CN114824647A - Lithium ion battery diaphragm based on aluminum hydroxide coaxial nanotube and preparation method thereof - Google Patents

Lithium ion battery diaphragm based on aluminum hydroxide coaxial nanotube and preparation method thereof Download PDF

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CN114824647A
CN114824647A CN202210553693.1A CN202210553693A CN114824647A CN 114824647 A CN114824647 A CN 114824647A CN 202210553693 A CN202210553693 A CN 202210553693A CN 114824647 A CN114824647 A CN 114824647A
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coaxial
glucose
nanotube
derived
diaphragm
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CN114824647B (en
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李帆
张立斌
赵海玉
沈亚定
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Jiangsu Housheng New Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)

Abstract

The invention provides a lithium ion battery diaphragm based on an aluminum hydroxide coaxial nanotube and a preparation method thereof, wherein glucose derivative C @ porous Al (OH) is introduced 3 The coaxial nanotube improves the mechanical strength and the heat shrinkage performance of the diaphragm, and greatly enhances the liquid absorption and retention capacity of the diaphragm; the COPNA resin is used as a binder, the complexity of a macromolecular cross-linked network in the diaphragm is effectively improved, the COPNA resin has excellent affinity with a carbon material, and the glucose-derived C @ porous Al (OH) is effectively improved 3 The coaxial nanotube has affinity to the diaphragm, so that the service life of the diaphragm is effectively prolonged; selectingSynthesizing COPNA resin by using bamboo tar as a raw material, terephthalyl alcohol as a cross-linking agent and p-toluenesulfonic acid as a catalyst; the adhesive is modified, so that the heat shrinkage, flame retardance and ionic conductivity of the diaphragm are effectively improved; introduction of DOPO and its derivatives, octaaminopropyl polyhedral oligomeric silsesquioxanes, glucose derived C @ porous Al (OH) 3 The coaxial nanotube is compounded with a plurality of flame retardant elements to realize synergistic flame retardance, and the safety of the diaphragm is effectively improved.

Description

Lithium ion battery diaphragm based on aluminum hydroxide coaxial nanotube and preparation method thereof
Technical Field
The invention relates to the field of battery diaphragms, in particular to a lithium ion battery diaphragm based on aluminum hydroxide coaxial nanotubes and a preparation method thereof.
Background
The lithium battery is a novel secondary battery, has the advantages of high energy density, long cycle life and the like, is widely applied to portable electronic devices, energy storage and power automobiles, and along with the development of new energy industries, more and more lithium batteries are applied to the power automobiles. The diaphragm is an important component of the lithium battery, and plays a role in effectively preventing the short circuit caused by the contact of the positive electrode and the negative electrode and ensuring the safety of the lithium battery, so that the diaphragm has higher requirements on the performance of the diaphragm.
The polyolefin separator which is the most widely used lithium battery separator at present, but the polyolefin separator on the existing market also has the following defects: firstly, the ionic conductivity is low, the internal resistance of the battery is increased, and the charging and discharging of the lithium ion battery under the condition of high multiplying power are not facilitated; secondly, the problems of poor battery hardness, poor cycle performance, low thermal stability, unstable interface between the pole piece and a diaphragm and the like caused by poor bonding performance of the counter pole piece and insufficient performance of the electrophilic electrolyte are solved, so that the improvement of the energy density of the battery and the development of the high-performance ultrathin battery are greatly limited; and thirdly, when the battery has thermal runaway, the melting point of the polyolefin material is very low, and the polyolefin diaphragm is easy to rupture to cause the aggravation of the thermal runaway, so that the battery burns and even explodes.
Therefore, the development of a lithium ion battery separator with high ionic conductivity, high electrolyte wettability and high flame retardance is a common pursuit target in the industry.
Disclosure of Invention
The invention aims to solve the problems in the prior art by using a lithium ion battery diaphragm based on an aluminum hydroxide coaxial nanotube and a preparation method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises a base film and a coating layer formed by coating the surface of the base film; the coating layer comprises the following components in parts by mass: 0.35 to 0.8 percent9% -23% of glucose-derived C @ porous Al (OH) 3 The coaxial nano-tube comprises a coaxial nano-tube, 0.2-0.85% of thickening agent, 0.6-1.3% of binder, 0.1-0.4% of wetting agent and the balance of deionized water.
Aiming at the problems of poor adhesion of the existing polyolefin diaphragm to a pole piece and poor electrolyte wettability, the main current solution is to coat a water system PVDF glue layer on one side or two sides of the polyolefin diaphragm, wherein the glue layer can effectively improve the adhesion of the diaphragm and has good wettability with the electrolyte, but the problem of easy falling exists; aiming at the problems of low ionic conductivity and poor heat resistance of the polyolefin diaphragm, the main current solution is to coat a high-temperature-resistant ceramic coating on one side or both sides of the polyolefin diaphragm, so that the pore closing of the diaphragm can be delayed to 150 ℃, but the pore closing temperature of 150 ℃ cannot completely avoid short circuit of a lithium battery at high temperature and spontaneous combustion caused by the short circuit, so that the heat resistance of the diaphragm needs to be further improved, and the risk of diaphragm rupture of the diaphragm is reduced, thereby improving the safety of the battery.
According to the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube, the glucose-derived C nanotube is selected as a coating material and added into the slurry component, wherein the glucose-derived C nanotube has good high temperature resistance and heat conduction performance, and is beneficial to improving the heat resistance of the coating, so that the heat resistance of the diaphragm is improved.
Further, the preparation of the glucose-derived C nanotube comprises the following steps:
adding the silicon dioxide nanowires after hydrophilic treatment into a glucose solution under the condition of continuous stirring, continuing magnetic stirring for 40-50min, then performing ultrasonic dispersion for 6-7h, transferring into a stainless steel autoclave with a PTFE liner, heating at 95-100 ℃ for 5-6h, naturally cooling to 18-25 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 70-80 ℃ for 20-24h, and keeping the vacuum degree at 0.08Mpa to obtain the carbon-coated silicon dioxide nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, keeping for 5-6h, then filtering, washing, placing at 70-80 ℃, drying for 10-12h, and obtaining the glucose-derived C nanotube after drying.
Furthermore, the mass molar ratio of the silicon dioxide nanowires after the hydrophilic treatment to the glucose in the glucose solution is 92mg:101.4 mmol.
The preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring hexadecyl trimethyl ammonium bromide, absolute ethyl alcohol and deionized water, adding an ammonia water solution and 0.1g of ethyl orthosilicate, adding (3-mercaptopropyl) trimethoxysilane with the mass fraction of 6%, immersing the indium tin oxide coated substrate, standing for 28h at 55-58 ℃, washing, aging at 100 ℃, washing by using a 0.15mol/L hydrochloric acid ethanol solution, treating by using a hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain the hydrophilic treated silicon dioxide nanowire.
Sulfonic acid groups are loaded on a vertical mesoporous silica pore channel in situ, the pore channel structure is not changed, the selective permeability of the nano channel is mainly caused by a size effect and a charge effect, and when the nano channel is completely occupied by an electric double layer, the selective permeability is optimal.
