CN109346645B - Preparation method of multifunctional seaweed polyethylene composite diaphragm for lithium battery - Google Patents
Preparation method of multifunctional seaweed polyethylene composite diaphragm for lithium battery Download PDFInfo
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- CN109346645B CN109346645B CN201811153416.1A CN201811153416A CN109346645B CN 109346645 B CN109346645 B CN 109346645B CN 201811153416 A CN201811153416 A CN 201811153416A CN 109346645 B CN109346645 B CN 109346645B
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- -1 polyethylene Polymers 0.000 title claims abstract description 61
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 56
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 241001474374 Blennius Species 0.000 title claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 14
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 26
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- 230000000593 degrading effect Effects 0.000 claims description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
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- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 16
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 12
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 12
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- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 6
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
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- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 5
- 229940072056 alginate Drugs 0.000 description 5
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- 229920000642 polymer Polymers 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
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- 239000011261 inert gas Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 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
- 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
- H01M50/411—Organic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Cell Separators (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to the field of battery diaphragms, and discloses a preparation method of a multifunctional seaweed polyethylene composite diaphragm for a lithium battery, which comprises the following steps of (A) preparing uronic acid oligomer; (B) modification of uronic acid oligomers; (C) polymerizing; (D) calcium salt modification; (E) granulating; (F) and (5) film preparation. Compared with the traditional diaphragm, the diaphragm prepared by the method has the advantages of thin thickness, good self flame retardance and high safety, so that a ceramic coating is not required to be coated externally, and the diaphragm has good wettability and liquid absorption rate on electrolyte.
Description
Technical Field
The invention relates to the field of battery diaphragms, in particular to a preparation method of a multifunctional seaweed polyethylene composite diaphragm for a lithium battery.
Background
In the construction of lithium batteries, the separator is one of the key internal components. The performance of the diaphragm determines the interface structure, internal resistance and the like of the battery, directly influences the capacity, circulation, safety performance and other characteristics of the battery, and the diaphragm with excellent performance plays an important role in improving the comprehensive performance of the battery. The separator material is non-conductive, and the physical and chemical properties of the separator have a great influence on the performance of the battery. The battery is different in the kind of battery and the separator used, and a polyolefin porous film having a high strength and a thin film, such as a polyethylene separator, is generally used.
In addition to the requirement of non-conductivity for the separator, in order to further improve the performance and safety performance of the lithium battery, the separator is generally required to have excellent flame retardancy (preventing explosion and combustion when the battery is short-circuited), good wettability and liquid absorption rate for the electrolyte, certain mechanical strength and the like. At present, the common practice is to coat a ceramic coating on the surface of the diaphragm to play roles of flame retardance and strength improvement, but the thickness of the diaphragm is correspondingly increased, and the wettability and the liquid absorption rate of the diaphragm to electrolyte are reduced.
Alginic acid is a viscous organic acid, also known as alginic acid and alginic acid. The product was a white to slightly yellowish brown powder. The average molecular weight is about 24 ten thousand. The natural world is widely existed in the cell walls of hundreds of brown algae such as kelp, fucus and gulfweed. Alginic acid is widely used in the fields of food, textile printing and dyeing, paper making, medicine, leather, cosmetics, rubber, paint, water treatment and the like.
SeaCell alginate fiber produced by Alceru Schwarza, Germany, is a fiber developed by utilizing the advantages of seaweed containing carbohydrate, protein (amino acid), fat, cellulose and abundant mineral substances, and the preparation method of the fiber is based on the production and manufacturing procedures of lyocell fiber, and is formed by adding finely ground seaweed powder or suspension into spinning solution and spinning.
The main value of alginate fiber is alginic acid, which has excellent flame resistance, and the fiber has high charring degree in the combustion process, is extinguished after leaving flame and has certain flame retardancy. Generally, the more heat the material burns, the faster the speed and the greater the risk of fire. The relevant experiment shows that the flame retardant property of the alginate fiber is better than that of common viscose fiber and polyethylene fiber.
In addition, alginic acid can also effectively improve fibrous moisture absorption performance, if be used for preparing battery diaphragm with alginate fiber, can effectively promote the infiltration nature and the imbibition volume of diaphragm to electrolyte.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a multifunctional seaweed polyethylene composite diaphragm for a lithium battery. Compared with the traditional diaphragm, the diaphragm prepared by the method has the advantages of thin thickness, good self flame retardance and high safety, so that a ceramic coating is not required to be coated externally, and the diaphragm has good wettability and liquid absorption rate on electrolyte.
