CN105514324B - A kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture and preparation method thereof - Google Patents
A kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture and preparation method thereof Download PDFInfo
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- CN105514324B CN105514324B CN201610073891.2A CN201610073891A CN105514324B CN 105514324 B CN105514324 B CN 105514324B CN 201610073891 A CN201610073891 A CN 201610073891A CN 105514324 B CN105514324 B CN 105514324B
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- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 144
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 230000004888 barrier function Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 65
- 229920000642 polymer Polymers 0.000 claims abstract description 59
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 34
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 34
- 238000005470 impregnation Methods 0.000 claims abstract description 17
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002604 ultrasonography Methods 0.000 claims abstract description 11
- 238000009827 uniform distribution Methods 0.000 claims abstract description 8
- 238000005098 hot rolling Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000008236 heating water Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229920002521 macromolecule Polymers 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 2
- 239000004744 fabric Substances 0.000 claims 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 19
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 229940068984 polyvinyl alcohol Drugs 0.000 description 28
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 28
- 238000007599 discharging Methods 0.000 description 7
- -1 polyethylene Polymers 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 230000004087 circulation Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000007704 transition Effects 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
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/403—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
- 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
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
-
- 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
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- 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)
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture and preparation method thereof, lithium ion battery separator of the invention is made up of following raw material：Hydrophilic PET non-woven fabrics base materials and high molecular polymer, 1 ~ 500nm aperture is uniform-distribution with the hydrophilic PET non-woven fabrics base materials, porosity is 50 ~ 70%, high molecular polymer is filled in the aperture of hydrophilic PET non-woven fabrics base materials, and described high molecular polymer is polyvinyl alcohol or sodium cellulose glycolate；Using ultrasound, vacuum impregnation, the method of hot-rolling pressure makes high molecular polymer be filled in the aperture of PET hydrophilic nonwoven fabrics after low temperature drying, the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture of the present invention are with higher porosity, less percent thermal shrinkage and lithium ion mass transfer impedance is small, the advantages of electrochemical performance, the preparation method step of the present invention is few, it is easily operated, preparation process is not related to the use of toxic reagent, it is safe, suitable for a variety of surface densities, the PET hydrophilic nonwoven fabrics of highly-breathable do matrix material, industrial production can be realized.
Description
Technical field
The present invention relates to electrochemical power source technical field, specifically a kind of PET nonwoven fabric bases with nano aperture are answered
Close lithium ion battery separator and preparation method thereof.
Background technology
As market is for the quick demand of New-energy electric vehicle and power energy storing device, promote lithium ion battery towards
The direction of big multiplying power fast charging and discharging is developed, but existing lithium ion battery separator uses polyethylene and polypropylene material more,
The small-sized movable electrical equipment such as mobile phone, tablet personal computer is only applicable to, is not particularly suited for electric automobile, unmanned vehicle and spacecraft
Deng large-scale electric equipment, because the barrier film porosity of polyalkenes is relatively low, generally less than 40%, can not be a large amount of quick of lithium ion
Transition provides passage, in addition, lithium ion battery carries out that during quick charge substantial amounts of heat can be produced under the conditions of big multiplying power, and
The heat endurance of polyalkenes barrier film is poor, and melting temperature is less than 170 DEG C, and too high temperature can cause the fusing of barrier film to deform and because of lithium
Ion battery internal short-circuit is caused danger, and therefore, is applied to there is an urgent need to developing that heat endurance is good, mechanical stability is excellent big
Type power lithium-ion battery；
PET nonwoven fabric base lithium ion battery separators make use of that PET non-woven fabrics heat endurance is good and aperture is big and widespread
Advantage, but existing PET nonwoven fabric bases lithium ion battery separator make it that polymer is difficult complete due to reasons such as capillary forces
It is filled into non-woven fabrics hole, and polymer is covered in nonwoven surface more, can not be completely filled in non-woven fabrics hole, therefore
Prepared composite is mostly layer structure, limited to the filling effect of non-woven fabrics hole, and larger hole easily make lithium from
The both positive and negative polarity of sub- battery is in contact and short-circuit, and this is also the most disaster that current nonwoven fabric base lithium ion battery separator material is faced
Topic.
