CN114552117A - Inorganic substance modified polymer composite diaphragm for battery and preparation method thereof - Google Patents
Inorganic substance modified polymer composite diaphragm for battery and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 229920000642 polymer Polymers 0.000 title claims abstract description 43
- 239000000126 substance Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 31
- 239000002121 nanofiber Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000009987 spinning Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000002033 PVDF binder Substances 0.000 claims description 44
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 43
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 14
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000010041 electrostatic spinning Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 238000001523 electrospinning Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 14
- 239000003792 electrolyte Substances 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 239000002356 single layer Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000005411 Van der Waals force Methods 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 31
- 239000000835 fiber Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
Classifications
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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
-
- 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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- 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
Abstract
The invention discloses an inorganic substance modified polymer composite diaphragm for a battery and a preparation method thereof. Weak van der waals force is formed among the single layers of the composite membrane due to the same substances, so that the bonding capacity among the layers of the composite membrane is remarkably improved; as a nanofiber material, the large specific surface area and porosity play an important role in the absorption capacity of electrolyte and the transmission of lithium ions; by adding inorganic matters and making the inorganic matters into a composite diaphragm, the mechanical property of the diaphragm is greatly improved. The preparation method is simple, the spinning environment has no excessive requirements, and simultaneously, a large amount of labor is not needed, so that the method meets the requirements of modern mechanical production.
Description
Technical Field
The invention belongs to the technical field of battery materials, relates to a polymer composite diaphragm modified by inorganic matters for batteries, and also relates to a preparation method of the polymer composite diaphragm.
Background
With the development of society and the progress of science and technology, the traditional fossil energy is faced with the problems of resource shortage and environmental pollution, and the traditional fossil energy cannot meet the requirements of human beings on the construction of a green and clean society. It follows that the traditional renewable clean energy is modernized to be developed and utilized on the basis of new materials and new technologies. Currently, renewable clean energy sources include wind energy, solar energy, biological energy, geothermal energy, tidal energy, and the like. The development and utilization of clean energy requires the establishment of a well-defined and uniform system, in which energy storage is an important step. Lithium ion batteries have been rapidly developed because of their advantages of high specific energy, wide operating voltage, low self-discharge rate, long cycle life, good safety, etc. The diaphragm plays the functions of isolating the positive electrode and the negative electrode in the lithium ion battery, preventing the battery from short circuit and the like, and the performance of the diaphragm material directly influences the safety of the battery. At present, the production technology of the lithium ion battery diaphragm is subjected to monopoly and constraint development of foreign enterprises for a long time and is relatively slow.
Currently, commercial membrane technology routes are mainly divided into dry process and wet process. The dry process is that polyolefin is first melt extruded and then high temperature annealed below the melting point to form crystal structure, and the regularly arranged crystal has parallel crystal plates perpendicular to the extruding direction. Subsequently, the film is uniaxially stretched at a relatively low temperature to obtain a porous structure. The porous diaphragm prepared by the dry process has lower tensile strength in the transverse direction. The wet process, also known as thermally induced phase separation process, is to add pore-forming agents such as paraffin oil into the polymer, extrude the mixed system into a film at high temperature, and extract the pore-forming agents from the film after the film is solidified to form the porous film. The diaphragm prepared by adopting a wet process has the advantages of easier control of porosity and pore size, better mechanical property and uniformity and more obvious advantages. But the wet process is complicated and high in cost.
Disclosure of Invention
The invention aims to provide an inorganic substance modified polymer composite diaphragm for a battery, which solves the problem of poor mechanical property in the prior art.
The invention adopts the technical scheme that the inorganic substance modified polymer composite diaphragm for the battery comprises a three-layer composite structure, wherein the three-layer composite structure is PVDF/PVDF-PAN/PVDF.
The invention is also characterized in that:
the three-layer composite structure is PVDF/PVDF-PAN-inorganic filler/PVDF.
The inorganic filler is silicon dioxide, aluminum oxide or zinc oxide.
The preparation method of the inorganic substance modified polymer composite diaphragm for the battery comprises the following steps:
step 1, mixing PVDF and PAN, dissolving into an organic solvent, and reacting to obtain a solution A;
step 2, dissolving PVDF in an organic solvent, and reacting to obtain a solution B;
step 3, sequentially carrying out electrostatic spinning according to the sequence of the solution B, the solution A and the solution B to obtain a nanofiber membrane;
and 4, drying the nanofiber membrane to obtain the polymer composite membrane with the structure of PVDF/PVDF-PAN/PVDF.