The specific technical scheme of the invention is as follows: a preparation method of a multifunctional seaweed polyethylene composite diaphragm for a lithium battery comprises the following steps:
(A) preparation of uronic acid oligomers: inoculating alginic acid degrading bacteria into a culture medium for culture and fermentation, taking fermentation liquor for centrifugal treatment, taking cell precipitates for washing with PBS buffer solution, crushing cells, and purifying to obtain alginic acid degrading enzyme; preparing 0.5-1.5wt% of alginic acid degrading enzyme into enzymolysis liquid, adding alginic acid into the enzymolysis liquid, adjusting pH to 6.5-7.5, adjusting temperature to 35-40 ℃, performing enzymolysis for 2-4h under ultrasonic conditions, performing centrifugal separation, and performing rotary evaporation to obtain uronic acid oligomer with polymerization degree mainly distributed between 2-4.
(B) Modification of uronic acid oligomers: adding uronic acid oligomer and stannic chloride into ethanol solution according to the weight ratio of 50-150:1, dispersing and mixing uniformly, heating to 85-90 ℃, dropwise adding allyl polyoxyalkyl epoxy ether under the condition of stirring, keeping the temperature for reaction until no longer reacting, cooling and filtering, evaporating the solvent and the allyl polyoxyalkyl epoxy ether under reduced pressure, and drying to obtain the modified uronic acid oligomer.
(C) Polymerization: adding triethyl aluminum and part of ethylene into a reaction kettle filled with hexane, and heating and pressurizing to perform prepolymerization; and then adding the residual ethylene and the modified uronic acid oligomer into the reaction kettle for final polymerization to generate the random polyethylene containing the hybrid block of the modified uronic acid oligomer.
(D) Calcium salt modification: and (C) adding 2-4wt% of calcium chloride solution into the reaction product obtained in the step (C) for reaction, and filtering to obtain the random polyethylene containing the modified calcium furfural oligomer hybrid block.
(E) And (3) granulation: and (D) purifying, drying and granulating the reaction product obtained in the step (D) to obtain the hybrid modified polyethylene master batch.
(F) Film preparation: melting the hybrid modified polyethylene master batch, and then performing biaxial stretching and heat setting twice to obtain the diaphragm.
In the prior art, in order to improve the flame retardance and the strength of the diaphragm, a ceramic coating is generally coated on the surface of the diaphragm, but the thickness of the diaphragm is correspondingly increased, and the wettability and the liquid absorption rate of the diaphragm to electrolyte are reduced. The special hybrid modified polyethylene is used as the base material of the diaphragm, the flame retardance of the base material is good, the wetting quality and the liquid absorption rate of the base material to electrolyte are good, a ceramic coating does not need to be coated outside, and the thickness of the diaphragm can be effectively reduced.
SeaCell algal fibers manufactured by Alceru Schwarza, Germany, are produced by spinning a finely ground algal powder or suspension added to a spinning solution based on the manufacturing process of lyocell fibers. Alginic acid is a linear block polyuronic acid, which is linked by 1, 4-glycosidic linkages, and has an average molecular weight of about 24 ten thousand, as shown below. In SeaCell alginate fibers, alginic acid is merely physically mixed in the fibers, and alginic acid itself cannot participate in polymerization reaction due to its large molecular weight and lack of reactive groups. In addition, the addition of the alginic acid with the ultrahigh molecular weight into the spinning solution can affect the spinnability of the spinning solution and the fiber performance; in addition, due to the physical mixing method, the alginic acid with ultra-high molecular weight is easy to be separated out from the fiber.
Therefore, alginic acid is degraded into oligomers with the polymerization degree of 2-4 in a special mode, then the oligomers are modified, double bond groups are grafted to ensure that the oligomers have the reaction capability of participating in polyethylene polymerization, and after hybrid modified polyethylene is obtained by polymerization, salinization modification is carried out to modify carboxyl on alginic acid molecules into calcium carboxylate, so that the flame retardance is further improved. And finally, preparing the film to obtain a finished product.
In the step (a), the degradation process needs to be strictly controlled to ensure the degradation degree, if the polymerization degree of the oligomer is too high, the viscosity is too high, the reaction is not facilitated, and if the polymerization degree is too low, the flame retardancy is affected. Repeated tests show that the polymerization degree is optimal between 2 and 4. Therefore, the degradation process is controlled, and the polymerization degree is controlled to be 2-4. In the invention, the degradation principle of alginic acid is as follows: firstly, the negative charge of carboxyl anion on alginic acid molecule is eliminated by enzymolysis liquid; in the process of transferring and catalyzing the C5 proton of the six-membered sugar ring, one residue can be used as a proton donor; after electron transfer from the carboxyl group, a double bond is formed between C4 and C5 of the six-membered sugar ring of the alginic acid monomer, thereby completing the entire β -elimination of the glycosidic bond.
