CN113517438A - Internal confinement heterojunction yolk-shell electrode material and preparation method and application thereof - Google Patents
Internal confinement heterojunction yolk-shell electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an internal confinement heterojunction yolk-shell electrode material and a preparation method and application thereof9S8And nano MoS2Nano Co9S8And nano MoS2The shell is nano Co loaded on the inner wall of the carbon shell9S8And nano MoS2Together forming a polyhedral structure. Hair brushThe electrode material effectively limits the growth direction of the heterojunction in the internal space of the yolk-shell polyhedron, so that the electrode material has a stable structure, high density space utilization rate, high specific surface area and rich lithium removal/insertion sites, and the volume expansion phenomenon is relieved. The construction of the heterojunction in the shell enables a built-in electric field to be generated in the material, so that the conductivity is enhanced, and the transmission and diffusion of electrons are promoted. The material is used as a lithium ion battery cathode material, shows excellent cycle stability and rate capability, and has a good application prospect.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, relates to a lithium ion battery cathode material, and particularly relates to an internal confinement heterojunction yolk-shell electrode material, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The room temperature lithium ion battery becomes a new secondary battery with great application prospect due to low cost, high safety and high energy density. Currently, materials that can be used as negative electrodes for lithium ion batteries include carbon materials (hard carbon, carbon black, carbon fibers, graphene, etc.), oxides/phosphates, lithium alloys/composites, etc., among these numerous candidate negative electrode materials, molybdenum disulfide (MoS)2) The graphene-like two-dimensional lamellar structure is provided, and the large interlayer spacing is beneficial to the transmission and transfer of lithium ions, so that the theoretical specific capacity is up to 670mAh/g, and the graphene-like two-dimensional lamellar structure is very suitable for being used as a lithium ion battery cathode electrode. However, the inventor researches and discovers that the practical specific capacity is low and the electrochemical stability is poor due to the defects that the lamellar structure is easy to gather and stack and is uncontrollable, the conductivity is poor and the like.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide an internal confinement heterojunction yolk-shell electrode material, a preparation method and application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
in one aspect, an internal confinement heterojunction yolk-shell electrode material is in a yolk-shell structure in a transmission electron microscope, and the yolk comprises nano Co supported on a carbon core9S8And nano MoS2Nano Co9S8And nano MoS2The heterojunction formed, the shell isNano Co loaded on inner wall of carbon shell9S8And nano MoS2Together forming a polyhedral structure.
In order to solve the problem of poor electrochemical performance of molybdenum disulfide as a lithium ion battery cathode material, the invention utilizes the yolk-shell structure to improve the stability and the space utilization rate, solves the problems of easy stacking and pulverization of a lamellar electrode structure, and simultaneously utilizes Co9S8-MoS2The heterojunction improves the conductivity and finally optimizes the lithium storage performance.
And secondly, the shell formed by the invention is of a polyhedral structure (such as a (regular) decahedron, a (regular) dodecahedron and the like), is favorable for improving the specific surface area, and is favorable for increasing the active sites of electrochemical reaction and shortening the ion transmission path when being used as a negative electrode material of a lithium ion battery, thereby improving the electrochemical performance of the lithium ion battery.
On the other hand, the preparation method of the internal confinement heterojunction yolk-shell electrode material comprises the steps of taking a metal organic framework compound containing cobalt as a template, carrying out gel coating on the surface of the template by utilizing polymerization reaction, carrying out primary calcination in an inert atmosphere, adding a sulfur source and a molybdenum source for carrying out ion exchange reaction, and then carrying out secondary calcination in the inert atmosphere to obtain the internal confinement heterojunction yolk-shell electrode material.
The method of the invention directly takes the metal organic framework as the self-sacrifice template, and the growth direction controllable Co can be derived through the process9S8-MoS2Heterojunction and loading it on the yolk-shell structure of carbon. Meanwhile, the metal organic framework can ensure that the formed shell is of a polyhedral structure, so that the specific surface area is favorably improved, and when the metal organic framework is used as a lithium ion battery cathode material, the metal organic framework is favorable for increasing electrochemical reaction active sites and shortening an ion transmission path, so that the electrochemical performance of the metal organic framework is improved.
