CN117293383A - Flame-retardant solid electrolyte adopting microcapsule technology and preparation method thereof - Google Patents

Flame-retardant solid electrolyte adopting microcapsule technology and preparation method thereof Download PDF

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CN117293383A
CN117293383A CN202311241163.4A CN202311241163A CN117293383A CN 117293383 A CN117293383 A CN 117293383A CN 202311241163 A CN202311241163 A CN 202311241163A CN 117293383 A CN117293383 A CN 117293383A
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solution
heating
hcp
hexachlorocyclotriphosphazene
preparation
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李彩霞
张超
马肖飞
王磊
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Qingdao University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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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Abstract

A flame-retardant solid electrolyte adopting microcapsule technology and a preparation method thereof belong to the technical field of organic composite materials. The flame-retardant solid electrolyte provided by the invention is prepared by firstly preparing a mixed solution containing hexachlorocyclotriphosphazene, urea and formaldehyde, then emulsifying the hexachlorocyclotriphosphazene by using a composite emulsifier, and then polymerizing under an acidic condition to generate the hexachlorocyclotriphosphazene@urea resin microcapsule. After that, the hexachlorocyclotriphosphazene@urea resin microcapsule is doped into a polyacrylonitrile mixed solution dissolved by NMP to obtain the flame-retardant solid electrolyte. The electrolyte provided by the invention has excellent flame retardant property and conductivity.

Description

Flame-retardant solid electrolyte adopting microcapsule technology and preparation method thereof
Technical Field
The invention belongs to the technical field of organic composite materials, and particularly relates to a flame-retardant electrolyte adopting a microcapsule technology and a preparation method thereof.
Background
Currently, in order to solve the deficiency of liquid electrolytes, researchers have proposed a practical alternative strategy, namely to use solid electrolytes to improve safety and high voltage stability. According to the method, lithium salt is doped into an organic polymer solution, a solid polymer electrolyte is prepared by using a thermal initiation or photoinitiation in-situ polymerization method and the like, and then the solid polymer electrolyte is combined with lithium metal to form the lithium battery. Compared with liquid electrolyte, solid electrolyte has the advantages that leakage and volatilization can not occur when the battery shell is damaged, and the shape of the material can not be changed at room temperature. Many solid electrolytes have been developed, including, for example, polyvinyl alcohol, polyethylene oxide, polyvinylidene fluoride, polyurethane, polyethylene glycol diacrylate, polymethyl methacrylate, and derivatives thereof.
As a novel organic polymer matrix material, polyacrylonitrile has excellent ion transmission property, strong mechanical strength, excellent chemical stability and good weather resistance. The polyacrylonitrile keeps stable physicochemical properties after being mixed with various chemical reagents, in particular to an acidic solution, an alkaline solution, an oxidant and a common organic reagent, and can still keep 77 percent of the strength of the original material after being placed outdoors for half a year. But also good compatibility with lithium salts and inorganic particles is of increasing interest. However, there are still two challenges that prevent the practical use of solid state electrolytes in lithium batteries: (1) For the solid electrolyte mentioned in published literature, the defects of high structural crosslinking degree, insufficient flow and still combustibility exist; (2) Typical solid electrolyte has an ionic conductivity of 10 at room temperature -7 ～10 -6 S cm -1 It is compatible with commercial liquid electrolytes (> 10) -3 S cm -1 ) Much lower. Therefore, how to improve the flame retardant effect and the electrical conductivity of the solid electrolyte is a problem that is urgently needed to be solved at present.
Disclosure of Invention
The invention provides a flame-retardant solid electrolyte adopting a microcapsule technology and a preparation method thereof, so as to prepare the solid electrolyte with high-efficiency flame retardance and conductivity.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in a first aspect, the present invention provides a method for preparing a flame retardant solid electrolyte using microcapsule technology, the method comprising the steps of:
(1) Preparing a suspension containing hexachlorocyclotriphosphazene, formaldehyde and urea;
(2) During the heating process, the hexachlorocyclotriphosphazene is emulsified by using a composite emulsifier, and then the hexachlorocyclotriphosphazene@urea resin microcapsule is obtained by using a curing agent to polymerize under an acidic condition;
(3) And adding the hexachlorocyclotriphosphazene@urea resin microcapsule into a polyacrylonitrile mixed solution dissolved by NMP, uniformly stirring, pouring into a mold, and heating to evaporate the solvent to obtain the organic solid electrolyte.