In step (B), if alginic acid alone is degraded, it cannot participate in the polymerization of polyethylene although its molecular weight is reduced. Therefore, hydroxyl on oligomer molecules is utilized, allyl polyoxyalkyl epoxy ether is adopted to modify the oligomer molecules, and the two ends of the molecule of the allyl polyoxyalkyl epoxy ether respectively contain double bond groups and epoxy groups. In the modification process, hydroxyl on oligomer molecules and epoxy groups on allyl polyoxyalkyl epoxy ether molecules are subjected to ring-opening reaction to form a whole, so that double bond groups are formed on the oligomer molecules and can participate in the polymerization of polyethylene.
In the step (C), the polymerization process of the invention is divided into two steps of prepolymerization and final polymerization, and in the prepolymerization, a prepolymer with a certain polymerization degree is obtained by polymerization, so as to ensure the initial formation of a high molecular chain. The modified uronic acid oligomers need to be added at the final polymerization, since premature participation in the polymerization of the modified uronic acid oligomers affects the regularity of the polymer molecular chain and thus the polymer properties. And the addition after prepolymerization has little influence on the regularity of molecular weight.
In step (D), in order to further improve the flame retardancy of the separator, the carboxyl groups on the partially modified uronic acid oligomer need to be converted into calcium carboxylate, and the copolymer of alginic acid and polyethylene has stronger flame retardancy compared to single polyethylene because the flame retardancy of alginic acid is mainly related to its own carboxyl group and calcium carboxylate, and because of the calcium ions, an alkaline environment may be generated during the combustion process, and further because of the hydroxyl groups on the sugar ring, under the combined influence of the alkaline environment and the hydroxyl groups, alginic acid is very susceptible to decarboxylation reaction, and generates incombustible CO to dilute the concentration of combustible gas; on the other hand, calcium ions may also produce CaO and Ca-CO precipitates to cover the molecular chain surface, and the covering or crosslinking effect occurs. In addition, alginic acid releases a large amount of water and carbon dioxide in the decomposition process, and the vaporization of water molecules can absorb a large amount of heat, reduce the surface temperature of the diaphragm and play a role in flame retardance; the vaporized water vapor and carbon dioxide belong to inert gases, and the concentration of the combustible gas is diluted, so that the flame-retardant effect can be achieved.
In the step (E), alginic acid oligomer in the molecular chain of the hybrid modified polyethylene master batch obtained by granulation is embedded in the molecular chain section of the polyethylene in a random block mode, and compared with the traditional physical mixing mode, the compatibility and the stability are better, the rheological property of the polymer cannot be influenced, and alginic acid is not easy to separate out at the later stage. The invention improves the flame retardance and the liquid absorption rate of the diaphragm by utilizing the characteristics of self flame retardance and good liquid absorption rate of alginic acid.
Preferably, in step (D), the molar ratio of carboxyl groups in the random polyethylene to calcium in the calcium chloride solution is 2-3: 1.
As mentioned above, alginic acid relies on the coordination of calcium ions with carboxyl and hydroxyl groups, so that the content of calcium element needs to be controlled.
Preferably, in step (a), the alginic acid degrading bacteria are selected from azotobacter, agrobacterium chlorobacter, fox bacteria and microballon bacteria having alginic acid degrading ability.
Preferably, in step (a), the culture conditions of the alginic acid degrading bacteria are as follows: the culture medium has pH of 6.5-7.5, temperature of 25-30 deg.C, and time of 3-5 days.
Preferably, in the step (A), the dosage ratio of the alginic acid to the enzymolysis liquid is 30-70 g/L.
Preferably, in the step (B), the allylpolyoxyalkyl epoxy ether is added dropwise in an excess amount.
Preferably, in step (C), the amount of ethylene added in the prepolymerization is 40-60% of the total amount added; the addition amount of triethyl aluminum is 0.05-0.5wt% of the total amount of ethylene; the molar ratio of the total amount of ethylene to the modified uronic acid oligomers is 96-99: 1-4.
The amount of each monomer is strictly controlled and too much affects the polymer properties.
