CN113224273A - Heterogeneous cavity structure material and preparation method and application thereof - Google Patents

Heterogeneous cavity structure material and preparation method and application thereof Download PDF

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CN113224273A
CN113224273A CN202010080699.2A CN202010080699A CN113224273A CN 113224273 A CN113224273 A CN 113224273A CN 202010080699 A CN202010080699 A CN 202010080699A CN 113224273 A CN113224273 A CN 113224273A
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shell layer
cavity structure
inner shell
outer shell
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何海勇
洪兴星
王德宇
潘林海
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The application discloses heterogeneous cavity structure material and a preparation method and application thereof, the heterogeneous cavity structure material is a hollow sphere, the spherical shell is composed of an outer shell layer and an inner shell layer, the conductivity of the inner shell layer is at least 2.5S/cm greater than that of the outer shell layer, the thickness of the inner shell layer is 10-50 nm, the thickness of the outer shell layer is 5-20 nm, and the outer diameter of the hollow sphere is 50-8000 nm. This heterogeneous cavity structure material inlayer electric property is good, and outer seal insulation electric conductivity is poor, when being applied to lithium ion battery, utilizes the different regulation and control electric field distributions of heterostructure conductivity, and then the selective deposition of induced lithium metal, makes inside the cavity that lithium metal can directional deposit the spherical shell formation, can effectively restrain the dendritic crystal growth, and isolated dendritic crystal and electrolyte contact improve lithium metal battery's security performance and cyclicity ability.

Description

Heterogeneous cavity structure material and preparation method and application thereof
Technical Field
The application relates to a heterogeneous cavity structure material and a preparation method and application thereof, belonging to the technical field of nano materials.
Background
The main cathode materials of the lithium battery comprise a lithium-based material, a carbon nano material, a graphene material and the like. The electrolyte of the lithium ion battery is inflammable, and the lithium-based material is taken as a negative electrode material to easily form dendritic crystals in the electrolyte, so that the dendritic crystals grow during charging, internal short circuit is easily caused, and even fire is caused. The lithium capacity of the carbon nano material and graphene material negative electrode is relatively low, generally 370mAh.g-1(1C), and dendrite is easily formed when the charging is too fast.
Scientific research shows that the design of the negative electrode material can effectively inhibit the growth of dendrites. For example, the U.S. intellectual property office granted a utility model patent US9833748-B2 in 2019, 12, 6, month, the utility model relates to a composite lithium metal negative electrode and lithium secondary battery, belonging to the technical field of secondary batteries. The composite lithium metal cathode of the utility model comprises metal lithium and a three-dimensional framework with a cavity; the three-dimensional framework comprises a conductive layer and an insulating layer wrapped outside the conductive layer, and the insulating layer is tightly attached to the conductive layer; the edge of the three-dimensional framework is of an open pore structure; and the metal lithium is filled in the cavity of the three-dimensional framework and is tightly attached to the conducting layer. The composite lithium metal cathode of the utility model can delay the occurrence time of lithium dendrite and control the growth direction of the dendrite, thereby the growth of the lithium dendrite is inhibited and regulated, and the potential safety hazard is eliminated in the electrochemical charging and discharging process; and because the insulating layer is wrapped outside the conducting layer, the lithium metal is protected in the operating environment, and the stability of the lithium metal in the operating environment is improved.
The open structure of the above materials does not solve the problem of side reactions caused by the contact of dendrites with the electrolyte.
Disclosure of Invention
According to one aspect of the application, a heterogeneous cavity structure material is provided, wherein the heterogeneous cavity structure material is in a hollow sphere shape, the spherical shell is composed of an outer shell layer and an inner shell layer, and the electrical conductivity of the inner shell layer is at least 2.5S/cm greater than that of the outer shell layer. The heterogeneous cavity structure material is hollow in the interior and compact in shell layer, and can be used for directionally loading and filling active substances. This heterogeneous cavity structure material inlayer electric property is good, and outer closed insulation electric conductivity is poor, works as the thickness of inner shell layer is 10 ~ 50nm, the thickness of outer shell layer is 5 ~ 20nm, just when the external diameter of clean shot is 50 ~ 8000nm, when being applied to lithium ion battery, because this heterostructure conductivity difference can regulate and control electric field distribution, and then induced lithium metal selectivity deposit, make inside lithium metal can directional deposit the cavity that the spherical shell formed, can effectively restrain the dendritic crystal growth, isolated dendritic crystal and electrolyte contact improve lithium metal battery's security performance and cyclicity ability.
Optionally, the outer diameter of the hollow ball is 80 nm-7000 nm; the upper limit of the outer diameter of the hollow sphere can be 8000nm, 7000nm, 1000nm, 500nm, 200nm or 120nm, and the lower limit can be 500nm, 200nm, 120nm, 80nm, 50nm or 20 nm.
