CN112909424B - In-situ modified barium sulfate whisker, preparation method thereof and lithium ion battery diaphragm - Google Patents
In-situ modified barium sulfate whisker, preparation method thereof and lithium ion battery diaphragm Download PDFInfo
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- CN112909424B CN112909424B CN202110062119.1A CN202110062119A CN112909424B CN 112909424 B CN112909424 B CN 112909424B CN 202110062119 A CN202110062119 A CN 202110062119A CN 112909424 B CN112909424 B CN 112909424B
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical class [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 104
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000002002 slurry Substances 0.000 claims abstract description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 11
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000003607 modifier Substances 0.000 claims abstract description 8
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims description 37
- -1 polyethylene Polymers 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 18
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 229920001661 Chitosan Polymers 0.000 claims description 8
- 235000012000 cholesterol Nutrition 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 239000004745 nonwoven fabric Substances 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006255 coating slurry Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims 3
- 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 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 239000012528 membrane Substances 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000009736 wetting Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
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Classifications
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Separators (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides an in-situ modified barium sulfate whisker and a preparation method thereof as well as a lithium ion battery diaphragm, wherein the preparation method of the modified barium sulfate whisker comprises the steps of adding ethanol and a modifier into a barium sulfate solution, heating and stirring to obtain a barium sulfate mixed solution, then adding a crystal form control agent into the barium sulfate mixed solution, keeping the temperature and stirring to obtain a precursor solution, dropwise adding a sodium sulfate solution into the precursor solution, controlling the dropwise stirring speed, filtering, washing, adjusting the pH value and drying to obtain the in-situ modified barium sulfate whisker, coating the slurry containing the in-situ modified barium sulfate whisker on the surface of a base membrane, and drying to obtain the lithium ion battery diaphragm, the barium sulfate whisker prepared by the method can improve the porosity and the average pore diameter of the surface of the battery diaphragm, has better wetting effect and better stability under the high-temperature condition, the barium sulfate whisker can replace alpha alumina to reduce the manufacturing cost of the diaphragm.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an in-situ modified barium sulfate whisker, a preparation method thereof and a lithium ion battery diaphragm.
Background
The diaphragm is a layer of permeable membrane material between the anode and the cathode of the lithium ion battery, is a key constituent part of the lithium ion battery, and the cost accounts for three to four times of the whole battery cost in the production summary of the lithium ion battery, so that the diaphragm has high technical content and added value compared with other lithium ion battery materials.
The lithium ion battery diaphragm has the main functions of separating the positive electrode and the negative electrode and blocking insulating electrons to prevent short circuit inside the battery, and the micropores in the diaphragm can allow lithium ions to freely pass through the micropores to ensure the transmission channel of the lithium ions in the charging and discharging process of the battery, so that the chemical reaction of the battery is more favorable. Therefore, the lithium ion battery separator needs to have good electrical insulation wire, mechanical properties, wettability to electrolyte, hygroscopicity and stability. Common lithium ion battery diaphragms in the prior art mainly comprise non-woven fabric diaphragms, inorganic composite diaphragms, organic polymer diaphragms and polymer/inorganic composite diaphragms, wherein the non-woven fabric diaphragms have good adsorption and permeability to electrolyte, but have large membrane pore size, low membrane strength and uneven pore size distribution, so that the membranes do not have good recyclability; the inorganic composite film has good performances, but the problems of adhesive deformation and inorganic coating shedding are easy to occur when the inorganic composite film works under a high-temperature condition, and the preparation process at the present stage is complex and immature and is not easy to popularize; the organic polymer diaphragm has a plurality of contradictions between wettability and pore size, good wettability and lower electrolyte transmittance cannot be achieved simultaneously, the polymer/inorganic composite diaphragm has greater potential, the inorganic filler with smaller size can be filled in macropores of the polymer diaphragm, the mechanical property and the thermal stability of the polymer diaphragm are improved, the membrane pore size is reduced, the uniformity of the membrane pore is improved, but the inorganic filler has the problem of poor wettability, and the inorganic filler is easy to agglomerate, so that the stability of the membrane pore size is influenced.