Preferably, in the step (C), the prepolymerization temperature is 70-80 ℃, the pressure is 2.3-2.8MPa, and the reaction time is 3-5 h; the final polymerization temperature is 75-85 ℃, the pressure is 2.6-3.0MPa, and the reaction time is 1-3 h.
Preferably, in the step (F), the stretching temperature of the first stretching is 60-70 ℃, and the stretching rate is 35-55%; the stretching temperature of the second stretching is 90-100 ℃, and the stretching rate is 140-180%.
Preferably, the membrane has a thickness of 40-60 microns and a porosity of 30-50%.
Compared with the prior art, the invention has the beneficial effects that: compared with the traditional diaphragm, the diaphragm prepared by the method has the advantages of thin thickness, good self flame retardance and high safety, so that a ceramic coating is not required to be coated externally, and the diaphragm has good wettability and liquid absorption rate on electrolyte.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of a multifunctional seaweed polyethylene composite diaphragm for a lithium battery comprises the following steps:
(A) preparation of uronic acid oligomers: inoculating alginic acid-degrading bacteria (Fox bacteria with alginic acid-degrading ability) into culture medium, and fermenting, wherein the pH of the culture medium is 7, the temperature is 28 deg.C, and the time is 4 days. Centrifuging the fermentation liquor, washing cell precipitates with PBS buffer solution, crushing cells, and purifying to obtain alginic acid degrading enzyme; preparing 1 wt% of an enzymolysis liquid from alginic acid degrading enzyme, adding alginic acid into the enzymolysis liquid, adjusting the dosage ratio of the alginic acid to the enzymolysis liquid to be 50g/L, adjusting the pH to be 7, carrying out enzymolysis for 3 hours at 37 ℃ under an ultrasonic condition, carrying out centrifugal separation, and carrying out rotary evaporation to obtain the uronic acid oligomer with the polymerization degree mainly distributed between 2 and 4.
(B) Modification of uronic acid oligomers: adding uronic acid oligomer and stannic chloride into an ethanol solution according to the weight ratio of 100: 1, dispersing and uniformly mixing, heating to 88 ℃, dropwise adding allyl polyoxyalkyl epoxy ether under the stirring condition, carrying out heat preservation reaction until the reaction does not occur, cooling and filtering, evaporating the solvent and the allyl polyoxyalkyl epoxy ether under reduced pressure, and drying to obtain the modified uronic acid oligomer.
(C) Polymerization: adding triethyl aluminum and 50 percent of total addition amount of ethylene into a reaction kettle filled with hexane, heating to 78 ℃, pressurizing to 2.6MPa, and carrying out prepolymerization for 4 h; and then adding the rest ethylene and the modified uronic acid oligomer into the reaction kettle, heating to 82 ℃, pressurizing to 2.9MPa, and carrying out final polymerization reaction for 2h to generate random polyethylene containing the hybrid block of the modified uronic acid oligomer. Wherein the addition amount of the triethyl aluminum is 0.15 wt% of the total amount of the ethylene; the molar ratio of total ethylene to modified uronic acid oligomers was 98.5: 1.5.
(D) Calcium salt modification: and (C) adding 3 wt% of calcium chloride solution into the reaction product of the step (C) to carry out reaction, wherein the molar ratio of the carboxyl groups in the random polyethylene to the calcium in the calcium chloride solution is 2.5: 1. And filtering to obtain the random polyethylene containing the modified calcium furfural oligomer hybrid block.
(E) And (3) granulation: and (D) purifying, drying and granulating the reaction product obtained in the step (D) to obtain the hybrid modified polyethylene master batch.
(F) Film preparation: melting the hybrid modified polyethylene master batch, and then carrying out biaxial stretching and heat setting twice, wherein the stretching temperature of the first stretching is 65 ℃, and the stretching rate is 45%; the second drawing was carried out at a drawing temperature of 95 ℃ and a drawing ratio of 160%. Finally, the diaphragm is obtained. The thickness of the separating film is about 48 microns, and the porosity is about 46%. Air permeability of 35cm3Sec, tensile strength in the machine direction of 172MPa, tensile strength in the transverse direction of 106MPa, and needling strength of 6.9N.