Optionally, the inner shell layer is a simple substance layer, and the outer shell layer is a compound layer;
the single layer is selected from at least one of a carbon layer, a silicon layer and a boron layer;
the compound layer is selected from at least one of an oxide layer, a carbide layer, a nitride layer, a halogen compound layer, and a boride layer.
Optionally, the inner shell layer is a carbon layer, and the outer shell layer is SiO2Layer, TiO2Layer or SnO2And (3) a layer.
In a second aspect of the present application, a method for preparing the heterogeneous cavity structure material is provided, which includes the following steps:
and preparing the inner shell layer and the outer shell layer to obtain the heterogeneous cavity structure material.
Optionally, the preparing the inner and outer shell layers comprises:
firstly, reacting a mixed solution containing a template agent and a shell precursor, and preparing the shell on the surface of the template agent;
and obtaining the inner shell layer by using the template agent, thereby obtaining the heterogeneous cavity structure material.
Optionally, the outer shell layer is SiO2The inner shell layer is a carbon layer, and the template agent is an organic microsphere, a surfactant or a hollow carbon sphere;
the organic microspheres are selected from at least one of polystyrene microspheres, sulfonated polystyrene composite polyaniline microspheres and polyaniline microspheres;
the surfactant is selected from at least one of hexadecyl trimethyl ammonium bromide, tetradecyl ammonium bromide and octadecyl dimethyl benzyl quaternary ammonium chloride;
the shell layer precursor is selected from at least one of ethyl orthosilicate, silicon tetrachloride and sodium silicate.
Optionally, the mixed solution further comprises a catalyst, wherein the catalyst is weak base or acid, the weak base is selected from ammonia water, and the acid is selected from hydrochloric acid and acetic acid; when the catalyst is acid, the pH value of the reaction system is preferably 2-3, when the catalyst is weak base, the pH value of the reaction system is preferably 9-11, and the solvent of the mixed solution can be at least one selected from water and ethanol.
Optionally, the template is an organic microsphere or a surfactant, and obtaining the inner shell layer from the template includes converting the template into the inner shell layer, specifically including:
converting the template into the inner shell layer by at least one of wet chemical method, high temperature pyrolysis method, solvent dissolution method.
Specifically, in the embodiment of the present invention, the high temperature pyrolysis method refers to that organic matter in the template is carbonized by sintering at high temperature to form a carbon layer; the wet chemical method is to remove at least part of the template agent by using a liquid compound reaction, and the solvent dissolution method is to remove at least part of the template agent by using a solvent for dissolution. Alternatively, the conversion of the templating agent into the inner shell layer is achieved by high temperature pyrolysis carbonization, wet chemical removal of a portion of the templating agent followed by high temperature pyrolysis carbonization of the remaining templating agent, or solvent dissolution removal of a portion of the templating agent followed by high temperature pyrolysis carbonization of the remaining templating agent.
In an alternative embodiment, the templating agent is an organic microsphere, such as a polystyrene microsphere, and converting the templating agent into the inner shell layer comprises:
the organic microspheres are converted into a carbon layer, i.e. the inner shell layer, by a high temperature pyrolysis process.
In a specific embodiment, the template is a polystyrene microsphere, and the method includes the steps of reacting a mixed solution containing the template and a shell precursor, and preparing the shell on the surface of the template, specifically including:
dispersing polystyrene microspheres in water to obtain a suspension of the polystyrene microspheres, wherein the mass concentration of the suspension of the polystyrene microspheres is preferably 5-25%;
adding the suspension of the polystyrene microspheres and a catalyst into an alcohol solvent to obtain a first mixed solution;
and (2) dropwise adding a silicon source into the first mixed solution at the temperature of 20-40 ℃, and obtaining a second mixed solution after dropwise adding, wherein the mass ratio of the silicon source to the polystyrene microspheres is preferably 20: 1-5: 1;
stirring and reacting the second mixed solution at the temperature of 60-80 ℃ for 10-15 h to obtain a suspension;
and separating, washing and drying the suspension to obtain the template agent and shell layer composite material.
In another alternative embodiment, the templating agent is a composite microsphere formed from two different organic materials, such as sulfonated polystyrene composite polyaniline microspheres, which converts the templating agent into the inner shell layer, including:
removing one organic matter in the template by a solvent dissolution method, and converting the other organic matter in the template into a carbon layer, namely the inner shell layer, by a high-temperature pyrolysis method.
Optionally said preparing said inner and outer shell layers comprises:
preparing the outer shell layer by a templating process;
and removing the template of the outer shell layer, soaking the outer shell layer into a solution containing a carbon source, taking out, washing, drying and carbonizing to obtain the inner shell layer.
Optionally, the template is an organic microsphere, such as polystyrene microsphere, and the carbon source may be selected from polystyrene.
The method can adjust the amount of the precursor or raw material and the amount of the catalyst to control the thickness and the shape of the heterostructure by selecting different surface charge templates.
