CN114069152A - Lithium ion battery diaphragm based on polypropylene heavy ion track membrane and preparation method thereof - Google Patents
Lithium ion battery diaphragm based on polypropylene heavy ion track membrane and preparation method thereof Download PDFInfo
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- 150000002500 ions Chemical class 0.000 title claims abstract description 90
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 83
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 81
- 239000012528 membrane Substances 0.000 title claims abstract description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 33
- -1 polypropylene Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 35
- 239000004094 surface-active agent Substances 0.000 claims abstract description 29
- 238000005530 etching Methods 0.000 claims abstract description 24
- 238000003486 chemical etching Methods 0.000 claims abstract description 23
- 230000001678 irradiating effect Effects 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 14
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 12
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 12
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 229910001460 tantalum ion Inorganic materials 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 238000010884 ion-beam technique Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
- Weting (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium ion battery diaphragm based on a polypropylene heavy ion track membrane and a preparation method thereof. The pore channels on the polypropylene heavy ion track membrane are directionally arranged straight-through pore channels, and the pore diameter of each pore channel is 50-150 nm. The preparation method of the polypropylene heavy ion track membrane comprises the following steps: s1, vertically irradiating the polypropylene film by heavy ions to obtain an irradiated polypropylene heavy ion track film; s2, chemically etching the irradiated polypropylene heavy ion track membrane to obtain the polypropylene heavy ion track membrane; the chemical etching adopts etching liquid added with surfactant. The invention realizes the chemical etching of the PP heavy ion track membrane, and the etched membrane has a straight-through pore channel, no blind hole and no zigzag hole, thereby ensuring that the membrane has lower internal resistance and higher ionic conductivity; in addition, the PP film after chemical etching has better lyophilic property, and can promote the rapid transportation of lithium ions in the pore channel, thereby enhancing the electrochemical performance of the lithium ion battery.
Description
Technical Field
The invention relates to a lithium ion battery diaphragm based on a polypropylene heavy ion track membrane and a preparation method thereof, belonging to the technical field of lithium ion batteries and polymer films.
Background
Since the first commercial lithium ion battery was released by sony corporation in 1991, the lithium ion battery has become one of the key research objects of various electrochemical energy storage devices, and has been widely applied to the energy storage fields of portable electronic devices, new energy vehicles, smart grids and the like. The lithium ion battery is composed of components such as a positive electrode material, a negative electrode material, a diaphragm, electrolyte and the like, wherein the diaphragm is used as a key component in a battery structure, is mainly used as a physical barrier for isolating the positive electrode and the negative electrode of the battery, is also used as a lithium ion transmission channel, and has important influences on the capacity, the safety performance, the cycle performance and the like of the battery.
The current commercially applied diaphragm is a polyolefin diaphragm, particularly a polypropylene (PP) diaphragm and a Polyethylene (PE) diaphragm, and the diaphragm is widely applied due to excellent mechanical property, high electrochemical stability and low price. However, the defects of the diaphragm are very obvious, firstly, the PP or PE material has high crystallinity and low polarity, and the electrolyte is generally an organic solvent with higher polarity, so that the affinity of the diaphragm in the electrolyte is lower; secondly, because the method is limited by a dry (melt-draw) or wet (thermally induced phase separation) drawing process of the polyolefin diaphragm, the diaphragm with uniform aperture is difficult to produce, the aperture is large (the aperture is between 100nm and 200nm), and the aperture size and the uniformity thereof have important influence on the safety performance and the electrochemical performance of the lithium ion battery.
The heavy ion track membrane is a film widely applied to the fields of ion separation, seawater desalination, sewage treatment, gas separation and the like, has a simple preparation process, and is mainly prepared by irradiating a polymer membrane by using a heavy ion irradiation technology and then obtaining the heavy ion track membrane with a certain pore density through a chemical etching process. The diaphragm has uniform and continuously adjustable aperture, and abundant negative electricity groups are distributed on the surface of the film after chemical etching, so the diaphragm can be used as one of the preferable materials of the lithium ion battery diaphragm. Therefore, there is a need to provide a lithium ion battery separator based on a heavy ion tracking membrane.
Disclosure of Invention
The invention aims to provide a lithium ion battery diaphragm based on a PP heavy ion track membrane, which overcomes the defects of low affinity, poor aperture uniformity and large aperture of the existing polyolefin diaphragm in electrolyte.
