CN114335884B - Method for preparing lithium ion battery diaphragm material by using biological film - Google Patents
Method for preparing lithium ion battery diaphragm material by using biological film Download PDFInfo
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- CN114335884B CN114335884B CN202111516609.0A CN202111516609A CN114335884B CN 114335884 B CN114335884 B CN 114335884B CN 202111516609 A CN202111516609 A CN 202111516609A CN 114335884 B CN114335884 B CN 114335884B
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- 239000000463 material Substances 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 20
- 210000003278 egg shell Anatomy 0.000 claims abstract description 56
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 46
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 40
- 239000012528 membrane Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 16
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007873 sieving Methods 0.000 claims abstract description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052582 BN Inorganic materials 0.000 claims abstract description 13
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 13
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 13
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910000271 hectorite Inorganic materials 0.000 claims abstract description 13
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 13
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 13
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000005086 pumping Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- JZKFHQMONDVVNF-UHFFFAOYSA-N dodecyl sulfate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCCCCCCOS(O)(=O)=O JZKFHQMONDVVNF-UHFFFAOYSA-N 0.000 claims description 10
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 6
- 230000035699 permeability Effects 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 3
- LIFHMKCDDVTICL-UHFFFAOYSA-N 6-(chloromethyl)phenanthridine Chemical compound C1=CC=C2C(CCl)=NC3=CC=CC=C3C2=C1 LIFHMKCDDVTICL-UHFFFAOYSA-N 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000008187 granular material Substances 0.000 description 12
- 229940012466 egg shell membrane Drugs 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229920006231 aramid fiber Polymers 0.000 description 8
- 239000004760 aramid Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- QBKSIHCSDPPLJI-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]tetradecan-1-ol;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCCCCCCCCCC(CO)N(CCO)CCO QBKSIHCSDPPLJI-UHFFFAOYSA-N 0.000 description 2
- -1 Polyethylene Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 102000034240 fibrous proteins Human genes 0.000 description 2
- 108091005899 fibrous proteins Proteins 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- DQJCDTNMLBYVAY-ZXXIYAEKSA-N (2S,5R,10R,13R)-16-{[(2R,3S,4R,5R)-3-{[(2S,3R,4R,5S,6R)-3-acetamido-4,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy}-5-(ethylamino)-6-hydroxy-2-(hydroxymethyl)oxan-4-yl]oxy}-5-(4-aminobutyl)-10-carbamoyl-2,13-dimethyl-4,7,12,15-tetraoxo-3,6,11,14-tetraazaheptadecan-1-oic acid Chemical compound NCCCC[C@H](C(=O)N[C@@H](C)C(O)=O)NC(=O)CC[C@H](C(N)=O)NC(=O)[C@@H](C)NC(=O)C(C)O[C@@H]1[C@@H](NCC)C(O)O[C@H](CO)[C@H]1O[C@H]1[C@H](NC(C)=O)[C@@H](O)[C@H](O)[C@@H](CO)O1 DQJCDTNMLBYVAY-ZXXIYAEKSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102000002068 Glycopeptides Human genes 0.000 description 1
- 108010015899 Glycopeptides Proteins 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 210000000998 shell membrane Anatomy 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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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- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Primary Cells (AREA)
Abstract
The invention discloses a method for preparing a lithium ion battery diaphragm material by using a biological film, which relates to the technical field of battery materials and comprises the following steps: drying eggshells with egg membranes, crushing and sieving; mixing eggshell powder, hectorite powder, aluminum isopropoxide and water to form paste; mixing with ethyl orthosilicate, stirring, adding into ethanol, stirring, heating for reflux, and pumping; mixing the gel material with boron nitride powder and water, stirring, mixing with sodium carboxymethylcellulose aqueous solution, adding polyacrylamide gel, stirring, adding triethanolamine lauryl sulfate, mechanically stirring at constant speed, and injecting into a mold on tin foil paper to form a film; drying and cooling to obtain the final product. The invention has the advantages that the obtained battery diaphragm material has the advantages of thin thickness, small heat shrinkage, high air permeability, high oxygen index, good safety performance, higher liquid absorption, contribution to the diffusion of lithium ions, high ion conductivity and capability of regulating charges.