Preferably, the specific procedure of step (1) for each 2.5g of hexachlorocyclotriphosphazene is as follows:
3g of urea and 10.4ml of formaldehyde are dissolved in 20ml of water, and 0.5mol/l of sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9, so as to obtain solution A;
heating the solution A in an oil bath at 65-85 ℃ for 1h, adding 60ml of water, cooling to room temperature, adding 2.5g of hexachlorocyclotriphosphazene, and uniformly stirring to obtain a suspension containing hexachlorocyclotriphosphazene;
preferably, the specific steps of the step (2) are as follows:
adding 300ul of composite emulsifier, heating at 50 ℃ for 10min, adding 10ml of 0.05g/ml ammonium chloride solution, and heating at 50 ℃ for 1h;
dropwise adding citric acid to adjust the PH=3-4 of the solution, increasing the temperature to 70 ℃, heating for 2 hours, and cooling for 24 hours at room temperature to obtain a solution B;
after suction filtration of the solution B, washing the solution B for three times by using deionized water and ethanol in sequence to obtain a white solid product;
after drying the white solid product by heating for 2 hours, hexachlorocyclotriphosphazene@urea resin microcapsules (HCP@UR) are obtained.
Preferably, the specific steps of the step (3) are as follows:
0.64g of polyacrylonitrile, 4g of bacterial cellulose with concentration of 0.4% and 0.2g of lithium bistrifluoromethylsulfonyl imide are mixed and dissolved in 10ml of NMP to obtain a precursor solution;
adding 0.16g of HCP@UR into the precursor solution, and stirring at room temperature until the mixture is completely uniform to obtain solution C;
pouring the solution C into a polytetrafluoroethylene template, and heating at 60-80 ℃ for 4-6h to obtain the flame-retardant solid electrolyte (PAN-HCP@UR).
Preferably, in said step (1), the concentration of formaldehyde is 8-14% w/v;
in the step (2), the composite emulsifier consists of OP-10 and JFC, and the ratio of the OP-10 to JFC in the composite emulsifier is 1:1.
In a second aspect, the invention provides a flame-retardant solid electrolyte adopting microcapsule technology, wherein the flame-retardant electrolyte is prepared by the preparation method of the flame-retardant solid electrolyte.
In a third aspect, the present invention provides a method for preparing a lithium battery using microcapsule technology, the method comprising the steps of:
(1) Lithium iron phosphate: carbon black: dispersing PVDF by using NMP according to the proportion of 8:1:1, uniformly grinding, then scraping and coating on an aluminum foil by using a scraper, and drying to obtain a lithium iron phosphate pole piece;
(2) And preparing the lithium battery by using a metal lithium sheet as a negative electrode, a lithium iron phosphate sheet as a positive electrode and a PAN-HCP@UR film as a solid electrolyte.
Preferably, the PAN-HCP@UR film is prepared by the preparation method of the flame-retardant solid electrolyte.
In a fourth aspect, the invention provides a lithium battery adopting microcapsule technology, which is characterized in that the lithium battery is prepared by the preparation method of the lithium battery.
The invention has the beneficial effects that:
according to the invention, the urea-formaldehyde resin is used for wrapping the flame retardant hexachlorocyclotriphosphazene, and the microcapsule with the urea-formaldehyde resin shell is doped into PAN, so that the solid electrolyte PAN-HCP@UR with excellent flame retardant effect is prepared. The microcapsule technology not only ensures that hexachlorocyclotriphosphazene exists in the solid electrolyte at room temperature stably and eliminates free radicals released by the combustion of polyacrylonitrile, thereby playing a role in flame retardance at a high temperature state and having remarkable effect.
And secondly, hexachlorocyclotriphosphazene serving as a flame retardant can absorb heat under the thermal runaway condition, the combustion reaction of combustible materials is controlled, urea resin can be coated on the surface of the flame retardant to prevent side reaction, and hydrogen bonds are formed between the urea resin and the functional groups of polyacrylonitrile to improve the mechanical properties of the polymer, inhibit the growth of lithium dendrites, and further improve the cycle performance of a lithium battery.