The heterogeneous cavity structure material with the hollow sphere shape is obtained by a wet chemical method, a high-temperature pyrolysis method and a solvent dissolution method, and the process is simple. The thickness and the shape of the heterostructure are controlled by selecting templates with different sizes and adjusting the sintering time and the sintering temperature in the high-temperature pyrolysis step.
Optionally, the preparing the inner and outer shell layers comprises:
firstly, preparing an inner shell layer from a mixed solution containing an inner shell layer raw material;
then adding the inner shell layer into a mixed solution containing an outer shell layer raw material, and coating the outer shell layer outside the inner shell layer;
wherein the inner shell layer is a carbon layer, and the outer shell layer is an oxide layer;
optionally, the raw material of the inner shell layer is at least one of sucrose, glucose and fructose; the shell layer raw material is a silicon source, a titanium source or a tin source;
the silicon source is at least one of ethyl orthosilicate, silicon tetrachloride and sodium silicate;
the titanium source is selected from at least one of tetrabutyl titanate, titanium tetrachloride, metatitanic acid and titanium isopropoxide;
the tin source is at least one of stannic chloride pentahydrate, stannate and stannous chloride.
OptionallyBy improving
Figure BDA0002380212330000041
At least one of a chemical vapor deposition method, an electroplating method, an atomic layer deposition method, and a molecular layer deposition method.
The template method is a main method for preparing a cavity structure at present, and can be classified into a soft template method, a hard template method and a self-template method according to the type of a template used. The method comprises the steps of forming a hollow inner cavity by guiding with a hard template or a soft template, and inducing a coating material to be assembled together to form a mesoporous shell by utilizing a mesoporous structure guiding agent through intermolecular forces such as electrostatic action, hydrogen bonds and the like. The template method has the advantages of simplicity, convenience and controllability, and the preparation of the hollow silica microspheres by using the template method is generally divided into three steps: (1) selecting or preparing a template; (2) self-assembling to form a shell material; (3) roasting or extracting to remove the template.
Improvement of the structure
Figure BDA0002380212330000051
The method is developed from the original method. Original source
Figure BDA0002380212330000053
The method is a physicochemical method for synthesizing monodisperse silicon particles, by Werner
Figure BDA0002380212330000052
And the first. Generally refers to a method of forming nano silica particles by adding tetraethyl orthosilicate to ethanol and ammonia water. To improve
Figure BDA0002380212330000054
The method is that catalyst and precursor are added into template solution with charge, and through electrostatic adsorption and hydrolysis, one layer of oxide shell is formed on the surface of the template.
Chemical Vapor Deposition (CVD) is a technique in which one or more gaseous compounds or elements containing thin film elements are chemically reacted on the surface of a substrate to form a thin film. Chemical vapor deposition is a new technique for preparing inorganic materials that has been developed in recent decades. Chemical vapor deposition has been widely used to purify substances, develop new crystals, and deposit various single-crystal, polycrystalline, or glassy inorganic thin film materials.
In a specific embodiment, the method for preparing the heterogeneous cavity structure material includes:
preparing a template phase material; by improvement of
Figure BDA0002380212330000055
Preparing the heterogeneous layer structure composite material by one or more of a method, a chemical vapor deposition method, atomic layer deposition and molecular layer deposition; and removing the template phase material of the composite material by adopting a wet chemical method, a high-temperature pyrolysis method and a solvent dissolution method.
Specifically, the method for preparing the heterogeneous cavity structure material provided by the embodiment includes the following steps:
step S100: preparing a nano or micro microsphere template;
step S200: by improvement of
Figure BDA0002380212330000056
Preparing the heterogeneous layer structure composite material by one or more of a method, a chemical vapor deposition method, atomic layer deposition and molecular layer deposition;
step S300: and removing the composite material template phase material by adopting a wet chemical method, a high-temperature pyrolysis method and a solvent dissolution method, and applying the composite material template phase material to lithium metal battery protection, wherein the sequence of the steps S200 and S300 can be adjusted according to a specific experimental process.
The present invention will be improved
Figure BDA0002380212330000057
The method combines two or more methods of chemical vapor deposition, atomic layer deposition, molecular layer deposition, wet chemical method, high-temperature pyrolysis method and solvent dissolution method, and aims to prepare a heterogeneous composite cavity which is hollow and is beneficial to loading and filling active substances. The diameter and the layer thickness of the cavity are adjustable. Meanwhile, the electric field distribution is regulated and controlled by the conductivity difference of the heterogeneous cavity structure, and lithium metal can be directionally deposited into the cavity. The method has the advantages of simple process, low cost and easy operation.
The method can be used for controllably adjusting the particle size of the template and the surface charge of the template by adjusting template synthesis conditions, such as the type of an initiator, the amount of raw materials, reaction time, reaction temperature, the molecular weight of a dispersing agent and the like. The method is simple and controllable, and is green and environment-friendly.