The content of the invention
To solve the above problems, it is an object of the invention to provide a kind of PET nonwoven fabric base complex lithiums with nano aperture
Ion battery barrier film and preparation method thereof.
The present invention to achieve the above object, is achieved through the following technical solutions：
A kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture, are made up of following raw material：It is hydrophilic
PET non-woven fabrics base materials and high molecular polymer, micron-sized aperture is uniform-distribution with the hydrophilic PET non-woven fabrics base materials, it is fine
Fineness≤3D is tieed up, porosity is 50 ~ 70%, and high molecular polymer is filled in the aperture of hydrophilic PET non-woven fabrics base materials, will be hydrophilic
The aperture of PET non-woven fabrics base materials is reduced into nanoscale, and described high molecular polymer is polyvinyl alcohol or sodium cellulose glycolate.
The specifications parameter of preferable hydrophilic PET non-woven fabrics base materials is 10 ~ 40g/m of surface density2, thickness is 10 ~ 80 μm, hole
The mm/s of air penetrability under the conditions of rate >=60%, 124Mpa >=2300.
Preferable high molecular polymer is polyvinyl alcohol.
Present invention additionally comprises the preparation method of the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture, bag
Include following steps：
Under conditions of heating water bath, high molecular polymer is dissolved in deionized water, obtains high molecular polymer
Solution；The high molecular polymer and the mass ratio of deionized water are 0.5 ~ 30:100, the temperature of heating water bath is 25 ~ 95 DEG C,
The time of heating water bath is 2 ~ 12 hours；Described high molecular polymer is polyvinyl alcohol or sodium cellulose glycolate；
Hydrophilic PET non-woven fabrics base materials are soaked in stepIn gained macromolecule polymer solution, ultrasound makes hydrophilic PET
Non-woven fabrics base material disperses in macromolecule polymer solution, then keeps heating water bath under vacuum 1 ~ 6 hour, obtains true
Hydrophilic PET non-woven fabrics after sky dipping；
By stepHydrophilic PET non-woven fabrics after gained vacuum impregnation is dried in 50 ~ 90 DEG C of air dry oven, so
Afterwards by 180 ~ 220 DEG C of hot roll, hot-roll forming obtain having the PET nonwoven fabric bases composite lithium ion cell of nano aperture every
Film.
Preferable preparation method, stepWater bath heating temperature corresponding to middle polyvinyl alcohol is 90 ~ 95 DEG C；
Preferable preparation method, bath temperature corresponding to sodium cellulose glycolate are 25 ~ 50 DEG C.
Preferable preparation method, stepHot roll is smooth roll hot rolling.
Further preferred preparation method, comprises the following steps：
Under conditions of heating water bath, high molecular polymer is dissolved in deionized water, obtains high molecular polymer
Solution；The high molecular polymer and the mass ratio of deionized water are 1:100, the temperature of heating water bath is 92 DEG C, heating water bath
Time be 6 hours；Described high molecular polymer is polyvinyl alcohol；
Hydrophilic PET non-woven fabrics base materials are soaked in stepIn gained macromolecule polymer solution, ultrasound makes hydrophilic PET
Non-woven fabrics base material disperses in macromolecule polymer solution, then keeps heating water bath under vacuum 4 hours, obtains vacuum
Hydrophilic PET non-woven fabrics after dipping；
By stepHydrophilic PET non-woven fabrics after gained vacuum impregnation is dried in 60 DEG C of air dry oven, then
By 200 DEG C of hot roll, smooth roll hot-roll forming obtain having the PET nonwoven fabric bases composite lithium ion cell of nano aperture every
Film.