Drawings
FIG. 1 is a scanning electron microscope image of the microcapsule obtained in example 1;
FIG. 2 is a transmission electron microscopic image of the microcapsule obtained in example 1;
FIG. 3 is a scanning electron microscope image of the PAN-HCP@UF membrane obtained in example 1;
FIG. 4 is a thermogravimetric plot of PAN-HCP@UF obtained in example 1;
FIG. 5 is a graph showing the combustion test of the PAN-HCP@UF membrane obtained in example 1;
FIG. 6 is a micro-scale calorimeter spectrum of the PAN-HCP@UF membrane obtained in example 1;
fig. 7 is a Nyquist diagram of the PAN-hcp@uf battery obtained in example 1;
fig. 8 is a graph of cycle-efficiency & specific capacity at 0.5C for the PAN-hcp@uf battery obtained in example 1;
fig. 9 is a graph of cycle-efficiency & specific capacity at 1C for the PAN-hcp@uf battery obtained in example 1;
fig. 10 is a graph of cycle-specific capacity at different rates for the PAN-hcp@uf battery obtained in example 1;
FIG. 11 is a scanning electron microscope image of the microcapsule obtained in example 2;
FIG. 12 is a scanning electron microscope image of the microcapsule obtained in example 3;
FIG. 13 is a scanning electron microscope image of the microcapsule obtained in example 4;
FIG. 14 is a scanning electron microscope image of the PEO-HCP@UF membrane obtained in example 20;
fig. 15 is a graph of cycle-efficiency & specific capacity at 0.5C for the PEO-hcp@uf cell obtained in example 20.
Detailed Description
The technical features of the present invention will be described with reference to the following specific experimental schemes and drawings, but the present invention is not limited thereto. The test methods described in the examples below, unless otherwise specified, are all conventional; the apparatus and materials are commercially available unless otherwise specified.
Example 1
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 2.5g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuing heating at 50 ℃ for 10min, adding 10ml of 0.05g/ml of ammonium chloride solution, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 70 ℃, and cooling for 24h at room temperature;
3. filtering the solution, sequentially cleaning with deionized water and ethanol for three times to obtain a white solid product, and heating and drying for 2 hours to obtain a product hexachlorocyclotriphosphazene@urea resin microcapsule (HCP@UF);
(2) Preparation of an organic solid electrolyte:
1.0.64g of polyacrylonitrile, 4g of bacterial cellulose and 0.2g of lithium bistrifluoromethanesulfonimide are mixed, dissolved in 10ml of NMP, 0.16g of HCP@UF is added to the precursor solution, and stirred at room temperature until completely uniform;
2. pouring the precursor solution into a polytetrafluoroethylene template, heating to 60-80 ℃ for 4-6 hours to obtain an organic polymer PAN-HCP@UF membrane, and preparing a wafer with the diameter of 16 mm;
(3) Preparing a positive electrode plate:
lithium iron phosphate (LFP for short): carbon black: dispersing PVDF=8:1:1 with NMP, uniformly grinding, then scraping and coating on an aluminum foil by using a scraper, and drying to obtain a lithium iron phosphate pole piece;
(4) Preparation of a lithium battery: a 2032 button cell was prepared using a metallic lithium sheet as the negative electrode, a lithium iron phosphate sheet as the positive electrode, and a PAN-hcp@uf membrane as the solid electrolyte.
Comparative example 1
PAN-HCP membranes were prepared as control 1 by the method of example 1 step (2) using HCP instead of the microcapsule formed membranes.
Comparative example 2
A 2032 coin cell was prepared as control 2 by the method of steps (3) and (4) of example 1 using PAN-HCP film as solid state electrolyte.
Experimental detection
1. The morphology of the microcapsule hcp@uf detected using scanning electron microscopy is shown in fig. 1.
As can be seen from FIG. 1, the surface of the microsphere is smooth and uniform and the radius is about 5. Mu.m.