Example 2
A preparation method of a multifunctional seaweed polyethylene composite diaphragm for a lithium battery comprises the following steps:
(A) preparation of uronic acid oligomers: inoculating alginic acid-degrading bacteria (Micrococcus lactis with alginic acid-degrading ability) into culture medium, and fermenting, wherein the pH of the culture medium is 6.8, the temperature is 26 deg.C, and the fermentation time is 5 days. Centrifuging the fermentation liquor, washing cell precipitates with PBS buffer solution, crushing cells, and purifying to obtain alginic acid degrading enzyme; preparing 1.2 wt% of an enzymolysis liquid from alginic acid degrading enzyme, adding alginic acid into the enzymolysis liquid, adjusting the dosage ratio of the alginic acid to the enzymolysis liquid to be 55g/L, adjusting the pH to be 6.8, adjusting the temperature to be 38 ℃, carrying out enzymolysis for 2.5h under an ultrasonic condition, carrying out centrifugal separation, and carrying out rotary steaming to obtain uronic acid oligomers with polymerization degrees mainly distributed between 2 and 4.
(B) Modification of uronic acid oligomers: adding uronic acid oligomer and stannic chloride into an ethanol solution according to the weight ratio of 90: 1, dispersing and uniformly mixing, heating to 85 ℃, dropwise adding allyl polyoxyalkyl epoxy ether under the stirring condition, carrying out heat preservation reaction until the reaction does not occur, cooling and filtering, evaporating the solvent and the allyl polyoxyalkyl epoxy ether under reduced pressure, and drying to obtain the modified uronic acid oligomer.
(C) Polymerization: adding triethyl aluminum and 55 percent of ethylene in the total addition amount into a reaction kettle filled with hexane, heating to 70 ℃, pressurizing to 2.8MPa, and carrying out prepolymerization for 5 h; and then adding the rest ethylene and the modified uronic acid oligomer into the reaction kettle, heating to 75 ℃, pressurizing to 3.0MPa, and carrying out final polymerization reaction for 3h to generate random polyethylene containing the hybrid block of the modified uronic acid oligomer. Wherein the addition amount of the triethyl aluminum is 0.05 wt% of the total amount of the ethylene; the molar ratio of total ethylene to modified uronic acid oligomers was 98.5: 1.5.
(D) Calcium salt modification: adding 2 wt% of calcium chloride solution into the reaction product of the step (C) to carry out reaction, wherein the molar ratio of the carboxyl groups in the random polyethylene to the calcium in the calcium chloride solution is 2: 1. And filtering to obtain the random polyethylene containing the modified calcium furfural oligomer hybrid block.
(E) And (3) granulation: and (D) purifying, drying and granulating the reaction product obtained in the step (D) to obtain the hybrid modified polyethylene master batch.
(F) Film preparation: melting the hybrid modified polyethylene master batch, and then carrying out biaxial stretching and heat setting twice, wherein the stretching temperature of the first stretching is 60 ℃, and the stretching rate is 35%; the second drawing was carried out at a drawing temperature of 90 ℃ and a drawing rate of 140%. Finally, the diaphragm is obtained. The thickness of the diaphragm is about 52 microns, and the porosity is about 41%. Air permeability of 28cm3Sec, tensile strength in the machine direction of 178MPa, tensile strength in the transverse direction of 111MPa, and puncture strength of 7.5N.
Example 3
A preparation method of a multifunctional seaweed polyethylene composite diaphragm for a lithium battery comprises the following steps:
(A) preparation of uronic acid oligomers: inoculating alginic acid-degrading bacteria (azotobacter with alginic acid-degrading ability) into culture medium, and fermenting, wherein the pH of the culture medium is 7.2, the temperature is 30 deg.C, and the time is 3 days. Centrifuging the fermentation liquor, washing cell precipitates with PBS buffer solution, crushing cells, and purifying to obtain alginic acid degrading enzyme; preparing 1.5wt% of an enzymolysis liquid from alginic acid degrading enzyme, adding alginic acid into the enzymolysis liquid, adjusting the dosage ratio of the alginic acid to the enzymolysis liquid to be 40g/L, adjusting the pH to be 7, adjusting the temperature to be 40 ℃, performing enzymolysis for 4 hours under an ultrasonic condition, performing centrifugal separation, and performing rotary evaporation to obtain uronic acid oligomers with polymerization degrees mainly distributed between 2 and 4.
(B) Modification of uronic acid oligomers: adding uronic acid oligomer and stannic chloride into an ethanol solution according to the weight ratio of 120: 1, dispersing and uniformly mixing, heating to 90 ℃, dropwise adding allyl polyoxyalkyl epoxy ether under the stirring condition, carrying out heat preservation reaction until the reaction does not occur, cooling and filtering, evaporating the solvent and the allyl polyoxyalkyl epoxy ether under reduced pressure, and drying to obtain the modified uronic acid oligomer.
