CN112421004A - Polypyrrole-coated polyacid-based metal organic framework composite material, negative electrode material, alkali metal ion battery and method - Google Patents

Polypyrrole-coated polyacid-based metal organic framework composite material, negative electrode material, alkali metal ion battery and method Download PDF

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CN112421004A
CN112421004A CN202011297673.XA CN202011297673A CN112421004A CN 112421004 A CN112421004 A CN 112421004A CN 202011297673 A CN202011297673 A CN 202011297673A CN 112421004 A CN112421004 A CN 112421004A
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polyacid
organic framework
polypyrrole
based metal
coated
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王霞
李劲龙
韩志远
李雪莹
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Qingdao University
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/24—Alkaline accumulators
    • H01M10/28—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The embodiment of the application provides a polypyrrole-coated polyacid-based metal organic framework composite material, a negative electrode material, an alkali metal ion battery and a method, wherein the composite material comprises a transition metal cation, a phenanthroline ligand, a polyoxoanion, a water molecule and polypyrrole, and the chemical formula of the composite material is [ Mm+ nz/m(1,10‑phen)x(H2O)y][An‑ z]@ PPy, where M is a transition metal and "1, 10-phen" is 1, 10-phenanthroline, An‑Is polyoxoanion, PPy is polypyrrole. The polypyrrole coated polyacid-based metal-organic framework composite provided by the embodiment of the applicationThe material used as the cathode of the alkali metal ion battery has the advantages of high specific capacity, long cycle life and good rate capability.

Description

Polypyrrole-coated polyacid-based metal organic framework composite material, negative electrode material, alkali metal ion battery and method
Technical Field
The application relates to the technical field of alkali metal ion batteries, in particular to a polypyrrole-coated polyacid-based metal organic framework composite material, a negative electrode material, an alkali metal ion battery and a method.
Background
The ion battery is a novel efficient chemical power supply, has the advantages of large energy density, long cycle life, high working voltage, no memory effect, small self-discharge, wide working temperature range and the like, is an ideal chemical power supply for various portable electronic products at present, is also an optimal power supply for future electric vehicles, and has wide application space and economic value.
An ion battery generally consists of a positive electrode, a negative electrode, and an electrolyte. When the ion battery is charged, ions are generated on the positive electrode of the battery, the generated ions move to the negative electrode through the electrolyte, and the ions reaching the negative electrode are embedded into the negative electrode, wherein the more the number of the ions embedded into the negative electrode is, the higher the charging capacity is; when the ion battery is discharged, ions embedded in the negative electrode are detached and returned to the positive electrode through the electrolyte, wherein the more ions are returned to the positive electrode, the higher the discharge capacity. That is, the capacity performance of the negative electrode material in an ion battery has an important influence on the energy density of the ion battery.
Polyoxometalates (POMs) are inorganic metal clusters with controllable shapes and variable structures, are often used in the fields of catalysis, light, electricity, magnetism and the like due to high activity and good selectivity, and are very suitable for realizing high-capacity energy storage application. For example, [ PMo ]12O40]3-(PMo12) As a negative electrode of a lithium ion battery, [ PMo ] during charging12O40]3-12 Mo in the solution6+The ions are reduced to Mo4+The POMs form a super-reduced state, i.e. [ PMo ]12O40]27-The 24 electrons are stored, and due to the large number of transferred electrons, the electron storage device is endowed with the property of an 'electron sponge'. However, the POMs have a relatively low specific surface area (<10m2/g) and has high solubility in electrolytes, resulting in a great reduction in capacity, hindering the application of POMs as negative electrode materials for lithium ion batteries.
Disclosure of Invention
The embodiment of the application provides a polypyrrole-coated polyacid-based metal organic framework composite material, a negative electrode material, an alkali metal ion battery and a method, and aims to solve the problem that POMs in the prior art are low in capacity when used as a negative electrode material of a lithium ion battery.
In a first aspect, embodiments of the present application provide a polypyrrole coated polyacid-based metal organic framework composite, the composite including a transition metal cation, a phenanthroline ligand, a polyoxoanion, a water molecule, and a polypyrrole, the composite having a chemical formula of [ M [ ]m+ nz/m(1,10-phen)x(H2O)y][An- z]@ PPy, where M is a transition metal and "1, 10-phen" is 1, 10-phenanthroline, An-Is polyoxoanion, PPy is polypyrrole.