2. The morphology of the microcapsule hcp@uf detected using transmission electron microscopy is shown in fig. 2.
As can be seen from fig. 2, the surface of the microspheres was smooth, indicating that HCP formed uniform microspheres by encapsulation with urea formaldehyde resin.
3. The morphology of the PAN-hcp@uf membrane detected using scanning electron microscopy is shown in fig. 3.
As can be seen from fig. 3, the microcapsules are contained in the film by heating to form a film, the formed surface is very uniform, and the pores are very few, which is favorable for close contact with the lithium negative electrode.
The results of thermogravimetric tests of the PAN-HCP membrane and PAN-hcp@uf membrane under nitrogen are shown in fig. 4.
As can be seen from fig. 4, the mass ratio of the microcapsules in the PAN-hcp@uf membrane is about 30%, the molecular chains of the urea-formaldehyde resin are broken at 80-410 ℃, the HCP is released from the thinner microcapsules of the shell, the volatilization occurs, the urea-formaldehyde resin begins to volatilize at 410-480 ℃, the HCP is also released from the thicker microcapsules of the shell, and the immediate volatilization indicates that the mass ratio of the microcapsules in the PAN-hcp@uf membrane is about 30%, and the flame retardant HCP can be released for flame retardance when the high temperature is encountered.
The results of the material flame retardant property test of the pan-hcp@uf membrane are shown in fig. 5 and 6.
Fig. 5 shows the results of the combustion test, and it can be seen from fig. 5 that the self-extinguishing time is only 4s, and the combustion area is very small, which intuitively indicates that the added microcapsule hcp@uf effectively prevents the combustion.
FIG. 6 shows the results of a micro-scale calorimeter, and as can be seen from FIG. 6, the heat release amount & temperature test shows that the heat release rate is also relatively low, the maximum peak value is 37W/g, and the added microcapsule HCP@UF is again proved to inhibit the burning of the film.
5. The results of the battery performance test of the PAN-HCP@UF battery prepared in example 1 are shown in FIGS. 7-10.
The results of the Nyquist test performed on a lithium-symmetric battery assembled using a PAN-HCP@UF membrane are shown in FIG. 7, and as can be seen from the graph, the test interval is 10mHZ-100kHZ, and the impedance value 215 omega of the battery is shown;
the PAN-HCP@UF membrane is used as electrolyte, a lithium sheet is used as a negative electrode, a lithium iron phosphate coating is used as a positive electrode to assemble a half battery, and the cycle-efficiency and specific capacity test of the PAN-HCP@UF lithium battery is carried out at room temperature under the condition of 0.5C multiplying power and 2.5-4.2V of cut-off voltage range, wherein the test result is shown in figure 8;
as can be seen from FIG. 8, after 300 cycles, the specific capacity starts to decrease slowly to 85mAh g after 800 cycles -1 ；
To further verify the cycle life of the battery, the cycle was repeated at a rate of 1C, and the detection results are shown in fig. 9;
as can be seen from FIG. 9, after 580 cycles of stabilization, the specific capacity began to drop to 80mAh/g at 750 cycles. In summary, the electrochemical performance of PAN-HCP@UF is very stable and can be successfully used in lithium batteries.
Next, battery rate performance tests were performed, in which charge and discharge cycles were performed at current densities of 0.2C, 0.5C, 1C, 2C, 3C, and 0.2C, respectively, with a test cut-off interval voltage of 2.5 to 4.2V, and charge and discharge cycles at each rate of 5 cycles, with the results shown in fig. 10.
As can be seen from fig. 10, the battery can be stably charged and discharged at different current densities, and the specific capacity values at the beginning and the end at 0.2C are similar, indicating that the electrochemical properties of PAN-hcp@uf are stable. At a maximum current density of 3C, the specific capacity reaches 110mAh/g, which proves that the range of current densities suitable for PAN-HCP@UF is very excellent.
Example 2: reducing the addition amount of HCP
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in oil bath at 65-85deg.C for 1 hr, adding 60ml of water to cool to room temperature, adding 2.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding emulsifier (OP-10:JFC=1:1) =150 μl:150 μl, continuously heating at 50deg.C for 10min, adding 10ml of 0.05g/ml ammonium chloride solution, heating for 1 hr, adding dropwise citric acid to adjust pH=3-4, heating to 70deg.C, heating for 2 hr, and cooling at room temperature for 24 hr;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for three times to obtain a white solid product, and carrying out heating and drying for 2 hours to obtain the product HCP@UF-2.