In a third aspect, the application of the inner confinement heterojunction yolk-shell electrode material in the negative electrode of the ion battery is provided.
In a fourth aspect, a lithium ion battery negative electrode comprises a current collector, a conductive material, a binder and an active material, wherein the binder binds the conductive material and the active material to the current collector, and the active material is the above-mentioned internal confinement heterojunction yolk-shell electrode material.
The invention increases the conductivity of the electrode by adding the conductive material, and collects the current generated by the battery active material through the current collector so as to form larger current to be output to the outside.
In a fifth aspect, a lithium ion battery comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm, wherein the negative electrode is the negative electrode of the lithium ion battery.
The invention has the beneficial effects that:
1. the invention adopts a metal organic framework compound containing cobalt as a template, has rich surface interface effect, and obtains Co by gel coating, ion exchange and annealing calcination strategies of a polymer (such as phenolic resin) formed by polymerization reaction in sequence9S8-MoS2Heterojunction, and embedding it in the yolk-shell diamond polyhedron of carbon. The method effectively mixes Co9S8-MoS2The growth direction of the heterojunction is controlled on the inner space of the carbon shell and the yolk core, so that the controllability of the structure is realized, the space utilization rate is improved, and the agglomeration and caking phenomena are reduced. Wherein, the polymer gel coating greatly improves the structural stability of the precursor in the subsequent ion exchange and annealing calcination processes, and is the subsequent Co9S8-MoS2The growth direction is defined by the generation of the heterojunction. The nano Co is promoted by ion exchange and annealing calcination9S8And nano MoS2A heterojunction is formed.
2. According to the internal confinement heterojunction yolk-shell electrode material provided by the invention, the shell has a porous structure, the stability of the electrode structure can be improved, rich active sites and transmission channels are provided, the problems of volume expansion effect and transmission channel blockage during charging and discharging are solved, and the electrochemical and pseudocapacitance reactions are promoted to be carried out at high efficiency; meanwhile, the construction of the heterojunction in the shell not only induces a built-in electric field, accelerates the electron and ion transfer speed at a multiphase interface and improves the conductivity, but also influences the reversible growth and decomposition processes of products at different charge and discharge stages and regulates the electrochemical and pseudocapacitance reaction processes. The formation of the polyhedron shell is beneficial to further improving the specific surface area, and when the polyhedron shell is used as a lithium ion battery cathode material, the polyhedron shell is beneficial to increasing the active sites of electrochemical reaction and shortening the ion transmission path, thereby improving the electrochemical performance of the polyhedron shell.
3. The internal confinement heterojunction yolk-shell electrode material provided by the invention enhances the cycle stability and reversible specific capacity of the lithium ion battery negative electrode material under the synergistic effect of structural engineering and electronic structural engineering.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows Co prepared in example 1 of the present invention9S8-MoS2@ C heterojunction yolk-shell polyhedral field emission scanning electron microscope pictures;
FIG. 2 shows Co prepared in example 1 of the present invention9S8-MoS2Low power transmission scanning electron microscopy of @ C heterojunction yolk-shell polyhedrons;
FIG. 3 shows Co prepared in example 1 of the present invention9S8-MoS2The XRD pattern of the @ C heterojunction yolk-shell polyhedron;
FIG. 4 shows Co prepared in example 19S8-MoS2@ C cyclic voltammogram of a heterojunction yolk-shell polyhedron;
FIG. 5 shows Co prepared in example 19S8-MoS2@ C heterojunction yolk-shell polyhedral electrochemical cycling performance.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the problem of poor electrochemical performance of molybdenum disulfide as a lithium ion battery cathode material, the invention provides an internal confinement heterojunction yolk-shell electrode material and a preparation method and application thereof.
