CN111106332A - Preparation method of carbon nano material, positive electrode material and preparation method thereof - Google Patents

Preparation method of carbon nano material, positive electrode material and preparation method thereof Download PDF

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CN111106332A
CN111106332A CN201911258768.8A CN201911258768A CN111106332A CN 111106332 A CN111106332 A CN 111106332A CN 201911258768 A CN201911258768 A CN 201911258768A CN 111106332 A CN111106332 A CN 111106332A
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cobalt
zinc
organic framework
gas
doped
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曾燮榕
金文武
邹继兆
S·因古瓦
曾绍忠
徐国忠
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Shenzhen 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
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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
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract

The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a carbon nano material, a positive electrode material and a preparation method of the positive electrode material. The preparation method of the carbon nano material comprises the following steps: providing a cobalt-doped zinc-based metal organic framework, wherein the organic framework in the cobalt-doped zinc-based metal organic framework contains nitrogen elements; and sequentially carrying out carbonization treatment and acid treatment on the cobalt-doped zinc-based metal organic framework, and then drying to obtain the Co/N Co-doped carbon nano material. The carbon nano material with the Co/N double-doped super carbon structure prepared by the preparation method has a controllable carbon structure and a larger specific surface area, realizes Co/N double doping, and can be used for Li-SeS2When the positive electrode material of the battery is used, the electrode material can effectively improve the active material SeS2Utilization of and prevention of polysulfide/polyseleniumThe compound can diffuse in the electrolyte, and has wide application prospect in the fields of energy storage, electrocatalysis, gas adsorption and the like.

Description

Preparation method of carbon nano material, positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a carbon nano material, a positive electrode material and a preparation method of the positive electrode material.
Background
The specific capacity, the cycling stability and the cycle life of the mobile energy storage equipment are considered as key parameters for measuring the superiority of the energy storage system, and the research and development of a new generation of energy storage system represented by a Li-S battery is an effective way for solving the problem of low specific capacity of the current lithium battery, mainly based on the fact that the Li-S battery has higher theoretical specific capacity (1675mA h)-1g-1) This is almost three to five times that of commercial lithium batteries. Meanwhile, S element serving as a positive electrode material is rich in resource and low in cost, so that the Li-S battery is once considered as an ideal candidate for replacing a lithium battery, unfortunately, S has high insulation, and therefore the rate performance of a Li-S battery system is generally poor and the utilization rate of an active substance S is low. In order to solve the above problems, an alternative to Se as an active material is proposed, and a Li-Se battery can provide a volume energy density (Li-Se: 3253mAh cm) similar to that of a Li-S battery-3；Li-S:3467mAh cm-3) And Se has higher ionic conductivity (Se is 1 multiplied by 10)-3S/cm, S is 5X 10-28S/cm), the utilization rate of active materials of the battery and the efficiency of electrochemical reaction are greatly improved. However, large-scale commercial production of Li-Se batteries is being shelved, limited by the relatively high production cost of the active material Se. In order to balance reasonably the higher conductivity of selenium and the higher theoretical specific capacity of sulfur, SeS is used2The idea of a representative Se and S blend electrode material was proposed by Abouimrane et al, and earlier studies showed that SeS2The electrode is suitable for an electrolyte system of lithium, sodium and potassium ions and the like, so that the limitation of the rising price of single metal on commercial production is eliminated. Furthermore, with SeS2As the anode material, the lithium ion battery can realize charge and discharge under a large voltage window, and simultaneously shows the rate capability obviously superior to that of a Li-S battery, thereby providing charge and discharge for realizing large currentThe requirements are met. However, like S positive electrode, SeS2The electrode may also suffer from active material loss and capacity fade due to dissolution of the active material in the electrolyte, due to SeS2Have similar chemical properties as S, so the strategy for stabilizing the S electrode is equally applicable to inhibit SeS2Dissolution in the electrolyte.