Experimental detection
The morphology of the microcapsule HCP@UF-2 detected by using a scanning electron microscope is shown in FIG. 11.
As can be seen from fig. 11, the radius of the microcapsules becomes smaller due to the decrease in mass of HCP, and the HCP contained in the microcapsules is decreased compared to the mass of HCP encapsulated by the microcapsules in example 1, indicating that 2.5g of HCP was added as the best mass.
Example 3: increase of the added amount of HCP
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in oil bath at 65-85deg.C for 1 hr, adding 60ml of water to cool to room temperature, adding 3.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding emulsifier (OP-10:JFC=1:1) =150 μl:150 μl, continuously heating at 50deg.C for 10min, adding 10ml of 0.05g/ml ammonium chloride solution, heating for 1 hr, adding dropwise citric acid to adjust pH=3-4, heating to 70deg.C, heating for 2 hr, and cooling at room temperature for 24 hr;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for three times to obtain a white solid product, and carrying out heating and drying for 2 hours to obtain the product HCP@UF-3.
Experimental detection
The morphology of the microcapsule HCP@UF-3 detected by using a scanning electron microscope is shown in FIG. 12.
As can be seen from fig. 12, the urea-formaldehyde resin as a shell of the microcapsule has failed to encapsulate all HCPs due to the mass increase of the HCPs, and the addition of the urea-formaldehyde resin to the PAN-hcp@uf resulted in direct contact of the HCPs with the PAN, decomposition of the HCPs within the battery, binding of the decomposition products to lithium ions, and blocking migration of lithium ions, indicating addition of 2.5g of HCPs as the optimal mass.
Example 4: continuously increasing the addition amount of HCP
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in oil bath at 65-85deg.C for 1 hr, adding 60ml of water to cool to room temperature, adding 4.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding emulsifier (OP-10:JFC=1:1) =150 μl:150 μl, continuously heating at 50deg.C for 10min, adding 10ml of 0.05g/ml ammonium chloride solution, heating for 1 hr, adding dropwise citric acid to adjust pH=3-4, heating to 70deg.C, heating for 2 hr, and cooling at room temperature for 24 hr;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for three times to obtain a white solid product, and carrying out heating and drying for 2 hours to obtain the product HCP@UF-4.
Experimental detection
The morphology of the microcapsule HCP@UF-4 detected by using a scanning electron microscope is shown in FIG. 13.
As can be seen from fig. 13, when the HCP is added in a larger amount, it is not completely encapsulated, and leakage causes side reactions.
Example 5: reducing the temperature of the package
(1) Preparation of microcapsules:
1. in a simple synthesis, 3g urea, 10.4ml formaldehyde (8-14% w/v) are dissolved in 20ml water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the solution ph=8-9;
2. heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 2.5g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 60 ℃, and cooling at room temperature for 24h;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for cleaning for three times, and dissolving part of white solid when the solution is cleaned by the ethanol to obtain a small amount of white solid product, and heating and drying for 2 hours to obtain the product HCP@UF-T60.
HCP was detected as not being fully encapsulated, so less product was obtained.
Example 6: simultaneously reduce the wrapping temperature and the HCP addition amount
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
3. heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 2.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 60 ℃, and cooling at room temperature for 24h;
filtering the solution, sequentially cleaning with deionized water and ethanol for three times, dissolving part of white solid when the solution is cleaned with ethanol to obtain a small amount of white solid product, and heating and drying for 2 hours to obtain a product HCP@UF-2-T60;
the results of the assay showed that HCP was not fully encapsulated and therefore less product was obtained.
Example 7: reduce the coating temperature and increase the HCP addition
(1) Preparation of microcapsules:
1. in a simple synthesis, 3g urea, 10.4ml formaldehyde (8-14% w/v) are dissolved in 20ml water and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the solution ph=8-9.
2. Heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 3.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 60 ℃, and cooling at room temperature for 24h.