Description
Technical Field
The invention relates to the technical field of new energy battery materials, in particular to a method for preparing a lithium ion battery diaphragm material by utilizing a biological membrane (eggshell and membrane thereof).
Background
Because lithium ions have the advantages of high working voltage, high energy density, long cycle life, no memory effect and the like, the lithium ions have been widely applied to the fields of '3C' (portable computer, communication and consumer electronics) markets, electric automobiles, aerospace, military and the like. A diaphragm material is arranged between the positive electrode and the negative electrode of the lithium ion battery, and the diaphragm material has the main functions of isolating the positive electrode from the negative electrode and enabling electrons in the battery not to pass through freely; ions (in the electrolyte solution) can freely pass between the positive electrode and the negative electrode. Polyethylene and polypropylene microporous membranes are commonly used at present, however, the materials have the defects of poor affinity for electrolyte and low membrane rupture temperature. Thus, researchers have utilized ceramic particles (e.g., al 2 O 3 、SiO 2 ) The composite membrane is prepared by coating the composite membrane on the surface of a polyolefin membrane or a non-woven fabric membrane after being combined with a polymer binder, so that the thermal stability of the membrane and the wettability of electrolyte are improved, and the safety performance of the lithium ion battery is further improved.
Chinese patent CN 107732106A discloses a battery diaphragm paste, a battery diaphragm, a lithium ion battery and respective preparation methods, the battery diaphragm paste preparation comprises the following steps: dissolving aramid fibers in an acidic solution to perform carboxylation treatment on the aramid fibers; adding the carboxylated aramid fibers into a first solvent, and diluting and dissolving to obtain a first mixed solution; adding a filler to the second solvent to obtain a second mixed solution; and mixing the first mixed solution with the second mixed solution to obtain battery diaphragm slurry in which aramid fibers are dissolved. Through the technical scheme, the battery diaphragm slurry and the preparation method thereof can effectively dissolve the aramid fibers, solve the problem that the aramid fibers are difficult to dissolve in the prior art, and provide conditions for preparing the battery diaphragm from the aramid fibers; as the aramid fiber is reasonably and effectively dissolved in the preparation process, the air permeability and the heat shrinkage are good.
Chinese patent CN 108682773A discloses a lithium battery separator. The lithium battery diaphragm is obtained by steps of dewatering and pre-treating aluminum isopropoxide and lithium-based montmorillonite, then gradually premixing the aluminum isopropoxide and the lithium-based montmorillonite with liquid materials, extruding the liquid materials with polyolefin resin, casting, stretching, extracting, drying and the like.
Chinese patent CN 111029513A A discloses a preparation method of new energy battery diaphragm material, comprising the following steps: preparing mullite powder; preparing a composite porous ceramic component; sequentially adding lithium oxide and a composite porous ceramic component into PVA aqueous solution, uniformly stirring, transferring to an electrostatic spinning instrument, spinning under the condition of 15kV electrostatic pressure and 20cm plate spacing, forming a film on tin pinning paper, drying the obtained film in a drying oven at 80-90 ℃ for 15-20h, then placing in a muffle furnace, heating to 600-650 ℃, preserving heat for 3-5h, and naturally cooling to room temperature to obtain a finished product.
However, the materials have poor mechanical properties, complex preparation process or poor normal-temperature conductivity, so that the materials are difficult to be practically used, and the colloidal polymer electrolyte is a thermodynamically unstable system in nature, and can be stored in an open environment or for a long time, so that the solvent can ooze out of the surface, thereby causing the conductivity to be reduced. There are a number of problems to be solved with the complete substitution of the polymer membrane by the colloidal polymer electrolyte.