Further, glucose-derived C @ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: stirring glucose derived C nano tube and ultrapure water magnetically for 80-90min, then performing ultrasonic dispersion for 190- 3 A coaxial nanotube.
Further, the mass ratio of the glucose-derived C nano tube to the aluminum sulfate to the urea is 1.97:13.46: 26.59.
Lithium ion battery separator based on aluminum hydroxide coaxial nanotubes, wherein glucose is derived from C @ porous Al (OH) 3 The introduction of coaxial nanotubes benefits from its excellent properties and the phase between different nanotubesThe mechanical strength and the heat shrinkage performance of the diaphragm are greatly improved due to mutual crosslinking; in addition, glucose-derived C nanotubes and porous Al (OH) having flame retardant properties 3 The two can act synergistically, which further improves the mechanical properties and heat shrinkage properties of the separator;
the introduction of the glucose-derived C nanotube not only increases the mechanical property of the diaphragm, but also enhances the conductivity of the diaphragm, thereby being beneficial to enhancing the rapid transmission of lithium ions; in addition, glucose-derived C @ porous Al (OH) 3 The coaxial nanotube has hollow structure and is coated with Al (OH) 3 The porous structure is presented, the lithium ion conductivity is further improved, and the specific surface area of the material is greatly increased, so that the liquid absorption and retention capacity of the diaphragm is greatly enhanced.
Al (OH) introduced into lithium ion battery diaphragm based on aluminum hydroxide coaxial nanotube 3 Greatly improving the flame retardant capability of the diaphragm, Al (OH) 3 The crystal water is decomposed by heat to form a carbonized layer, and when the temperature rises to the decomposition temperature, Al (OH) 3 The water vapor is decomposed and released, latent heat is absorbed, and the concentration of oxygen and combustible gas near the surface of a combustion object is diluted, so that the surface combustion is difficult to carry out; the carbonized layer formed on the surface prevents oxygen and heat from entering, and meanwhile, the alumina generated by decomposition of the carbonized layer is a good refractory material, has good high temperature resistance and heat conductivity, and can improve the capability of the material for resisting open fire.
Further, the base film is a polyolefin separator; the dispersant is hydrolyzed polymaleic anhydride dispersant, the thickening agent is carboxymethylcellulose sodium dispersant, the binder is COPNA resin binder, and the wetting agent is silanol nonionic surfactant.
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises the following steps:
s1: mixing dispersant, glucose derived C @ porous Al (OH) 3 Premixing the coaxial nanotube in ultrapure water for 10-90min at the rotation speed of 100-600 rpm; adding the thickening agent and continuing stirring for 10-90min at the rotation speed of 350-900 rpm; adding binder, and stirring for 40-120min at rotation speed of350-700 rpm; adding a wetting agent and stirring for 30-90min at the rotation speed of 400-900 rpm; filtering to remove iron to obtain glucose derivative C @ porous Al (OH) 3 Coating slurry on the coaxial nanotube;
s2: adopting a micro gravure roller coating process to lead the prepared glucose derived C @ porous Al (OH) 3 And (3) rolling the coaxial nanotube coating slurry on two sides of the base film in a roller manner step by step, baking at 65-70 ℃ and then rolling to obtain the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube.
The COPNA resin is used as a binder, the complexity of a macromolecular cross-linked network in the diaphragm is effectively improved, the COPNA resin has excellent affinity with a carbon material, and the glucose-derived C @ porous Al (OH) is effectively improved 3 The affinity of the coaxial nanotube and the diaphragm effectively prolongs the service life of the diaphragm.
The prior market mostly adopts nonrenewable petrochemical raw material COPNA resin, which not only has complex working procedure and large pollution in the processing process, but also has low cross-linking density, poor carbon residue rate and poor heat resistance caused by high density and large steric hindrance of monomer condensed rings.
The invention takes bamboo as renewable raw material, selects bamboo tar as raw material, takes terephthalyl alcohol as cross-linking agent, takes p-toluenesulfonic acid as catalyst to synthesize COPNA resin, the pretreatment process is simple, the cost is low, and the discharge of waste is reduced.
Further, the preparation of the COPNA resin comprises the following steps: weighing bamboo tar and terephthalyl alcohol according to the mass ratio of 1:1 in a nitrogen environment, adding 5.4-6.8% of p-toluenesulfonic acid in mass fraction, reacting at 130-150 ℃ until a filament winding phenomenon occurs, stopping heating, discharging and cooling to obtain the COPNA resin.
In an acid environment, terephthalyl alcohol can generate active carbonium ions, electrophilic substitution reaction is carried out on the terephthalyl alcohol and benzene rings in a large number of phenols and derivatives of phenols in bamboo tar, alcoholic hydroxyl groups in generated products are dehydrated under the action of acid to generate carbonium ions again, the carbonium ions react with aromatic hydrocarbon to generate cross-linked macromolecules, the viscosity of the system is increased along with the deepening of the cross-linking degree, moisture does not escape any more, the cross-linked macromolecules are cross-linked to form a net structure, the COPNA resin is obtained, and the softening point and the heat resistance of the obtained COPNA resin are improved by controlling the addition amount of p-toluenesulfonic acid.
The modification treatment is carried out on the binding agent, so as to effectively improve the glucose-derived C @ porous Al (OH) 3 The binding force among the coaxial nanotube, the thickening agent, the binder and the wetting agent effectively improves the thermal shrinkage, the flame retardance and the ionic conductivity of the diaphragm.
Further, the adhesive is modified COPNA resin, and the preparation method comprises the following steps:
(1) reacting itaconic acid, deionized water and 1, 6-hexamethylene diamine at 55-60 ℃ for 20-30min under a nitrogen environment to obtain itaconic acid mixed liquid;
(2) mixing deionized water, absolute ethyl alcohol, acetonitrile, triethylamine and tetraethyl ammonium hydroxide in a constant-temperature water bath at 52-56 ℃; adding 3-aminopropyltriethoxysilane, refluxing at 52-56 deg.C for 20-22h, vacuum distilling for concentrating, adding concentrated solution into petroleum ether, standing, vacuum filtering, washing with acetone for 2-5 times, and vacuum drying to obtain octaaminopropyl cage-type silsesquioxane;
(3) mixing and stirring the mixed solution of DOPO and itaconic acid, heating to 85-88 ℃ and reacting for 2.5-3 h; carrying out suction filtration while the mixture is hot, cooling to 18-25 ℃, transferring to an ice water bath for cooling for 9-11h, and carrying out suction filtration to obtain a water-soluble flame retardant; adding octaaminopropyl polyhedral oligomeric silsesquioxane and COPNA resin, and ultrasonically stirring for 30-60min to obtain the modified COPNA resin.
Further, the molar volume ratio of the itaconic acid to the 1, 6-hexanediamine to the deionized water is 0.2mol:0.2mol:320 mL; the volume ratio of the deionized water to the absolute ethyl alcohol to the acetonitrile to the triethylamine to the tetraethylammonium hydroxide is 80mL to 36mL to 9mL to 5 mL; the molar ratio of DOPO to itaconic acid was 1.2: 1.