The lithium ion battery diaphragm based on the PP heavy ion tracking membrane provided by the invention has the characteristics that:
the pore channels on the lithium ion battery diaphragm are direct pore channels which are arranged in a directional manner;
the pore diameter of the pore channel is 50-150 nm, such as 60 +/-5 nm, 80 +/-5 nm or 100 +/-20 nm;
the thickness of the lithium ion battery diaphragm is 10-30 μm, such as 12-25 μm;
the pore density of the pore passage on the lithium ion battery diaphragm is 1 multiplied by 109～5×1010/cm2。
The invention adopts a surfactant-assisted chemical etching method, and the surfactant is added into chromic acid solution to chemically etch the PP film after heavy ion irradiation, thereby obtaining the straight-through pore canal with uniform and smaller pore diameter.
Specifically, the preparation method of the lithium ion battery diaphragm provided by the invention comprises the following steps:
s1, vertically irradiating the PP film by using heavy ions to obtain an irradiated PP heavy ion track film;
s2, chemically etching the irradiated PP heavy ion track membrane to obtain the lithium ion battery diaphragm;
and adding a surfactant into etching liquid adopted by the chemical etching.
In the above preparation method, in step S1, the heavy ions may be xenon ions (Xe), bismuth ions (Bi), or tantalum ions (Ta);
the ion energy of the heavy ions can be 0.1-100 MeV/u, for example, 19.5MeV/u for xenon ions, 12.5MeV/u for tantalum ions, and 9.8MeV/u for bismuth ions.
In the above-described preparation method, in step S1, the density of the vertical irradiation may be 1 × 109～5×1010ions/cm2。
In the above preparation method, in step S2, the etching solution used in the chemical etching may be a chromic acid solution, and the molar concentration of the chromic acid solution may be 6 to 12mol/L, such as 8 to 10 mol/L.
In the above preparation method, in step S2, the mass percentage concentration of the surfactant in the etching solution may be 0.025% to 0.5%, preferably 0.05% to 0.2%, 0.05% to 0.1%, 0.1% to 0.2%, 0.05%, 0.1%, or 0.2%.
In the preparation method, the chemical etching temperature can be 60-90 ℃, and the time can be 30-60 min.
In the above preparation method, in step S2, the surfactant is any one of an anionic surfactant, a nonionic surfactant, an anionic fluorocarbon surfactant and a nonionic fluorocarbon surfactant;
the anionic surfactant is Sodium Dodecyl Benzene Sulfonate (SDBS) and/or sodium dodecyl diphenyl ether disulfonate (CR-MADS);
the nonionic surfactant is ethyl phenyl polyethylene glycol (NP-40) and/or fatty alcohol polyoxyethylene ether (AEO);
the anionic fluorocarbon surfactant is DuPont
FSA and/or DuPont
FS-62。
The non-ionic fluorocarbon surfactant is DuPont
FSO。
The invention adds surfactant into etching liquid, when chemical etching is carried out, etchant molecules can diffuse through the surfactant adsorbed on the surface of the film and etch from the surface of the film to the inside along a latent track formed by heavy ion irradiation, and then the surfactant molecules can also permeate into the track and cover the track wall. In the process of the whole latent track through and expansion, surfactant molecules are always attached to the wall of the pore channel, so that the etching rate of the body is delayed, and the whole pore channel is kept straight.
The lithium ion battery diaphragm based on the PP heavy ion track membrane provided by the invention has the same material as the conventional PP diaphragm in the field, but the pore structure, the pore diameter and the distribution thereof are completely different.
The PP heavy ion track membrane with uniform and smaller aperture prepared by the surfactant-assisted chemical etching method disclosed by the invention can be applied to other fields such as ion separation, sewage treatment, seawater desalination and the like besides the application in the field of lithium ion battery diaphragms.
The invention provides a chemical etching method assisted by a surfactant, and realizes chemical etching of a PP heavy ion track membrane, and the etched membrane has a straight-through pore channel, no blind hole and no zigzag hole, so that the membrane is ensured to have lower internal resistance and higher ion conductivity. In addition, the PP film after chemical etching has better lyophilic property, and can promote the rapid transportation of lithium ions in the pore channel, thereby enhancing the electrochemical performance of the lithium ion battery. And the film has uniform and small aperture, so that uniform lithium ion flow can be realized, uniform deposition of lithium ions on the surface of the negative electrode can be realized by the uniform lithium ion flow, and the long-term circulating safety of the lithium ion battery is ensured.
Drawings
FIG. 1 is an SEM front view of a PP heavy ion tracking membrane prepared in example 1 of the present invention.
FIG. 2 is an SEM cross-section of a PP heavy ion tracking membrane prepared in example 1 of the present invention.