In an exemplary embodiment of the invention, an inner confinement heterojunction yolk-shell electrode material is provided, wherein in a transmission electron microscope, the electrode material has a yolk-shell structure, and the yolk comprises nano Co supported on a carbon core9S8And nano MoS2Nano Co9S8And nano MoS2The shell is nano Co loaded on the inner wall of the carbon shell9S8And nano MoS2Together forming a polyhedral structure.
Firstly, the invention utilizes the yolk-shell structure to improve the stability and the space utilization rate, solves the problems of easy stacking and pulverization of the lamellar electrode structure, and simultaneously utilizes Co9S8-MoS2The heterojunction improves the conductivity and finally optimizes the lithium storage performance.
And secondly, the shell formed by the invention is of a polyhedral structure (such as a (regular) decahedron, a (regular) dodecahedron and the like), is favorable for improving the specific surface area, and is favorable for increasing the active sites of electrochemical reaction and shortening the ion transmission path when being used as a negative electrode material of a lithium ion battery, thereby improving the electrochemical performance of the lithium ion battery.
The shell of the invention is of a porous structure.
In some examples of this embodiment, the egg yolk includes a porous carbon structure, Co9S8Nanoparticles and MoS2Nanosheets.
In some embodiments of this embodiment, the shell has a thickness on the order of nanometers.
In another embodiment of the invention, a preparation method of the internal confinement heterojunction yolk-shell electrode material is provided, wherein a metal organic framework compound containing cobalt is used as a template, gel coating is carried out on the surface of the template by using polymerization reaction, then primary calcination is carried out in an inert atmosphere, a sulfur source and a molybdenum source are added for ion exchange reaction, and then secondary calcination is carried out in the inert atmosphere to obtain the internal confinement heterojunction yolk-shell electrode material.
The method of the invention directly uses the metal organic framework as the self-sacrifice template, and the growth direction controllable Co can be derived through the process9S8-MoS2Heterojunction and loading it on the yolk-shell structure of carbon. Meanwhile, the metal organic framework can ensure that the formed shell is of a polyhedral structure, so that the specific surface area is favorably improved, and when the metal organic framework is used as a lithium ion battery cathode material, the metal organic framework is favorable for increasing electrochemical reaction active sites and shortening an ion transmission path, so that the electrochemical performance of the metal organic framework is improved.
In some examples of this embodiment, the cobalt-containing metal organic framework compound is ZIF-67. The preparation method of the metal organic framework compound is simpler and is beneficial to reducing the cost.
In some examples of this embodiment, the polymerization reaction is used as the reaction to prepare the phenolic resin. The adoption of the phenolic resin is more beneficial to the structural stability in the calcining process of the ion exchanger, thereby being capable of better limiting Co9S8-MoS2The growth direction of the heterojunction.
In one or more embodiments, the phenolic resin is a mixture of resorcinol and formaldehyde. Specifically, the formaldehyde-free aqueous solution is obtained by dissolving dodecyl trimethyl ammonium bromide (CTAB), resorcinol and ammonia water, uniformly mixing, and then adding a formaldehyde solution. The gel coating process comprises the steps of dissolving a metal organic framework compound containing cobalt, adding CTAB, resorcinol and ammonia water, uniformly mixing, and adding a formaldehyde solution to obtain the product. The mass ratio of CTAB to resorcinol is 1500-2000: 1-5, and the volume ratio of ammonia water to formaldehyde is 1-2: 6. The concentration of the ammonia water is 25.0-28.0 wt.%.
The primary calcination is aimed at carbonizing the polymer to form a porous carbon structure, which facilitates ion exchange. In some examples of this embodiment, the temperature of the first calcination is 300 to 800 ℃. The temperature rise rate of the primary calcination is 2-5 ℃/min.
In some examples of this embodiment, ammonium tetrathiomolybdate is used as the sulfur source and the molybdenum source.
In some examples of this embodiment, the temperature of the second calcination is 400 to 800 ℃. The temperature rise rate of the secondary calcination is 4-8 ℃/min. The time of the secondary calcination is 2-3 h.