DOPO is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
the cage-type silsesquioxane has high thermal oxidation stability and excellent mechanical property; in the invention, by introducing DOPO and derivatives thereof, octaaminopropyl cage type silsesquioxane, glucose-derived C @ porous Al (OH) 3 The coaxial nanotube is compounded with a plurality of flame retardant elements to realize synergistic flame retardant;
in the presence of Al (OH) 3 The crystal water is decomposed by heat and absorbs heat to form a carbonized layerOn the basis, the DOPO and the derivative thereof can be decomposed to generate the oxyphosphoric acid to promote the dehydration and carbonization of the material, and the silicon dioxide particles generated by the decomposition of the cage-type silsesquioxane can cover the surface to generate the flame-retardant synergistic effect together.
The three components are cooperatively used for flame retardance of the diaphragm, and the DOPO and the derivatives thereof, Al (OH) are enhanced by utilizing silicon dioxide particles generated by decomposition of the cage type silsesquioxane 3 The quality and the strength of the carbon layer formed by catalysis can form a stable ceramic layer compounded by silicon dioxide and aluminum oxide, the stability of the carbon layer is enhanced, and the contact between external heat flow and oxygen and internal materials and combustible gas is blocked, so that the combustion reaction is prevented, and the flame retardant property of the diaphragm is improved in a synergistic manner.
The COPNA resin is modified, a P-H bond is introduced into the COPNA resin, the COPNA resin has high activity on olefin, epoxy bond and carbonyl in the raw material of the diaphragm, and the heat shrinkage of the diaphragm is greatly improved; and the introduction of the active sites is beneficial to improving the ion exchange capacity of the diaphragm, effectively preventing the danger of thermal runaway and improving the safety of the diaphragm.
The COPNA resin is condensed polycyclic polynuclear aromatic resin; DOPO is 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
The invention has the beneficial effects that:
the invention provides a lithium ion battery diaphragm based on an aluminum hydroxide coaxial nanotube and a preparation method thereof, and the lithium ion battery diaphragm with high liquid absorption and retention capacity, high flame retardance and high safety is prepared through component limitation and process adjustment;
wherein the glucose derivative C @ porous Al (OH) 3 The introduction of the coaxial nanotube greatly improves the mechanical strength and the heat shrinkage performance of the diaphragm; the introduction of the glucose-derived C nanotube not only increases the mechanical property of the diaphragm, but also enhances the conductivity of the diaphragm, and the hydrophilic treatment of the silicon dioxide is beneficial to enhancing the rapid transmission of lithium ions; in addition, glucose-derived C @ porous Al (OH) 3 The coaxial nanotube has hollow structure and is coated with Al (OH) 3 Exhibits a porous structure, which further improves the lithium ion conductivity, andthe specific surface area of the material is greatly increased, so that the liquid absorption and retention capacity of the diaphragm is greatly enhanced;
the COPNA resin is used as a binder, the complexity of a macromolecular cross-linked network in the diaphragm is effectively improved, the COPNA resin has excellent affinity with a carbon material, and the glucose-derived C @ porous Al (OH) is effectively improved 3 The affinity of the coaxial nanotube and the diaphragm effectively prolongs the service life of the diaphragm;
the method takes bamboo as a renewable raw material, selects bamboo tar as a raw material, takes terephthalyl alcohol as a cross-linking agent, takes p-toluenesulfonic acid as a catalyst to synthesize the COPNA resin, improves the softening point and the heat resistance of the obtained COPNA resin by controlling the addition of the p-toluenesulfonic acid, has simple pretreatment process and low cost, and reduces the discharge of wastes;
the modification treatment is carried out on the binding agent, so as to effectively improve the glucose-derived C @ porous Al (OH) 3 The bonding force among the coaxial nanotube, the thickening agent, the binder and the wetting agent effectively improves the heat shrinkage, the flame retardance and the ionic conductivity of the diaphragm;
in the invention, by introducing DOPO and derivatives thereof, octaaminopropyl cage type silsesquioxane, glucose-derived C @ porous Al (OH) 3 The coaxial nanotube is compounded with a plurality of flame retardant elements to realize synergistic flame retardant; the three components are cooperatively used for flame retardation of the diaphragm, and the DOPO and the derivatives thereof, Al (OH) are enhanced by using silicon dioxide particles generated by decomposition of the cage type silsesquioxane 3 The quality and strength of the carbon layer formed by catalysis can form a stable ceramic layer compounded by silicon dioxide and aluminum oxide, so that the stability of the carbon layer is enhanced, and the contact between external heat flow and oxygen and internal materials and combustible gas is blocked, so that the combustion reaction is prevented, and the flame retardant property of the diaphragm is synergistically and greatly improved; and the introduction of a large number of active sites is beneficial to improving the ion exchange capacity of the diaphragm and effectively improving the safety of the diaphragm.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that if directional indications such as up, down, left, right, front, and back … … are involved in the embodiment of the present invention, the directional indications are only used to explain a specific posture, such as a relative positional relationship between components, a motion situation, and the like, and if the specific posture changes, the directional indications also change accordingly. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The technical solutions of the present invention are further described in detail with reference to specific examples, which should be understood that the following examples are only illustrative and not limiting.
Example 1
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises the following steps:
s1: mixing dispersant, glucose derived C @ porous Al (OH) 3 Premixing the coaxial nanotube in ultrapure water for 10min at the rotation speed of 600 rpm; adding the thickening agent and continuing stirring for 10min at the rotating speed of 900 rpm; adding the binder and continuously stirring for 40min at the rotating speed of 700 rpm; adding wetting agent and stirring for 30min at the rotation speed of 900 rpm; filtering to remove iron to obtain glucose derivative C @ porous Al (OH) 3 Coating slurry on the coaxial nanotube;
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises a base film and a formed coating layer coated on the surface of the base film; the coating layer comprises the following components in parts by mass: 0.35% of dispersant, 9% of glucose-derived C @ porous Al (OH) 3 The coaxial nano-tube comprises a coaxial nano-tube, 0.2% of thickening agent, 0.6% of binding agent, 0.1% of wetting agent and the balance of deionized water;
the base film is a polyethylene diaphragm; the dispersant is hydrolyzed polymaleic anhydride, the thickening agent is sodium carboxymethylcellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotube comprises the following steps:
adding 92mg of hydrophilically treated silicon dioxide nanowires into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing magnetic stirring for 40min, then performing ultrasonic dispersion for 7h, transferring to a stainless steel high-pressure kettle with a PTFE liner, heating at 95 ℃ for 6h, naturally cooling to 18 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 70 ℃ for 24h, and keeping the vacuum degree at 0.08MPa to obtain the carbon-coated silicon dioxide nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, keeping for 5 hours, then filtering, washing, placing at 70 ℃ for drying for 10 hours, and obtaining a glucose-derived C nanotube after drying;
glucose derived C @ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring 1.97g of glucose-derived C nanotube and 215mL of ultrapure water for 80min, then performing ultrasonic dispersion for 200min, adding 13.46g of aluminum sulfate and 26.59g of urea, continuously stirring until the mixture is dissolved, heating to 90 ℃ for reaction for 15h, performing suction filtration, washing with ultrapure water, placing the mixture in a vacuum drying chamber at 75 ℃ for 36h, drying, heating to 115 ℃ from 18 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 155min, and cooling to obtain glucose-derived C @ porous Al (OH) 3 A coaxial nanotube;
the preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of hexadecyl trimethyl ammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 muL of ammonia water solution and 0.1g of ethyl orthosilicate, adding (3-mercaptopropyl) trimethoxysilane with the mass fraction of 6%, immersing the indium tin oxide coated substrate, standing for 28h at 55 ℃, washing, aging at 100 ℃, washing by using 0.15mol/L of hydrochloric acid ethanol solution, treating by using a hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire subjected to hydrophilic treatment;
s2: adopting a micro gravure roll coating process, and using a coater to make the prepared glucose-derived C @ porous Al (OH) 3 The coaxial nanotube coating slurry is coated on two sides of a 9-micron base film in a rolling mode step by step, the thickness of a single-side coating is 3 microns, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained after baking at 65 ℃ and rolling.