FIG. 3 is a SEM front view of a commercial PP membrane (Celgard 2400)
FIG. 4 shows the results of contact angle measurements of a PP heavy ion track membrane prepared in example 1 of the present invention and a commercial PP membrane (Celgard 2400).
FIG. 5 shows the results of internal resistance measurements of PP heavy ion tracking membranes (PP-TEMs) and commercial PP membranes (Celgard 2400) prepared in example 1 of the present invention.
FIG. 6 shows the results of alternating current impedance spectroscopy (EIS) tests of lithium iron phosphate-lithium button cells assembled from PP heavy ion tracking membranes (PP-TEMs) and commercial PP membrane (Celgard 2400) prepared in example 1 of the present invention.
Fig. 7 is an SEM elevation of a PP heavy ion track membrane prepared in comparative example 1 of the present invention.
FIG. 8 is an SEM cross-section of a PP heavy ion tracking membrane prepared according to comparative example 1 of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The preparation method of the lithium ion battery diaphragm based on the PP heavy ion track membrane provided by the invention is mainly characterized in that the surfactant is added into chromic acid solution, so that the surfactant-assisted chemical etching of the PP track membrane is realized, the PP heavy ion track membrane with small aperture, good aperture uniformity and thin membrane thickness is prepared, and the long-term stable circulation of the lithium ion battery can be realized by utilizing the advantages.
Examples 1,
1) The high-energy heavy ion beam current provided by the heavy ion accelerator is heavy ion xenon (the energy of the heavy ion is 19.5MeV/u), the PP film with the thickness of 12 mu m is vertically irradiated, and the irradiation density is 5 multiplied by 109ions/cm2。
2) Carrying out chemical etching on the PP membrane subjected to heavy ion irradiation at the water bath temperature of 80 ℃, wherein the etching solution is a chromic acid solution with the molar concentration of 8mol/L, and adding 0.1% by mass of ethyl phenyl polyethylene glycol (NP-40) surfactant into the chromic acid solution, wherein the etching time is 30min, so as to obtain the PP heavy ion track membrane with a vertical pore passage with the diameter of 80 +/-5 nm.
Fig. 1 and 2 are front SEM images and cross-sectional SEM images of the PP heavy ion tracking membrane of the present example, respectively. From the front SEM image of this example, it can be seen that the PP heavy ion track membrane prepared by the method of the present invention has a relatively flat surface, a relatively small pore diameter, a uniform pore diameter, and a high pore density, which indicates that the chemical etching method assisted by the surfactant provided by the present invention can achieve etching of the PP heavy ion track membrane, and the cross-sectional view also indicates that the PP heavy ion track membrane prepared by the method of the present invention has vertically distributed through channels, no blind holes, and no tortuous holes.
SEM images of commercial PP membranes are shown in fig. 3, where it can be seen that the pore sizes are not the same.
The PP heavy ion track membrane after chemical etching has better lyophilic property, as shown in FIG. 4, the contact angle test results of a commercial PP membrane and a heavy ion track PP membrane are respectively shown, and as can be seen from the figure, the contact angle of the commercial PP membrane is 115 degrees, the contact angle of the heavy ion track PP membrane is 73 degrees, and the high lyophilic property of the PP heavy ion track membrane prepared by the method is proved. .
The etched film has straight-through pore channels, blind holes and zigzag holes, so that the film is ensured to have lower internal resistance. As shown in fig. 5, the results of the internal resistance test of the commercial PP film and the heavy ion tracking PP film prepared in this example show that the internal resistance of the commercial PP film is 5.5ohm, and the internal resistance of the heavy ion tracking PP film is 3.6ohm, which proves that the heavy ion tracking PP film has lower internal resistance and thus higher ion conductivity.
The PP heavy ion tracking film and the commercial diaphragm are respectively assembled into a lithium iron phosphate-lithium button cell, and electrochemical impedance spectroscopy test is performed on the lithium iron phosphate-lithium button cell, and the test result is shown in fig. 6, and the result shows that the interface resistance of the cell provided with the PP heavy ion tracking film is smaller than that of the cell provided with the commercial diaphragm, which is consistent with the result that the PP heavy ion tracking film has smaller internal resistance.
Examples 2,
1) The high-energy heavy ion beam current provided by a heavy ion accelerator is heavy ion Bi (the energy of the heavy ion is 9.8MeV/u), a PP film with the thickness of 25 mu m is vertically irradiated, and the irradiation density is 1 multiplied by 109ions/cm2。
2) Carrying out chemical etching on the PP membrane irradiated by heavy ions at a water bath temperature of 90 ℃, wherein the etching solution is chromic acid solution with the molar concentration of 9mol/L, and adding 0.2 mass percent of sodium dodecyl diphenyl ether disulfonate (CR-MADS) surfactant into the chromic acid solution, wherein the etching time is 40min, so as to obtain the PP heavy ion track membrane with a vertical pore passage with the diameter of 100 +/-20 nm.