In a third embodiment of the invention, the application of the internal confinement heterojunction yolk-shell electrode material in the negative electrode of the ion battery is provided.
In a fourth embodiment of the present invention, a lithium ion battery negative electrode is provided, which includes a current collector, a conductive material, a binder and an active material, wherein the binder binds the conductive material and the active material to the current collector, and the active material is the above-mentioned internal confinement heterojunction yolk-shell electrode material.
The invention increases the conductivity of the electrode by adding the conductive material, and collects the current generated by the battery active material through the current collector so as to form larger current to be output to the outside.
In a fifth embodiment of the present invention, a lithium ion battery is provided, which includes a positive electrode, a negative electrode, an electrolyte and a separator, wherein the negative electrode is the above-mentioned negative electrode of the lithium ion battery.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
Internal confinement MOFs-derived Co9S8-MoS2The preparation method of the @ C heterojunction yolk-shell electrode material comprises the following steps:
(1) dissolving hexahydrate, cobalt nitrate and a 2-methylimidazole organic ligand in a mass ratio of 5:1 in methanol, aging for 24 hours, filtering, washing, drying in vacuum, and collecting solid ZIF-67.
(2)50mg of ZIF-67 was dissolved in a mixed solution of water and ethanol, dodecyltrimethylammonium bromide (CTAB) and resorcinol and aqueous ammonia (26.0 wt.%) were sequentially added, stirred for 30 minutes, then the formalin was added, and stirring was continued for 4 hours to obtain a precipitate, wherein the mass ratio of CTAB to resorcinol was 1500:1, and the volume ratio of aqueous ammonia to formaldehyde was 1: 6. And washing the precipitate with ethanol and deionized water, drying in vacuum, annealing and calcining, controlling the temperature rise speed to be 2 ℃/min, the annealing and calcining temperature to be 450 ℃, the annealing time to be 2 hours, and the annealing and calcining atmosphere to be argon atmosphere. Obtaining the gel-coated ZIF-67 which is marked as ZIF-67-PU.
(3) ZIF-67-PU and ammonium tetrathiomolybdate in a mass ratio of 1:3 are respectively dissolved in ethanol and an aqueous solution, and then the two solutions are mixed and stirred for 12 hours to obtain a precipitate. Washing the obtained product with ethanol and deionized water, and then annealing and calcining the obtained product, wherein the atmosphere of the annealing and calcining is argon, the temperature is 600 ℃, the time is 2 hours, and the heating rate is 5 ℃/min, so that the internal confinement MOFs derived Co is obtained9S8-MoS2@ C heterojunction yolk-shell polyhedrons, as shown in FIGS. 1-3.
As can be seen from FIG. 2, the present invention strictly couples Co9S8-MoS2The growth of the crystal is limited in the polyhedron, and the controllability of the limited-area growth is realized.
FIG. 3 shows that the structure prepared in this example is a core-shell structure, the average size is 1.0 μm, and on the inner wall of the shell and the inner core, burr-like MoS grows2The interlayer spacing was enlarged to 0.65 nm. The special structure of the invention can improve the space utilization rate of the electrode material and simultaneously increase the structural stability of the material.
70 wt% MoS2-Co9S8@ C, 20 wt% carbon black and 10 wt% polyvinylidene fluoride (PVDF) were mixed in N-methylpyrrolidone (NMP) solution to form a uniform slurry and coated on a copper foil as a negative electrode. Lithium metal foil was used as a counter electrode. To contain 1.0M LiPF6The electrolyte is a solution of (1): (1) (% EMC) (% by volume). A model 2025 half cell was assembled in an Ar glove box.
The half-cell charge/discharge test was performed on the LANDCT2001A battery test system (wuhan, china). The cyclic voltammetry of which was performed on an electrochemical workstation (PARSTAT 2273). Pseudocapacitance contributionThe ratio of amounts is according to I (V) ═ k1v+k2v1/2And (4) calculating.