In a third aspect of the present application, there is provided a heterocavity structure material electrode, including an active material, a conductive agent, a binder and a current collector, where the active material is at least one of the heterocavity structure material described in any one of the above and the heterocavity structure material prepared by the preparation method described in any one of the above.
Optionally, the active material, the conductive agent and the binder are mixed in percentage by mass:
20% -80% of active material;
0-40% of conductive agent:
10 to 40 percent of binder.
In a fourth aspect of the present application, a method for preparing any one of the above heterogeneous cavity structure material electrodes is provided, in which an active material, a conductive agent and a binder are mixed in proportion to form a slurry, and the slurry is compounded on a current collector to obtain the heterogeneous cavity structure material electrode.
Optionally, the mass percentage ratio of the active material, the conductive agent and the binder is 20-80% of the active material, 0-40% of the conductive agent and 10-40% of the binder.
The conductive agent can be at least one of conductive carbon black, Ketjen black or carbon nanotubes;
the binder is selected from at least one of polytetrafluoroethylene emulsion, polyvinylidene fluoride, hydroxypropyl cellulose, styrene-butadiene rubber and polyethylene;
the current collector is selected from at least one of a stainless steel net, a stainless steel sheet, a titanium net, a copper net and a porous aluminum foil;
the compounding mode is at least one of film coating, rolling and extrusion.
In a fifth aspect of the present application, there is provided a lithium ion half cell, wherein the negative electrode is the electrode made of the heterogeneous cavity structure material provided in any one of the above;
optionally, the positive electrode of the lithium-ion half cell is a lithium sheet.
The lithium ion half-cell also comprises electrolyte, and the solute of the electrolyte is LiPF6The solvent is prepared by mixing ethylene carbonate and diethyl carbonate according to the volume ratio of 1: 1.
The beneficial effects that this application can produce include:
(1) the heterogeneous cavity structure material provided by the invention can adjust the particle size and the shell thicknesses with different properties according to requirements, is beneficial to loading and filling active substances, and meets different application requirements.
(2) The invention provides a preparation method of a heterogeneous cavity structure material, which is improved by
Figure BDA0002380212330000071
Preparing the heterogeneous layer structure composite material by one or more of a method, a chemical vapor deposition method, atomic layer deposition and molecular layer deposition; and removing the template phase material of the composite material by adopting a wet chemical method, a high-temperature pyrolysis method and a solvent dissolution method to form a cavity structure compounded by materials with different conductivities. The preparation method has simple process, and the used equipment is industrialized experimental equipment and has good application prospect. The method has the advantages of simple process, low cost and easy operation, and can prepare the impurity-free compact nano-scale or micro-scale heterogeneous cavity structure material.
(3) According to the heterogeneous cavity structure material provided by the invention, the conductivity of the heterogeneous material is different, the special electric field is regulated and controlled, and the whole structure is compact and closed, so that lithium metal can be directionally deposited in the cavity. The lithium metal negative electrode protection agent is applied to lithium metal negative electrode protection, can effectively inhibit dendritic crystal growth and volume change, isolate lithium metal from being in contact with electrolyte, inhibit side reaction, and improve the safety performance and the cycling stability of a lithium metal battery.
Drawings
FIG. 1 is a TEM image of a heterogeneous cavity structure material 1# prepared in example 1 of the present invention;
FIG. 2 shows the energy spectrum distribution of the 1# Si element of the heterogeneous cavity structure material prepared in example 1 of the present invention;
FIG. 3 shows the energy spectrum distribution of the 1# C element of the heterogeneous cavity structure material prepared in example 1 of the present invention;
FIG. 4 is a graph of the charge and discharge electrochemical performance of the heterostructure material 1# prepared in example 1 of the present invention;
FIG. 5 is a schematic diagram of the cycle performance of the heterogeneous cavity structure material 1# prepared in example 1 of the present invention.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
EXAMPLE 1 preparation of heterogeneous Cavity Structure Material 1#
Suspension polymerization to prepare a polystyrene template:
pretreatment: preparing a sodium hydroxide solution with the mass concentration of 10%, carrying out alkali washing on styrene (St) for three times, and carrying out water washing for three times. Dissolving Azobisisobutyronitrile (AIBN) in ethanol at 40 ℃, cooling, recrystallizing and purifying;
a250 mL flask was charged with 1g polyvinylpyrrolidone (PVP, molecular weight 13000),30mL ethanol and 70.0mL H2O，N2Mechanically stirring at room temperature for 30min at the rotation speed of 200rpm, adding 10.0mL of pretreated St, adding 0.2g of pretreated AIBN, and heating to 70 ℃ to react for 12 h.
The suspension after the reaction is cooled to room temperature, centrifuged at 9000rpm for 10min, washed with ethanol three times, and placed in a vacuum drying oven to be dried for 5h at 40 ℃ to obtain solid Polystyrene (PS) powder.