Disclosure of Invention
In view of the above, the invention provides an in-situ modified barium sulfate whisker which has good electrolyte wettability and more uniform and stable membrane pores, a preparation method thereof and a lithium ion battery diaphragm.
The technical scheme of the invention is realized in such a way that the invention provides a preparation method of in-situ modified barium sulfate whiskers, which comprises the following steps:
step one, mixing barium sulfide and water, stirring until the barium sulfide and the water are dissolved, adding ethanol and a modifier, heating to 50-60 ℃, and keeping the temperature and stirring to obtain a barium sulfide mixed solution;
step two, adding a crystal form control agent into the barium sulfide mixed solution, keeping the temperature at 50-60 ℃, and stirring until the crystal form control agent is dissolved to obtain a precursor solution;
and step three, dropwise adding a sodium sulfate solution into the precursor solution, keeping the stirring speed at 20-30r/min during dropwise adding, keeping the stirring speed unchanged after dropwise adding is finished, cooling to 25-30 ℃, filtering, and drying a filter cake to obtain the in-situ modified barium sulfate whisker.
On the basis of the technical scheme, the pH value of the filter cake is adjusted to 7-8 by adopting a water washing and acid washing mode in the preferable filtering process, and the acid washing mode generally adopts sulfuric acid or phosphoric acid.
On the basis of the technical scheme, the concentration of the sodium sulfate solution is preferably 1-3 mol/L.
In the technical scheme, a mirabilite method is adopted to prepare the barium sulfate precipitate, sodium sulfate is added in a dropwise manner to enable the initial state crystal nucleus particle size of the obtained barium sulfate precipitate to be smaller, the reaction process is more moderate, a modifier and ethanol are added in a precipitation reaction system, barium sulfate is modified in the process of generating the precipitate through reaction, so that the modification effect is more uniform and stable, a crystal form control agent is added in the reaction system, so that crystals of barium sulfate can directionally grow to form a whisker structure, when the temperature is 50-60 ℃, the crystal directional growth effect is better, as the optimization, a program cooling manner is adopted in the cooling process, the cooling is best through 5-6 ℃/h, the length of the whisker prepared by adopting the technical scheme is 10-100 mu m, and the length-diameter ratio is 20-200.
On the basis of the technical scheme, preferably, the modifier is chitosan cholesterol carbonate.
On the basis of the technical scheme, preferably, the crystal form control agent is alpha-sodium alkenyl sulfonate.
On the basis of the above technical solution, preferably, in the step one, the barium sulfide: water: ethanol: the mass ratio of the modifier is 1: (20-30): (4-6): (0.025-0.1).
Still further preferably, the barium sulfide: the mass ratio of the crystal form control agent is 1: (0.1-0.2).
On the basis of the above technical scheme, preferably, the third step further comprises placing the precursor solution in a stable magnetic field, then dropwise adding a sodium sulfate solution into the precursor solution, after dropwise adding, keeping the precursor solution in the stable magnetic field, keeping the stirring speed unchanged, and cooling to 25-30 ℃.
In the above technical scheme, in order to further improve the performance of the whisker and enable the crystal to have better directional growth capability, it is found that the whisker has larger size and better performance when grown in a stable magnetic field with certain strength.
Based on the above technical solution, preferably, the intensity of the stable magnetic field is 5 × 10-4-2*10-3T。
In the above technical means, preferably, the direction of the steady magnetic field and the horizontal direction are parallel to each other, in which case the length of the whisker may be maintained at 20 to 400 μm, and the aspect ratio is 40 to 600.
The invention also provides the in-situ modified barium sulfate whisker prepared by the preparation method.
The invention also provides a lithium ion battery diaphragm which comprises a base film and a coating, wherein the coating is obtained by coating the slurry containing the in-situ modified barium sulfate whisker prepared by the preparation method on the surface of the base film and drying the coating.
On the basis of the technical scheme, preferably, the slurry comprises in-situ modified barium sulfate whiskers, deionized water and a binder, and as the preferred slurry, other auxiliary additives can be added into the slurry according to performance requirements.