The results are shown in FIGS. 4 and 5, and it can be seen from FIG. 4 that Co is swept at 0.5mA/S9S8-MoS2The pseudo-capacitance contribution of the @ C electrode material accounts for 61%. As can be seen from FIG. 5, Co9S8-MoS2Of @ C electrode material in 1Ag-1The specific capacity of 600 circulating circles under the current density is 1054mAh g-1。
Example 2
Internal confinement MOFs-derived Co9S8-MoS2The preparation method of the @ C heterojunction yolk-shell electrode material comprises the following steps:
(1) dissolving hexahydrate, cobalt nitrate and a 2-methylimidazole organic ligand in a mass ratio of 4:1 in methanol, aging for 24 hours, filtering, washing, drying in vacuum, and collecting solid ZIF-67.
(2)100mg of ZIF-67 was dissolved in a mixed solution of water and ethanol, dodecyltrimethylammonium bromide (CTAB), resorcinol and aqueous ammonia (26.0 wt.%) were sequentially added, and stirred for 40 minutes, then the formalin was added, and stirring was continued for 8 hours to obtain a precipitate, wherein the mass ratio of CTAB to resorcinol was 1500:5, and the volume ratio of aqueous ammonia to formaldehyde was 1: 6. And washing the precipitate with ethanol and deionized water, drying in vacuum, annealing and calcining, controlling the temperature rise speed at2 ℃/min, the annealing and calcining temperature at 300 ℃, the annealing time for 2 hours, and the annealing and calcining atmosphere is argon atmosphere. Obtaining the gel-coated ZIF-67 which is marked as ZIF-67-PU.
(3) ZIF-67-PU and ammonium tetrathiomolybdate in a mass ratio of 1:2 are respectively dissolved in ethanol and an aqueous solution, and then the two solutions are mixed and stirred for 6 hours to obtain a precipitate. Washing the obtained product with ethanol and deionized water, and then annealing and calcining the obtained product, wherein the atmosphere of the annealing and calcining is argon, the temperature is 400 ℃, the time is 2 hours, and the heating rate is 5 ℃/min, so that the internal confinement MOFs derived Co is obtained9S8-MoS2@ C heterojunction yolk-shell polyhedrons.
Example 3
Internal confinement MOFs-derived Co9S8-MoS2The preparation method of the @ C heterojunction yolk-shell electrode material comprises the following steps:
(1) dissolving hexahydrate, cobalt nitrate and a 2-methylimidazole organic ligand in a mass ratio of 5:1 in methanol, aging for 24 hours, filtering, washing, drying in vacuum, and collecting solid ZIF-67.
(2)150mg of ZIF-67 was dissolved in a mixed solution of water and ethanol, dodecyltrimethylammonium bromide (CTAB) and resorcinol and aqueous ammonia (26.0 wt.%) were added in this order, and stirred for 50 minutes, then the formalin was added, and stirring was continued for 12 hours to obtain a precipitate, wherein the mass ratio of CTAB to resorcinol was 2000:1, and the volume ratio of aqueous ammonia to formaldehyde was 2: 6. And washing the precipitate with ethanol and deionized water, drying in vacuum, annealing and calcining, controlling the temperature rise speed to be 5 ℃/min, the annealing and calcining temperature to be 650 ℃, the annealing time to be 2 hours, and the annealing and calcining atmosphere to be argon atmosphere. Obtaining the gel-coated ZIF-67 which is marked as ZIF-67-PU.
(3) ZIF-67-PU and ammonium tetrathiomolybdate in a mass ratio of 1:4 are respectively dissolved in ethanol and an aqueous solution, and then the two solutions are mixed and stirred for 8 hours to obtain a precipitate. Washing the obtained product with ethanol and deionized water, and then annealing and calcining the obtained product, wherein the atmosphere of the annealing and calcining is argon, the temperature is 500 ℃, the time is 2 hours, and the heating rate is 5 ℃/min, so as to obtain the internal confinement MOFs-derived Co9S8-MoS2@ C heterojunction yolk-shell polyhedrons.
