers cellulose fiber；
S3, micrometer fibers cellulose fiber, nano-cellulose alcosol and inorganic particulate are mixed, is 100-600r/min's in rotating speed
Dry grind 0.5-1.5h in ball mill, and 60min-120min is stirred by ultrasonic after adding in the deionized water of 10-50 parts by weight later, prepares
Obtain mixed slurry；
S4, mixed slurry made from step S3 is slowly poured on film plate, and is gently moved back and forth with glass bar, spread slurries
Completely on film plate, wet film is obtained using vacuum dehydration method removing moisture, the vacuum degree of the vacuum dehydration is 50-100Kpa；
S5, wet film made from step S4 is peeled from film plate, carrying out hot pressing after dry obtains having special 3 D pore canal knot
The micropore complex lithium electric separator of structure；Wherein, the temperature of the drying is 80-180 DEG C, drying time 2-10h, and hot pressing temperature is
150-200 DEG C, pressure 5-40MPa.
6. the preparation method of micropore complex lithium electric separator according to claim 5, which is characterized in that institute in the step S1
The acid stated is H2SO4、HCl、HBr、H3PO4One or more of；Alkali is NaoH, Na2O、Na2O2、K2O, one kind in KOH or
It is several.
7. the preparation method of micropore complex lithium electric separator according to claim 5, which is characterized in that institute in the step S1
The plant fiber stated is 1 with the mass ratio of acid solution or lye:1-1:5.
8. the preparation method of micropore complex lithium electric separator according to claim 5, which is characterized in that institute in the step S1
The rotating speed for stating high energy ball milling is 200-600r/min, and ball milling temperature is 60-100 DEG C.
9. the preparation method of micropore complex lithium electric separator according to claim 5, which is characterized in that institute in the step S2
The centrifugal rotational speed of first-stage centrifugal separation is stated as 5000-8000r/min, centrifugation time 5-10min, two-stage centrifugal separation
Centrifugal rotational speed be 2000-3000r/min, centrifugation time 10-15min.
10. micropore complex lithium electric separator according to claim 5 and preparation method thereof, which is characterized in that the step S3
Described in the supersonic frequency that is stirred by ultrasonic be 10kHz-90kHz, ultrasound intensity 1w/cm2-5w/cm2, ultrasonic temperature for 30 DEG C-
50℃。
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