Improvement of the structure
Figure BDA0002380212330000081
Cladding of SiO by a process2：
0.5g of the PS powder prepared above was taken and put into 5mLH2And O, performing ultrasonic treatment for 30min to form a PS suspension.
0.850g of ammonia water solution (25-28 wt%) and 5.5g of PS suspension are added to 95.0g of ethanol with stirring, 5mL of tetraethyl orthosilicate (TEOS) and 5mL of ethanol are added dropwise while maintaining the temperature at 30 ℃, and stirring is continued at 70 ℃ for 12 hours after the dropwise addition is finished.
The mixture is cooled to room temperature, centrifuged at 9000rpm for 10min, washed with ethanol three times, and dried in a vacuum drying oven at 40 ℃ for 5h to obtain solid powder (polystyrene and silicon dioxide composite).
And (3) high-temperature sintering:
and putting the prepared solid powder into a tubular furnace, continuously introducing argon at the rate of 100sccm, heating to 400 ℃ at the heating rate of 1 ℃/min, sintering for 4h, carbonizing polystyrene in the composite material, and attaching the carbonized polystyrene to the inner side of the silicon dioxide wall to form a heterogeneous cavity structure material 1# with a carbon layer as an inner layer and a silicon dioxide layer as an outer layer.
A scanning electron microscope and a transmission electron microscope are used for characterization, and the heterogeneous cavity structure material 1# is of a hollow spherical structure, the outer diameter is 200nm, the thickness of a silicon dioxide layer is 20nm, and the thickness of a carbon layer is 10 nm.
Example 2 preparation of heterostructure material 2#
Suspension polymerization to prepare a polystyrene template:
pretreatment: preparing a sodium hydroxide solution with the mass concentration of 10%, carrying out alkali washing on the styrene for three times, and carrying out water washing for three times; dissolving azodiisobutyronitrile in ethanol at 40 deg.c, cooling and re-crystallizing to purify;
a250 mL flask was charged with 1g PVP, 100.0mL H2O, in N2Mechanically stirring at room temperature for 30min under the atmosphere, rotating at the speed of 200rpm, adding 10.0mL of pretreated St, adding 0.2g of pretreated AIBN, and heating to 70 ℃ to react for 12 h.
And cooling the reacted suspension to room temperature, centrifuging at 12000rpm for 10min, washing with ethanol for three times, and drying in a vacuum drying oven at 40 ℃ for 5h to obtain solid PS powder.
Improvement of the structure
Figure BDA0002380212330000091
Cladding of SiO by a process2：
0.5g of the PS powder prepared above was taken and put into 5mLH2O, ultrasonic treatment for 30min to form PS suspensionAnd (4) floating liquid.
0.850g of an aqueous ammonia solution (25 to 28 wt%) and 5.5g of PS suspension were added to 95.0g of ethanol with stirring, and a 10ml of an ethanol solution (50 wt%) of EOS was added dropwise while maintaining the temperature at 30 ℃. After the end of the dropwise addition, stirring was continued at 70 ℃ for 12 h.
Cooling the mixture to room temperature, centrifuging at 9000rpm for 10min, washing with ethanol for three times, and drying in a vacuum drying oven at 40 deg.C for 5h to obtain solid powder.
And (3) high-temperature sintering:
and putting the prepared solid powder into a tubular furnace, continuously introducing argon at the rate of 100sccm, heating to 400 ℃ at the heating rate of 1 ℃/min, sintering for 4h, carbonizing polystyrene in the composite material, and attaching the carbonized polystyrene to the inner side of the silicon dioxide wall to form a heterogeneous cavity structure material 2# with a carbon layer as an inner layer and a silicon dioxide layer as an outer layer.
The heterogeneous cavity structure material No. 2 is a hollow spherical structure with the outer diameter of 120nm, the thickness of a silicon dioxide layer of 20nm and the thickness of a carbon layer of 10 nm.
Example 3 preparation of heterocavity structure Material 3#
This example is essentially the same as example 1, except that TEOS was added in an amount of 10 mL. The heterogeneous cavity structure material 3# is a hollow sphere, the outer diameter is 135nm, the thickness of the silicon dioxide layer is 35nm, and the thickness of the carbon layer is 10 nm. The obtained silicon dioxide layer on the surface of the heterogeneous cavity structure is too thick, so that particles are not dense.