China has rich eggshell resources, however, most eggshell resources are treated as waste, so that a great deal of resource waste is caused. Eggshell is a completely highly bound biological calcium, which is formed by combining inorganic matters and organic proteins, wherein the content of the calcium carbonate, the magnesium carbonate, the calcium phosphate and magnesium phosphate inorganic matters and the organic matters are 3.2% and 2.8% respectively, and the organic matrixes mainly comprise glycoprotein and glycopeptide. The eggshell structure is divided into a shell membrane layer, a cone layer and a columnar structure from inside to outsideLayer and surface layer. Air holes are distributed among the cones, on the cones and in the cone core holes. 1000-12000 air holes are formed in the eggshell, and the aperture is 4-40 mu m. The eggshell high-content calcium carbonate has strong solution adsorption capacity, and the air holes are favorable for flowing small molecules. The eggshell membrane is composed of fibrous protein and has a complex network structure, so that the eggshell membrane has large surface area and can show good adsorption performance. Eggshell membrane contains amino (-NH) and amide (-CO-NH) 2 ) Groups that allow the eggshell membrane surface to be positively or negatively charged under different pH conditions. In the current research on eggshells at home and abroad, a part of people aim at the adsorption property of eggshells and eggshell membranes, and expect that the eggshells and eggshell membranes have ideal effects in the application of wastewater treatment, and are less frequently used in the field of membrane material preparation.
Disclosure of Invention
The invention aims to at least solve one of the technical problems in the prior art, and provides a method for preparing a lithium ion battery diaphragm by using a biological film.
The technical scheme of the invention is as follows:
a method for preparing a lithium ion battery diaphragm material by using a biological film, which comprises the following steps:
(1) Oven drying eggshell with egg membrane, pulverizing, and sieving.
(2) Mixing the sieved eggshell powder, hectorite powder, aluminum isopropoxide and water to form a paste;
(3) Stirring and mixing the paste obtained in the step (2) with tetraethoxysilane uniformly, then adding the mixture into ethanol, stirring, heating, refluxing, and pumping to obtain a gel material;
(4) Mixing the gel material obtained in the step (3) with boron nitride powder and water, stirring for a certain time, mixing with sodium carboxymethyl cellulose water solution, adding polyacrylamide gel, stirring for a certain time, adding dodecyl sulfate triethanolamine, continuously stirring at a constant speed, and injecting into a die to form a film on tinfoil paper; and (5) drying the obtained film body in a drying oven, and cooling to room temperature to obtain a finished product.
In the step (1), eggshells with egg membranes are dried in an oven at the temperature of between 90 and 100 ℃, taken out for natural cooling, crushed by a crusher and screened by a 100-mesh screen.
In the step (2), 450-550 g of sieved eggshell powder, 150-250 g of hectorite powder, 80-120 g of aluminum isopropoxide and 80-120 g of deionized water are mixed into a paste.
In the step (3), the paste obtained in the step (2) is stirred and mixed with 80-100 g of ethyl orthosilicate, and then added into 1000ml of ethanol, and the mixture is stirred and heated and refluxed for 9-11 hours.
In a specific embodiment of the present invention, in the step (4), the gel material obtained in the step (3) is mixed with 45 to 55g of boron nitride powder and 100g of water, and stirred for 1.5 to 2.5 hours and then mixed with 45 to 55g of sodium carboxymethyl cellulose aqueous solution.
In the step (4), 70-90 g of polyacrylamide gel is added, mechanical stirring is carried out for 30-50 min at 1000-1200 r/min, 45-55 g of lauryl triethanolamine sulfate is added, mechanical stirring is carried out for 15-25 min at a constant speed, the mixture is poured into a die, tinfoil paper is poured onto the die to form a film, the obtained film is placed in a drying box to be dried for 15-20h at 100-110 ℃, and the film is naturally cooled to room temperature, thus obtaining the finished product.
The invention has at least one of the following beneficial effects:
the invention takes the abandoned eggshell as the raw material, because the eggshell contains a large amount of inorganic matters such as calcium carbonate and a small amount of organic matters, the structure of the eggshell is provided with a plurality of pores, the high content of calcium carbonate in the eggshell has strong capability of absorbing solution, the pores are beneficial to the flow of small molecules, and the eggshell membrane is composed of fibrous proteins with complex network structures, so that the eggshell membrane has large surface area, thereby showing good adsorption performance, has good hydrophilicity due to amino groups and amide groups, and can adjust the charge of the membrane under different pH conditions. Therefore, the lithium ion battery diaphragm is prepared by using the eggshells and the eggshell membranes as raw materials, the obtained diaphragm material is thin in thickness, small in thermal shrinkage, high in air permeability and oxygen index, good in safety performance, high in liquid absorption capacity, favorable for diffusion of lithium ions, high in ion conductivity and capable of adjusting charges; and the recycling of resources can be realized, so that a great deal of resource waste caused by the fact that most eggshell resources are treated as waste is avoided.