At present, the most effective and low-cost method for solving the problems is to use a hybrid material of polar metal and carbon material as a positive electrode material, the electrode material can anchor polysulfide and selenide compound by a chemical method, the conductivity of the positive electrode can be improved, and the multiplying power of the battery is further improved. Therefore, polar metal, metal nitride and metal sulfide doped carbon materials are widely used in Li-SeS2The field of batteries. Key laboratory in electronic technology states reports that a Co/N Co-doped carbon material derived from ZIF-67 is adopted as Li-SeS in 20182Battery positive electrode material (Jianrui He, Weiqiang Lv, Yuanfu Chen, Jie Xiong, Kechun Wen, Chen Xu, Wanli Zhang, Yanong Li, Wu Qin, Weidong He, Direct approximation of SeS)2into a MOF-derived 3 Dnnaoporous Co-N-C architecture aware beyond technical usable lithium batteries, J.Mater.chem.A.2018, 6, 10466-doped 10473) to improve Li-SeS2The method has the advantages that the specific surface area of the carbon material prepared by the method is low, and the morphology of the prepared carbon structure is too single. Therefore, the prior art is in need of improvement.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon nano material, a cathode material and a preparation method thereof, and aims to solve the technical problems that a Co/N Co-doped carbon material prepared by the existing method is low in specific surface area, the structure is not easy to adjust, and the in-situ doping of catalytic metal/heteroatom cannot be rapidly realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a carbon nano material, which comprises the following steps:
providing a cobalt-doped zinc-based metal organic framework, wherein the organic framework in the cobalt-doped zinc-based metal organic framework contains nitrogen elements;
and sequentially carrying out carbonization treatment and acid treatment on the cobalt-doped zinc-based metal organic framework, and then drying to obtain the Co/N Co-doped carbon nano material.
According to the preparation method of the carbon nano material, the cobalt-doped zinc-based metal organic framework is taken as a precursor material, carbonization and acid treatment are sequentially carried out, and the carbon nano material with the Co/N double-doped super carbon structure is finally obtained; the preparation method does not need an activation process and a template stripping process, so that the influence on the environment is small, the preparation process is simple, the cost is low, and the obtained carbon nano material is used for Li-SeS2The positive electrode of the battery can improve active material (SeS)2) The utilization rate of the electrolyte can be reduced, and the diffusion of the polysulfide/polysulfide compound in the electrolyte can be prevented, so that the loss of the polysulfide/polysulfide compound can be effectively prevented in the Li-SeS2The Co/N Co-doped carbon nanomaterial has good application prospect in batteries, and can be applied to the related fields of dye adsorption, catalysis and the like.
The invention also provides a positive electrode material which comprises the carbon nano material obtained by the preparation method and selenium disulfide loaded in the carbon nano material.
The anode material provided by the invention contains the carbon nano material obtained by the special preparation method, has a controllable carbon structure and a larger specific surface area, realizes Co/N double doping, and is used for Li-SeS2The positive electrode of the battery can effectively prevent the loss of the polyselenium/polysulfide compound, so the positive electrode can be well applied to Li-SeS2The positive electrode of the battery.
Finally, the invention also provides a preparation method of the cathode material, which comprises the following steps: and mixing the carbon nano material with selenium disulfide, then heating at 140-200 ℃, and cooling to obtain the cathode material.
The preparation method of the cathode material comprises the carbon nano material obtained by the special preparation method of the invention and selenium disulfide (SeS)2) Fully mixing, heating the mixed sample at 140-200 ℃ to melt the selenium disulfide and fully infiltrate the selenium disulfide into the carbon nano material, and effectively preventing the loss of the selenium/polysulfide compound in the finally obtained anode material in Li-SeS2Has good application prospect in the battery.