Example 2
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises the following steps:
s1: mixing dispersant, glucose derived C @ porous Al (OH) 3 Premixing the coaxial nanotube in ultrapure water for 60min at the rotation speed of 400 rpm; adding the thickening agent, and continuously stirring for 70min at the rotating speed of 500 rpm; adding the binder and continuously stirring for 80min at the rotating speed of 600 rpm; adding wetting agent and stirring for 80min at the rotating speed of 800 rpm; filtering to remove iron to obtain glucose derivative C @ porous Al (OH) 3 Coating slurry on the coaxial nanotube;
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises a base film and a formed coating layer coated on the surface of the base film; the coating layer comprises the following components in parts by mass: 0.6% of dispersant, 20% of glucose-derived C @ porous Al (OH) 3 The coaxial nano-tube comprises a coaxial nano-tube, 0.8% of thickening agent, 1% of binder, 0.3% of wetting agent and the balance of deionized water;
the base film is a polyethylene diaphragm; the dispersant is hydrolyzed polymaleic anhydride, the thickening agent is sodium carboxymethylcellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotube comprises the following steps:
adding 92mg of hydrophilically treated silicon dioxide nanowires into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing magnetic stirring for 45min, then performing ultrasonic dispersion for 6.5h, transferring to a stainless steel autoclave with a PTFE liner, heating at 98 ℃ for 5.5h, naturally cooling to 20 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 75 ℃ for 22h, and obtaining the carbon-coated silicon dioxide nanowire coaxial composite material with the vacuum degree of 0.08 Mpa; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, keeping for 5.5h, then filtering, washing, drying at 75 ℃ for 11h, and drying to obtain a glucose-derived C nanotube;
glucose derived C @ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring 1.97g of glucose-derived C nanotube and 215mL of ultrapure water for 85min, then performing ultrasonic dispersion for 195min, adding 13.46g of aluminum sulfate and 26.59g of urea, continuously stirring until the mixture is dissolved, heating to 90-95 ℃ for reaction for 12-15h, performing suction filtration, washing with ultrapure water, placing the mixture in a vacuum at 78 ℃ for 34h, drying, raising the temperature from 20 ℃ to 118 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 152min, and cooling to obtain glucose-derived C @ porous Al (OH) 3 A coaxial nanotube;
the preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of hexadecyl trimethyl ammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 muL of ammonia water solution and 0.1g of ethyl orthosilicate, adding (3-mercaptopropyl) trimethoxysilane with the mass fraction of 6%, immersing the indium tin oxide coated substrate, standing for 28h at 56 ℃, washing, aging at 100 ℃, washing by using 0.15mol/L of hydrochloric acid ethanol solution, treating by using a hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire subjected to hydrophilic treatment;
s2: adopting a micro gravure roll coating process, and using a coater to make the prepared glucose-derived C @ porous Al (OH) 3 The coaxial nanotube coating slurry is coated on two sides of a 9-micron base film in a rolling mode step by step, the thickness of a single-side coating is 3 microns, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained after baking at 68 ℃ and rolling.
Example 3
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises the following steps:
s1: mixing dispersant, glucose derived C @ porous Al (OH) 3 Premixing the coaxial nanotube in ultrapure water for 90min at the rotation speed of 100 rpm; adding thickener, stirring for 90min at 350rpm; adding the binder and continuously stirring for 120min at the rotating speed of 350 rpm; adding a wetting agent and stirring for 90min at the rotating speed of 400 rpm; filtering to remove iron to obtain glucose derivative C @ porous Al (OH) 3 Coating slurry on the coaxial nanotube;
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises a base film and a formed coating layer coated on the surface of the base film; the coating layer comprises the following components in parts by mass: 0.8% of dispersant, 23% of glucose-derived C @ porous Al (OH) 3 The coaxial nano-tube comprises a coaxial nano-tube, 0.85% of thickening agent, 1.3% of binder, 0.4% of wetting agent and the balance of deionized water;
the base film is a polyethylene diaphragm; the dispersant is hydrolyzed polymaleic anhydride, the thickening agent is sodium carboxymethylcellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotube comprises the following steps:
adding 92mg of hydrophilically treated silicon dioxide nanowires into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing magnetic stirring for 50min, then performing ultrasonic dispersion for 6h, transferring to a stainless steel autoclave with a PTFE liner, heating at 100 ℃ for 5h, naturally cooling to 25 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 80 ℃ for 20h, and keeping the vacuum degree at 0.08Mpa to obtain the carbon-coated silicon dioxide nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, keeping for 6 hours, then filtering, washing, placing at 80 ℃, drying for 10 hours, and obtaining a glucose-derived C nanotube after drying;
glucose derived C @ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring 1.97g of glucose-derived C nanotube and 215mL of ultrapure water for 90min, then performing ultrasonic dispersion for 200min, adding 13.46g of aluminum sulfate and 26.59g of urea, continuously stirring until the mixture is dissolved, heating to 95 ℃ for reaction for 12h, performing suction filtration, washing with ultrapure water, placing the mixture in a vacuum drying chamber at 80 ℃ for 32h, drying, heating to 120 ℃ from 25 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 155min, and cooling to obtain glucose-derived C @ porous Al (OH) 3 A coaxial nanotube;
the preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of hexadecyl trimethyl ammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 muL of ammonia water solution and 0.1g of ethyl orthosilicate, adding (3-mercaptopropyl) trimethoxysilane with the mass fraction of 6%, immersing the indium tin oxide coated substrate, standing for 28h at 58 ℃, washing, aging at 100 ℃, washing by using 0.15mol/L of hydrochloric acid ethanol solution, treating by using a hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire subjected to hydrophilic treatment;
s2: adopting a micro gravure roll coating process, and using a coater to make the prepared glucose-derived C @ porous Al (OH) 3 The coaxial nanotube coating slurry is coated on two sides of a 9-micron base film in a rolling way step by step, the thickness of a single-side coating is 3 microns, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained after baking at 70 ℃ and rolling.