Detailed Description
A method for preparing a lithium ion battery diaphragm by using a biological film, comprising the following steps:
(1) Weighing eggshells with egg membranes, drying the eggshells and the eggshell membranes in a baking oven at 90-100 ℃, taking out, and naturally cooling. Pulverizing eggshell and membrane with a crusher, sieving with 100 mesh sieve, continuously crushing coarse granule, continuously sieving with 100 mesh sieve, and discarding coarse granule.
(2) Weighing 450-550 g of sieved eggshell powder, 150-250 g of hectorite powder, 80-120 g of aluminum isopropoxide and 80-120 g of deionized water, and mixing to form a paste. Preferably, 480 to 520g of the sieved eggshell powder is weighed and mixed with 180 to 220g of the hectorite powder, 90 to 110g of the aluminum isopropoxide and 90 to 110g of the deionized water to form a paste. More preferably, 500g of the sieved eggshell powder is mixed with 200g of the hectorite powder, 100g of aluminum isopropoxide and 100g of deionized water to form a paste.
(3) And (3) uniformly stirring and mixing the paste obtained in the step (2) with 80-100 g of tetraethoxysilane, adding the mixture into 1000ml of ethanol, stirring, heating, refluxing for 9-11 h, and pumping to obtain the gel material. Preferably, the paste obtained in the step (2) is stirred and mixed with 85-95 g of tetraethoxysilane, then added into 1000ml of ethanol, stirred and heated for reflux for 9.5-10.5 h; more preferably, the paste obtained in the step (2) is stirred and mixed with 90g of ethyl orthosilicate, and then added into 1000ml of ethanol, and the mixture is stirred and heated and refluxed for 10 hours.
(4) Mixing the gel material with 45-55 g of boron nitride powder and 100g of water, stirring for 1.5-2.5 hours, mixing with 45-55 g of sodium carboxymethyl cellulose water solution, adding 70-90 g of polyacrylamide gel, mechanically stirring for 30-50 minutes at 1000-1200 r/min, adding 45-55 g of triethanolamine dodecyl sulfate, mechanically stirring for 15-25 minutes at a constant speed, and injecting into a tin foil in a mold to form a film. And (3) placing the obtained film body in a drying oven to be dried for 15-20 hours at the temperature of 100-110 ℃, and naturally cooling to room temperature to obtain a finished product. Preferably, the gel material is mixed with 48 to 52g of boron nitride powder and 100g of water, stirred for 1.5 to 2.5 hours, then mixed with 48 to 52g of sodium carboxymethyl cellulose water solution, 75 to 85g of polyacrylamide gel is added, mechanically stirred for 35 to 45 minutes at 1000 to 1200r/min, then 48 to 52g of lauryl triethanolamine sulfate is added, mechanically stirred for 18 to 22 minutes at a constant speed, and finally the mixture is poured into a die to form a film on the tinfoil paper. And (3) placing the obtained film body in a drying oven to be dried for 15-20h at the temperature of 102-108 ℃. More preferably, the gel material is mixed with 50g of boron nitride powder and 100g of water, stirred for 2 hours, then mixed with 50g of sodium carboxymethyl cellulose water solution, 80g of polyacrylamide gel is added, after mechanical stirring for 40 minutes at 1000-1200 r/min, 50g of triethanolamine dodecyl sulfate is added, after mechanical stirring for 20 minutes at a constant speed, the mixture is poured onto tinfoil paper in a mould to form a film, and the obtained film body is dried in a drying box at 105 ℃ for 18 hours.
The present invention will be described in further detail with reference to the following specific examples, but the present invention is not limited to the following specific examples.
Example 1
A method for preparing a lithium ion battery diaphragm by using a biological film comprises the following steps:
(1) 1000g of eggshell with egg membrane is weighed, placed in a 95 ℃ oven for baking for 4 hours, taken out and naturally cooled. Pulverizing eggshell and membrane with a crusher, sieving with 100 mesh sieve, continuously crushing coarse granule, sieving, and discarding coarse granule.