Preferably, the transition metal is Fe, Co, Ni or Cu; the polyoxoanion is [ Mo ]6O20]4-、[W3O10]2-Or [ V ]13O34]3-。
In a second aspect, embodiments of the present application provide a method for preparing a polypyrrole coated polyacid-based metal organic framework composite, including:
preparing a polyacid-based metal-organic framework material having the chemical formula [ Mm+ nz/m(1,10-phen)x(H2O)y][An- z]Wherein M is a transition metal, 1,10-phen is phenanthroline, An-Is a polyoxoanion;
preparing the polypyrrole coated polyacid-based metal-organic framework composite material of any one of the first aspect using pyrrole monomers and the polyacid-based metal-organic framework material.
Preferably, the preparing the polyacid-based metal-organic framework material comprises:
dissolving transition metal salt, polyoxometallate and 1, 10-phenanthroline in water, and adjusting the pH value by adopting NaOH to obtain a first solution;
and adding the first solution into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction, cooling to room temperature, collecting crystals, washing the crystals with deionized water and ethanol, and drying to obtain the polyacid-based metal organic framework material.
Preferably, the molar ratio of the transition metal salt to the polyoxometallate to the 1, 10-phenanthroline is 1: 0.1-2.
Preferably, the metal element in the transition metal salt is Fe, Co, Ni or Cu; the anion in the transition metal salt is NO3 -、SO4 2-、CH3COO-Or Cl-。
Preferably, the temperature of the hydrothermal reaction is 120-200 ℃, the time of the hydrothermal reaction is 10-100 h, and the temperature reduction time is 10-50 h.
Preferably, the preparation of the polypyrrole coated polyacid based metal-organic framework composite material of any one of the first aspect with pyrrole monomers and the polyacid based metal-organic framework material comprises:
dispersing pyrrole monomers in water to obtain a second solution;
and adding the polyacid-based metal-organic framework material, an initiator and an oxidant into the second solution, and stirring, centrifuging, washing and drying to obtain the polypyrrole-coated polyacid-based metal-organic framework composite material.
In a third aspect, embodiments herein provide an alkali metal ion battery anode material, including the polypyrrole coated polyacid-based metal organic framework composite material described in any one of the first aspects.
In a fourth aspect, embodiments of the present application provide an alkali metal ion battery, including the alkali metal ion battery anode material of the third aspect.
The polypyrrole coated polyacid-based metal organic framework composite material provided by the embodiment of the application has the following advantages:
1. the nitrogenous phenanthroline organic ligand and polypyrrole are introduced, and POMs as 'electronic sponges' can accept a large amount of electrons, so that higher alkali metal ion storage capacity can be provided in the circulation process;
2. the POMs are encapsulated in the MOFs frame, so that the POMs can be effectively prevented from being dissolved in electrolyte, the stability of the POMs is improved, and additional active sites can be provided;
3. and the conductive PPy is combined, so that the conductivity of the electrode material can be improved, and the actual reversible discharge capacity of the cathode material is improved under the synergistic effect.
Therefore, the polypyrrole coated polyacid-based metal organic framework composite material provided by the embodiment of the application has the advantages of high specific capacity, long cycle life and good rate capability when being used as the negative electrode of the alkali metal ion battery.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph of the optimization strategy and cycle performance of a polypyrrole-coated polyacid-based metal organic framework composite provided in the examples of the present application;
FIG. 2 is a schematic flow chart of a method for preparing a polypyrrole coated polyacid-based metal organic framework composite according to an embodiment of the present application;
FIG. 3 is a scanning electron microscope image of Cu-POMOFs prepared in the examples of the present application;
FIG. 4 is a schematic diagram of structural units of Cu-POMOFs prepared in the embodiment of the present application;
FIG. 5 is a schematic view of one-dimensional polymer chains of Cu-POMOFs prepared in examples of the present application;
FIG. 6 is a schematic diagram of three-dimensional supramolecular structures of Cu-POMOFs prepared in the examples of the present application;
FIG. 7 is a rate performance graph of the Cu-POMOFs @ PPy prepared in the embodiment of the application as a lithium ion battery anode material.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, 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 application.