Example 4 preparation of heterostructure material 4#
0.15g of Cetyl Trimethyl Ammonium Bromide (CTAB) as a surfactant, 15mL of ethanol and 30mL of water are weighed into a beaker (the total volume of the ethanol and the water is 45mL), stirred uniformly and poured into a three-neck flask provided with an electric stirring rod and a reflux condenser tube, and stirring is continued for 20min to completely dissolve the surfactant. And then adding 1g (25-28 wt%) of catalyst ammonia water and 0.45mL of silicon source TEOs, reacting at room temperature for 4h, centrifuging, drying the product in a 60 ℃ oven, and sintering in 100scm argon atmosphere for 2h to obtain a heterogeneous cavity structure material 4# with a carbon layer as an inner layer and a silicon dioxide layer as an outer layer. The heterogeneous cavity structure material No. 4 is a hollow sphere, the outer diameter of the hollow sphere is 80nm, the thickness of the silicon dioxide layer is 35nm, and the thickness of the carbon layer is 5 nm.
EXAMPLE 5 preparation of heterostructure material 5#
Preparing carbon spheres:
0.02mol of sucrose was dissolved in 20ml of water to form a clear solution. The solution was then sealed in a teflon-lined 30ml autoclave and held at 180 ℃ for 8 h. The product was centrifuged, washed and redispersed in water, and the cycle was repeated five times. And then drying the obtained product at 80 ℃ for 5 hours to obtain the carbon spheres.
2ml of ethanol and 18ml of water were mixed and adjusted to pH 2 with HCl, and then 1ml of TEOS was added to the solution with vigorous stirring (400 r 'p'm). TEOS was hydrolyzed by stirring for 30 minutes to obtain a hydrolysis mixture. 0.2g of the prepared carbon spheres was added to the hydrolysis mixture, and silica was coated on the surfaces of the carbon spheres with vigorous stirring (rotation speed of 400 rpm). After 24 hours of reaction, the product was centrifuged. Next, the product was redispersed, washed and centrifuged in ethanol, and the cycle was repeated 3 times. Drying the sample at 40 ℃ for 12 hours, and cooling the sample to room temperature to obtain white powder, wherein the white powder is the heterogeneous cavity structure material with the inner layer being the carbon layer and the outer layer being the silicon dioxide layer No. 5.
Example 6 preparation of heterostructure material 6#
This example is substantially the same as example 5, except that tetrabutyl titanate, a titanium source, is used to replace TEOS to obtain a heterostructure material # 6.
Example 7 preparation of heterostructure material 7#
This example is substantially the same as example 5, except that tin chloride pentahydrate is used instead of TEOS as a tin source to obtain a heterostructure material # 7.
EXAMPLE 8 preparation of heterostructure material 8#
The polystyrene and silica composite obtained in example 1 was sintered at 400 ℃ for 4 hours in 100scm air or soaked in a toluene solution for 8 hours to obtain hollow silica spheres, which were soaked in an ethanol solution of a phenol resin (m-urotropine: mPF ═ 1: 10) containing hexamethylenetetramine (urotropine) as a crosslinking agent. Washing with alcohol for three times, and vacuum drying at 30 deg.C for 4 hr. Putting the mixture into a box-type atmosphere furnace, heating to 100scm (the heating rate is 1 ℃/min) under the protection of nitrogen, and completing the carbonization process of PF, thereby obtaining the heterogeneous cavity structure material No. 8.
Example 9 preparation of heterostructure material 9#
Preparation of polystyrene composite polyaniline microspheres
0.85g of the polystyrene powder obtained in example 1 was dissolved in 30mL of 98 wt% concentrated sulfuric acid, stirred at 40 ℃ for 4h, centrifuged, washed and dried under vacuum for 2h to obtain a pale yellow solid powder (sulfonated polystyrene). Dissolving sulfonated polystyrene 0.58g in 10mLH2And in O, stirring in an ice bath for 30min, dropwise adding an aniline solution (prepared by adding 0.127g of aniline into 2mL of 2M HCl solution), continuing stirring in the ice bath for 5h, dropwise adding an ammonium sulfite solution (formed by dissolving 0.2g of ammonium sulfite solid in 2.5mL of deionized water), and continuing performing ice bath for 12h to obtain a green solution. And centrifugally washing and drying to obtain green powder solid.
And (3) dispersing 0.25g of the green powder solid in 5mL of ethanol, stirring at 45 ℃ for 30min, sequentially dropping 1.5mL of deionized water and a certain amount of ammonia water, adjusting the pH value of the solution to 10.5, slowly dropping 0.2mL of TEOS, and continuing to react for 12 h.
And after the reaction is finished, centrifugally washing and drying, dissolving the solid in DMF for 12h, washing and drying with ethanol, and sintering the solid in 100scm argon at 900 ℃ for 4h to obtain a heterogeneous cavity structure 9 #.
Comparative example 1
The preparation method is basically the same as that of example 1, except that the addition amount of TEOs is 1mL, the inner layer of the obtained heterogeneous cavity structure material D1 is a carbon layer, the outer layer of the obtained heterogeneous cavity structure material D1 is a silicon dioxide layer, the morphology of the obtained heterogeneous cavity structure material D1 is a hollow sphere, the outer diameter of the hollow sphere is 110nm, the thickness of the silicon dioxide layer is 3nm, and the thickness of the carbon layer is 10 nm.