Drawings
FIG. 1 shows a positive electrode material CMC-SeS according to an embodiment of the present invention2The preparation flow is schematic;
FIG. 2 is an electron micrograph of a precursor according to an embodiment of the present invention: (a, d) is CMJ-0.03, (b, e) is CMJ-0.05, (c, f) is CMJ-0.07, (g) is PCMJ-0.5/0.06, (h) is PCMJ-0.8/0.06, (i) is PCMJ-1.1/0.06;
FIG. 3 shows the results of the precursor testing of the present invention: (a, b) XRD, (c) DR-UV-Vis spectra, (d) FT-IR spectra, and (e, f) TGA thermogravimetric analysis;
FIG. 4 is an optical photograph of a precursor powder sample of an embodiment of the present invention: (a) is CMJ-0, (b) is CMJ-0.03, (c) is CMJ-0.05and (d) is CMJ-0.07;
fig. 5 shows the test results of the carbon nanomaterial of the embodiment of the present invention: (a, d) is a CMC-0.03 electron microscope picture, (b, e) is a CMC-0.05 electron microscope picture, (c, f) is a CMC-0.07 electron microscope picture, (g) is a PCMC-0.5/0.06 electron microscope picture, (h) is a PCMC-0.8/0.06 electron microscope picture, (i) is a PCMC-1.1/0.06 electron microscope picture, (z) is an XRD of the carbon nano material, and (k, l) is a BET and pore size distribution of the carbon nano material;
FIG. 6 is a transmission electron micrograph of a carbon nanomaterial of an embodiment of the present invention: A1-A3 is CMC-0.03, B1-B3 is CMC-0.05, C1-C3 is CMC-0.07, D1-D3 is PCMC-0.8;
fig. 7 is an EDS photograph of a carbon nanomaterial of an embodiment of the present invention: (A) is CMJ-0.03, (B) is CMJ-0.05, and (C) is CMJ-0.07
Fig. 8 is a test result of the positive electrode material of the embodiment of the invention: (a, b) is thermogravimetric curve, and (c, d) is XRD curve; (e, f) is a Raman curve;
FIG. 9 shows a CMJ-0.07/SeS positive electrode material according to an embodiment of the present invention2EDS photograph of (a);
FIG. 10 shows a CMJ-0.05/SeS positive electrode material according to an embodiment of the present invention2EDS photograph of (a);
FIG. 11 shows a CMJ-0.03/SeS positive electrode material according to an embodiment of the present invention2EDS photograph of (a);
FIG. 12 shows a positive electrode material CMC-n/SeS according to an embodiment of the present invention2And PCMC-m/SeS2Testing the multiplying power of (1);
FIG. 13 shows a positive electrode material CMC-n/SeS according to an embodiment of the present invention2And PCMC-m/SeS2And (5) testing the resistance of the electrode.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, an embodiment of the present invention provides a method for preparing a carbon nanomaterial, including the following steps:
s01: providing a cobalt-doped zinc-based metal organic framework, wherein the organic framework in the cobalt-doped zinc-based metal organic framework contains nitrogen elements;
s02: and sequentially carrying out carbonization treatment and acid treatment on the cobalt-doped zinc-based metal organic framework, and then drying to obtain the Co/N Co-doped carbon nano material.
According to the preparation method of the carbon nano material provided by the embodiment of the invention, the cobalt-doped zinc-based metal organic framework is taken as a precursor material, the cobalt-doped zinc-based metal organic framework is sequentially subjected to carbonization and acid treatment, and finally the carbon nano material with the Co/N double-doped super carbon structure is obtained; the preparation method does not need an activation process and a stripping process, so the preparation method has small influence on the environment and the preparationThe process is simple, the cost is low, and the obtained carbon nano material is used for Li-SeS2The positive electrode of the battery can improve active material (SeS)2) The utilization rate of the electrolyte can be reduced, and the diffusion of the polysulfide/polysulfide compound in the electrolyte can be prevented, so that the loss of the polysulfide/polysulfide compound can be effectively prevented in the Li-SeS2The Co/N Co-doped carbon nanomaterial has good application prospect in the battery, and in addition, the Co/N Co-doped carbon nanomaterial has great application prospect in the fields of energy storage, electrocatalysis (oxygen generation reaction OER and hydrogen evolution reaction HER), gas adsorption and the like.