It is understood that the alkali metal ion battery includes a lithium ion battery, a sodium ion battery, a potassium ion battery, and the like. The lithium ion battery has the advantages of high energy density, small volume, light weight, no memory effect, small self-discharge, long cycle life and the like, and becomes a novel chemical power supply with great potential in the 21 st century. Following the lithium ion battery, the sodium ion battery and the potassium ion battery are expected to be applied to a large-scale energy storage system due to wide sources and low price of key raw materials. Research shows that sodium ion batteries and potassium ion batteries are different from lithium ion batteries in that graphite is not suitable to be used as a negative electrode material because sodium ions are difficult to be inserted into graphite layers to form stable interlayer compounds, and potassium ions are relatively large in intercalation amount in the graphite but cause volume expansion of up to 61%, so that the capacity of the material is rapidly attenuated, and the cycle performance is poor. Therefore, development of an anode material having a higher capacity, a long cycle life and a high rate has been a research object in the field of ion batteries.
Polyoxometalates (POMs) are inorganic metal clusters with controllable shapes and variable structures, are often used in the fields of catalysis, light, electricity, magnetism and the like due to high activity and good selectivity, and are very suitable for realizing high-capacity energy storage application. For example, [ PMo ]12O40]3-(PMo12) As a negative electrode of a lithium ion battery, [ PMo ] during charging12O40]3-12 Mo in the solution6+The ions are reduced to Mo4+The POMs form a super-reduced state, i.e. [ PMo ]12O40]27-Storing 24 electrons, given an "electron sponge" because of the large number of transferred electronsAnd (4) properties. However, the POMs have a relatively low specific surface area (<10m2/g) and has high solubility in electrolytes, resulting in a great reduction in capacity, hindering the application of POMs as negative electrode materials for lithium ion batteries.
In order to solve the above problems, in the embodiments of the present application, metal organic framework Materials (MOFs) are combined with POMs to prepare polyacid based metal organic framework materials (pomofos) with a high specific surface area by using the characteristics of high surface area and porosity of the MOFs, and the dissolution of POMs in an electrolyte can be reduced. In addition, in order to improve the conductivity of the POMOFs, the POMOFs and polypyrrole (PPy) are compounded, wherein the POMOFs particles can be effectively coated by the PPy, so that the conductivity of the composite material is improved, and the polypyrrole-coated polyacid-based metal organic framework composite material (M-POMOF @ PPy) with high capacity, long cycle life and high multiplying power is obtained. The details will be described below.
Specifically, the composite material comprises transition metal cations, phenanthroline ligands, polyoxoanions, water molecules and polypyrrole, and the chemical formula of the composite material is [ Mm+ nz/m(1,10-phen)x(H2O)y][An- z]@ PPy, abbreviated as M-POMOF @ PPy, wherein M is a transition metal and "1, 10-phen" is 1, 10-phenanthroline, An-Is polyoxoanion, PPy is polypyrrole. It is understood that nz/m in the formula represents the number of transition metal cations, x represents the number of 1, 10-phenanthroline, y represents the number of coordinated water molecules, z represents the number of polyoxoanions, m + represents the valence of the transition metal cations, and n-represents the valence of the polyoxoanions. Wherein x may be 2, 3, 4, 5, etc.
In an alternative embodiment, the transition metal is Fe, Co, Ni, or Cu; the polyoxoanion is [ Mo ]6O20]4-、[W3O10]2-Or [ V ]13O34]3-。
Referring to the optimization strategy of the polypyrrole coated polyacid-organic framework composite material in fig. 1, the polypyrrole coated polyacid-organic framework composite material provided in the embodiment of the present application has the following advantages:
1. the nitrogenous phenanthroline organic ligand and polypyrrole are introduced, and POMs as 'electronic sponges' can accept a large amount of electrons, so that higher alkali metal ion storage capacity can be provided in the circulation process;
2. the POMs are encapsulated in the MOFs frame, so that the POMs can be effectively prevented from being dissolved in electrolyte, the stability of the POMs is improved, and additional active sites can be provided;
3. and the conductive PPy is combined, so that the conductivity of the electrode material can be improved, and the actual reversible discharge capacity of the cathode material is improved under the synergistic effect.
Therefore, the polypyrrole coated polyacid-based metal organic framework composite material provided by the embodiment of the application has the advantages of high specific capacity, long cycle life and good rate capability when being used as the negative electrode of the alkali metal ion battery.
Corresponding to the polypyrrole-coated polyacid-based metal-organic framework composite material, the application also provides a preparation method of the polypyrrole-coated polyacid-based metal-organic framework composite material.
Referring to fig. 2, a schematic flow chart of a method for preparing a polypyrrole-coated polyacid-based metal organic framework composite material is provided in the embodiments of the present application. As shown in fig. 2, it mainly includes the following steps.