3. And (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for three times, and dissolving part of white solid when the solution is washed by the ethanol to obtain a small amount of white solid product, and heating and drying for 2 hours to obtain the product HCP@UF-3-T60.
The results of the assay showed that HCP was not fully encapsulated and therefore less product was obtained.
Example 8: decreasing the coating temperature and continuing to increase HCP addition
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 4.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 60 ℃, and cooling at room temperature for 24h;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for cleaning for three times, and dissolving part of white solid when the solution is cleaned by the ethanol to obtain a small amount of white solid product, and heating and drying for 2 hours to obtain the product HCP@UF-4-T60.
The results of the assay showed that HCP was not fully encapsulated and therefore less product was obtained.
Example 9: increasing the temperature of the package and reducing the amount of HCP added
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in oil bath at 65-85deg.C for 1 hr, adding 60ml of water to cool to room temperature, adding 2.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding emulsifier (OP-10:JFC=1:1) =150 μl:150 μl, continuously heating at 50deg.C for 10min, adding 10ml of 0.05g/ml ammonium chloride solution, heating for 1 hr, adding dropwise citric acid to adjust pH=3-4, heating to 80deg.C, heating for 2 hr, and cooling at room temperature for 24 hr;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for three times to obtain a white solid product, and carrying out heating drying for 2 hours to obtain a product HCP@UF-2-T80.
The detection result shows that the product is aggregated into small particles and cannot be formed into powder.
Example 10: increasing the coating temperature and increasing the amount of HCP added
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in oil bath at 65-85deg.C for 1 hr, adding 60ml of water to cool to room temperature, adding 3.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding emulsifier (OP-10:JFC=1:1) =150 μl:150 μl, continuously heating at 50deg.C for 10min, adding 10ml of 0.05g/ml ammonium chloride solution, heating for 1 hr, adding dropwise citric acid to adjust pH=3-4, heating to 80deg.C, heating for 2 hr, and cooling at room temperature for 24 hr;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for three times to obtain a white solid product, and carrying out heating drying for 2 hours to obtain a product HCP@UF-3-T80.
The detection result shows that the product is aggregated into small particles and cannot be formed into powder.
Example 11: increasing the temperature of the package and continuing to increase the amount of HCP added
(1) Preparation of microcapsules:
1. in a simple synthesis, 3g urea, 10.4ml formaldehyde (8-14% w/v) are dissolved in 20ml water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the solution ph=8-9;
2. heating in oil bath at 65-85deg.C for 1 hr, adding 60ml of water to cool to room temperature, adding 4.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding emulsifier (OP-10:JFC=1:1) =150 μl:150 μl, continuously heating at 50deg.C for 10min, adding 10ml of 0.05g/ml ammonium chloride solution, heating for 1 hr, adding dropwise citric acid to adjust pH=3-4, heating to 80deg.C, heating for 2 hr, and cooling at room temperature for 24 hr;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for three times to obtain a white solid product, and carrying out heating drying for 2 hours to obtain a product HCP@UF-4-T80.
The detection result shows that the product is aggregated into small particles and cannot be formed into powder.
Example 12: reducing package time
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 2.5g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 70 ℃, and cooling at room temperature for 24h;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for cleaning for three times, and dissolving part of white solid when the solution is cleaned by the ethanol to obtain a small amount of white solid product, and heating and drying for 2 hours to obtain the product HCP@UF-H1.
The results of the assay showed that HCP was not fully encapsulated and therefore less product was obtained.
Example 13: reduction of package time and HCP addition
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 2.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 70 ℃, and cooling at room temperature for 24h;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for cleaning for three times, and dissolving part of white solid when the solution is cleaned by the ethanol to obtain a small amount of white solid product, and heating and drying for 2 hours to obtain the product HCP@UF-2-H1.
The results of the assay showed that HCP was not fully encapsulated and therefore less product was obtained.
Example 14: decreasing package time and increasing HCP addition
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 3.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 70 ℃, and cooling at room temperature for 24h;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for cleaning for three times, and dissolving part of white solid when the solution is cleaned by the ethanol to obtain a small amount of white solid product, and heating and drying for 2 hours to obtain the product HCP@UF-3-H1.
The results of the assay showed that HCP was not fully encapsulated and therefore less product was obtained.
