CN112480345B - Metal salt @ ammonia aldehyde polymer nanosphere, preparation method and application - Google Patents
Metal salt @ ammonia aldehyde polymer nanosphere, preparation method and application Download PDFInfo
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Abstract
The invention discloses metal salt @ ammonia-aldehyde polymer nanospheres, a preparation method and application. The invention uses amino-containing monomer and aldehyde-containing monomer to condense and polymerize into polymer ball under the catalysis of phosphorous acid, then adds aniline into the system, and etches the polymer ball into hollow ball through the competition reaction between the primary amine group contained in aniline in solution and the dynamic imine bond in the polymer ball; and then, after the polymer hollow sphere is placed in a metal salt solution with a certain concentration, the metal salt permeates into the cavity through the pore canal on the sphere wall by utilizing the difference of the internal concentration and the external concentration of the hollow sphere and is crystallized inside, so that the metal salt @ amino aldehyde polymer nanosphere is obtained. In the case of encapsulating easily migrating metal cations (e.g. Li)+) And then, the pore passage on the outer spherical shell of the polymer is beneficial to the migration of ions, so that higher ionic conductivity is obtained, and the material has better application prospect as a solid electrolyte.
Description
Technical Field
The invention relates to metal salt @ ammonia aldehyde polymer nanospheres, a preparation method and application.
Background
The problem of fossil energy consumption in the world is becoming more and more serious nowadays, and various energy conversion and storage technologies are developed rapidly in order to meet application requirements in different fields. Lithium batteries have high energy density (mass energy density and volume energy density) and are a research hotspot in recent years, most of the existing commercial lithium ion batteries use liquid electrolytes composed of organic carbonates and lithium salts, and the electrolytes are easy to combust at high temperature, so that the safety and electrochemical performance of the batteries are greatly reduced, and the lithium batteries cannot be well suitable for large-scale power supplies. In order to solve the above problems, solid electrolytes are becoming important for researchers. Currently, solid-state electrolytes mainly include two major types: a solid polymer electrolyte and an inorganic solid electrolyte, the solid polymer electrolyte comprising: PEO solid polymer electrolyte, polycarbonate electrolyte, polyion liquid electrolyte, single ion conductive polymer electrolyte and the like; the inorganic solid electrolyte includes: oxide-type inorganic solid electrolytes, sulfide-type inorganic solid electrolytes, halide-type inorganic solid electrolytes, LiAl-PEO hybrid electrolytes, nitride or lithium nitrate electrolytes, and the like. Compared with an organic liquid electrolyte, the solid electrolyte has the advantages of higher electrochemistry and thermal stability, good plasticity, capability of effectively inhibiting the growth of lithium dendrites on a lithium electrode and the like. Compared with liquid electrolytes and inorganic solid electrolytes, the solid polymer electrolytes have good safety, excellent flexibility and processability, and can effectively adapt to the change of the electrode volume in the charging and discharging processes.
The application of the core-shell structure in the lithium ion battery is mostly concentrated on the aspects of positive and negative electrode materials, and the core-shell structure material serving as a solid electrolyte needs to provide certain mechanical strength and ionic conductivity, so that the core-shell structure material is less involved in the solid electrolyte.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides metal salt @ amino aldehyde polymer nanospheres, a preparation method and application.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: a preparation method of metal salt @ ammonia-aldehyde polymer nanospheres is provided, and comprises the following steps:
1) preparation of polymer spheres: carrying out condensation polymerization on an amino-containing monomer and an aldehyde-containing monomer under the catalysis of phosphorous acid to obtain an amino-aldehyde polymer ball;
2) etching: adding aniline to etch the polymer spheres to form polymer hollow spheres;
3) and (3) crystallization: and (3) placing the polymer hollow sphere in a metal salt solution, and generating metal salt crystals inside the polymer hollow sphere by using the concentration difference to obtain the metal salt @ amino aldehyde polymer nanosphere.