Example 4
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises the following steps:
s1: mixing dispersant, glucose derived C @ porous Al (OH) 3 Premixing the coaxial nanotube in ultrapure water for 10min at the rotation speed of 600 rpm; adding the thickening agent and continuing stirring for 10min at the rotating speed of 900 rpm; adding the binder and continuously stirring for 40min at the rotating speed of 700 rpm; adding wetting agent and stirring for 30min at the rotation speed of 900 rpm; filtering to remove iron to obtain glucose derivative C @ porous Al (OH) 3 Coating slurry on the coaxial nanotube;
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises a base film and a formed coating layer coated on the surface of the base film; the coating layer comprises the following components in parts by mass: 0.35% of dispersant, 9% of glucose-derived C @ porous Al (OH) 3 The coaxial nano-tube comprises a coaxial nano-tube, 0.2% of thickening agent, 0.6% of binding agent, 0.1% of wetting agent and the balance of deionized water;
the base film is a polyethylene diaphragm; the dispersant is hydrolyzed polymaleic anhydride, the thickening agent is sodium carboxymethylcellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotube comprises the following steps:
adding 92mg of hydrophilically treated silicon dioxide nanowires into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing magnetic stirring for 40min, then performing ultrasonic dispersion for 7h, transferring to a stainless steel high-pressure kettle with a PTFE liner, heating at 95 ℃ for 6h, naturally cooling to 18 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 70 ℃ for 24h, and keeping the vacuum degree at 0.08MPa to obtain the carbon-coated silicon dioxide nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, keeping for 5 hours, then filtering, washing, placing at 70 ℃ for drying for 10 hours, and obtaining a glucose-derived C nanotube after drying;
glucose derived C @ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring 1.97g of glucose-derived C nanotube and 215mL of ultrapure water for 80min, then performing ultrasonic dispersion for 200min, adding 13.46g of aluminum sulfate and 26.59g of urea, continuously stirring until the mixture is dissolved, heating to 90 ℃ for reaction for 15h, performing suction filtration, washing with ultrapure water, placing the mixture in a vacuum drying chamber at 75 ℃ for 36h, drying, heating to 115 ℃ from 18 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 155min, and cooling to obtain glucose-derived C @ porous Al (OH) 3 A coaxial nanotube;
the preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of hexadecyl trimethyl ammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 muL of ammonia water solution and 0.1g of ethyl orthosilicate, adding (3-mercaptopropyl) trimethoxysilane with the mass fraction of 6%, immersing the indium tin oxide coated substrate, standing for 28h at 55 ℃, washing, aging at 100 ℃, washing by using 0.15mol/L of hydrochloric acid ethanol solution, treating by using a hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire subjected to hydrophilic treatment;
the adhesive is modified COPNA resin, and the preparation method comprises the following steps:
(1) reacting 0.2mol of itaconic acid, 320mL of deionized water and 0.2mol of 1, 6-hexamethylene diamine at 55 ℃ for 30min under a nitrogen environment to obtain itaconic acid mixed liquor;
(2) mixing 80mL of deionized water, 36mL of absolute ethyl alcohol, 9mL of acetonitrile, 9mL of triethylamine and 5mL of tetraethylammonium hydroxide in a constant-temperature water bath at 52 ℃; adding 221mL of 3-aminopropyltriethoxysilane, refluxing for 22h at 52 ℃, carrying out reduced pressure distillation and concentration, adding the concentrated solution into petroleum ether, standing, carrying out reduced pressure suction filtration, washing for 2 times by using acetone, and carrying out vacuum drying to obtain octaaminopropyl cage-type silsesquioxane;
(3) mixing and stirring mixed solution of 0.24mol of DOPO and 0.2mol of itaconic acid, and heating to 85 ℃ for reaction for 2.5 h; carrying out suction filtration while the flame retardant is hot, cooling to 18 ℃, transferring to an ice water bath for cooling for 9h, and carrying out suction filtration to obtain a water-soluble flame retardant; adding 2g of octaaminopropyl cage type silsesquioxane and 10g of COPNA resin, and ultrasonically stirring for 30min to obtain modified COPNA resin;
the preparation of the COPNA resin comprises the following steps: under the nitrogen environment, adding 2g of bamboo tar and 2g of terephthalyl alcohol, adding 5.4% by mass of p-toluenesulfonic acid, reacting at 130 ℃ until a filament winding phenomenon occurs, stopping heating, discharging and cooling to obtain COPNA resin;
s2: adopting a micro gravure roll coating process, and using a coater to make the prepared glucose-derived C @ porous Al (OH) 3 The coaxial nanotube coating slurry is coated on two sides of a 9-micron base film in a rolling mode step by step, the thickness of a single-side coating is 3 microns, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained after baking at 65 ℃ and rolling.
Example 5
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises the following steps:
s1: mixing dispersant, glucose derived C @ porous Al (OH) 3 Premixing the coaxial nanotube in ultrapure water for 60min at the rotation speed of 400 rpm; adding the thickening agent, and continuously stirring for 70min at the rotating speed of 500 rpm; adding the binder and continuously stirring for 80min at the rotating speed of 600 rpm; adding wetting agent and stirring for 80min at the rotating speed of 800 rpm; filtering to remove iron to obtain glucose derivative C @ porous Al (OH) 3 Coating slurry on the coaxial nanotube;
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises a base film and a formed coating layer coated on the surface of the base film; the coating layer comprises the following components in parts by mass: 0.6% of dispersant, 20% of glucose-derived C @ porous Al (OH) 3 The coaxial nano-tube comprises a coaxial nano-tube, 0.8% of thickening agent, 1% of binder, 0.3% of wetting agent and the balance of deionized water;
the base film is a polyethylene diaphragm; the dispersant is hydrolyzed polymaleic anhydride, the thickening agent is sodium carboxymethylcellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotube comprises the following steps:
adding 92mg of hydrophilically treated silicon dioxide nanowires into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing magnetic stirring for 45min, then performing ultrasonic dispersion for 6.5h, transferring to a stainless steel autoclave with a PTFE liner, heating at 98 ℃ for 5.5h, naturally cooling to 20 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 75 ℃ for 22h, and obtaining the carbon-coated silicon dioxide nanowire coaxial composite material with the vacuum degree of 0.08 Mpa; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, keeping for 5.5h, then filtering, washing, drying at 75 ℃ for 11h, and drying to obtain a glucose-derived C nanotube;
glucose derived C @ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetically stirring 1.97g of glucose-derived C nanotube and 215mL of ultrapure water for 85min, then performing ultrasonic dispersion for 195min, adding 13.46g of aluminum sulfate and 26.59g of urea, continuously stirring until the mixture is dissolved, heating to 90-95 ℃ for reaction for 12-15h, performing suction filtration, washing with ultrapure water, placing the mixture in a vacuum at 78 ℃ for 34h, drying, raising the temperature from 20 ℃ to 118 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 152min, and cooling to obtain glucose-derived C @ porous Al (OH) 3 A coaxial nanotube;
the preparation of the silicon dioxide nanowire after hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of hexadecyl trimethyl ammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 muL of ammonia water solution and 0.1g of ethyl orthosilicate, adding (3-mercaptopropyl) trimethoxysilane with the mass fraction of 6%, immersing the indium tin oxide coated substrate, standing for 28h at 56 ℃, washing, aging at 100 ℃, washing by using 0.15mol/L of hydrochloric acid ethanol solution, treating by using a hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire subjected to hydrophilic treatment;
the adhesive is modified COPNA resin, and the preparation method comprises the following steps:
(1) reacting 0.2mol of itaconic acid, 320mL of deionized water and 0.2mol of 1, 6-hexamethylene diamine at 58 ℃ for 25min under a nitrogen environment to obtain itaconic acid mixed liquor;
(2) mixing 80mL of deionized water, 36mL of absolute ethyl alcohol, 9mL of acetonitrile, 9mL of triethylamine and 5mL of tetraethylammonium hydroxide in a constant-temperature water bath at 54 ℃; adding 221mL of 3-aminopropyltriethoxysilane, refluxing for 21h at 54 ℃, carrying out reduced pressure distillation and concentration, adding the concentrated solution into petroleum ether, standing, carrying out reduced pressure suction filtration, washing for 4 times with acetone, and carrying out vacuum drying to obtain octaaminopropyl cage-type silsesquioxane;
(3) mixing and stirring mixed solution of 0.24mol of DOPO and 0.2mol of itaconic acid, and heating to 87 ℃ for reaction for 2.6 h; carrying out suction filtration while the flame retardant is hot, cooling to 22 ℃, transferring to an ice water bath for cooling for 10h, and carrying out suction filtration to obtain a water-soluble flame retardant; adding 2g of octaaminopropyl cage type silsesquioxane and 10g of COPNA resin, and ultrasonically stirring for 50min to obtain modified COPNA resin;
the preparation of the COPNA resin comprises the following steps: under the nitrogen environment, adding 2g of bamboo tar and 2g of terephthalyl alcohol, adding 6.2% by mass of p-toluenesulfonic acid, reacting at 140 ℃ until a filament winding phenomenon occurs, stopping heating, discharging and cooling to obtain COPNA resin;
s2: adopting a micro gravure roll coating process, and using a coater to make the prepared glucose-derived C @ porous Al (OH) 3 The coaxial nanotube coating slurry is coated on two sides of a 9-micron base film in a step-by-step roll manner, the thickness of a single-side coating is 3 microns, the coating is baked at 68 ℃ and then wound, and the lithium ion based on the aluminum hydroxide coaxial nanotube is obtainedAnd a sub-battery separator.