(2) 500g of the sieved eggshell powder was weighed and mixed with 200g of hectorite powder, 100g of aluminum isopropoxide and 100g of deionized water to form a paste.
(3) Then mixing with 90g of tetraethoxysilane, adding into 1000ml of ethanol, stirring, heating, refluxing for 10h, and pumping to obtain gel material.
(4) Mixing the gel material with 50g of boron nitride powder and 100g of water, stirring for 2 hours, mixing with 50g of sodium carboxymethyl cellulose water solution with the mass fraction of 5%, adding 80g of polyacrylamide gel, mechanically stirring for 40min at 1100r/min, adding 50g of triethanolamine dodecyl sulfate, mechanically stirring for 20min at a constant speed, and injecting the mixture into a die to form a film on tinfoil paper. And (3) drying the obtained film body in a drying oven at 105 ℃ for 18 hours, and naturally cooling to room temperature to obtain a finished product.
Example 2
A method for preparing a lithium ion battery diaphragm by using a biological film comprises the following steps:
(1) Weighing eggshell with egg membrane, oven drying eggshell and eggshell membrane at 90deg.C, taking out, and naturally cooling. Pulverizing eggshell and membrane with a crusher, sieving with 100 mesh sieve, continuously crushing coarse granule, continuously sieving with 100 mesh sieve, and discarding coarse granule.
(2) 450g of the sieved eggshell powder was weighed and mixed with 150g of hectorite powder, 80g of aluminum isopropoxide and 80g of deionized water to form a paste.
(3) And (3) uniformly stirring and mixing the paste obtained in the step (2) with 80g of tetraethoxysilane, adding the mixture into 1000ml of ethanol, stirring, heating and refluxing for 9 hours, and pumping to obtain the gel material.
(4) Mixing the gel material with 45g of boron nitride powder and 100g of water, stirring for 1.5 hours, mixing with 45g of sodium carboxymethyl cellulose water solution with the mass fraction of 5%, adding 70g of polyacrylamide gel, mechanically stirring for 50 minutes at 1000r/min, adding 45g of triethanolamine dodecyl sulfate, mechanically stirring for 15 minutes at a constant speed, and injecting the mixture into a die to form a film on tin foil. And (3) drying the obtained film body in a drying oven at 100 ℃ for 20 hours, and naturally cooling to room temperature to obtain a finished product.
Example 3
A method for preparing a lithium ion battery diaphragm by using a biological film, comprising the following steps:
(1) Weighing eggshell with egg membrane, oven drying eggshell and eggshell membrane at 90deg.C, taking out, and naturally cooling. Pulverizing eggshell and membrane with a crusher, sieving with 100 mesh sieve, continuously crushing coarse granule, continuously sieving with 100 mesh sieve, and discarding coarse granule.
(2) 480g of the sieved eggshell powder was weighed and mixed with 180g of hectorite powder, 90g of aluminum isopropoxide and 90g of deionized water to form a paste.
(3) And (3) uniformly stirring and mixing the paste obtained in the step (2) with 90g of tetraethoxysilane, adding the mixture into 1000ml of ethanol, stirring, heating and refluxing for 9.5 hours, and pumping to obtain the gel material.
(4) Mixing the gel material with 48g of boron nitride powder and 100g of water, stirring for 1.8 hours, mixing with 48g of sodium carboxymethyl cellulose water solution with the mass fraction of 5%, adding 75g of polyacrylamide gel, mechanically stirring for 50 minutes at 1000r/min, adding 48g of triethanolamine dodecyl sulfate, mechanically stirring for 18 minutes at a constant speed, and injecting the mixture into a die to form a film on tin foil. And (3) drying the obtained film body in a drying oven at 105 ℃ for 17 hours, and naturally cooling to room temperature to obtain a finished product.
Example 4
A method for preparing a lithium ion battery diaphragm by using a biological film, comprising the following steps:
(1) Weighing eggshell with egg membrane, oven drying eggshell and eggshell membrane at 95deg.C, taking out, and naturally cooling. Pulverizing eggshell and membrane with a crusher, sieving with 100 mesh sieve, continuously crushing coarse granule, continuously sieving with 100 mesh sieve, and discarding coarse granule.