In a preferred embodiment of the present invention, the step 3) includes the following steps:
preparing a metal salt solution with the concentration of 5-20 mg/mL by using lower alcohol or distilled water, dispersing the polymer hollow spheres in the lower alcohol, then adding the polymer hollow spheres into the prepared metal salt solution, stirring and reacting for 1-12 h at 20-40 ℃, centrifuging to obtain a precipitate, and performing vacuum drying to obtain the metal salt @ amino aldehyde polymer nanospheres.
In a preferred embodiment of the invention, the temperature of the vacuum drying is 40-60 ℃ and the time is 12-24 h.
In a preferred embodiment of the present invention, the lower alcohol is methanol or ethanol.
In a preferred embodiment of the present invention, the step 1) includes the following steps:
ultrasonically dissolving an amino-containing monomer and an aldehyde-containing monomer in a mixed solvent of ethanol and dichloromethane to obtain a solution A; dissolving phosphorous acid in a mixed solvent of ethanol and dichloromethane by ultrasonic waves to obtain a solution B; dropwise adding the solution B into the solution A while stirring at 20-40 ℃, and stirring for reacting for 12-24 hours after dropwise adding; and centrifuging the material obtained by the reaction to obtain a precipitate, and washing to obtain the amino-aldehyde polymer ball.
In a preferred embodiment of the present invention, the amino group-containing monomer (e.g., rigid monomer: 1,3, 5-tris (4-aminophenyl) benzene, melamine, tris (4-aminophenyl) amine, etc.; flexible monomer: tris (2-aminoethyl) amine, etc.) and the aldehyde group-containing monomer (e.g., rigid monomer: terephthalaldehyde, 4' -biphenyldicarbaldehyde, etc.; flexible monomer: glutaraldehyde, etc.) are used, the amino group-containing monomer is a rigid monomer, the aldehyde group-containing monomer is a flexible monomer, and the molar ratio of the amino group-containing rigid monomer, the aldehyde group-containing flexible monomer, and phosphorous acid is 2-100:3-200: 4-100.
In a preferred embodiment of the present invention, the ultrasonic dissolution in the step 3) is performed for 5-20 min under a power of 40-50W.
In a preferred embodiment of the present invention, the mixed solvent is composed of ethanol and dichloromethane at a volume ratio of 0.8-1.2: 0.8-1.2.
In a preferred embodiment of the present invention, the step 2) includes the following steps:
dispersing the amino-aldehyde polymer spheres in lower alcohol, then dropwise adding aniline liquid, and stirring and reacting at 20-40 ℃ for 12-24 hours; wherein the dosage ratio of the amino-aldehyde polymer ball to the aniline is 40-80 mg: 2-8 mL.
In a preferred embodiment of the present invention, the dropping time is 1-2 hours.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the metal salt @ ammonia-aldehyde polymer nanosphere prepared by the method is provided, and has a spherical shell formed by ammonia-aldehyde polymer, the interior of the spherical shell is wrapped by metal salt which is a core structure, pore channels with the pore diameter of 5-20nm are distributed on the spherical shell, and the size of the nanosphere is 400-600 nm.
The third technical scheme adopted by the invention for solving the technical problems is as follows: there is provided the use of the above metal salt @ aminoaldehyde polymer nanospheres in a solid state electrolyte, said metal salt being a lithium metal salt, including LiCl. In the case of encapsulating easily migrating metal cations (e.g. Li)+) And then, the pore passage on the outer spherical shell of the polymer is beneficial to the migration of ions, so that higher ionic conductivity is obtained, and the material has better application prospect as a solid electrolyte.
Compared with the background technology, the technical scheme has the following advantages:
1. the scheme provides a simple and feasible method for coating metal salt with a polymer, wherein an amino-containing monomer and an aldehyde-containing monomer are condensed and polymerized into a polymer ball under the catalysis of phosphorous acid, then the polymer ball is etched into a hollow ball by utilizing the competitive reaction between a primary amine group contained in aniline and a dynamic imine bond in the polymer ball, and then the hollow ball is placed in a metal salt solution with a certain concentration, and then the metal salt can permeate into the cavity through a pore channel on the wall of the ball and is crystallized inside the cavity by utilizing the concentration difference of the hollow ball;
2. the method realizes the regulation and control of the whole mechanical property of the nanosphere and the pore canal of the spherical shell by controlling the types, the proportions and the like of the amino-containing monomer and the aldehyde-containing monomer of the ammonia-aldehyde polymer with the spherical shell structure;
3. the solution is coated with metal cations (such as Li) which are easy to migrate+) And meanwhile, the flexible monomer and the rigid monomer are combined in a specific ratio, so that certain mechanical strength is ensured, and the rigid monomer can effectively inhibit the growth of Li dendrites, so that the material has a good application prospect as a solid electrolyte.