(C) Polymerization: adding triethyl aluminum and 60 percent of total addition amount of ethylene into a reaction kettle filled with hexane, heating to 80 ℃, pressurizing to 2.3MPa, and carrying out prepolymerization for 3 h; and then adding the rest ethylene and the modified uronic acid oligomer into the reaction kettle, heating to 85 ℃, pressurizing to 2.6MPa, and carrying out final polymerization reaction for 1h to generate random polyethylene containing the hybrid block of the modified uronic acid oligomer. Wherein the addition amount of the triethyl aluminum is 0.3 wt% of the total amount of the ethylene; the molar ratio of total ethylene to modified uronic acid oligomers was 98.5: 1.5.
(D) Calcium salt modification: and (C) adding a 4wt% calcium chloride solution into the reaction product of the step (C) to perform reaction, wherein the molar ratio of the carboxyl groups in the random polyethylene to the calcium in the calcium chloride solution is 3: 1. And filtering to obtain the random polyethylene containing the modified calcium furfural oligomer hybrid block.
(E) And (3) granulation: and (D) purifying, drying and granulating the reaction product obtained in the step (D) to obtain the hybrid modified polyethylene master batch.
(F) Film preparation: melting the hybrid modified polyethylene master batch, and then carrying out biaxial stretching and heat setting twice, wherein the stretching temperature of the first stretching is 70 ℃, and the stretching rate is 55%; the second drawing was conducted at a drawing temperature of 100 ℃ and a drawing ratio of 180%. Finally, the diaphragm is obtained. The thickness of the separating film is about 42 microns, and the porosity is about 48%. Air permeability of 37cm3Sec, a tensile strength in the machine direction of 159MPa, a tensile strength in the transverse direction of 98MPa, and a puncture strength of 6.6N.
Example 4
A preparation method of a multifunctional seaweed polyethylene composite diaphragm for a lithium battery comprises the following steps:
(A) preparation of uronic acid oligomers: inoculating alginic acid-degrading bacteria (Agrobacterium tumefaciens with alginic acid-degrading ability) into culture medium, and fermenting, wherein the pH of the culture medium is 6.8, the temperature is 25 deg.C, and the time is 5 days. Centrifuging the fermentation liquor, washing cell precipitates with PBS buffer solution, crushing cells, and purifying to obtain alginic acid degrading enzyme; preparing 0.5wt% of an enzymolysis liquid from alginic acid degrading enzyme, adding alginic acid into the enzymolysis liquid, adjusting the dosage ratio of the alginic acid to the enzymolysis liquid to be 70g/L, adjusting the pH to be 7, adjusting the temperature to be 40 ℃, performing enzymolysis for 4 hours under an ultrasonic condition, performing centrifugal separation, and performing rotary evaporation to obtain uronic acid oligomers with polymerization degrees mainly distributed between 2 and 4.
(B) Modification of uronic acid oligomers: adding uronic acid oligomer and stannic chloride into an ethanol solution according to the weight ratio of 150:1, dispersing and uniformly mixing, heating to 90 ℃, dropwise adding allyl polyoxyalkyl epoxy ether under the stirring condition, carrying out heat preservation reaction until the reaction does not occur, cooling and filtering, evaporating the solvent and the allyl polyoxyalkyl epoxy ether under reduced pressure, and drying to obtain the modified uronic acid oligomer.
(C) Polymerization: adding triethyl aluminum and 40 percent of total addition amount of ethylene into a reaction kettle filled with hexane, heating to 72 ℃, pressurizing to 2.7MPa, and carrying out prepolymerization for 3.5 h; and then adding the rest ethylene and the modified uronic acid oligomer into the reaction kettle, heating to 78 ℃, pressurizing to 2.9MPa, and carrying out final polymerization reaction for 2.5h to generate the random polyethylene containing the hybrid block of the modified uronic acid oligomer. Wherein the addition amount of the triethyl aluminum is 0.2 wt% of the total amount of the ethylene; the molar ratio of total ethylene to modified uronic acid oligomers was 98.5: 1.5.
(D) Calcium salt modification: adding 2.5 wt% of calcium chloride solution into the reaction product of the step (C) to carry out reaction, wherein the molar ratio of the carboxyl groups in the random polyethylene to the calcium in the calcium chloride solution is 3: 1. And filtering to obtain the random polyethylene containing the modified calcium furfural oligomer hybrid block.
(E) And (3) granulation: and (D) purifying, drying and granulating the reaction product obtained in the step (D) to obtain the hybrid modified polyethylene master batch.