Example 15
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 4.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 70 ℃, and cooling at room temperature for 24h. And (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for cleaning for three times, and dissolving part of white solid when the solution is cleaned by the ethanol to obtain a small amount of white solid product, and heating and drying for 2 hours to obtain the product HCP@UF-4-H1.
The results of the assay showed that HCP was not fully encapsulated and therefore less product was obtained.
Example 16: increasing package time
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 2.5g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 70 ℃, and cooling at room temperature for 24h;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for three times to obtain a white solid product, and carrying out heating and drying for 2 hours to obtain a product HCP@UF-H3.
The detection result shows that the product is aggregated into small particles and cannot be formed into powder.
Example 17: increasing package time and reducing HCP addition
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 2.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 70 ℃, and cooling at room temperature for 24h;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for three times to obtain a white solid product, and carrying out heating and drying for 2 hours to obtain a product HCP@UF-2-H3.
The detection result shows that the product is aggregated into small particles and cannot be formed into powder.
Example 18: increase package time and increase HCP addition
(1) Preparation of microcapsules:
1. 3g of urea, 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to 8-9.
2. Heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 3.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 70 ℃, and cooling at room temperature for 24h;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for three times to obtain a white solid product, and carrying out heating drying for 2 hours to obtain a product HCP@UF-3-H3.
The detection result shows that the product is aggregated into small particles and cannot be formed into powder.
Example 19: increasing package time and continuing to increase HCP add-on
(1) Preparation of microcapsules:
1. 3g of urea and 10.4ml of formaldehyde (8-14% w/v) are dissolved in 20ml of water, and 0.5mol/L sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9;
2. heating in an oil bath at 75 ℃ for 1h, adding 60ml of water to cool to room temperature, adding 4.0g of hexachlorocyclotriphosphazene, stirring for 10min, adding 150 μl of emulsifier (OP-10:JFC=1:1) =150 μl, continuously heating at 50 ℃, adding 10ml of 0.05g/ml ammonium chloride solution after 10min, heating for 1h, dripping citric acid to adjust the pH of the solution to be 3-4, heating to 70 ℃, and cooling at room temperature for 24h;
3. and (3) carrying out suction filtration on the solution, sequentially using deionized water and ethanol for three times to obtain a white solid product, and carrying out heating drying for 2 hours to obtain a product HCP@UF-4-H3.
The detection result shows that the product is aggregated into small particles and cannot be formed into powder.
Example 20: use of PEO instead of PAN matrix
(1) Preparation of microcapsules
Procedure as in example 1
(2) Preparation of an organic solid electrolyte:
1.0.64g of polyethylene oxide, 4g of bacterial cellulose and 0.2g of lithium bistrifluoromethane sulfonyl imide are mixed, dissolved in 10ml of NMP, 0.16g of HCP@UF is added into the precursor solution, and stirred at room temperature until completely uniform;
2. pouring the precursor solution into a polytetrafluoroethylene template, heating to 60-80 ℃ for 4-6 hours to obtain the organic polymer PEO-HCP@UF membrane, and preparing a wafer with the diameter of 16 mm.
Experimental detection
The morphology of PEO-HCP@UF detected by a scanning electron microscope is shown in FIG. 14.
As can be seen from fig. 14, the surface of the thin film is very uneven, and has many small particle protrusions, which are unfavorable for close contact with the lithium negative electrode, resulting in rapid deterioration of the specific capacity of the assembled battery and shortened cycle life. This result illustrates that simple application of microcapsule technology to solid state electrolytes is not feasible.
The cycle-efficiency & specific capacity test of the PEO-hcp@uf lithium battery was performed at room temperature at a rate of 0.5C with a cut-off voltage ranging from 2.5 to 4.2V, and the results are shown in fig. 15.