The present invention has advantages below compared with prior art：
The PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture of the present invention are by PET non-woven fabrics and high score
Sub- polymer has been combined into an entirety, and be prepared for nanoscale hole be used for lithium ion migration, solve it is existing it is compound every
The problem of membrane material is easily layered, the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture are somebody's turn to do with higher hole
Gap rate, less percent thermal shrinkage and the advantages of lithium ion mass transfer impedance is small, electrochemical performance；In the preparation method of the present invention
High molecular polymer is realized using vacuum impregnation technology to be filled up completely with non-woven fabrics fiber hole, solves existing composite diaphragm
High molecular polymer fills incomplete problem to non-woven fabrics in material；And in chilling process caused by the slow evaporation of hydrone
Unnecessary hole and can prevents non-woven fabrics hole to be completely plugged, and its aperture size is contracted into Nano grade by micron, solved
The shortcomings that existing nonwoven fabric base diaphragm material hole is excessive, so as to keep this that there is the PET nonwoven fabric base complex lithiums of nano aperture
The higher porosity of ion battery barrier film；The preparation method step of the present invention is few, and easily operated, preparation process is not related to poisonous examination
The use of agent, it is safe, matrix material is done suitable for the PET hydrophilic nonwoven fabrics of a variety of surface densities, highly-breathable, can be realized
Industrial production；The PET nonwoven fabric base composite lithium ion cells barrier film with nano aperture of the present invention is portable available for preparing
Or power-type lithium ion battery.
Brief description of the drawings
Fig. 1 is the specific discharge capacity figure before and after circulating battery 50 times；
Fig. 2 is the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture of embodiment 1 under 0.1C multiplying powers
50 circulations are front and rear and the electrochemical AC impedance EIS of commercialization polyethylene diagrams schemes；
Fig. 3 is the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture by embodiment 1 at different times
Charging and discharging capacity figure under rate.
Embodiment
It is an object of the invention to provide a kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture and its
Preparation method, it is achieved through the following technical solutions：
A kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture, are made up of following raw material：It is hydrophilic
PET non-woven fabrics base materials and high molecular polymer, micron-sized aperture is uniform-distribution with the hydrophilic PET non-woven fabrics base materials, it is fine
Fineness≤3D is tieed up, porosity is 50 ~ 70%, and high molecular polymer is filled in the aperture of hydrophilic PET non-woven fabrics base materials, will be hydrophilic
The aperture of PET non-woven fabrics base materials is reduced into nanoscale, and described high molecular polymer is polyvinyl alcohol or sodium cellulose glycolate.
The specifications parameter of preferable hydrophilic PET non-woven fabrics base materials is 10 ~ 40g/m of surface density2, thickness is 10 ~ 80 μm, hole
Air penetrability >=2300mm/s under the conditions of rate >=60%, 124Mpa.
Preferable high molecular polymer is polyvinyl alcohol.
Present invention additionally comprises the preparation method of the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture, bag
Include following steps：
Under conditions of heating water bath, high molecular polymer is dissolved in deionized water, obtains high molecular polymer
Solution；The high molecular polymer and the mass ratio of deionized water are 0.5 ~ 30:100, the temperature of heating water bath is 25 ~ 95 DEG C,
The time of heating water bath is 2 ~ 12 hours；Described high molecular polymer is polyvinyl alcohol or sodium cellulose glycolate；
Hydrophilic PET non-woven fabrics base materials are soaked in stepIn gained macromolecule polymer solution, ultrasound makes hydrophilic PET
Non-woven fabrics base material disperses in macromolecule polymer solution, then keeps heating water bath under vacuum 1 ~ 6 hour, obtains true
Hydrophilic PET non-woven fabrics after sky dipping；
By stepHydrophilic PET non-woven fabrics after gained vacuum impregnation is dried in 50 ~ 90 DEG C of air dry oven, so
Afterwards by 180 ~ 220 DEG C of hot roll, hot-roll forming obtain having the PET nonwoven fabric bases composite lithium ion cell of nano aperture every
Film.
Preferable preparation method, stepWater bath heating temperature corresponding to middle polyvinyl alcohol is 90 ~ 95 DEG C；
Preferable preparation method, bath temperature corresponding to sodium cellulose glycolate are 25 ~ 50 DEG C.
Preferable preparation method, stepHot roll is smooth roll hot rolling, and course of hot rolling causes polymer more closely to fill
In non-woven fabrics fiber hole, the strength of materials is improved so that composite diaphragm will not occur big thermal contraction and ensure that compound
The homogeneity of material thickness.