(F) Film preparation: melting the hybrid modified polyethylene master batch, and then carrying out biaxial stretching and heat setting twice, wherein the stretching temperature of the first stretching is 70 ℃, and the stretching rate is 55%; the second drawing was conducted at a drawing temperature of 100 ℃ and a drawing ratio of 180%. Finally, the diaphragm is obtained. The thickness of the separating film is about 43 microns, and the porosity is about 48 percent. Air permeability of 34cm3Sec, a tensile strength in the machine direction of 161MPa, a tensile strength in the transverse direction of 102MPa, and a puncture strength of 6.8N.
Comparative example 1
In the comparative example, alginic acid was added by physical blending:
(A) preparation of polyethylene melt: adding the conventional polyethylene master batch into a double-screw extruder for melting to obtain a conventional polyethylene melt, adding 1.5 mol% of alginic acid into the melt, and uniformly mixing.
(B) Film preparation: melting the melt, and then carrying out biaxial stretching and heat setting twice, wherein the stretching temperature of the first stretching is 65 ℃, and the stretching rate is 45%; the second drawing was carried out at a drawing temperature of 95 ℃ and a drawing ratio of 160%. Finally, the diaphragm is obtained. The thickness of the separating film is about 49 microns, and the porosity is about 45%. Air permeability of 27cm3Sec, tensile strength in the machine direction of 171MPa, tensile strength in the transverse direction of 107MPa, and puncture strength of 7.0N.
Comparative example 2
In comparative example 2, the difference from example 1 is that: uronic acid oligomers differ in degree of polymerization:
(A) preparation of uronic acid monomers or oligomers: inoculating alginic acid-degrading bacteria (Fox bacteria with alginic acid-degrading ability) into culture medium, and fermenting, wherein the pH of the culture medium is 7, the temperature is 28 deg.C, and the time is 4 days. Centrifuging the fermentation liquor, washing cell precipitates with PBS buffer solution, crushing cells, and purifying to obtain alginic acid degrading enzyme; preparing 2 wt% of an enzymolysis liquid from alginic acid degrading enzyme, adding alginic acid into the enzymolysis liquid, adjusting the dosage ratio of the alginic acid to the enzymolysis liquid to be 300g/L, adjusting the pH to be 7, carrying out enzymolysis for 6h at 37 ℃ under an ultrasonic condition, carrying out centrifugal separation, and carrying out rotary evaporation to obtain a mixture of uronic acid monomers and oligomers with polymerization degrees mainly distributed between 1 and 2.
Comparative example 3
In comparative example 3, the difference from example 1 is that: without calcium salt modification.
Comparison of Performance
1. Mechanical properties: as can be seen from comparison of the thickness, porosity, air permeability c, tensile strength in the machine direction, tensile strength in the transverse direction, and needle punching strength of the separators of examples 1 to 4 and comparative example 1, the mechanical strength of the separators of examples 1 to 4 was similar to that of comparative example 1, which was obtained by a conventional method.
2. Flame retardant property: the membranes of example 1 and comparative examples 1-3 were subjected to a limiting oxygen LOI test with the following results:
LOI value for example 1: 32.2; LOI value for comparative example 1: 29.8; LOI value for comparative example 2: 29.5; LOI value for comparative example 3: 30.1.
as can be seen from the above, alginic acid in comparative example 1 is simply blended to affect the flame retardancy, alginic acid in comparative example 2 has a polymerization degree not in a preferable range, and thus has poor flame retardancy, and alginic acid has no calcium salt, and alginic acid flame retardancy depends on the synergistic combination of carboxyl, hydroxyl and calcium carboxylate, and the absence of calcium leads to poor flame retardancy.
3. The separators of example 1 and comparative examples 1 to 3 were subjected to the electrolyte liquid absorption rate test, and the results were as follows:
example 1 was 345%; comparative example 1 was 339%; comparative example 2 was 333%; comparative example 3 was 351%.
As can be seen from the above, the liquid absorption rates of the separators of example 1 and comparative examples 1 to 3 were substantially the same.