Step S201: preparing the polyacid-based metal-organic framework material.
Specifically, dissolving transition metal salt, polyoxometallate and 1, 10-phenanthroline in water, and adjusting the pH value by adopting NaOH to obtain a first solution; and adding the first solution into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction, cooling to room temperature, collecting crystals, washing the crystals with deionized water and ethanol, and drying to obtain the polyacid-based metal organic framework material. The polyacid-based metal-organic framework material has a chemical formula of [ Mm+ nz/m(1,10-phen)x(H2O)y][An- z]Wherein M is a transition metal, 1,10-phen is phenanthroline, An-Is polyoxoanion.
In an alternative embodiment, the transition metal salt isThe metal element of (A) is Fe, Co, Ni or Cu; the anion in the transition metal salt is NO3 -、SO4 2-、CH3COO-Or Cl-。
In an optional embodiment, the molar ratio of the transition metal salt, the polyoxometallate and the 1, 10-phenanthroline is 1: 0.1-2. For example, the molar ratio of the transition metal salt, the polyoxometallate and the 1, 10-phenanthroline is 1:1:1,1:1.5:1.5, and the like. Wherein, too little polyoxometallate can cause too low yield, and too much polyoxometallate can cause structural damage; too little 1, 10-phenanthroline may result in incomplete coordination, too much may result in waste of raw materials, and therefore the preferred ratio is 1:1: 1.
In an alternative embodiment, NaOH is used to adjust the pH to 3-6, for example, pH 4 or 5. Among them, the pH is preferably 5 because too high or too low of pH causes poor crystallinity.
In an optional embodiment, the temperature of the hydrothermal reaction is 120 to 200 ℃, for example, 140 ℃, 160 ℃, or 180 ℃ is adopted as the temperature of the hydrothermal reaction. Wherein, the temperature of the hydrothermal reaction is too low to cause reaction; a too high temperature will destroy the product structure, so it is preferably 140 ℃.
In an optional embodiment, the hydrothermal reaction time is controlled to be 10-100 h, for example, 50h or 60 h. Among them, the hydrothermal reaction time is preferably 72 hours because the reaction is incomplete due to an excessively short time and the yield is excessively low.
In an optional embodiment, the temperature reduction time after the hydrothermal reaction is completed is 10 to 50 hours, for example, 15 hours or 20 hours. Among them, the cooling time is preferably 24 hours because an excessively short cooling time results in an excessively small crystal grain size.
Step S202: preparing the polypyrrole-coated polyacid-based metal-organic framework composite material by adopting a pyrrole monomer and the polyacid-based metal-organic framework material.
Specifically, pyrrole monomers are dispersed in water to obtain a second solution; and adding the polyacid-based metal-organic framework material, an initiator and an oxidant into the second solution, and stirring, centrifuging, washing and drying to obtain the polypyrrole-coated polyacid-based metal-organic framework composite material.
In an alternative embodiment, 0.1-5 mL of pyrrole monomer is dispersed in 30mL of water to obtain a second solution with corresponding concentration.
In an alternative embodiment, the stirring time of the second solution is 1 to 3 hours, for example, 1.5 hours or 2 hours. Wherein, too long stirring time can cause too high carbon content and consequently lower reversible capacity; too short a time causes poor conductivity, and therefore 2 hours is preferable.
In order to facilitate understanding, the embodiment of the application provides a specific implementation manner of a preparation method of a polypyrrole coated polyacid-based metal organic framework composite material. It should be noted that the following is only a specific implementation manner, and should not be taken as a limitation of the protection scope of the present application, and the person skilled in the art can make appropriate adjustments according to actual needs, and all should fall within the protection scope of the present application.
In the present application, taking Cu-pomofos @ PPy as an example, a detailed description is given to a preparation method of a polypyrrole-coated polyacid-based metal-organic framework composite material, which mainly includes the following steps.
Step S301: 0.1mmol of 1, 10-phenanthroline, 0.1mmol of copper nitrate and 0.1mmol of phosphomolybdic acid are added into 10mL of water, and after complete dissolution, the mixture is stirred at a constant speed for 30 minutes to be uniformly dispersed.
Step S302: to the above solution, 1mol/L NaOH was slowly added until the pH was adjusted to 5, to obtain a green solution.
Step S303: the green solution was transferred to a 20 mL-scale reaction vessel and reacted in a 140 ℃ oven for 72 hours, and the time to room temperature was set to 24 hours.