On the basis of the above technical scheme, preferably, the base film is one of a polyethylene diaphragm, a polypropylene diaphragm, a polyimide diaphragm, a polyvinylidene fluoride diaphragm, a polyethylene non-woven fabric diaphragm, a polypropylene non-woven fabric diaphragm and a polyimide non-woven fabric diaphragm, and the in-situ modified barium sulfate whisker slurry is a suspension of in-situ modified barium sulfate whiskers.
Compared with the prior art, the in-situ modified barium sulfate whisker, the preparation method thereof and the lithium ion battery diaphragm have the following beneficial effects:
(1) the invention provides a preparation method of in-situ modified barium sulfate whiskers, which is characterized in that barium sulfate is modified by in-situ modification, the modification effect is improved, the amphipathy of the barium sulfate whiskers is improved, the whiskers are used for replacing conventional orthorhombic crystals, the agglomeration of barium sulfate is reduced, the agglomeration problem when barium sulfate is used as a coating is avoided, the barium sulfate whiskers are more uniformly dispersed in a suspension, a uniform three-dimensional grid structure can be formed after coating and drying, the barium sulfate whiskers are more stable, and the coating has a uniform three-dimensional net-shaped pore structure;
(2) when the in-situ modified barium sulfate whisker prepared by the preparation method is applied to a lithium ion battery diaphragm, the in-situ modified barium sulfate whisker can be used as a substitute product of a conventional alpha alumina coating, is lower in price, has good structural strength and heat resistance, can form a uniformly covered grid-shaped structure on a lonely loving surface layer as a coating structure on the surface layer of a base film, has uniformly distributed holes between grids, improves the amphipathy by adopting chitosan cholesterol carbonate as a modifier of the barium sulfate whisker, can ensure better infiltration effect on electrolyte after being modified, is more stable in relative position and structure and is not easy to agglomerate and shrink holes, the obtained battery diaphragm can also keep the original size under high-temperature impact, and can also keep the performance of a battery in the process of long-term use, the circulation effect is better.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of barium sulfate whiskers coated on a base film prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of barium sulfate whiskers coated on a base film prepared in example 2 of the present invention;
FIG. 3 is a scanning electron microscope image of barium sulfate whiskers coated on a base film prepared in example 3 of the present invention;
FIG. 4 is a scanning electron microscope image of barium sulfate whiskers coated on a base film prepared in example 4 of the present invention;
FIG. 5 is a scanning electron microscope image of barium sulfate whiskers coated on a base film prepared in example 5 of the present invention;
FIG. 6 is an enlarged view of the microspur of the barium sulfate whisker prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Weighing 100g of barium sulfide, adding the barium sulfide into 2L of water, stirring until the barium sulfide is dissolved, adding 400g of ethanol and 2.5g of chitosan cholesterol carbonate, stirring, heating to 50 ℃, preserving heat and stirring uniformly to obtain a barium sulfide mixed solution;
adding 10g of alpha-sodium alkenyl sulfonate into the barium sulfide mixed solution, keeping the temperature of 50 ℃, and stirring until the alpha-sodium alkenyl sulfonate is dissolved to obtain a precursor solution;
and (3) dropwise adding 1mol/L sodium sulfate solution into the precursor solution, keeping the stirring speed at 20r/min during dropwise adding, keeping the stirring speed unchanged after 500ml of solution is dropwise added, slowly cooling to 30 ℃ for 4h, after cooling is finished, filtering, taking a filter cake, and drying in a vacuum drying oven to obtain the barium sulfate whisker, wherein the microspur appearance of the whisker is shown in figure 6.