Example 4
Internal confinement MOFs-derived Co9S8-MoS2The preparation method of the @ C heterojunction yolk-shell electrode material comprises the following steps:
(1) dissolving hexahydrate, cobalt nitrate and a 2-methylimidazole organic ligand in a mass ratio of 6:1 in methanol, aging for 24 hours, filtering, washing, drying in vacuum, and collecting solid ZIF-67.
(2)200mg of ZIF-67 was dissolved in a mixed solution of water and ethanol, dodecyltrimethylammonium bromide (CTAB) and resorcinol and aqueous ammonia (26.0 wt.%) were sequentially added, and stirred for 60 minutes, then the formalin was added, and stirring was continued for 16 hours to obtain a precipitate, wherein the mass ratio of CTAB to resorcinol was 2000:5, and the volume ratio of aqueous ammonia to formaldehyde was 2: 6. And washing the precipitate with ethanol and deionized water, drying in vacuum, annealing and calcining, wherein the temperature rise speed is controlled to be 5 ℃/min, the annealing and calcining temperature is 800 ℃, the annealing time is 2 hours, and the annealing and calcining atmosphere is argon atmosphere. Obtaining the gel-coated ZIF-67 which is marked as ZIF-67-PU.
(3) ZIF-67-PU and ammonium tetrathiomolybdate in a mass ratio of 1:6 were dissolved in ethanol and an aqueous solution, respectively, and then the two solutions were mixed and stirred for 18 hours to obtain a precipitate. Washing the obtained product with ethanol and deionized water, and then annealing and calcining the obtained product, wherein the atmosphere of the annealing and calcining is argon, the temperature is 800 ℃, the time is 2 hours, and the heating rate is 5 ℃/min, so that the internal confinement MOFs derived Co is obtained9S8-MoS2@ C heterojunction yolk-shell polyhedrons.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The internal confinement heterojunction yolk-shell electrode material is characterized in that in a transmission electron microscope, the electrode material is of a yolk-shell structure, and yolk comprises nano Co loaded on a carbon core9S8And nano MoS2Nano Co9S8And nano MoS2The shell is nano Co loaded on the inner wall of the carbon shell9S8And nano MoS2Together forming a polyhedral structure.
2. The inner confinement heterojunction yolk-shell electrode material of claim 1, wherein the yolk comprises a porous carbon structure, Co9S8Nanoparticles and MoS2Nanosheets.
3. The internal confinement heterojunction yolk-shell electrode material of claim 1, wherein the thickness of the shell is in the order of nanometers.
4. A preparation method of an internal confinement heterojunction yolk-shell electrode material is characterized in that a metal organic framework compound containing cobalt is used as a template, gel coating is carried out on the surface of the template by utilizing polymerization reaction, then primary calcination is carried out in inert atmosphere, a sulfur source and a molybdenum source are added for ion exchange reaction, and then secondary calcination is carried out in inert atmosphere to obtain the internal confinement heterojunction yolk-shell electrode material.
5. The method for preparing an inner confinement heterojunction yolk-shell electrode material as claimed in claim 4, wherein the metal-organic framework compound containing cobalt is ZIF-67;
alternatively, ammonium tetrathiomolybdate is used as the sulfur source and the molybdenum source.
6. The method for preparing an inner confinement heterojunction yolk-shell electrode material as claimed in claim 4, wherein the polymerization reaction is a reaction for preparing a phenolic resin;
preferably, the raw materials of the phenolic resin are resorcinol and formaldehyde; further preferably, the gel coating process comprises dissolving a metal organic framework compound containing cobalt, adding CTAB, resorcinol and ammonia water, mixing uniformly, and adding a formaldehyde solution to obtain the gel; further preferably, the mass ratio of CTAB and resorcinol is 1500-2000: 1-5; further preferably, the volume ratio of the ammonia water to the formaldehyde is 1-2: 6.