Step S304: obtaining green crystals after the temperature reduction is finished, selecting the crystals under a microscope, washing the crystals for 3 times respectively by deionized water and ethanol, and drying the crystals in a 60 ℃ oven for 12 hours to prepare the [ Cu (1,10-phen) (H)2O)2]2[Mo6O20](Cu-POMOFs)。
Step S305: first, 0.15mL of pyrrole was dispersed in 30mL of deionized water and stirred for 10 minutesMixing completely, adding 0.15g of Cu-POMOFs into the pyrrole solution under stirring, dispersing uniformly, adding 0.405g of FeCl3And stirring at a constant speed for reaction for 2 hours at room temperature to prepare black powder, namely the Cu-POMOFs @ PPy composite material.
Referring to fig. 3, it is a scanning electron micrograph of Cu-pomofos prepared in the examples of the present application. As shown in fig. 3, the Cu-pomofos prepared in the examples of the present application have a regular cubic morphology, and the outer layer thereof is conductive polypyrrole.
Referring to fig. 4, it is a schematic diagram of structural units of Cu-pomofos prepared in the embodiments of the present application. As shown in FIG. 4, in Cu-POMOFs, each penta-coordinated Cu (II) cation is attached to two nitrogen atoms of a phenanthroline ligand, one from the hexamolybdate [ Mo ]6O20]4-The terminal oxygen atom of the fragment, and the oxygen atoms from the two coordinated water molecules. [ Mo ]6O20]4-The clusters are gathered along the a axis to form one-dimensional molybdate chains which are parallel to each other through a large number of Mo-O bonds, and the one-dimensional hybrid compound is formed by simultaneously coordinating Cu (II) and terminal oxygen atoms on the one-dimensional chains.
Referring to fig. 5, a schematic diagram of one-dimensional polymer chains of Cu-pomofos prepared for the examples of the present application, wherein the polyhedral representation corresponds to MoO. As shown in FIG. 5, [ Mo ]6O20]4-The clusters are gathered along the a axis to form one-dimensional molybdate chains which are parallel to each other through a large number of Mo-O bonds, and the one-dimensional hybrid compound is formed by simultaneously coordinating Cu (II) and terminal oxygen atoms on the one-dimensional chains.
Referring to fig. 6, a schematic diagram of three-dimensional supramolecular structures of Cu-pomofos prepared in the examples of the present application, wherein the polyhedral representation corresponds to { MoO }. As shown in fig. 6, since one-dimensional molybdate chains and two-dimensional supramolecular layers are perpendicular to each other, a three-dimensional supramolecular structure is constructed.
Correspondingly, the embodiment of the application also provides an alkali metal ion battery anode material, which comprises the polypyrrole-coated polyacid-based metal organic framework composite material shown in fig. 3.
For example, the Cu-POMOFs @ PPy prepared in the above example, carbon black, CMC in the ratio of 7: 2: 1, uniformly grinding, uniformly coating the slurry on a copper foil current collector, and drying to obtain the alkali metal ion battery negative electrode material.
Corresponding to the anode material, the embodiment of the application also provides an alkali metal ion battery, and the alkali metal ion battery comprises the anode material in the embodiment.
For example, the negative electrode material prepared in the above example was used to assemble an alkali metal ion battery in an argon atmosphere, in which Celgard2400 polypropylene porous membrane was used as a separator, a lithium sheet was used as a counter electrode, and an electrolyte was 1mol/L LiPF6Dissolving in a solvent with the volume ratio of 1:1:1 EC, DMC, EMC.
The assembled cells were tested for electrochemical performance on the nova cell test system, cycle performance at a current density of 1A/g, and rate performance at current densities of 0.1, 0.2, 0.4, 0.5, 1, 2, 4, 5, and 0.1A/g.
Fig. 1 is a diagram of an optimization strategy and a Cycle performance of a polypyrrole-coated polyacid-based metal organic framework composite provided in an embodiment of the present application, where the Cycle performance is a diagram of a Cycle performance of a Cu-pomofos @ PPy prepared in an embodiment of the present application as a negative electrode material of a lithium ion battery, fig. 7 is a diagram of a rate performance of a Cu-pomofos @ PPy prepared in an embodiment of the present application as a negative electrode material of a lithium ion battery, where a Cycle number is a number of cycles of a battery, a Cycle is one Cycle of discharge and charge, and a Specific capacity is a Specific capacity corresponding to each Cycle of the battery, and a unit is mAh/g. As shown in FIGS. 1 and 7, the specific capacity of 300mAh/g can be maintained after 500 cycles of the cycle at the current density of 2A/g, the specific capacity of 583.94, 463.94, 399.83, 381.33, 298.83, 202.17, 133.27 and 115.25mAh/g is respectively at the current densities of 0.1, 0.2, 0.4, 0.5, 1, 2, 4 and 5A/g, and the specific capacity of 602mAh/g can still be recovered when the current density is returned to 0.1A/g.