Example 6
The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises the following steps:
s1: mixing dispersant, glucose derived C @ porous Al (OH) 3 Premixing the coaxial nanotube in ultrapure water for 90min at the rotation speed of 100 rpm; adding the thickening agent and continuing stirring for 90min at the rotating speed of 350 rpm; adding the binder and continuously stirring for 120min at the rotating speed of 350 rpm; adding a wetting agent and stirring for 90min at the rotating speed of 400 rpm; filtering to remove iron to obtain glucose derivative C @ porous Al (OH) 3 Coating slurry on the coaxial nanotube;
the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube comprises a base film and a formed coating layer coated on the surface of the base film; the coating layer comprises the following components in parts by mass: 0.8% of dispersant, 23% of glucose-derived C @ porous Al (OH) 3 The coaxial nano-tube comprises a coaxial nano-tube, 0.85% of thickening agent, 1.3% of binder, 0.4% of wetting agent and the balance of deionized water;
the base film is a polyethylene diaphragm; the dispersant is hydrolyzed polymaleic anhydride, the thickening agent is sodium carboxymethylcellulose, the binder is COPNA resin, and the wetting agent is silanol nonionic surfactant;
the preparation of the glucose-derived C nanotube comprises the following steps:
adding 92mg of hydrophilically treated silicon dioxide nanowires into a glucose solution containing 101.4mmol of glucose under the condition of continuous stirring, continuing magnetic stirring for 50min, then performing ultrasonic dispersion for 6h, transferring to a stainless steel autoclave with a PTFE liner, heating at 100 ℃ for 5h, naturally cooling to 25 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 80 ℃ for 20h, and keeping the vacuum degree at 0.08MPa to obtain the carbon-coated silicon dioxide nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, keeping for 6 hours, then filtering, washing, placing at 80 ℃, drying for 10 hours, and obtaining a glucose-derived C nanotube after drying;
glucose derived C @ porous Al (OH) 3 Manufacture of co-axial nanotubesThe preparation method comprises the following steps: magnetically stirring 1.97g of glucose-derived C nanotube and 215mL of ultrapure water for 90min, then performing ultrasonic dispersion for 200min, adding 13.46g of aluminum sulfate and 26.59g of urea, continuously stirring until the mixture is dissolved, heating to 95 ℃ for reaction for 12h, performing suction filtration, washing with ultrapure water, placing the mixture in a vacuum drying chamber at 80 ℃ for 32h, drying, heating to 120 ℃ from 25 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 155min, and cooling to obtain glucose-derived C @ porous Al (OH) 3 A coaxial nanotube;
the preparation of the silicon dioxide nanowire subjected to hydrophilic treatment comprises the following steps: mixing and stirring 0.16g of hexadecyl trimethyl ammonium bromide, 30mL of absolute ethyl alcohol and 70mL of deionized water, adding 9 muL of ammonia water solution and 0.1g of ethyl orthosilicate, adding (3-mercaptopropyl) trimethoxysilane with the mass fraction of 6%, immersing the indium tin oxide coated substrate, standing for 28h at 58 ℃, washing, aging at 100 ℃, washing by using 0.15mol/L of hydrochloric acid ethanol solution, treating by using a hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire subjected to hydrophilic treatment;
the adhesive is modified COPNA resin, and the preparation method comprises the following steps:
(1) reacting 0.2mol of itaconic acid, 320mL of deionized water and 0.2mol of 1, 6-hexamethylene diamine at 60 ℃ for 20min under a nitrogen environment to obtain itaconic acid mixed solution;
(2) mixing 80mL of deionized water, 36mL of absolute ethyl alcohol, 9mL of acetonitrile, 9mL of triethylamine and 5mL of tetraethylammonium hydroxide in a constant-temperature water bath at 56 ℃; adding 221mL of 3-aminopropyltriethoxysilane, refluxing for 20h at 56 ℃, carrying out reduced pressure distillation and concentration, adding the concentrated solution into petroleum ether, standing, carrying out reduced pressure suction filtration, washing for 5 times with acetone, and carrying out vacuum drying to obtain octaaminopropyl cage-type silsesquioxane;
(3) mixing and stirring mixed solution of 0.24mol of DOPO and 0.2mol of itaconic acid, and heating to 88 ℃ for reaction for 2.5 h; carrying out suction filtration while the flame retardant is hot, cooling to 25 ℃, transferring to an ice water bath for cooling for 9 hours, and carrying out suction filtration to obtain a water-soluble flame retardant; adding 2g of octaaminopropyl cage type silsesquioxane and 10g of COPNA resin, and ultrasonically stirring for 60min to obtain modified COPNA resin;
the preparation of the COPNA resin comprises the following steps: under the nitrogen environment, adding 2g of bamboo tar and 2g of terephthalyl alcohol, adding 6.8% by mass of p-toluenesulfonic acid, reacting at 150 ℃ until a filament winding phenomenon occurs, stopping heating, discharging and cooling to obtain COPNA resin;
s2: adopting a micro gravure roll coating process, and using a coater to make the prepared glucose-derived C @ porous Al (OH) 3 The coaxial nanotube coating slurry is coated on two sides of a 9-micron base film in a rolling way step by step, the thickness of a single-side coating is 3 microns, and the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is obtained after baking at 70 ℃ and rolling.