(2) 520g of the sieved eggshell powder was weighed and mixed with 220g of hectorite powder, 110g of aluminum isopropoxide and 110g of deionized water to form a paste.
(3) And (3) uniformly stirring and mixing the paste obtained in the step (2) with 95g of ethyl orthosilicate, adding the mixture into 1000ml of ethanol, stirring, heating and refluxing for 10.5 hours, and pumping to obtain the gel material.
(4) Mixing the gel material with 52g of boron nitride powder and 100g of water, stirring for 2.2 hours, mixing with 52g of sodium carboxymethyl cellulose water solution with the mass fraction of 5%, adding 85g of polyacrylamide gel, mechanically stirring for 40min at 1200r/min, adding 50g of triethanolamine dodecyl sulfate, mechanically stirring for 20min at a constant speed, and injecting the mixture into a die to form a film on tin foil. And (3) drying the obtained film body in a drying oven at 1005 ℃ for 20 hours, and naturally cooling to room temperature to obtain a finished product.
Example 5
A method for preparing a lithium ion battery diaphragm by using a biological film, comprising the following steps:
(1) Weighing eggshell with egg membrane, oven drying eggshell and eggshell membrane at 100deg.C, taking out, and naturally cooling. Pulverizing eggshell and membrane with a crusher, sieving with 100 mesh sieve, continuously crushing coarse granule, continuously sieving with 100 mesh sieve, and discarding coarse granule.
(2) 550g of sieved eggshell powder is weighed, mixed with 250g of hectorite powder, 120g of aluminum isopropoxide and 120g of deionized water to form a paste, and placed in an oven at 110 ℃ for 2 hours.
(3) And (3) uniformly stirring and mixing the paste obtained in the step (2) with 100g of tetraethoxysilane, adding the mixture into 1000ml of ethanol, stirring, heating and refluxing for 11 hours, and pumping to obtain the gel material.
(4) Mixing the gel material with 55g of boron nitride powder and 100g of water, stirring for 2.5 hours, mixing with 55g of sodium carboxymethyl cellulose water solution with the mass fraction of 5%, adding 90g of polyacrylamide gel, mechanically stirring for 50 minutes at 1200r/min, adding 55g of triethanolamine dodecyl sulfate, mechanically stirring for 25 minutes at a constant speed, and injecting the mixture into a die to form a film on tin foil. And (3) drying the obtained film body in a drying oven at 110 ℃ for 20 hours, and naturally cooling to room temperature to obtain a finished product.
Testing
The performance of ion battery separators prepared by taking biological membranes (eggshells and membranes thereof) as raw materials in examples 1 to 5 was tested, and the specific test method is as follows:
(1) The thermal shrinkage test method comprises the following steps: and (3) adjusting the temperature of the oven, keeping the temperature to 100 ℃, quickly placing a sample, starting timing, adopting a flat-laying method, taking out after keeping for one hour, and measuring the length to be accurate to two decimal places.
(2) Air permeability: and placing the dried sample into a sample chamber, screwing the upper clamp and the lower clamp to ensure the sealing of the sample chamber, mounting the sample chamber on a porous material performance detector, starting the detector, adjusting a pressure knob to enable the pressure difference to reach a certain value, observing the pressure difference and the change of flow through a digital display meter, and recording the corresponding flow value when the pressure difference is stable. Along with the continuous decline of the differential pressure, 5-10 groups of corresponding flow values under different differential pressures are recorded. Repeating the experiment for at least three times, recording the flow value corresponding to the same pressure difference of the first group, taking an average value, substituting Kgas=Q/(delta P×A), fitting a curve of P, Q and the ratio, and obtaining the slope as the air permeability.
(3) Oxygen index test method: instrument KS-653BH oxygen index meter. The top of the sample is 100mm shorter than the top of the combustion cylinder, the sample is vertically arranged on the sample clamp and coincides with the center line of the combustion cylinder, the oxygen concentration is estimated to be 25% according to experience, oxygen and nitrogen gas are mixed by a person at the (40+/-10) mL/s from the bottom of the combustion cylinder, the sample is ignited from the upper end by an igniter, and the oxygen concentration in the mixed gas is changed until the flame front just reaches the marked line of the sample or the combustion time reaches 180 s. From this oxygen concentration, the oxygen index of the material was calculated.