Claims (8)
1. A preparation method of a multifunctional seaweed polyethylene composite diaphragm for a lithium battery is characterized by comprising the following steps:
(A) preparation of uronic acid oligomers: inoculating alginic acid degrading bacteria into a culture medium for culture and fermentation, taking fermentation liquor for centrifugal treatment, taking cell precipitates for washing with PBS buffer solution, crushing cells, and purifying to obtain alginic acid degrading enzyme; preparing 0.5-1.5wt% of an enzymolysis liquid from alginic acid degrading enzyme, adding alginic acid into the enzymolysis liquid, adjusting the pH to 6.5-7.5, adjusting the temperature to 35-40 ℃, performing enzymolysis for 2-4h under an ultrasonic condition, performing centrifugal separation, and performing rotary evaporation to obtain uronic acid oligomers with polymerization degrees mainly distributed between 2 and 4;
(B) modification of uronic acid oligomers: adding uronic acid oligomer and stannic chloride into an ethanol solution according to the weight ratio of 50-150:1, dispersing and uniformly mixing, heating to 85-90 ℃, dropwise adding allyl polyoxyalkyl epoxy ether under the stirring condition, keeping the temperature for reaction until no more reaction occurs, cooling and filtering, evaporating the solvent and the allyl polyoxyalkyl epoxy ether under reduced pressure, and drying to obtain the modified uronic acid oligomer;
(C) polymerization: adding triethyl aluminum and part of ethylene into a reaction kettle filled with hexane, heating and pressurizing to perform prepolymerization, wherein the addition amount of the ethylene in the prepolymerization is 40-60% of the total addition amount; the addition amount of triethyl aluminum is 0.05-0.5wt% of the total amount of ethylene; the prepolymerization temperature is 70-80 ℃, the pressure is 2.3-2.8MPa, and the reaction time is 3-5 h; then adding the rest ethylene and the modified uronic acid oligomer into the reaction kettle for final polymerization at the temperature of 75-85 ℃ and the pressure of 2.6-3.0MPa for 1-3 h; generating random polyethylene containing the hybrid block of the modified uronic acid oligomer; the molar ratio of the total amount of ethylene to the modified uronic acid oligomers is 96-99: 1-4;
(D) calcium salt modification: adding 2-4wt% of calcium chloride solution into the reaction product obtained in the step (C) for reaction, and filtering to obtain random polyethylene containing the modified calcium furfural oligomer hybrid block;
(E) and (3) granulation: purifying, drying and granulating the reaction product obtained in the step (D) to obtain the hybrid modified polyethylene master batch;
(F) film preparation: melting the hybrid modified polyethylene master batch, and then performing biaxial stretching and heat setting twice to obtain the diaphragm.
2. The method of claim 1, wherein in the step (D), the molar ratio of the carboxyl groups in the random polyethylene to the calcium in the calcium chloride solution is 2-3: 1.
3. The method of claim 1, wherein in step (A), the alginic acid degrading bacteria are selected from azotobacter, Agrobacterium aeruginosa, Fox bacteria and Micrococcus with alginic acid degrading ability.
4. The method for preparing the multifunctional seaweed polyethylene composite diaphragm for the lithium battery as claimed in claim 1 or 3, wherein in the step (A), the culture conditions of the alginic acid degrading bacteria are as follows: the culture medium has pH of 6.5-7.5, temperature of 25-30 deg.C, and time of 3-5 days.
5. The method of claim 1 or 3, wherein the ratio of alginic acid to the enzymolysis solution used in the step (A) is 30-70 g/L.
6. The method of claim 1, wherein in the step (B), the allyl polyoxyalkyl epoxy ether is added dropwise in an excessive amount.
7. The method of claim 1, wherein in the step (F), the first stretching temperature is 60-70 ℃ and the stretching rate is 35-55%; the stretching temperature of the second stretching is 90-100 ℃, and the stretching rate is 140-180%.
8. The method of claim 1, wherein the separator has a thickness of 40-60 μm and a porosity of 30-50%.
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| US20160365558A1 (en) * | 2015-06-09 | 2016-12-15 | GM Global Technology Operations LLC | Separator for lithium-based batteries |
| CN106384800A (en) * | 2016-09-28 | 2017-02-08 | 河南师范大学 | Preparation method of modified diaphragm for lithium-sulfur batteries |
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| US20160365558A1 (en) * | 2015-06-09 | 2016-12-15 | GM Global Technology Operations LLC | Separator for lithium-based batteries |
| CN106384800A (en) * | 2016-09-28 | 2017-02-08 | 河南师范大学 | Preparation method of modified diaphragm for lithium-sulfur batteries |
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| Electrostatic Shield Effect: An Effective Way to Modify Celgard Membrane Separator Used in Lithium-sulfur Battery;Xie et al.;《INTERNATIONAL JOURNAL OF ELECTROCHEMICAL SCIENCE》;20170731;第12卷(第7期);全文 * |
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