The mass ratio of PVDF to PAN is 3:7-7: 3.
The reaction temperature of the step 1 and the step 2 is 20-60 ℃, and the reaction time is 9-24 h.
In the step 1 and the step 2, the organic solvent is N, N-dimethylformamide.
The physical parameters of the electrostatic spinning process are as follows: the spinning voltage is 10-28kV, and the spinning speed is 0.0010-0.0040 mm/s.
In the step 4, the drying temperature is 40-100 ℃, and the drying time is 12-24 h.
The method comprises the following steps:
step 1, mixing PVDF and PAN, dissolving the mixture in an organic solvent, adding 2-10% of inorganic matters, and reacting to obtain a solution A;
step 2, dissolving PVDF in an organic solvent, and reacting to obtain a solution B;
step 3, sequentially carrying out electrostatic spinning according to the sequence of the solution B, the solution A and the solution B to obtain a nanofiber membrane;
and 4, drying the nanofiber membrane to obtain the polymer composite diaphragm with the structure of PVDF/PVDF-PAN-inorganic filler/PVDF.
The invention has the beneficial effects that: according to the inorganic substance modified polymer composite diaphragm for the battery, weak van der Waals force is formed among the single layers of the diaphragm due to the same substance, so that the bonding capacity among the layers of the composite film is remarkably improved; as a nanofiber material, the large specific surface area and porosity play an important role in the absorption capacity of electrolyte and the transmission of lithium ions; by adding inorganic matters and making the inorganic matters into a composite diaphragm, the mechanical property of the diaphragm is greatly improved. The preparation method of the inorganic substance modified polymer composite diaphragm for the battery is simple, the spinning environment has no excessive requirements, and simultaneously, a large amount of labor is not needed, so that the modern mechanical production is met.
Drawings
FIG. 1 is a macro-topographical view of a polymer composite separator membrane modified with inorganic material for a battery according to the present invention;
FIG. 2a is a scanning electron microscope image of example 1 of an inorganic modified polymer composite separator for a battery according to the present invention;
FIG. 2b is an enlarged scanning electron microscope image of example 1 of an inorganic modified polymer composite separator for a battery according to the present invention;
fig. 3 is an electrochemical impedance spectrum of a polymer composite separator modified with inorganic substances for a battery according to the present invention;
FIG. 4 is a second cycle charge and discharge graph of a polymer composite separator modified with inorganic substances for a battery according to the present invention;
FIG. 5a is a scanning electron microscope image of example 2 of a battery inorganic modified polymer composite separator according to the present invention;
FIG. 5b is an enlarged scanning electron microscope image of example 2 of an inorganic modified polymer composite separator for a battery according to the present invention;
fig. 6 is a graph comparing the wetting ability of PP electrolyte solutions for inorganic modified polymer composite separators for batteries of the present invention with commercial separators.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The inorganic substance modified polymer composite diaphragm for the battery comprises a three-layer composite structure, wherein the three-layer composite structure is PVDF/PVDF-PAN/PVDF. The three-layer composite structure is PVDF/PVDF-PAN-inorganic filler/PVDF, and the inorganic filler can be nano silicon dioxide (titanium dioxide, aluminum oxide, zinc oxide and the like).
PAN and PVDF have the general formula I:
the preparation method of the inorganic substance modified polymer composite diaphragm for the battery comprises the following steps:
step 1, mixing PVDF and PAN according to the mass ratio of 3:7-7:3, dissolving the mixture in N, N-dimethylformamide, adding 2-10% of inorganic matter, and stirring in an oil bath at 20-60 ℃ for 9-24 hours to obtain a solution A;
step 2, dissolving PVDF in N, N-dimethylformamide, and stirring in an oil bath at the temperature of 20-60 ℃ for 9-24h to obtain a solution B;
step 3, placing the solution A and the solution B at room temperature for 0.5-2 h; carrying out electrostatic spinning in sequence according to the sequence of the solution B, the solution A and the solution B, wherein the spinning voltage is 10-28kV, and the spinning speed is 0.0010-0.0040mm/s, so as to obtain a nanofiber membrane;
and 4, putting the nanofiber membrane in an oven, and drying the nanofiber membrane for 12-24 hours under pressure at the temperature of 40-100 ℃ to obtain the polymer composite membrane with the structure of PVDF/PVDF-PAN-inorganic filler/PVDF.