Drawings
FIG. 1 is an infrared spectrum of the ammal-aldehyde polymer nanospheres prepared in examples 1 to 6.
FIG. 2 is a transmission electron microscope image of the hollow nanospheres of the amino-aldehyde polymer, wherein a is examples 1-7, b is comparative example 1, and c is comparative example 2.
FIG. 3 is a transmission electron microscope image of the amino-aldehyde polymer nanospheres coated with the respective metal salts prepared in example 1 (left) and 2 (right).
FIG. 4 is an electrochemical impedance spectrum of a material of hollow amino aldehyde polymer nanospheres (LiCl @ NOPs-5) having LiCl-contained cavities obtained in example 1.
Example 1
A metal salt @ aminoaldehyde polymer nanosphere (LiCl @ NOPs-5/-20) of the present example was prepared by the method comprising the steps of:
(1) ultrasonically dissolving 60mg of 1,3, 5-tri (4-aminophenyl) benzene (TAPB) and 35mg of terephthalaldehyde (PDA) in 60mL of mixed solvent consisting of ethanol and dichloromethane (the volume ratio of the ethanol to the dichloromethane is 1: 1);
(2) dissolving 70mg of phosphorous acid in a mixed solvent consisting of ethanol and dichloromethane (the volume ratio of the ethanol to the dichloromethane is 1:1) by ultrasonic;
(3) dripping the material obtained in the step (2) into the mixed solution obtained in the step (1) at 23 ℃ while stirring, and stirring for reacting for 24 hours after dripping;
(4) centrifuging the material obtained in the step (3) to obtain a precipitate;
(5) washing the precipitate with ethanol for 2 times, and ultrasonically dispersing in 50mL of ethanol;
(6) dropwise adding 6mL of aniline liquid into the dispersion liquid obtained in the step (5), and stirring and reacting for 24h at 23 ℃;
(7) centrifuging the material obtained in the step (6) to obtain a precipitate, and performing vacuum drying to obtain solid powder of the hollow nano-Spheres (NOPs) of the amino-aldehyde polymer;
(8) dispersing the solid powder obtained in the step (7) in 20mL of ethanol;
(9) preparing 10mL of LiCl solution with 5mg/mL and 20mg/mL by using methanol;
(10) adding the solution obtained in the step (9) into the solution obtained in the step (8), and stirring and reacting for 1h at 23 ℃;
(11) and (3) centrifuging the material obtained in the step (10) to obtain a precipitate, and drying in vacuum to obtain solid powder of the ammonia-aldehyde polymer hollow nanospheres (LiCl @ NOPs-5/-20) with LiCl-contained cavities.
The LiCl @ NOPs-5/-20 prepared in this example was prepared by condensation polymerization of an amino-containing rigid monomer, 1,3, 5-tris (4-aminophenyl) benzene, and an aldehyde-containing flexible monomer, terephthalaldehyde, at a molar ratio of 2:3, to form an aminoaldehyde polymer, NOP, as the shell and LiCl, as the core. The size of the nanosphere is 400-600nm, the nanosphere has good mechanical strength by combining the flexibility and the rigidity in a specific ratio, and pore channels with the pore diameter of 5-20nm are distributed on the spherical shell, so that the transfer of ions is facilitated, and higher ionic conductivity is hopefully obtained.
Example 2
Example 2 differs from example 1 in that: and (9) preparing 10mL of 15mg/mL KCl solution by using distilled water to obtain solid powder of the ammonia-aldehyde polymer hollow nanospheres (KCl @ NOPs-15) with KCl in cavities.