The structural design of the polar metal/heteroatom doped carbon material can well improve Li-SeS2The performance of the battery. In the embodiment of the invention, a Metal Organic Framework (MOF), namely, a cobalt-doped zinc-based Metal organic Framework, is used as a precursor to prepare the carbon nanomaterial, when the zinc-based Metal organic Framework is subjected to high-temperature carbonization treatment (for example, when the zinc-based Metal organic Framework is subjected to carbonization treatment at a temperature close to or higher than 900 ℃), a zinc element (with a boiling point of 907 ℃) contained in the zinc-based MOF is heated and volatilized to further play a role in foaming and pore-forming, so that the prepared carbon material usually has a large specific surface area and a hierarchical porous structure, while the cobalt doping can play a role in catalyzing the carbon substrate at a lower carbonization temperature, so that the graphitization degree of the carbon substrate is improved, and the carbon substrate with high graphitization degree obtained in the way has high conductivity. In the embodiment of the invention, the Co/N codoped self-assembled carbon nano material derived from the metal organic framework is firstly used for Li-SeS2The field of batteries; the cobalt-doped zinc-based metal organic framework obtained by different methods forms a series of carbon super structure materials with novel appearance, namely, the cobalt-doped zinc-based metal organic framework is used as a precursor to prepare a self-assembled carbon material with an easily regulated and controlled structure, and in-situ doping of catalytic metal and heteroatoms can be realized in the self carbonization process of the cobalt-doped zinc-based metal organic framework, so that the preparation process is greatly simplified, the production cost is reduced, the prepared Co/N Co-doped carbon nano material has larger specific surface area, the loading capacity of active substances of the electrode is improved, and the unique carbon nano structure can effectively relieve the problem of larger volume expansion of the electrode in the charging and discharging process, thereby avoiding the damage of the electrode。
Common carbon structures can be divided into zero-dimensional, one-dimensional, two-dimensional and three-dimensional materials, but different dimensional materials have respective advantages, for example, one-dimensional materials are favorable for transmission of electrons, two-dimensional materials generally have larger specific surface area and can load more active substances, and the like. Aiming at the hybrid structure of the carbon nano-sheet and the nanotube prepared in the experiment, the hybrid structure not only reserves the larger specific surface area of a two-dimensional material, but also has the better conductivity of a one-dimensional material, and because the main carbon structure is formed by self-assembling the carbon nano-sheet structure (a larger interlayer residual space is reserved between the sheet layers of the carbon nano-sheet structure), the structure can be used as an anode material to effectively prevent the irreversible damage of an electrode caused by the volume expansion of the anode in the charging and discharging process. Meanwhile, in the carbon nanomaterial: the doping of cobalt can effectively improve the graphitization degree of the carbon matrix so as to improve the conductivity of the carbon matrix, and the doping of N can improve the conductivity of the carbon matrix; but is directed to application to Li-SeS2For a battery system, the Co doping with catalysis can catalyze long-chain polysulfide/polyselenide, so that the long-chain polysulfide/polyselenide is promoted to be converted into short-chain polysulfide/polyselenide, the shuttle effect is effectively prevented, and the Li-SeS is prolonged2Cycle life of the cell and improved utilization of active material, while N-doping oxidizes short-chain polysulfide/polyselene compounds (Li)2SnAnd Li2Sen(n-4-8)) and forms a concerted catalytic action with cobalt, which greatly increases Li-SeS2The rate performance and the cycling stability of the battery are improved, and the utilization rate of active substances is improved; in this patent, when the Co/N Co-doped carbon nanomaterial is applied to Li-SeS2The battery anode has higher active material loading capacity which can reach 73 percent, and Li-SeS2The battery performance is effectively improved, and stable charge and discharge under a large current of 10 ℃ are realized.