Through the mode, the inorganic substance modified polymer composite diaphragm for the battery has the advantages that weak van der Waals force is formed among the single layers due to the same substances, so that the bonding capacity among the layers of the composite film is remarkably improved; as a nanofiber material, the large specific surface area and porosity play an important role in the absorption capacity of electrolyte and the transmission of lithium ions; by adding inorganic matters and making the inorganic matters into a composite diaphragm, the mechanical property of the diaphragm is greatly improved. The preparation method of the inorganic substance modified polymer composite diaphragm for the battery is simple, the spinning environment has no excessive requirements, and simultaneously, a large amount of labor is not needed, so that the modern mechanical production is met.
Example 1
Step 1, mixing 0.6g of PVDF with the purity of 99% and 1.4g of PAN with the purity of 99%, dissolving the mixture in 19mL of N, N-dimethylformamide, adding 0.1g of nano-silicon dioxide, and stirring in an oil bath at 40 ℃ for 15 hours to obtain a solution A;
step 2, dissolving 2g of PVDF with the purity of 99% in 19mL of N, N-dimethylformamide, and stirring in an oil bath at 40 ℃ for 15 hours to obtain a solution B;
step 3, placing the solution A and the solution B at room temperature for 0.5 h; carrying out electrostatic spinning in sequence according to the sequence of the solution B, the solution A and the solution B, wherein the spinning voltage is 17kV, and the spinning speed is 0.0035mm/s, so as to obtain a nanofiber membrane;
step 4, putting the nanofiber membrane in an oven, and drying the nanofiber membrane for 15 hours under the pressure of 80 ℃ to obtain the structure PVDF/PVDF-PAN-SiO2PVDF polymer composite membranes.
The macro topography of the polymer composite membrane obtained in the embodiment is shown in fig. 1, and as can be seen from fig. 1, the material prepared by a simple chemical synthesis method has a uniform appearance, the initial thickness is 60 μm, and the membrane thickness is about 30 μm after hot pressing at 10 MPa. The Scanning Electron Microscope (SEM) spectra are shown in fig. 2a and 2b, and as can be seen from fig. 2a and 2b, the electrospun fiber has a uniformly cross-linked network structure, which facilitates the sufficient infiltration of the electrolyte, and the fiber diameter is about 90nm, and the addition of the inorganic filler further regulates the fiber diameter.
The composite three-layer diaphragm obtained in the embodiment is used as a lithium ion battery diaphragm, commercial graphite is used as a negative electrode material, a lithium ion battery half-cell is assembled, and LiPF is used6(lithium hexafluorophosphate) is taken as an electrolyte, and the specific steps are as follows:preparing graphite into an electrode plate as a negative electrode material of a lithium ion battery, and performing half-battery assembly, wherein the mass ratio of an active substance, Super P and PVDF (polytetrafluoroethylene) (a solvent is N-methyl pyrrolidone) is 7:2:1, metal lithium is used as a counter battery, a modified three-layer diaphragm is a diaphragm, and an electrolyte is 1mol/L LiPF6The electrochemical impedance spectrogram obtained by assembling the battery is shown in figure 3 after the battery is dissolved in a mixed solution of EC (ethylene carbonate), DEC (diethyl carbonate) and DMC (dimethyl carbonate) according to the volume ratio of 1:1:1, the current density is 37mA/g, and the electrochemical impedance spectrogram before circulation is shown in figure 3. A typical reversible charge-discharge curve with the current density of 37mA/g is shown in figure 4, and as can be seen from figure 4, the reversible specific capacity and the electricity are 330mAh/g, so that the reaction kinetics are rapid, and the reaction kinetics are consistent with the impedance test result.
Example 2
Step 1, mixing 0.6g of PVDF with the purity of 99% and 1.4g of PAN with the purity of 99%, dissolving the mixture in 19mL of N, N-dimethylformamide, and stirring the mixture in oil bath at 40 ℃ for 15 hours to obtain a solution A;
step 2, dissolving 2g of PVDF with the purity of 99% in 19mL of N, N-dimethylformamide, and stirring in an oil bath at 40 ℃ for 15 hours to obtain a solution B;
step 3, placing the solution A and the solution B at room temperature for 0.5 h; carrying out electrostatic spinning in sequence according to the sequence of the solution B, the solution A and the solution B, wherein the spinning voltage is 17kV, and the spinning speed is 0.0035mm/s, so as to obtain a nanofiber membrane;
and 4, putting the nanofiber membrane in an oven, and drying the nanofiber membrane for 15 hours under the pressure of 80 ℃ to obtain the polymer composite membrane with the structure of PVDF/PVDF-PAN/PVDF.