In summary, the polypyrrole coated polyacid-based metal organic framework composite material provided by the embodiment of the present application has the following advantages:
1. the nitrogenous phenanthroline organic ligand and polypyrrole are introduced, and POMs as 'electronic sponges' can accept a large amount of electrons, so that higher alkali metal ion storage capacity can be provided in the circulation process;
2. the POMs are encapsulated in the MOFs frame, so that the POMs can be effectively prevented from being dissolved in electrolyte, the stability of the POMs is improved, and additional active sites can be provided;
3. and the conductive PPy is combined, so that the conductivity of the electrode material can be improved, and the actual reversible discharge capacity of the cathode material is improved under the synergistic effect.
Therefore, the polypyrrole coated polyacid-based metal organic framework composite material provided by the embodiment of the application has the advantages of high specific capacity, long cycle life and good rate capability when being used as the negative electrode of the alkali metal ion battery.
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The polypyrrole-coated polyacid-based metal organic framework composite material is characterized by comprising a transition metal cation, a phenanthroline ligand, a polyoxoanion, a water molecule and polypyrrole, wherein the chemical formula of the composite material is [ M ]m + nz/m(1,10-phen)x(H2O)y][An- z]@ PPy, where M is a transition metal and "1, 10-phen" is 1, 10-phenanthroline, An-Is polyoxoanion, PPy is polypyrrole.
2. The composite material of claim 1, wherein the transition metal is Fe, Co, Ni, or Cu; the polyoxoanion is [ Mo ]6O20]4-、[W3O10]2-Or [ V ]13O34]3-。
3. A preparation method of a polypyrrole-coated polyacid-based metal organic framework composite material is characterized by comprising the following steps of:
preparing a polyacid-based metal-organic framework material having the chemical formula [ Mm+ nz/m(1,10-phen)x(H2O)y][An- z]Wherein M is a transition metal, 1,10-phen is phenanthroline, An-Is a polyoxoanion;
preparing the polypyrrole coated polyacid based metal organic framework composite of claim 1 or 2 using pyrrole monomers and the polyacid based metal organic framework material.
4. The method of claim 3, wherein the preparing the polyacid-based metal-organic framework material comprises:
dissolving transition metal salt, polyoxometallate and 1, 10-phenanthroline in water, and adjusting the pH value by adopting NaOH to obtain a first solution;
and adding the first solution into a reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction, cooling to room temperature, collecting crystals, washing the crystals with deionized water and ethanol, and drying to obtain the polyacid-based metal organic framework material.
5. The method according to claim 4, wherein the molar ratio of the transition metal salt, the polyoxometalate and the 1, 10-phenanthroline is 1: 0.1-2.
6. The method according to claim 4, wherein the metal element in the transition metal salt is Fe, Co, Ni or Cu; the anion in the transition metal salt is NO3 -、SO4 2-、CH3COO-Or Cl-。
7. The method according to claim 4, wherein the temperature of the hydrothermal reaction is 120-200 ℃, the time of the hydrothermal reaction is 10-100 h, and the temperature reduction time is 10-50 h.
8. The method of claim 3, wherein the preparing the polypyrrole coated polyacid-organic framework composite of claim 1 or 2 from pyrrole monomers and the polyacid-organic framework material comprises:
dispersing pyrrole monomers in water to obtain a second solution;
and adding the polyacid-based metal-organic framework material, an initiator and an oxidant into the second solution, and stirring, centrifuging, washing and drying to obtain the polypyrrole-coated polyacid-based metal-organic framework composite material.
9. An alkali metal ion battery negative electrode material, comprising the polypyrrole-coated polyacid-based metal organic framework composite material according to claim 1 or 2.
10. An alkali metal ion battery comprising the alkali metal ion battery negative electrode material according to claim 9.
CN202011297673.XA 2020-11-18 2020-11-18 Polypyrrole-coated polyacid-based metal organic framework composite material, negative electrode material, alkali metal ion battery and method Pending CN112421004A (en)

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