Comparative example 2
The preparation method is basically the same as that of example 1, except that the addition amount of TEOs is 30mL, the obtained heterogeneous cavity structure material D2 has a carbon layer as an inner layer and a silicon dioxide layer as an outer layer, the shape of the heterogeneous cavity structure material D2 is a hollow sphere, the outer diameter of the heterogeneous cavity structure material D is 115nm, the thickness of the silicon dioxide layer is 35nm, free particles are not arranged on the silicon layer, and the thickness of the carbon layer is 10 nm.
Example 10 characterization of heterostructure materials
TEM images of the materials obtained in examples 1-9 are obtained by using an HT7700 Transmission Electron Microscope (TEM) (Hitachi, Japan), wherein the typical representation is the material obtained in example 1, the TEM image is shown in FIG. 1, it can be seen that the shape of the heterogeneous cavity structure material 1# is a hollow sphere, and the shapes of the materials obtained in examples 2-9 are consistent with those of example 1 and are hollow spheres;
performing energy spectrum analysis on the materials obtained in the embodiments 1-9 by adopting a Talos F200x transmission electron microscope (TEM-EDX), wherein a typical representative is the material obtained in the embodiment 1, an Si element energy spectrum is shown in figure 2, a C element energy spectrum is shown in figure 3, as can be seen from figures 2 and 3, the inner layer of the No. 1 spherical shell of the heterogeneous cavity structure material is a carbon layer, the outer layer of the heterogeneous cavity structure material is a silicon dioxide layer, and the thickness of each layer is tested by Nanomeasure software to determine that the thickness of the silicon dioxide layer is 20nm and the thickness of the carbon layer is 10 nm; the analysis results of the materials obtained in examples 2 to 9 were identical or similar to those of example 1.
Example 11 preparation of electrode of hetero-cavity Structure Material
The heterogeneous cavity structure materials obtained in examples 1-9 and comparative examples 1 and 2 are respectively used as active materials, mixed with conductive carbon black super-P serving as a conductive agent and polyvinylidene fluoride PVDF serving as a binder in a mass ratio of 4:5:5, and stirred at room temperature for 12 hours by using N-methylpyrrolidone NMP as a mixed solvent to obtain mixed slurry. And (3) coating the mixed slurry on the surface of a copper mesh by using a film coating machine, carrying out vacuum drying at 120 ℃ for 24 hours to obtain electrode materials 1-9, 1 'and 2', and respectively cutting the electrode materials 1-9, 1 'and 2' into pole pieces with the diameters of 16mm to obtain electrodes 1-9 (respectively corresponding to examples 1-9) and electrodes 1 'and 2' (respectively corresponding to comparative examples 1 and 2).
EXAMPLE 12 preparation of half cell
And preparing half batteries 1-9 and half batteries 1 'and 2' by respectively adopting electrodes 1-9 and electrodes 1 'and 2'.
The specific steps for installing the battery are as follows:
firstly, respectively taking electrodes 1-9, electrodes 1 'and 2' as working electrodes, taking a lithium sheet as a counter electrode, and taking the electrolyte as a component V (EC); (DEC) ═ 1:1 as solvent and 1M LiPF6 as solute. The materials were then assembled into 2032 button cells 1-9, 1 'and 2' in a glove box.
Example 13 lithium cell Charge and discharge electrochemical Performance test
The half cell made in example 12 was tested for electrochemical performance according to the following procedure:
2032 button cells 1 to 9, 1 'and 2' obtained in example 12 and a blue light tester were used as a test instrument.
At 0.5mA/cm2The current density of (1) and the test condition of 2 h. The cell voltage test was performed after 1, 2, 10, 50, 100 cycles with charge-discharge as one cycle, which is referred to as 1 cycle.
A 2032 button cell 1 (made of the material obtained in example 1) is typically used as a representative, and the charge and discharge electrochemical performance test chart is shown in fig. 4. The over-potential of the electrode material discharge is about 100mv, and after 100 cycles, the over-potential has no obvious change. The material exhibits good electrochemical stability. The 2032 button cell 2-9 test result is consistent with the 2032 button cell 1. While 2032 button cells 1 'and 2' overpotential reaches 500 mV.