Examples 3 to 6
Examples 3 to 6 differ from example 1 in that: step (9) preparing 10mg/mL NaCl and MgCl with distilled water respectively2、MgSO4And CuSO410mL of solution is obtained, and the amino-aldehyde polymer nano hollow sphere (NaCl/MgCl) with different metal salts in the cavity is obtained2/MgSO4/CuSO4@ NOPs-15) solid powder.
Example 7
Example 7 differs from example 1 in that: step (1), ultrasonically dissolving 60mg of 1,3, 5-tri (4-aminophenyl) benzene (TAPB) and 35mg of Biphenyldicarboxaldehyde (BPAL) in 60mL of mixed solvent consisting of ethanol and dichloromethane (the volume ratio of the ethanol to the dichloromethane is 1: 1); a new nano hollow sphere (LiCl @ N 'OPs-5/-20) solid powder with shell of N' OP and core of LiCl, which is made of amino-aldehyde polymer and condensed and polymerized by different monomers, is obtained.
Comparative example 1
Steps (1) to (5) are the same as in example 1 except that: and (3) dropwise adding 9mL of aniline liquid into the dispersion liquid obtained in the step (5), and stirring and reacting at 23 ℃ for 24h to obtain a translucent brown solid-liquid mixture containing only a small amount of solid precipitate.
Comparative example 2
Steps (1) and (3) to (6) are the same as in example 1 except that: step (2) 350mg of phosphorous acid was dissolved in a mixed solvent of ethanol and dichloromethane (volume ratio of ethanol to dichloromethane is 1:1) by ultrasonic. Finally, a solid-liquid mixture which is brown in color is obtained.
The infrared spectrogram of the amino-aldehyde polymer nanospheres prepared in examples 1-6 is shown in FIG. 1, and the spectrogram shows that: 1621cm-1、1196cm-1And 1012cm-1The stretching shock absorption peaks for the C ═ N bond, P ═ O bond and P — OH bond, respectively, indicate the successful incorporation of phosphorous acid.
FIG. 2a is a transmission electron microscope image of the hollow amino-aldehyde polymer nanospheres prepared in examples 1-7, which shows that the prepared amino-aldehyde polymer nanospheres exhibit an obvious hollow spherical structure after being etched by aniline; b is a transmission electron microscope image of the hollow amino-aldehyde polymer nanospheres prepared in example 8, which shows that the prepared amino-aldehyde polymer nanospheres are excessively etched by excessive aniline, and even most of the polymer sphere structure is damaged; and c is a transmission electron microscope image of the hollow amino-aldehyde polymer nanosphere prepared in example 9, which shows that the size of the hollow amino-aldehyde polymer nanosphere is reduced after 5 times of phosphorous acid is used for reaction, and the spherical structure is easily damaged due to excessive etching of aniline.
Fig. 3 is a transmission electron microscope image of the hollow amino-aldehyde polymer nanospheres prepared in examples 1 and 2, wherein the cavities of the hollow amino-aldehyde polymer nanospheres respectively contain LiCl and KCl, and the electron microscope image shows that the prepared hollow amino-aldehyde polymer nanospheres crystallize corresponding metal salts in a metal salt solution to form an obvious core-shell structure.
Fig. 4 is an electrochemical impedance spectrum of the material of the hollow amino aldehyde polymer nanospheres (LiCl @ NOPs-5) with the cavities containing LiCl obtained in example 1, which shows the ion conductivity of the material and can obtain a solid electrolyte material with better performance at a proper metal salt concentration.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (8)
1. A preparation method of metal salt @ ammonia-aldehyde polymer nanospheres is characterized by comprising the following steps: the method comprises the following steps:
1) preparation of polymer spheres: carrying out condensation polymerization on an amino-containing monomer and an aldehyde-containing monomer under the catalysis of phosphorous acid to obtain an amino-aldehyde polymer ball; the amino-containing monomer is selected from rigid monomer 1,3, 5-tri (4-aminophenyl) benzene; the aldehyde group-containing monomer is selected from terephthalaldehyde, 4' -biphenyl diformaldehyde or glutaraldehyde;
when the amino-containing monomer is rigid monomer and the aldehyde-containing monomer is flexible monomer glutaraldehyde, the molar ratio of the amino-containing rigid monomer to the aldehyde-containing flexible monomer glutaraldehyde to phosphorous acid is 2-100:3-200: 4-100;
when the aldehyde group-containing monomer adopts terephthalaldehyde or 4,4' -biphenyl diformaldehyde, the mass ratio of the rigid monomer containing amino groups, the aldehyde group-containing monomer and phosphorous acid is 60:35: 70;
2) etching: adding aniline to etch the polymer spheres to form polymer hollow spheres; the dosage ratio of the amino-aldehyde polymer ball to the aniline is 40-80 mg: 2-8 mL;
3) and (3) crystallization: and (3) placing the polymer hollow sphere in a metal salt solution, and generating metal salt crystals inside the polymer hollow sphere by using the concentration difference to obtain the metal salt @ amino aldehyde polymer nanosphere.