Further preferred preparation method, comprises the following steps：
Under conditions of heating water bath, high molecular polymer is dissolved in deionized water, obtains high molecular polymer
Solution；The high molecular polymer and the mass ratio of deionized water are 1:100, the temperature of heating water bath is 92 DEG C, heating water bath
Time be 6 hours；Described high molecular polymer is polyvinyl alcohol；
Hydrophilic PET non-woven fabrics base materials are soaked in stepIn gained macromolecule polymer solution, ultrasound makes hydrophilic PET
Non-woven fabrics base material disperses in macromolecule polymer solution, then keeps heating water bath under vacuum 4 hours, obtains vacuum
Hydrophilic PET non-woven fabrics after dipping；
By stepHydrophilic PET non-woven fabrics after gained vacuum impregnation is dried in 60 DEG C of air dry oven, then
By 200 DEG C of hot roll, smooth roll hot-roll forming obtain having the PET nonwoven fabric bases composite lithium ion cell of nano aperture every
Film.Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
A kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture, including hydrophilic PET non-woven fabrics base materials
And polyvinyl alcohol, micron-sized aperture is uniform-distribution with the hydrophilic PET non-woven fabrics base materials, porosity 68%, described is poly-
Vinyl alcohol is filled in the aperture of hydrophilic PET non-woven fabrics base materials, and the aperture of hydrophilic PET non-woven fabrics base materials is reduced into nanoscale,
The surface density of hydrophilic PET non-woven fabrics base materials is 20g/m2, fibre fineness 1.3D, thickness is 45 μm, saturating under the conditions of 124Mpa
Gas rate is 4000mm/s.
Embodiment 2
A kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture, including hydrophilic PET non-woven fabrics base materials
And sodium cellulose glycolate, micron-sized aperture, porosity 52%, institute are uniform-distribution with the hydrophilic PET non-woven fabrics base materials
The high molecular polymer stated is filled in the aperture of hydrophilic PET non-woven fabrics base materials, and the aperture of hydrophilic PET non-woven fabrics base materials is reduced
For nanoscale, the surface density of hydrophilic PET non-woven fabrics base materials is 30g/m2, fibre fineness 1.7D, thickness is 60 μm, 124Mpa bars
Air penetrability under part is 2753mm/s.
Embodiment 3
A kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture, including hydrophilic PET non-woven fabrics base materials
And polyvinyl alcohol, micron-sized aperture is uniform-distribution with described hydrophilic PET non-woven fabrics base materials, and porosity 51% is described
Polyvinyl alcohol be filled in the aperture of hydrophilic PET non-woven fabrics base materials, the aperture of hydrophilic PET non-woven fabrics base materials is reduced into nanometer
Level, the surface density of hydrophilic PET non-woven fabrics base materials is 40g/m2, fibre fineness 3.0D, thickness is 80 μm, under the conditions of 124Mpa
Air penetrability is 2239mm/s.
Embodiment 4
A kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture, including hydrophilic PET non-woven fabrics base materials
And polyvinyl alcohol, micron-sized aperture is uniform-distribution with described hydrophilic PET non-woven fabrics base materials, and porosity 56% is described
Polyvinyl alcohol is filled in the aperture of hydrophilic PET non-woven fabrics base materials, and the aperture of hydrophilic PET non-woven fabrics base materials is reduced into nanometer
Level, the surface density of hydrophilic PET non-woven fabrics base materials is 20g/m2, fibre fineness 1.3D, thickness is 45 μm, under the conditions of 124Mpa
Air penetrability is 4000mm/s.