Example 2
Weighing 100g of barium sulfide, adding the barium sulfide into 2.2L of water, stirring until the barium sulfide is dissolved, adding 450g of ethanol and 4.5g of chitosan cholesterol carbonate, stirring, heating to 52 ℃, preserving heat and stirring uniformly to obtain a barium sulfide mixed solution;
adding 12g of alpha-sodium alkenyl sulfonate into the barium sulfide mixed solution, keeping the temperature at 52 ℃, and stirring until the alpha-sodium alkenyl sulfonate is dissolved to obtain a precursor solution;
and (2) placing the precursor solution in a stable magnetic field, wherein the direction of the magnetic field is horizontal, the magnetic field intensity is 0.0005T, dropwise adding 2mol/L sodium sulfate solution into the precursor solution, keeping the stirring speed at 25r/min during dropwise adding, keeping the stirring speed unchanged after dropwise adding 300ml, slowly cooling to 25 ℃, keeping the cooling time at 5h, after cooling, filtering, taking a filter cake, and drying in a vacuum drying oven to obtain the barium sulfate whisker.
Example 3
Weighing 100g of barium sulfide, adding the barium sulfide into 2.5L of water, stirring until the barium sulfide is dissolved, adding 500g of ethanol and 5g of chitosan cholesterol carbonate, stirring, heating to 55 ℃, preserving heat and stirring uniformly to obtain a barium sulfide mixed solution;
adding 14g of alpha-sodium alkenyl sulfonate into the barium sulfide mixed solution, keeping the temperature at 55 ℃, and stirring until the alpha-sodium alkenyl sulfonate is dissolved to obtain a precursor solution;
and (2) placing the precursor solution in a stable magnetic field, wherein the direction of the magnetic field is horizontal, the magnetic field intensity is 0.001T, dropwise adding 3mol/L sodium sulfate solution into the precursor solution, keeping the stirring speed at 25r/min during dropwise adding, keeping the stirring speed unchanged after dropwise adding 250ml, slowly cooling to 28 ℃, keeping the cooling time at 6h, after cooling, filtering, taking a filter cake, and drying in a vacuum drying oven to obtain the barium sulfate whisker.
Example 4
Weighing 100g of barium sulfide, adding the barium sulfide into 2.8L of water, stirring until the barium sulfide is dissolved, adding 550g of ethanol and 8g of chitosan cholesterol carbonate, stirring, heating to 58 ℃, preserving heat and stirring uniformly to obtain a barium sulfide mixed solution;
adding 18g of alpha-sodium alkenyl sulfonate into the barium sulfide mixed solution, keeping the temperature at 58 ℃, and stirring until the alpha-sodium alkenyl sulfonate is dissolved to obtain a precursor solution;
and (2) placing the precursor solution in a stable magnetic field, wherein the direction of the magnetic field is the horizontal direction, the magnetic field intensity is 0.0015T, dropwise adding 2mol/L sodium sulfate solution into the precursor solution, keeping the stirring speed at 25r/min during dropwise adding, keeping the stirring speed unchanged after dropwise adding 300ml, slowly cooling to 27 ℃ for 6h, after cooling, filtering, taking a filter cake, and drying in a vacuum drying oven to obtain the barium sulfate whisker.
Example 5
Weighing 100g of barium sulfide, adding the barium sulfide into 3L of water, stirring until the barium sulfide is dissolved, adding 550g of ethanol and 8g of chitosan cholesterol carbonate, stirring, heating to 58 ℃, preserving heat and stirring uniformly to obtain a barium sulfide mixed solution;
adding 18g of alpha-sodium alkenyl sulfonate into the barium sulfide mixed solution, keeping the temperature at 58 ℃, and stirring until the alpha-sodium alkenyl sulfonate is dissolved to obtain a precursor solution;
and (2) placing the precursor solution in a stable magnetic field, wherein the direction of the magnetic field is the horizontal direction, the magnetic field intensity is 0.002T, dropwise adding 2mol/L sodium sulfate solution into the precursor solution, keeping the stirring speed at 25r/min during dropwise adding, keeping the stirring speed unchanged after dropwise adding 300ml, slowly cooling to 27 ℃, keeping the cooling time at 6h, after cooling, filtering, taking a filter cake, and drying in a vacuum drying oven to obtain the barium sulfate whisker.
The barium sulfate whiskers prepared in the above embodiments are used for preparing lithium ion battery separators, respectively, and the preparation method includes mixing and stirring barium sulfate whiskers, gelatin and deionized water to form coating slurry, wherein the barium sulfate whiskers: gelatin: and (3) uniformly coating the coating slurry on the surface of the base film according to the mass ratio of the deionized water to 1:1:3, and drying to obtain the lithium ion battery diaphragm.