As can be seen from fig. 15, the specific capacity values decayed rapidly to 0 within 75 cycles, indicating that hcp@uf was not uniformly dispersed upon addition of PEO, resulting in rapid decay of the specific capacity of the assembled battery and a shortened cycle life.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (9)

1. The preparation method of the flame-retardant solid electrolyte by adopting the microcapsule technology is characterized by comprising the following steps of:
(1) Preparing a suspension containing hexachlorocyclotriphosphazene, formaldehyde and urea;
(2) During the heating process, the hexachlorocyclotriphosphazene is emulsified by using a composite emulsifier, and then the hexachlorocyclotriphosphazene@urea resin microcapsule is obtained by using a curing agent to polymerize under an acidic condition;
(3) And adding the hexachlorocyclotriphosphazene@urea resin microcapsule into a polyacrylonitrile mixed solution dissolved by NMP, uniformly stirring, pouring into a mold, and heating to evaporate the solvent to obtain the organic solid electrolyte.
2. The preparation method according to claim 1, wherein the specific process of the step (1) corresponding to each 2.5g of hexachlorocyclotriphosphazene is as follows:
3g of urea and 10.4ml of formaldehyde are dissolved in 20ml of water, and 0.5mol/l of sodium hydroxide solution is added dropwise to adjust the pH of the solution to be 8-9, so as to obtain solution A;
after heating the solution A in an oil bath at 65-85 ℃ for 1h, adding 60ml of water, cooling to room temperature, adding 2.5g of hexachlorocyclotriphosphazene, and stirring for 20min to obtain a suspension containing hexachlorocyclotriphosphazene.
3. The preparation method according to claim 2, wherein the specific steps of step (2) are as follows:
adding 300ul of composite emulsifier, heating at 50 ℃ for 10min, adding 10ml of 0.05g/ml ammonium chloride solution, and heating at 50 ℃ for 1h;
dropwise adding citric acid to adjust the PH=3-4 of the solution, increasing the temperature to 70 ℃, heating for 2 hours, and cooling for 24 hours at room temperature to obtain a solution B;
after suction filtration of the solution B, washing the solution B for three times by using deionized water and ethanol in sequence to obtain a white solid product;
after drying the white solid product by heating for 2 hours, hexachlorocyclotriphosphazene@urea resin microcapsules (HCP@UR) are obtained.
4. A method according to claim 3, wherein the specific steps of step (3) are:
0.64g of polyacrylonitrile, 4g of bacterial cellulose with concentration of 0.4% and 0.2g of lithium bistrifluoromethylsulfonyl imide are mixed and dissolved in 10ml of NMP to obtain a precursor solution;
adding 0.16g of HCP@UR into the precursor solution, and stirring at room temperature until the mixture is completely uniform to obtain solution C;
pouring the solution C into a polytetrafluoroethylene template, and heating at 60-80 ℃ for 4-6h to obtain the flame-retardant solid electrolyte (PAN-HCP@UR).
5. The process according to claim 4, wherein in step (1), the concentration of formaldehyde is 8-14% w/v;
in the step (2), the composite emulsifier consists of OP-10 and JFC, and the ratio of the OP-10 to JFC in the composite emulsifier is 1:1.
6. A flame retardant solid electrolyte adopting microcapsule technology, which is characterized in that the flame retardant electrolyte is prepared by the preparation method of claim 5.
7. The preparation method of the lithium battery adopting the microcapsule technology is characterized by comprising the following steps of:
(1) Lithium iron phosphate: carbon black: dispersing PVDF by using NMP according to the proportion of 8:1:1, uniformly grinding, then scraping and coating on an aluminum foil by using a scraper, and drying to obtain a lithium iron phosphate pole piece;
(2) And preparing the lithium battery by using a metal lithium sheet as a negative electrode, a lithium iron phosphate sheet as a positive electrode and a PAN-HCP@UR film as a solid electrolyte.
8. The method of claim 7, wherein the PAN-hcp@ur membrane is prepared by the method of claim 5.
9. A lithium battery adopting microcapsule technology, wherein the lithium battery is prepared by the preparation method of claim 8.
CN202311241163.4A 2023-09-25 2023-09-25 Flame-retardant solid electrolyte adopting microcapsule technology and preparation method thereof Pending CN117293383A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115895226A (en) * 2022-11-18 2023-04-04 福州大学 High-nitrogen-phosphorus core-shell type flame retardant and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115895226A (en) * 2022-11-18 2023-04-04 福州大学 High-nitrogen-phosphorus core-shell type flame retardant and preparation method and application thereof

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