Embodiment 5
The preparation method of the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture of embodiment 1, including with
Lower step：
Under conditions of heating water bath, 0.5g polyvinyl alcohol is dissolved in 100ml deionized waters, obtains polyvinyl alcohol
Solution；The temperature of heating water bath is 95 DEG C, and the time of heating water bath is 2 hours；
By 1g, the surface density that area is 10cm × 10cm is 20g/m2, fibre fineness 1.3D, thickness is 45 μm,
The hydrophilic PET non-woven fabrics base materials that air penetrability under the conditions of 124Mpa is 4000mm/s are soaked in stepGained poly-vinyl alcohol solution
In, ultrasound makes hydrophilic PET non-woven fabrics base materials disperse in poly-vinyl alcohol solution, then keeps heating water bath 1 under vacuum
Hour, obtain the hydrophilic PET non-woven fabrics after vacuum impregnation；
By stepHydrophilic PET non-woven fabrics after gained vacuum impregnation is dried in 90 DEG C of air dry oven, then
By 180 DEG C of hot roll, hot-roll forming obtains the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture.
Embodiment 6
The preparation method of the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture of embodiment 2, including with
Lower step：
Under conditions of heating water bath, 1.5g sodium cellulose glycolates are dissolved in 100ml deionized waters, obtain hydroxyl
Methylcellulose sodium solution；The temperature of heating water bath is 25 DEG C, and the time of heating water bath is 12 hours；
It is 30g/m by the surface density that 1.5g areas are 10cm × 10cm2, fibre fineness 1.7D, thickness is 60 μm,
The hydrophilic PET non-woven fabrics base materials that air penetrability under the conditions of 124Mpa is 2753mm/s are soaked in stepGained hydroxymethyl cellulose
In sodium solution, ultrasound makes hydrophilic PET non-woven fabrics base materials disperse in sodium cellulose glycolate solution, then protects under vacuum
Hold heating water bath 6 hours, obtain the hydrophilic PET non-woven fabrics after vacuum impregnation；
By stepHydrophilic PET non-woven fabrics after gained vacuum impregnation is dried in 50 DEG C of air dry oven, then
By 220 DEG C of hot roll, hot-roll forming obtains the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture.
Embodiment 7
The preparation method of the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture of embodiment 3, including with
Lower step：
Under conditions of heating water bath, 30g polyvinyl alcohol is dissolved in 100ml deionized waters, obtains polyvinyl alcohol
Solution；The temperature of heating water bath is 45 DEG C, and the time of heating water bath is 6 hours；
It is 40g/m by the surface density that 2g areas are 10cm × 10cm2, fibre fineness 3.0D, thickness is 80 μm,
The hydrophilic PET non-woven fabrics base materials that air penetrability under the conditions of 124Mpa is 2239mm/s are soaked in stepGained poly-vinyl alcohol solution
In, ultrasound makes hydrophilic PET non-woven fabrics base materials disperse in poly-vinyl alcohol solution, then keeps heating water bath 4 under vacuum
Hour, obtain the hydrophilic PET non-woven fabrics after vacuum impregnation；
By stepHydrophilic PET non-woven fabrics after gained vacuum impregnation is dried in 50 ~ 90 DEG C of air dry oven, so
Afterwards by 180 ~ 220 DEG C of hot roll, hot-roll forming obtain having the PET nonwoven fabric bases composite lithium ion cell of nano aperture every
Film.
Embodiment 8
The preparation method of the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture of embodiment 4, including with
Lower step：
Under conditions of heating water bath, 1g polyvinyl alcohol is dissolved in 100ml deionized waters, it is molten to obtain polyvinyl alcohol
Liquid；The temperature of heating water bath is 92 DEG C, and the time of heating water bath is 6 hours；
It is 20g/m by surface density2, fibre fineness 1.3D, thickness is 45 μm, and the air penetrability under the conditions of 124Mpa is
4000mm/s hydrophilic PET non-woven fabrics base materials are soaked in stepIn gained poly-vinyl alcohol solution, ultrasound makes hydrophilic PET non-woven fabrics
Base material disperses in poly-vinyl alcohol solution, then keeps heating water bath under vacuum 4 hours, obtains the parent after vacuum impregnation
Water PET non-woven fabrics；
By stepHydrophilic PET non-woven fabrics after gained vacuum impregnation is dried in 60 DEG C of air dry oven, then
By 200 DEG C of hot roll, smooth roll hot-roll forming obtain having the PET nonwoven fabric bases composite lithium ion cell of nano aperture every
Film.
The PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture of embodiment 1 ~ 4 are detected, will
Product prepared by the embodiment is used as lithium ion battery separator, and positive pole uses LiFePO4 LiFePO4, and negative pole uses metal
Lithium, CR2032 type button half-cells are assembled into by electrolyte of the LiPO4F6 solution of industrialized production, concrete operations are as follows：
In the glove box full of argon gas, according to anode cover-iron phosphate lithium electrode piece-electrolyte-barrier film-electrolyte-stone
The order of electrode ink piece-pad-spring leaf-negative electrode casing is assembled successively, recycles sealing machine by cell sealing, you can be made
CR2032 type button half-cells.
Using the A713-2008S-3TGF-A type high accuracy discharge and recharge instrument of Xin Wei Electronics Co., Ltd.s of Shenzhen production to electricity
Pond carries out constant current charge-discharge test.Charging/discharging voltage is respectively 3.0V ~ 4.3V and 3.0 ~ 4.8V.
Wherein 0.1C multiplying powers first charge-discharge capacity is measured in 2.0 ~ 4.3V of voltage, as a result as shown in table 1.
The detection data of the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture of the embodiment 1 ~ 4 of table 1
Table
The result of table 1 shows, the PET nonwoven fabric bases composite lithium ion cell with nano aperture of the embodiment of the present invention every
The porosity of film has higher electrolyte absorptivity and good mechanical performance between 50 ~ 70%, in charging/discharging voltage point
Not Wei 2.0~4.3V, 2.0~4.8V when, 0.1C multiplying power first charge-discharge specific capacity values are larger, have good electrochemistry
Can, the requirement of big rate battery discharge and recharge can be met.
Lithium ion battery is formed to the PET nonwoven fabric base composite lithium ion cells barrier film with nano aperture of embodiment 1
The front and rear charging and discharging curve contrast of 50 circulations under 0.1C multiplying powers afterwards, as a result as shown in Figure 1.
It can be seen from Fig. 1 result when charging/discharging voltage is respectively 2.0~4.3V, 2.0~4.8V, 0.1C multiplying powers
For first charge-discharge specific capacity respectively up to 154 .5mAh/g and 156.9 mAh/g, corresponding coulombic efficiency first is 98.5%, and is filled
Discharge voltage plateau is sufficiently stable, and electrode polarization is smaller.Specific discharge capacity of the circulating battery after 50 weeks is maintained at 154.6mAh/g,
Coulombic efficiency is stable 98.5%.Although charge and discharge platform polarization phenomena compared with first increased, its charging/discharging voltage is put down
Platform is still sufficiently stable, and compared with first charge-discharge curve, change is little.
Lithium ion battery is formed to the PET nonwoven fabric base composite lithium ion cells barrier film with nano aperture of embodiment 1
Cyclic voltammetry and testing impedance are carried out, Fig. 2 results show that the interfacial mass transfer impedance of non-woven fabric compounded barrier film is 67 Ω (Z '
Intercept on axle high frequency region), the Ω of impedance 123 under 0.1C multiplying powers after 50 circulations, still less than commercial polyethylene
Barrier film (327 Ω), is more beneficial for the transmission of lithium ion.Fig. 3 results are by 0.1C, 0.2C, 0.5C, 1C, 2C, 4C, 5C and 8C
Discharge capacity is up to 141.1mAh/g after 0.1C is circulated 5 times again after repeatedly being circulated under the conditions of big multiplying power, far above existing business
103 mAh/g of polyethylene diagrams.