7. The method for preparing an inner confinement heterojunction yolk-shell electrode material as claimed in claim 4, wherein the temperature of primary calcination is 300-800 ℃; preferably, the temperature rise rate of the primary calcination is 2-5 ℃/min;
or, the temperature of the secondary calcination is 400-800 ℃; preferably, the temperature rise rate of the secondary calcination is 4-8 ℃/min; preferably, the time of the secondary calcination is 2-3 h.
8. Use of the internal confinement heterojunction yolk-shell electrode material as defined in any one of claims 1 to 3 or the internal confinement heterojunction yolk-shell electrode material obtained by the preparation method as defined in any one of claims 4 to 7 in an ion battery negative electrode.
9. A lithium ion battery negative electrode is characterized by comprising a current collector, a conductive material, a binder and an active material, wherein the binder is used for binding the conductive material and the active material on the current collector, and the active material is the internal confinement heterojunction yolk-shell electrode material as defined in any one of claims 1 to 3 or the internal confinement heterojunction yolk-shell electrode material obtained by the preparation method as defined in any one of claims 4 to 7.
10. A lithium ion battery, which is characterized by comprising a positive electrode, a negative electrode, an electrolyte and a diaphragm, wherein the negative electrode is the negative electrode of the lithium ion battery of claim 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114438538A (en) * | 2022-02-25 | 2022-05-06 | 洛阳理工学院 | Electrocatalytic double-function material with few layers of tungsten disulfide anchored on surface of cobalt-nitrogen-doped carbon-based polyhedron and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130224594A1 (en) * | 2012-02-28 | 2013-08-29 | Sila Nanotechnologies Inc. | Core-Shell Composites for Sulfur-Based Cathodes in Metal-Ion Batteries |
| US20170207448A1 (en) * | 2014-06-06 | 2017-07-20 | Robert Bosch Gmbh | Cathode material for lithium sulphur cells |
| CN107215898A (en) * | 2017-06-27 | 2017-09-29 | 淮北师范大学 | A kind of preparation method of single dispersing yolk shell structure mos2 microspheres |
| US20180297849A1 (en) * | 2015-10-26 | 2018-10-18 | Sabic Global Technologies B.V. | Preparation of carbon nanotube shell materials |
| CN108855145A (en) * | 2018-06-21 | 2018-11-23 | 青岛大学 | A kind of two-step method prepares cobalt sulfide/vulcanization molybdenum composite material and in hydrogen evolution reaction application |
| WO2018226158A1 (en) * | 2017-06-05 | 2018-12-13 | Agency For Science, Technology And Research | A core-shell composite |
| CN109192949A (en) * | 2018-08-31 | 2019-01-11 | 扬州大学 | Suede shell hollow polyhedral Co is obtained by ZIF-67 multi-panel derivatization9S8@MoS2Method |
| CN109192974A (en) * | 2018-10-30 | 2019-01-11 | 吉林大学 | The preparation method of cobalt sulfide/molybdenum disulfide core-shell structure lithium cell cathode material |
| CN110575842A (en) * | 2019-10-12 | 2019-12-17 | 福州大学 | Preparation method of adjustable and controllable yolk-shell structure nitrogen-carbon-doped cobalt molybdenum sulfide counter electrode catalyst |
| CN111545238A (en) * | 2020-05-27 | 2020-08-18 | 嵊州市芝草科技有限公司 | Co9S8-MoS2Load g-C3N4Electrocatalytic hydrogen production catalyst and preparation method thereof |
| WO2020190560A2 (en) * | 2019-03-07 | 2020-09-24 | Cornell University | Mof-sulfur materials and composite materials, methods of making same, and uses thereof |