Comparative example 1
The same polyethylene-based film as in examples 1-6, the other procedures were normal.
Comparative example 2
Example 3 as a control with porous Al (OH) 3 Nanotube substituted glucose derivatized C @ porous Al (OH) 3 And (4) the coaxial nanotube and other procedures are normal.
Comparative example 3
Replacement of glucose-derived C with glucose-derived C @ porous Al (OH) by glucose-derived C as control in example 3 3 And (4) the coaxial nanotube and other procedures are normal.
Comparative example 4
The procedure was normal except that the hydrophilic silica was replaced with silica in example 3 as a control.
Comparative example 5
Example 6 was used as a control, and no octaaminopropyl cage-type silsesquioxane was added, and the other steps were normal.
Comparative example 6
Control of example 6 without addition of glucose-derived C @ porous Al (OH) 3 And (4) the coaxial nanotube and other procedures are normal.
And (4) performance testing: the performance of the diaphragms prepared in the examples 1-6 and the comparative examples 1-6 is tested, and the thickness, the air permeability value, the needling strength, the ionic conductivity and the thermal shrinkage are tested by referring to GB/T36363-2018;
and (3) oxygen index determination: reference IOS 4589-2: putting oxygen-nitrogen mixed gas in a transparent combustion cylinder, wherein the temperature of the mixed gas is 24 ℃, and putting a diaphragm into the transparent combustion cylinder; when the top surface is ignited, the time for the flame to contact the top surface is 25s, the flame is moved away every 5s, whether the diaphragm burns or not is observed, and the minimum oxygen concentration just needed for maintaining the combustion is the oxygen index;
and (3) measuring the liquid absorption rate: a sample of 50mm × 50mm was cut out from the obtained separator, taken out after the sample was placed in a desiccator for 24 hours, and weighed to record as M (to the accuracy of 0.01 g); the sample was immersed in a beaker containing the electrolyte, held for 10min and then gently held at one corner with a plastic forceps, removed and weighed immediately, recorded as M1 (accurate to 0.01 g); the liquid absorption rate is (M1-M)/M;
and (3) measuring the liquid retention rate: a sample of 50mm × 50mm was cut out from the obtained separator, taken out after the sample was placed in a desiccator for 24 hours, and weighed to record as M (to the accuracy of 0.01 g); immersing the sample in a beaker filled with electrolyte, keeping for 10min, slightly clamping one corner of the sample by using a plastic forceps, taking out and suspending for 3min until part of the electrolyte is naturally dripped off, and weighing, wherein the record is M2 (accurate to 0.01 g); the liquid retention rate is (M2-M)/M; namely, the results are shown in Table 1;
Figure BDA0003654057010000161
Figure BDA0003654057010000171
TABLE 1
By comparing example 3 with comparative examples 1, 2 and 3, in which glucose-derived C @ porous Al (OH) 3 The introduction of the coaxial nanotube greatly improves the mechanical strength and the heat shrinkage performance of the diaphragm; the introduction of the glucose-derived C nanotube not only increases the mechanical property of the diaphragm, but also enhances the conductivity of the diaphragm, thereby being beneficial to enhancing the rapid transmission of lithium ions; in addition, glucose-derived C @ porous Al (OH) 3 The coaxial nanotube has hollow structure and is coated with Al (OH) 3 Exhibits a porous structure, which further improves the lithium ion conductivityThe specific surface area of the material is greatly increased, so that the liquid absorption and retention capacity of the diaphragm is greatly enhanced;
comparing the example 3 with the comparative example 4, it can be known that sulfonic acid groups are loaded on the vertical mesoporous silica pore channels in situ by a co-condensation method without changing the pore channel structure, the selective permeability of the nanochannel is mainly caused by a size effect and a charge effect, and when the nanochannel is completely occupied by an electric double layer, the selective permeability is optimal;
comparing the embodiment 6 with the comparative example 5, it can be seen that bamboo is a renewable raw material, bamboo tar is selected as a raw material, terephthalyl alcohol is a cross-linking agent, and p-toluenesulfonic acid is used as a catalyst to synthesize COPNA resin, under an acidic environment, terephthalyl alcohol can generate activated carbonium ions, the activated carbonium ions can generate electrophilic substitution reaction with benzene rings in a large amount of phenols and derivatives thereof in the bamboo tar, alcoholic hydroxyl groups in the generated product are dehydrated under the action of acid to generate carbonium ions again, the carbonium ions can react with aromatic hydrocarbon to generate cross-linked macromolecules, as the cross-linking degree is deepened, the system viscosity is increased, water vapor is not released any more, and the cross-linked macromolecules are in a net structure to obtain COPNA resin, the softening point and the heat resistance of the COPNA resin obtained by controlling the addition amount of the p-toluenesulfonic acid are improved, the pretreatment process is simple, the cost is low, and the emission of wastes is reduced; effectively improves the complexity of a macromolecular cross-linked network in the diaphragm, ensures that the COPNA resin and the carbon material have excellent affinity, and effectively improves the glucose-derived C @ porous Al (OH) 3 The affinity of the coaxial nanotube and the diaphragm effectively prolongs the service life of the diaphragm;
the modification treatment is carried out on the binding agent, so as to effectively improve the glucose-derived C @ porous Al (OH) 3 The binding force among the coaxial nanotube, the thickening agent, the binder and the wetting agent effectively improves the heat shrinkage, the flame retardance and the ionic conductivity of the diaphragm;
by comparing example 6 with example 3, comparative example 5 and comparative example 6, it can be seen that by introducing DOPO and its derivatives, octaaminopropyl polyhedral oligomeric silsesquioxane, glucose-derived C @ porous Al (C) ((C))OH) 3 The coaxial nanotube is compounded with a plurality of flame retardant elements to realize synergistic flame retardant; the three components are cooperatively used for flame retardation of the diaphragm, and the DOPO and the derivatives thereof, Al (OH) are enhanced by using silicon dioxide particles generated by decomposition of the cage type silsesquioxane 3 The quality and strength of the carbon layer formed by catalysis can form a stable ceramic layer compounded by silicon dioxide and aluminum oxide, so that the stability of the carbon layer is enhanced, and the contact between external heat flow and oxygen and internal materials and combustible gas is blocked, so that the combustion reaction is prevented, and the flame retardant property of the diaphragm is synergistically and greatly improved; and the introduction of a large number of active sites is beneficial to improving the ion exchange capacity of the diaphragm and effectively improving the safety of the diaphragm.
In conclusion, the diaphragm prepared by the method has good application prospect in the field of diaphragms.
The above description is only an example of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (10)

1. The lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is characterized by comprising a base film and a coating layer formed by coating the surface of the base film; the coating layer comprises the following components in parts by mass: 0.35% -0.8% of a dispersant, 9% -23% of glucose-derived C @ porous Al (OH) 3 The coaxial nano-tube comprises a coaxial nano-tube, 0.2-0.85% of thickening agent, 0.6-1.3% of binder, 0.1-0.4% of wetting agent and the balance of deionized water.