Specifically, slurry prepared from the barium sulfate whisker prepared in example 1 is coated on the surface of the polyethylene diaphragm; the slurry prepared from the barium sulfate whisker prepared in the embodiment 2 is coated on the surface of the polypropylene diaphragm; the slurry prepared from the barium sulfate whisker prepared in the embodiment 3 is coated on the surface of the polyimide diaphragm; the slurry prepared by the barium sulfate whisker prepared in the embodiment 4 is coated on the surface of the polyvinylidene fluoride diaphragm; the slurry prepared from the barium sulfate whiskers prepared in example 5 was coated on the surface of a polyethylene nonwoven membrane.
The performance test and the surface electron microscope scanning are respectively carried out on the lithium ion battery diaphragm obtained by the preparation, and the scanning results are shown in fig. 1-5, wherein the barium sulfate whisker prepared in example 1 is relatively more uneven in shape, irregular in growth exists, a small amount of orthorhombic crystals exist, and the barium sulfate whisker prepared in examples 2-4 is more stable in shape.
Physical index tests are respectively carried out on lithium ion battery diaphragms correspondingly prepared by adopting the modified barium sulfate whiskers prepared in the examples 1-5, meanwhile, nano barium sulfate powder is adopted as a slurry raw material, is coated on a polyethylene diaphragm after being prepared with gelatin and deionized water, and is dried to prepare a comparative diaphragm, and the diaphragms corresponding to the examples 1-5 and the comparative example are compared in performance, and the results are as follows:
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A preparation method of in-situ modified barium sulfate whiskers for a lithium ion battery diaphragm is characterized by comprising the following steps:
the method comprises the following steps: mixing barium sulfide with water, stirring until the barium sulfide is dissolved, adding ethanol and a modifier, namely chitosan cholesterol carbonate, heating to 50-60 ℃, and keeping the temperature and stirring to obtain a barium sulfide mixed solution;
step two, adding a crystal form control agent alpha-alkenyl sodium sulfonate into the barium sulfide mixed solution, keeping the temperature at 50-60 ℃, and stirring until the crystal form control agent is dissolved to obtain a precursor solution;
and step three, placing the precursor solution in a stable magnetic field, dropwise adding a sodium sulfate solution into the precursor solution, keeping the stirring speed at 20-30r/min during dropwise adding, keeping the temperature of the precursor solution at 50-60 ℃, keeping the stirring speed unchanged, cooling to 25-30 ℃ after dropwise adding, filtering, taking the filter cake, and drying to obtain the in-situ modified barium sulfate whisker.
2. The method for preparing in-situ modified barium sulfate whiskers for a lithium ion battery separator according to claim 1, wherein in the first step, the barium sulfide: water: ethanol: the mass ratio of the modifier is 1: (20-30): (4-6): (0.025-0.1).
3. The method for preparing in-situ modified barium sulfate whiskers for a lithium ion battery separator according to claim 1, wherein the barium sulfide: the mass ratio of the crystal form control agent is 1: (0.1-0.2).
4. The method for preparing in-situ modified barium sulfate whiskers for a lithium ion battery separator according to claim 1, wherein the strength of the stable magnetic field is 5 x 10-4-2*10-3T。
5. The in-situ modified barium sulfate whisker for the lithium ion battery separator, which is prepared by the preparation method of any one of claims 1 to 4.
6. A lithium ion battery separator, which is characterized by comprising a base film and a coating layer, wherein the coating layer is obtained by coating slurry containing the in-situ modified barium sulfate whiskers of claim 5 on the surface of the base film and drying the coating layer.
7. The lithium ion battery separator according to claim 6, wherein the base film is one of a polyethylene separator, a polypropylene separator, a polyimide separator, a polyvinylidene fluoride separator, a polyethylene non-woven fabric separator, a polypropylene non-woven fabric separator and a polyimide non-woven fabric separator, and the in-situ modified barium sulfate whisker slurry is a suspension of in-situ modified barium sulfate whiskers.
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