Claims (7)
- A kind of 1. PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture, it is characterised in that：By following raw material group Into：Hydrophilic PET non-woven fabrics base materials and high molecular polymer, it is uniform-distribution with the hydrophilic PET non-woven fabrics base materials micron-sized Aperture, fibre fineness≤3D, porosity are 50 ~ 70%, and high molecular polymer is filled in the aperture of hydrophilic PET non-woven fabrics base materials, The aperture of hydrophilic PET non-woven fabrics base materials is reduced into nanoscale, described high molecular polymer is that polyvinyl alcohol or methylol are fine Tie up plain sodium；The PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture are prepared according to following steps：Under conditions of heating water bath, high molecular polymer is dissolved in deionized water, obtains macromolecule polymer solution； The high molecular polymer and the mass ratio of deionized water are 0.5 ~ 30:100, the temperature of heating water bath is 25 ~ 95 DEG C, and water-bath adds The time of heat is 2 ~ 12 hours；Described high molecular polymer is polyvinyl alcohol or sodium cellulose glycolate；Hydrophilic PET non-woven fabrics base materials are soaked in stepIn gained macromolecule polymer solution, ultrasound makes hydrophilic PET nonwovens Cloth base material disperses in macromolecule polymer solution, then keeps heating water bath under vacuum 1 ~ 6 hour, obtains Vaccum Permeating Hydrophilic PET non-woven fabrics after stain；By stepHydrophilic PET non-woven fabrics after gained vacuum impregnation is dried in 50 ~ 90 DEG C of air dry oven, Ran Houtong 180 ~ 220 DEG C of hot roll is crossed, hot-roll forming obtains the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture.
- 2. a kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture according to claim 1, it is special Sign is：The specifications parameter of hydrophilic PET non-woven fabrics base materials is 10 ~ 40g/m of surface density2, thickness is 10 ~ 80 μm, porosity of= Air penetrability >=2300mm/s under the conditions of 60%, 124Mpa.
- 3. a kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture according to claim 1, it is special Sign is：Described high molecular polymer is polyvinyl alcohol.
- 4. a kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture according to claim 1, it is special Sign is：StepWater bath heating temperature corresponding to middle polyvinyl alcohol is 90 ~ 95 DEG C.
- 5. a kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture according to claim 1, it is special Sign is：Bath temperature corresponding to sodium cellulose glycolate is 25 ~ 50 DEG C.
- 6. a kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture according to claim 1, it is special Sign is：StepHot roll is smooth roll hot rolling.
- 7. a kind of PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture according to claim 1, it is special Sign is：The PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture are prepared according to following steps：Under conditions of heating water bath, high molecular polymer is dissolved in deionized water, obtains macromolecule polymer solution； The high molecular polymer and the mass ratio of deionized water are 1:100, the temperature of heating water bath is 92 DEG C, the time of heating water bath For 6 hours；Described high molecular polymer is polyvinyl alcohol；Hydrophilic PET non-woven fabrics base materials are soaked in stepIn gained macromolecule polymer solution, ultrasound makes hydrophilic PET nonwovens Cloth base material disperses in macromolecule polymer solution, then keeps heating water bath under vacuum 4 hours, obtains vacuum impregnation Hydrophilic PET non-woven fabrics afterwards；By stepHydrophilic PET non-woven fabrics after gained vacuum impregnation is dried in 60 DEG C of air dry oven, is then passed through 200 DEG C of hot roll, smooth roll hot-roll forming obtain the PET nonwoven fabric base composite lithium ion cell barrier films with nano aperture.
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| CN105914324B (en) * | 2016-05-09 | 2018-07-10 | 江苏华富储能新技术股份有限公司 | A kind of consumer battery diaphragm |
| CN105826506B (en) * | 2016-05-09 | 2018-07-10 | 江苏华富储能新技术股份有限公司 | A kind of safe consumer battery diaphragm |
| CN108666508A (en) * | 2018-05-16 | 2018-10-16 | 温岭市聚智高分子材料有限公司 | A kind of battery diaphragm and preparation method thereof |
| JP2023062215A (en) * | 2020-03-24 | 2023-05-08 | 株式会社クラレ | Separator for non-aqueous electrolyte battery |
| CN112838330B (en) * | 2021-01-08 | 2022-02-18 | 厦门大学 | High-temperature-resistant modified diaphragm and preparation method thereof |
| CN113675529B (en) * | 2021-08-19 | 2022-10-25 | 安徽今希新材料科技有限公司 | Lithium ion battery diaphragm material for new energy automobile and preparation method thereof |
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