The Scanning Electron Microscope (SEM) spectra of the polymer composite membrane obtained in this example are shown in fig. 5a and 5b, and as can be seen from fig. 5a and 5b, the electrospun fiber has a uniformly cross-linked network structure, the fiber is a porous structure, which is beneficial to the sufficient infiltration of the electrolyte, and the fiber diameter is 150 nm and 160 nm.
And (3) a photo comparing the wetting capacity of the PP/PE/PP electrolyte of the polymer composite diaphragm prepared by the invention with that of a commercial diaphragm. And respectively dripping the electrolyte on the single-layer diaphragm, the three-layer composite diaphragm and the commercial PP/PE/PP composite diaphragm by using a dropper. As can be seen from fig. 6, during the initial test from 1 to 7s, the contact angle of the single-layer separator decreased from 39.05 ° to 0 °, and the change of the contact angle was large, so that the liquid absorption was good; the contact angle of the PP film is reduced from 63.11 degrees to 47.16 degrees, and the change of the contact angle is small; while the contact angle of the three-layer composite membrane had dropped from 37.75 ° to 0 ° at 5 s. Therefore, the diaphragm prepared by electrostatic spinning has better hydrophilicity, and the increased thickness of the three-layer composite diaphragm enables the wetting performance of the electrolyte to be more excellent, thereby being more beneficial to the conduction of ions in the diaphragm.
Claims (10)
1. The inorganic substance modified polymer composite diaphragm for the battery is characterized by comprising a three-layer composite structure, wherein the three-layer composite structure is PVDF/PVDF-PAN/PVDF.
2. The inorganic-modified polymer composite separator for batteries according to claim 1, wherein the three-layer composite structure is PVDF/PVDF-PAN-inorganic filler/PVDF.
3. The inorganic-modified polymer composite separator for batteries according to claim 2, wherein the inorganic filler is silica, alumina or zinc oxide.
4. The preparation method of the inorganic substance modified polymer composite diaphragm for the battery is characterized by comprising the following steps:
step 1, mixing PVDF and PAN, dissolving into an organic solvent, and reacting to obtain a solution A;
step 2, dissolving PVDF in an organic solvent, and reacting to obtain a solution B;
step 3, sequentially carrying out electrostatic spinning according to the sequence of the solution B, the solution A and the solution B to obtain a nanofiber membrane;
and 4, drying the nanofiber membrane to obtain the polymer composite membrane with the structure of PVDF/PVDF-PAN/PVDF.
5. The method for producing the inorganic-modified polymer composite separator for batteries according to claim 4, wherein the mass ratio of PVDF to PAN is 3:7-7: 3.
6. The method for preparing the inorganic substance modified polymer composite separator for the battery according to claim 4, wherein the reaction temperature of the step 1 and the step 2 is 20-60 ℃ and the reaction time is 9-24 h.
7. The method for preparing the inorganic substance-modified polymer composite separator for batteries according to claim 4, wherein the organic solvent used in the steps 1 and 2 is N, N-dimethylformamide.
8. The method for preparing the inorganic substance modified polymer composite separator for the battery according to claim 4, wherein the physical parameters of the electrospinning process are as follows: the spinning voltage is 10-28kV, and the spinning speed is 0.0010-0.0040 mm/s.
9. The method for preparing the inorganic substance-modified polymer composite separator for batteries according to claim 4, wherein the drying temperature in step 4 is 40 to 100 ℃ and the drying time is 12 to 24 hours.
10. The method for preparing the inorganic-modified polymer composite separator for batteries according to claim 4, comprising the steps of:
step 1, mixing PVDF and PAN, dissolving the mixture in an organic solvent, adding 2-10% of inorganic matters, and reacting to obtain a solution A;
step 2, dissolving PVDF in an organic solvent, and reacting to obtain a solution B;
step 3, sequentially carrying out electrostatic spinning according to the sequence of the solution B, the solution A and the solution B to obtain a nanofiber membrane;
and 4, drying the nanofiber membrane to obtain the polymer composite membrane with the structure of PVDF/PVDF-PAN-inorganic filler/PVDF.
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| CN101626097A (en) * | 2009-06-05 | 2010-01-13 | 长沙高新开发区材盛新能源科技有限公司 | High-liquid absorbing rate micro-nano structure polymer electrolyte membrane and preparation method thereof |
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| CN103474610A (en) * | 2013-09-29 | 2013-12-25 | 天津工业大学 | Method for preparing composite lithium-ion battery separator through electrostatic spinning/electrostatic spraying |
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