2. The aluminum hydroxide coaxial nanotube based lithium ion battery separator according to claim 1, wherein the base membrane is a polyolefin separator; the dispersant is a hydrolyzed polymaleic anhydride dispersant, the thickener is a sodium carboxymethylcellulose dispersant, the binder is a COPNA resin binder, and the wetting agent is a silanol nonionic surfactant.
3. The aluminum hydroxide coaxial nanotube-based lithium ion battery separator according to claim 1, wherein the preparation of the glucose-derived C nanotubes comprises the steps of:
1) mixing and stirring hexadecyl trimethyl ammonium bromide, absolute ethyl alcohol and deionized water, adding an ammonia water solution and ethyl orthosilicate, adding (3-mercaptopropyl) trimethoxysilane, immersing the indium tin oxide coated substrate, standing for 28 hours at 55-58 ℃, washing, aging at 100 ℃, washing by using a 0.15mol/L hydrochloric acid ethanol solution, treating by using a hydrogen peroxide solution to obtain sulfonated silicon dioxide deposited on the indium tin oxide coated substrate, taking down, drying and grinding to obtain a silicon dioxide nanowire subjected to hydrophilic treatment;
2) adding the silicon dioxide nanowires after hydrophilic treatment into a glucose solution under the condition of continuous stirring, continuing magnetic stirring for 40-50min, then performing ultrasonic dispersion for 6-7h, transferring into a stainless steel autoclave with a PTFE liner, heating at 95-100 ℃ for 5-6h, naturally cooling to 18-25 ℃, filtering, washing with absolute ethyl alcohol and deionized water, drying at 70-80 ℃ for 20-24h, and keeping the vacuum degree at 0.08Mpa to obtain the carbon-coated silicon dioxide nanowire coaxial composite material; adding the carbon-coated silicon dioxide nanowire coaxial composite material into 5.0mol/L sodium hydroxide solution, keeping for 5-6h, then filtering, washing, placing at 70-80 ℃, drying for 10-12h, and obtaining the glucose-derived C nanotube after drying.
4. The aluminum hydroxide coaxial nanotube-based lithium ion battery separator as claimed in claim 3, wherein the preparation of the hydrophilic-treated silica nanowires comprises the steps of: the mass molar ratio of the silicon dioxide nanowires after the hydrophilic treatment to the glucose in the glucose solution is 92mg:101.4 mmol.
5. The aluminum hydroxide coaxial nanotube-based lithium ion battery separator as claimed in claim 1, wherein glucose-derived C @ porous Al (OH) 3 The preparation of the coaxial nanotube comprises the following steps: magnetizing glucose-derived C nanotube and ultrapure waterStirring for 80-90min, then carrying out ultrasonic dispersion for 190-200min, adding aluminum sulfate and urea, continuously stirring until the aluminum sulfate and the urea are dissolved, heating to 90-95 ℃ for reaction for 12-15h, carrying out suction filtration, washing with ultrapure water, placing in vacuum drying at 75-80 ℃ for 32-36h, heating from 18-25 ℃ to 115-120 ℃ at the heating rate of 2 ℃/min after drying, keeping the temperature constant for 150-155min, and cooling to obtain glucose derivative C @ porous Al (OH) 3 A coaxial nanotube.
6. The aluminum hydroxide coaxial nanotube-based lithium ion battery separator according to claim 5, wherein the mass ratio of the glucose-derived C nanotubes to aluminum sulfate to urea is 1.97:13.46: 26.59.
7. The preparation method of the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube is characterized by comprising the following steps:
s1: mixing dispersant, glucose derived C @ porous Al (OH) 3 Premixing the coaxial nanotube in ultrapure water for 10-90min at the rotation speed of 100-600 rpm; adding the thickening agent and continuing stirring for 10-90min at the rotation speed of 350-900 rpm; adding the binder and continuously stirring for 40-120min at the rotating speed of 350-700 rpm; adding a wetting agent and stirring for 30-90min at the rotation speed of 400-900 rpm; filtering to remove iron to obtain glucose derivative C @ porous Al (OH) 3 Coating slurry on the coaxial nanotube;
s2: adopting a micro gravure roller coating process to lead the prepared glucose derived C @ porous Al (OH) 3 And (3) rolling the coaxial nanotube coating slurry on two sides of the base film in a roller manner step by step, baking at 65-70 ℃ and then rolling to obtain the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube.
8. The method for preparing the lithium ion battery separator based on the aluminum hydroxide coaxial nanotube according to claim 7, wherein the binder is modified COPNA resin, and the preparation method comprises the following steps:
(1) reacting itaconic acid, deionized water and 1, 6-hexamethylene diamine at 55-60 ℃ for 20-30min under a nitrogen environment to obtain itaconic acid mixed liquor;
(2) mixing deionized water, absolute ethyl alcohol, acetonitrile, triethylamine and tetraethyl ammonium hydroxide in a constant-temperature water bath at 52-56 ℃; adding 3-aminopropyltriethoxysilane, refluxing at 52-56 deg.C for 20-22h, vacuum distilling for concentrating, adding concentrated solution into petroleum ether, standing, vacuum filtering, washing with acetone for 2-5 times, and vacuum drying to obtain octaaminopropyl cage-type silsesquioxane;
(3) mixing and stirring the mixed solution of DOPO and itaconic acid, heating to 85-88 ℃ and reacting for 2.5-3 h; carrying out suction filtration while the mixture is hot, cooling to 18-25 ℃, transferring to an ice water bath for cooling for 9-11h, and carrying out suction filtration to obtain a water-soluble flame retardant; adding octaaminopropyl polyhedral oligomeric silsesquioxane and COPNA resin, and ultrasonically stirring for 30-60min to obtain the modified COPNA resin.
9. The method for preparing the lithium ion battery diaphragm based on the aluminum hydroxide coaxial nanotube according to claim 8, wherein the molar volume ratio of the itaconic acid to the 1, 6-hexanediamine to the deionized water is 0.2mol:0.2mol:320 mL; the volume ratio of the deionized water to the absolute ethyl alcohol to the acetonitrile to the triethylamine to the tetraethylammonium hydroxide is 80mL to 36mL to 9mL to 5 mL; the molar ratio of DOPO to itaconic acid was 1.2: 1.
10. The method for preparing the lithium ion battery separator based on the aluminum hydroxide coaxial nanotube according to claim 8, wherein the preparation of the COPNA resin comprises the following steps: weighing bamboo tar and terephthalyl alcohol according to the mass ratio of 1:1 in a nitrogen environment, adding 5.4-6.8% of p-toluenesulfonic acid in mass fraction, reacting at 130-150 ℃ until a filament winding phenomenon occurs, stopping heating, discharging and cooling to obtain the COPNA resin.
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CN111403661A (en) * 2020-03-23 2020-07-10 南京航空航天大学 Composite diaphragm for power lithium ion battery and preparation method thereof
CN113904060A (en) * 2021-09-30 2022-01-07 江苏厚生新能源科技有限公司 Lithium ion battery coating diaphragm and preparation method thereof

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CN106519742A (en) * 2016-11-01 2017-03-22 旭成（福建）科技股份有限公司 Anti-flaming ceramic modified size and lithium ion battery membrane coated with same
CN111403661A (en) * 2020-03-23 2020-07-10 南京航空航天大学 Composite diaphragm for power lithium ion battery and preparation method thereof
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