The Co/N Co-doped carbon nanomaterial disclosed by the embodiment of the invention is more diverse in structure, and the carbon bone can be effectively adjusted by adjusting the Co doping amount and the Co doping modeA frame structure. Specifically, the cobalt-doped zinc-based metal organic framework can be synthesized from the beginning or obtained by post-processing the existing zinc-based metal organic framework Zn-MOF. The Co/N Co-doped carbon nanomaterial derived from the cobalt-doped zinc-based metal organic framework and obtained by different methods has the specific surface area of 408-530 m2g, application to Li-SeS2After the battery positive electrode material is adopted, the active material loading is higher.
In one embodiment, a method of making the cobalt-doped zinc-based metal organic framework by de novo synthesis comprises:
dissolving benzimidazole, 2-methylbenzimidazole and a cobalt source in a first solvent to obtain a first solution;
dissolving a zinc source in a second solvent to obtain a second solution;
and mixing the first solution and the second solution, and then carrying out solid-liquid separation to obtain the cobalt-doped zinc-based metal organic framework.
Benzimidazole and 2-methylbenzimidazole adopted in the embodiment are imidazole ligands, the ligands are used for preparing zeolite molecular sieve type MOF and have good thermal stability, and the imidazole ligands can also provide in-situ N doping in the carbonization process, so that the subsequent complex N doping process is omitted.
In the above step, the zinc source is selected from at least one of zinc acetate, zinc sulfate and zinc chloride; the cobalt source is at least one selected from cobalt acetate, cobalt sulfate, cobalt nitrate and cobalt chloride; the first solvent and the second solvent are both N, N-Dimethylformamide (DMF). As shown in fig. 1, the first solution and the second solution are mixed, particles in the mixed solution are agglomerated, incomplete oriented attachment growth is carried out, and then solid-liquid separation is carried out, so as to obtain a precursor material (named as CMJ) of the Co-doped Zn-MOF. The precursor material is subjected to subsequent carbonization and other processes to form a carbon nano material (CMC), and finally the carbon nano material is used for loading SeS2Formation of SeS2Positive electrode material CMC-SeS in battery2。
In one embodiment, the molar ratio of the zinc element in the zinc source to the cobalt element in the cobalt source is 1 (0.07-0.2), and taking the zinc source as zinc acetate and the cobalt source as cobalt chloride hexahydrate as an example, the mass ratio of the zinc acetate to the cobalt chloride hexahydrate is as follows: 0.29539 (0.03-0.072), under the condition of the proportion, the cobalt doped zinc-based MOF material can be better prepared, and the prepared cobalt doped zinc-based MOF changes from the white color of the original zinc-based MOF to a darker color. And the mass ratio of zinc acetate to benzimidazole and 2-methylbenzimidazole is 0.49394:0.29539:0.26432, at which zinc-based MOF can be better prepared for better cobalt doping.
In one embodiment, the de novo synthesis comprises: benzimidazole (0.29539g), 2-methylbenzimidazole (0.26432g) and cobalt chloride (0.07-0.03g) were dissolved in 40mL of DMF and stirred for 20min to form a solution A. Zinc acetate (0.49394g) was dissolved in 30mL of DMF to form solution B. Slowly adding the solution B into the solution A, strongly stirring for 24h at room temperature, filtering, washing with ethanol for three times, and drying at 70 ℃ overnight to obtain a Co-doped Zn-MOF precursor. According to the doping amount of different cobalt sources, the precursor materials of the Co-doped Zn-MOF are respectively named as CMJ-0.03, CMJ-0.05and CMJ-0.07, and the doping amounts of the Co-doped Zn-MOF are respectively 0.03g, 0.05g and 0.07 g.