| CN111883753A (en) * | 2020-07-16 | 2020-11-03 | 樊梦林 | MoS with hierarchical shell-core structure2Negative active material of-C composite porous microsphere |
| WO2020258554A1 (en) * | 2019-06-24 | 2020-12-30 | 浙江天能能源科技股份有限公司 | Mof derivative-coated ncm ternary positive electrode material and preparation method therefor |
| WO2021059004A1 (en) * | 2019-09-26 | 2021-04-01 | Abu Dhabi National Oil Company | Yolk-shell nanoparticles for the removal of h2s from gas streams |
-
2021
- 2021-04-23 CN CN202110443262.5A patent/CN113517438B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130224594A1 (en) * | 2012-02-28 | 2013-08-29 | Sila Nanotechnologies Inc. | Core-Shell Composites for Sulfur-Based Cathodes in Metal-Ion Batteries |
| US20170207448A1 (en) * | 2014-06-06 | 2017-07-20 | Robert Bosch Gmbh | Cathode material for lithium sulphur cells |
| US20180297849A1 (en) * | 2015-10-26 | 2018-10-18 | Sabic Global Technologies B.V. | Preparation of carbon nanotube shell materials |
| WO2018226158A1 (en) * | 2017-06-05 | 2018-12-13 | Agency For Science, Technology And Research | A core-shell composite |
| CN107215898A (en) * | 2017-06-27 | 2017-09-29 | 淮北师范大学 | A kind of preparation method of single dispersing yolk shell structure mos2 microspheres |
| CN108855145A (en) * | 2018-06-21 | 2018-11-23 | 青岛大学 | A kind of two-step method prepares cobalt sulfide/vulcanization molybdenum composite material and in hydrogen evolution reaction application |
| CN109192949A (en) * | 2018-08-31 | 2019-01-11 | 扬州大学 | Suede shell hollow polyhedral Co is obtained by ZIF-67 multi-panel derivatization9S8@MoS2Method |
| CN109192974A (en) * | 2018-10-30 | 2019-01-11 | 吉林大学 | The preparation method of cobalt sulfide/molybdenum disulfide core-shell structure lithium cell cathode material |
| WO2020190560A2 (en) * | 2019-03-07 | 2020-09-24 | Cornell University | Mof-sulfur materials and composite materials, methods of making same, and uses thereof |
| WO2020258554A1 (en) * | 2019-06-24 | 2020-12-30 | 浙江天能能源科技股份有限公司 | Mof derivative-coated ncm ternary positive electrode material and preparation method therefor |
| WO2021059004A1 (en) * | 2019-09-26 | 2021-04-01 | Abu Dhabi National Oil Company | Yolk-shell nanoparticles for the removal of h2s from gas streams |
| CN110575842A (en) * | 2019-10-12 | 2019-12-17 | 福州大学 | Preparation method of adjustable and controllable yolk-shell structure nitrogen-carbon-doped cobalt molybdenum sulfide counter electrode catalyst |
| CN111545238A (en) * | 2020-05-27 | 2020-08-18 | 嵊州市芝草科技有限公司 | Co9S8-MoS2Load g-C3N4Electrocatalytic hydrogen production catalyst and preparation method thereof |
| CN111883753A (en) * | 2020-07-16 | 2020-11-03 | 樊梦林 | MoS with hierarchical shell-core structure2Negative active material of-C composite porous microsphere |
Non-Patent Citations (4)
| Title |
|---|
| LECHEN DIAO，ET AL.: "An in-plane Co9S8@MoS2 heterostructure for hydrogen evolution reaction in alkaline media", 《NANOSCALE》 * |
| YUYU WANG，ET AL.: "A yolk-shelled Co9S8/MoS2-CN nanocomposite derived from a metal-organic framework as a high performance anode for sodium ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 张宇，等: "Co9S8/MoS2异质结构的构筑及电催化析氢性能研究", 《化学学报》 * |
| 王换换，等: "MoS2@Co9S8蛋黄壳复合材料的制备及其电化学性能", 《应用化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114438538A (en) * | 2022-02-25 | 2022-05-06 | 洛阳理工学院 | Electrocatalytic double-function material with few layers of tungsten disulfide anchored on surface of cobalt-nitrogen-doped carbon-based polyhedron and preparation method thereof |
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