Example 14 lithium Battery cycle Performance test
The 2032 button cell batteries 1-9, 1 'and 2' prepared in example 12 were tested for cycling performance by the following steps:
at 0.5mA/cm2The current density of (1) and the test condition of 2 h. The test was performed after 1, 2, 10, 50, and 100 cycles with charge-discharge as one cycle, which is referred to as 1 cycle. Represented typically by 2032 button cell 1 (made from the material from example 1), a schematic diagram of the electrochemical performance cycle is shown in fig. 5. When the heterogeneous cavity structure 1# is used as an electrode material, the coulombic efficiency of the battery can reach 95% after 100 cycles, no obvious change is caused, and the material shows good electrochemical stability. The 2032 button cell 2-9 test result is consistent with the 2032 button cell 1. While 2032 button cells 1 'and 2' cycle only 36 cycles.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. The heterogeneous cavity structure material is characterized in that the heterogeneous cavity structure material is a hollow sphere, a spherical shell is composed of an outer shell layer and an inner shell layer, the conductivity of the inner shell layer is at least 2.5S/cm greater than that of the outer shell layer, the thickness of the inner shell layer is 10-50 nm, the thickness of the outer shell layer is 5-20 nm, and the outer diameter of the hollow sphere is 50-8000 nm.
2. The heterostructure material of claim 1, wherein the hollow spheres have an outer diameter of 80 to 7000 nm;
preferably, the inner shell layer is a simple substance layer, and the outer shell layer is a compound layer;
the single layer is selected from at least one of a carbon layer, a silicon layer and a boron layer;
the compound layer is selected from at least one of an oxide layer, a carbide layer, a nitride layer, a halogen compound layer and a boride layer;
preferably, the inner shell layer is a carbon layer, and the outer shell layer is SiO2Layer, TiO2Layer or SnO2And (3) a layer.
3. The method for preparing the heterostructure material of claim 1 or 2, comprising the steps of:
and preparing the inner shell layer and the outer shell layer to obtain the heterogeneous cavity structure material.
4. The method for preparing a heterostructure material of claim 3, wherein the preparing the inner and outer shell layers comprises:
firstly, reacting a mixed solution containing a template agent and a shell precursor, and preparing the shell on the surface of the template agent;
obtaining the inner shell layer by the template agent so as to obtain the heterogeneous cavity structure material;
preferably, the outer shell layer is SiO2A layer, the inner shell layer being a carbon layer;
preferably, the template agent is an organic microsphere, a surfactant or a hollow carbon sphere;
the organic microspheres are selected from at least one of polystyrene microspheres, sulfonated polystyrene composite polyaniline microspheres and polyaniline microspheres;
the surfactant is selected from at least one of hexadecyl trimethyl ammonium bromide, tetradecyl ammonium bromide and octadecyl dimethyl benzyl quaternary ammonium chloride;
the shell layer precursor is selected from at least one of ethyl orthosilicate, silicon tetrachloride and sodium silicate;
preferably, the template is an organic microsphere or a surfactant, and the obtaining of the inner shell layer by the template includes:
converting the template into the inner shell layer by at least one of wet chemical method, high temperature pyrolysis method, solvent dissolution method.
5. The method for preparing a heterostructure material of claim 3, wherein the preparing the inner and outer shell layers comprises:
firstly, preparing an inner shell layer from a mixed solution containing an inner shell layer raw material;
then adding the inner shell layer into a mixed solution containing an outer shell layer raw material, and coating the outer shell layer outside the inner shell layer;
preferably, the inner shell layer is a carbon layer, and the outer shell layer is an oxide layer;
the raw material of the inner shell layer is at least one of sucrose, glucose and fructose;
the shell layer raw material is a silicon source, a titanium source or a tin source;
the silicon source is at least one of ethyl orthosilicate, silicon tetrachloride and sodium silicate;
the titanium source is selected from at least one of tetrabutyl titanate, titanium tetrachloride, metatitanic acid and titanium isopropoxide;
the tin source is at least one of stannic chloride pentahydrate, stannate and stannous chloride.
6. The method for preparing a heterostructure material of claim 3, wherein the preparing the inner and outer shell layers comprises:
preparing the outer shell layer by a templating process;
removing the template of the outer shell, soaking the outer shell into a solution containing a carbon source, taking out, washing, drying and carbonizing to obtain the inner shell;
preferably, by improvement
Figure FDA0002380212320000021
At least one of a chemical vapor deposition method, an electroplating method, an atomic layer deposition method, and a molecular layer deposition method.
7. A heterogeneous cavity structure material electrode, which comprises an active material, a conductive agent, a binder and a current collector, wherein the active material is at least one of the heterogeneous cavity structure material of claim 1 or 2 and the heterogeneous cavity structure material prepared by the preparation method of any one of claims 3 to 6.
8. The heterocavity structure material electrode of claim 7, comprising the following components in percentage by mass:
20% -80% of the active material;
0% -40% of the conductive agent:
10% -40% of the binder.
9. The method for preparing the electrode of the heterostructure material of claim 7 or 8, wherein the active material is mixed with a conductive agent and a binder to form slurry, and the slurry is compounded on a current collector to obtain the electrode of the heterostructure material.
10. A lithium ion half cell, wherein the negative electrode is at least one of the electrode of the hetero-cavity structure material provided in claim 7 or 8 and the electrode of the hetero-cavity structure material prepared by the preparation method provided in claim 9.
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