(4) The liquid absorption testing method comprises the following steps: the pole piece 1 is horizontally placed on a table top, and a white line vertical to the height of the pole piece is respectively drawn at the positions h1 and h2 (h 1 is less than h 2) from the tail part. White line h2 drops of a few drops of purple litmus solution. The pole piece 1 is M1 at this time by an electronic balance. The pole piece electrolyte was wiped dry with cloth and the weight was recorded as M2. Substitution formula M (liquid absorption per unit time) = (M2-M1)/t
(5) The internal resistance testing method comprises the following steps: BSB-616 internal resistance tester deduced by Shenzhen Maitred technology
(6) Ion conductivity testing method: the resistance values under the multilayer separator were tested multiple times using an ac impedance method, and the results of the test were linearly fitted. The slope is the resistance value and the inverse is the conductivity.
The results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the battery separator materials prepared in examples 1 to 5 have a very thin thickness, a small thermal shrinkage, a high air permeability and oxygen index, a good safety performance, and a high liquid absorption, and are favorable for diffusion of lithium ions, low in internal resistance, and high in ion conductivity, so that the battery separator material prepared by the method of the invention has a good performance and can be used in lithium ion batteries.
The above is merely exemplary embodiments of the present invention, and the scope of the present invention is not limited in any way. All technical schemes formed by adopting equivalent exchange or equivalent substitution fall within the protection scope of the invention.
Claims (5)
1. The method for preparing the lithium ion battery diaphragm material by using the biological film is characterized by comprising the following steps of:
(1) Drying eggshell with egg membrane, pulverizing, and sieving;
(2) Mixing the sieved eggshell powder, hectorite powder, aluminum isopropoxide and water to form a paste;
(3) Stirring and mixing the paste obtained in the step (2) with tetraethoxysilane uniformly, then adding the mixture into ethanol, stirring, heating, refluxing, and pumping to obtain a gel material;
(4) Mixing the gel material obtained in the step (3) with boron nitride powder and water, stirring for a certain time, mixing with sodium carboxymethyl cellulose water solution, adding polyacrylamide gel, stirring for a certain time, adding triethanolamine dodecyl sulfate, continuously stirring at a constant speed, and injecting into a die to form a film on tin foil paper; drying the obtained film body in a drying oven, and cooling to room temperature to obtain a finished product;
in the step (2), 450-550 g of sieved eggshell powder, 150-250 g of hectorite powder, 80-120 g of aluminum isopropoxide and 80-120 g of deionized water are mixed into paste.
2. The method for preparing the lithium ion battery diaphragm material by using the biological membrane according to claim 1, wherein in the step (1), eggshells with egg membranes are dried in an oven at the temperature of between 90 and 100 ℃, taken out and naturally cooled, crushed by a crusher and sieved by a 100-mesh sieve.
3. The method for preparing the lithium ion battery diaphragm material by using the biological membrane according to claim 1, wherein in the step (3), the paste obtained in the step (2) is stirred and mixed with 80-100 g of tetraethoxysilane, then added into 1000ml of ethanol, and stirred and heated for reflux for 9-11 h.
4. The method for preparing a lithium ion battery separator material by using a biological film according to claim 1, wherein in the step (4), the gel material obtained in the step (3) is mixed with 45-55 g of boron nitride powder and 100g of water, and is mixed with 45-55 g of sodium carboxymethyl cellulose aqueous solution after stirring for 1.5-2.5 hours.
5. The method for preparing the lithium ion battery diaphragm material by using the biological film according to claim 1, wherein in the step (4), 70-90 g of polyacrylamide gel is added, after mechanical stirring for 30-50 min at 1000-1200 r/min, 45-55 g of triethanolamine dodecyl sulfate is added, after mechanical stirring for 15-25 min at a constant speed, the mixture is poured into a mold, the film is formed on tinfoil paper, and the obtained film body is placed in a drying box for drying at 100-110 ℃ for 15-20h, and naturally cooled to room temperature, thus obtaining the finished product.
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