Examples 3,
1) The high-energy heavy ion beam current provided by the heavy ion accelerator is heavy ion tantalum (the energy of the heavy ion is 12.5MeV/u), the PP film with the thickness of 12 mu m is vertically irradiated, and the irradiation density is 1 multiplied by 1010ions/cm2。
2) Performing chemical etching on the PP film subjected to heavy ion irradiation at the water bath temperature of 80 ℃, wherein the etching solution is chromic acid solution with the molar concentration of 10mol/L, and 0.2 mass percent of fluorocarbon surfactant (DuPont) is added into the etching solution
FSA) and the etching time is 60min, thus obtaining the PP heavy ion track membrane with vertical pore channels with the diameter of 60 +/-5 nm.
Comparative examples 1,
1) The high-energy heavy ion beam current provided by the heavy ion accelerator is heavy ion xenon (the energy of the heavy ion is 19.5MeV/u), the PP film of 12um is vertically irradiated, and the irradiation density is 5 multiplied by 109ions/cm2。
2) And chemically etching the PP film irradiated by heavy ions at the water bath temperature of 80 ℃, wherein the etching solution is chromic acid solution with the molar concentration of 8mol/L, and the etching time is 30min, so that the PP heavy ion track film with the surface aperture of 200 +/-50 nm is obtained.
Fig. 7 is a front SEM of comparative example 1, and fig. 8 is a cross-sectional SEM of comparative example 1. As can be seen from fig. 7, the surface holes are severely etched, and have a certain taper angle, and the hole diameter is large and different. As can be seen from fig. 8, the surface of the comparative example film was heavily etched, but the inside of the film was not penetrated, and only a small number of tapered holes were present.
Comparing the separator prepared in comparative example 1 and example 1, the method provided by the invention can improve the etching of the PP heavy ion tracking film, thereby being used as the separator of the lithium ion battery.
Claims (10)
1. A polypropylene heavy ion track membrane is characterized in that: the pore channels on the polypropylene heavy ion track membrane are directionally arranged straight-through pore channels;
the pore diameter of the pore channel is 50-150 nm.
2. The polypropylene heavy ion track membrane of claim 1, wherein: the thickness of the polypropylene heavy ion track membrane is 10-30 mu m;
the pore density of the pore channels on the polypropylene heavy ion track membrane is 1 multiplied by 109～5×1010/cm2。
3. A process for preparing a polypropylene heavy ion track membrane as defined in claim 1 or 2, comprising the steps of:
s1, vertically irradiating the polypropylene film by heavy ions to obtain an irradiated polypropylene heavy ion track film;
s2, chemically etching the irradiated polypropylene heavy ion track membrane to obtain the polypropylene heavy ion track membrane;
and adding a surfactant into etching liquid adopted by the chemical etching.
4. The production method according to claim 3, characterized in that: in step S1, the heavy ions are xenon ions, bismuth ions, or tantalum ions;
the ion energy of the heavy ions is 0.1-100 MeV/u;
the density of the vertical irradiation is 1 × 109～5×1010ions/cm2。
5. The production method according to claim 3 or 4, characterized in that: in the step S2, the etching solution adopted by the chemical etching is chromic acid solution, and the molar concentration of the chromic acid solution is 6-12 mol/L.
6. The production method according to any one of claims 3 to 5, characterized in that: in the step S2, the mass percentage concentration of the surfactant in the etching solution is 0.025-0.5%.
7. The production method according to any one of claims 3 to 6, characterized in that: in step S2, the chemical etching temperature is 60-90 ℃ and the time is 30-60 min.
8. The production method according to any one of claims 3 to 7, characterized in that: in step S2, the surfactant is any one of an anionic surfactant, a nonionic surfactant, an anionic fluorocarbon surfactant, and a zwitterionic fluorocarbon surfactant.
9. The method of claim 8, wherein: the anionic surfactant is sodium dodecyl benzene sulfonate and/or sodium dodecyl diphenyl ether disulfonate;
the nonionic surfactant is ethyl phenyl polyethylene glycol and/or fatty alcohol-polyoxyethylene ether;
the anionic fluorocarbon surfactant is DuPont
FSA and/or DuPont
FS-62。
The non-ionic fluorocarbon surfactant is DuPont
FSO。
10. Use of the polypropylene heavy ion track membrane of claim 1 or 2 as or in the preparation of a lithium ion battery separator.
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