2. The method of claim 1, wherein said nanospheres are prepared from a metal salt @ aminoaldehyde polymer, wherein said nanospheres comprise: the step 3) comprises the following steps:
preparing a metal salt solution with the concentration of 5-20 mg/mL by using lower alcohol or distilled water, dispersing the polymer hollow spheres in the lower alcohol, then adding the polymer hollow spheres into the prepared metal salt solution, stirring and reacting for 1-12 h at 20-40 ℃, centrifuging to obtain a precipitate, and performing vacuum drying to obtain the metal salt @ amino aldehyde polymer nanospheres.
3. The method of claim 1, wherein said nanospheres are prepared from a metal salt @ aminoaldehyde polymer, wherein said nanospheres comprise: the step 1) comprises the following steps:
ultrasonically dissolving an amino-containing monomer and an aldehyde-containing monomer in a mixed solvent of ethanol and dichloromethane to obtain a solution A; dissolving phosphorous acid in a mixed solvent of ethanol and dichloromethane by ultrasonic waves to obtain a solution B; dropwise adding the solution B into the solution A while stirring at 20-40 ℃, and stirring for reacting for 12-24 hours after dropwise adding; and centrifuging the material obtained by the reaction to obtain a precipitate, and washing to obtain the amino-aldehyde polymer nanospheres.
4. The method of claim 3, wherein said nanospheres are prepared from a metal salt @ aminoaldehyde polymer as defined in claim: the ultrasonic dissolution in the step 1) is ultrasonic for 5-20 min under the power of 40-50W.
5. The method of claim 3, wherein said nanospheres are prepared from a metal salt @ aminoaldehyde polymer as defined in claim: the mixed solvent is composed of ethanol and dichloromethane in a volume ratio of 0.8-1.2: 0.8-1.2.
6. The method of claim 1, wherein said nanospheres are prepared from a metal salt @ aminoaldehyde polymer, wherein said nanospheres comprise: the step 2) comprises the following steps:
dispersing the amino-aldehyde polymer spheres in lower alcohol, then dropwise adding aniline liquid, and stirring and reacting at 20-40 ℃ for 12-24 h.
7. A metal salt @ aminoaldehyde polymer nanosphere prepared by the process of any one of claims 1-6 wherein: the nanosphere is provided with a spherical shell formed by an amino-aldehyde polymer, the interior of the nanosphere is wrapped with a structure taking metal salt as a core, pore channels with the pore diameter of 5-20nm are distributed on the spherical shell, and the size of the nanosphere is 400-600 nm.
8. The use of a metal salt @ aminoaldehyde polymer nanosphere according to claim 7 in a lithium ion battery, wherein: LiCl @ NOPs nanospheres were prepared by wrapping LiCl inside as solid electrolyte.
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| "A Scalable General Synthetic Approach toward Ultrathin Imine-Linked Two-Dimensional Covalent Organic Framework Nanosheets for Photocatalytic CO2 Reduction";Wenbo Liu et al.;《J.Am.Chem.Soc.》;20191013;第141卷;第17431-17440页 * |
| "Nanoscrolls Formed from Two-Dimensional Covalent Organic Frameworks";Haoyuan Li et al.;《Chem. Mater.》;20190402;第31卷;第3265-3273页 * |
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