In one embodiment, a method of making a post-treatment of the cobalt-doped zinc-based metal-organic framework comprises:
dissolving cobalt salt and a zinc-based metal organic framework containing nitrogen elements in an alcohol solvent, and then drying and removing the alcohol solvent to obtain the cobalt-doped zinc-based metal organic framework.
In the above steps, the zinc-based metal organic bone containing nitrogen element is the existing Zn-MOF (for example, mJUC-160, which is not doped with cobalt), and the cobalt-doped Zn-MOF is obtained by post-treatment. The molar ratio of the zinc element in the zinc-based metal organic framework containing the nitrogen element to the cobalt element in the cobalt source is 1 (0.07-0.2); taking cobalt chloride as an example, wherein the mass ratio of the Zn-MOF containing the nitrogen element to the cobalt chloride is (0.5-1.1): 0.06; the cobalt source can also be selected from at least one of cobalt acetate, cobalt sulfate and cobalt nitrate with the same molar cobalt doping amount; the alcohol solvent is at least one selected from methanol, ethanol and propanol.
In a specific embodiment, the post-processing method includes: adding Zn-MOF containing nitrogen elements and cobalt chloride into 120mL of ethanol solution, stirring vigorously at room temperature for 24h, and drying to remove ethanol to obtain a Co-doped Zn-MOF precursor. According to different Zn-MOF/cobalt source mass ratios, the obtained precursor materials of the Co-doped Zn-MOF are respectively named as PCMJ-0.5/0.06, PCMJ-0.8/0.06 and PCMJ-1.1/0.06.
In step S02 of the method for preparing a carbon nanomaterial of the embodiment of the present invention, the temperature of the carbonization treatment is 600-1100 ℃, and preferably the temperature of the carbonization treatment is 900-1000 ℃; the carbonization time is 4-6 h; the temperature rise rate of the carbonization treatment is 5 ℃/min, the carbonization condition can fully volatilize zinc from the carbon matrix, and the nitrogen content can be maintained. If the carbonization temperature is too high or the carbonization time is too long, the nitrogen content is not maintained. Further, the carbonization treatment is performed in an inert atmosphere, such as an inert gas, under which the carbon nanomaterial can be stably formed. Wherein the acid treatment is to remove aluminum element, in one embodiment, the acid treatment comprises: and (3) placing the carbonized product in an acid solution for ultrasonic treatment. Specifically, the acid solution is a hydrochloric acid solution, such as a 10 wt% hydrochloric acid solution; the ultrasonic treatment time is 20-40 min. The early carbonization treatment can volatilize a large amount of zinc, and the further acid treatment can wash off part of inactive cobalt (namely cobalt particles without carbon matrix fixation), and the cobalt fixed by the carbon matrix is reserved in the cobalt particles, so that the carbon matrix can realize cobalt doping, more holes can be exposed, active substances can be loaded, and the holes can prevent the irreversible damage of the electrode caused by electrode expansion in the charging and discharging processes. After acid treatment, cleaning and drying; specifically, after acid treatment, the mixture was washed with ethanol and deionized water and dried in an oven at 70 ℃.
In the examples of the present invention, the finally obtained Co/N Co-doped carbon nanomaterial samples were named CMC-N (N ═ 0.03, 0.05, and 0.07, corresponding to carbon structures derived with cobalt doping amounts of 0.03g, 0.05g, and 0.07g, respectively); and PCMC-m (m ═ 0.5/0.06, 0.8/0.06, and 1.1/0.06, corresponding to the amounts of 0.5g, 0.8g, and 1.1g of the derived carbon structure, respectively, of Zn-based MOF, with the cobalt doping amount kept at 0.06 g).
The embodiment of the invention provides a carbon nano material, which is a Co/N Co-doped carbon nano material prepared by the preparation method of the carbon nano material in the embodiment of the invention2And (4) characterizing the electrochemical performance of the battery cathode material.
On the other hand, the embodiment of the invention provides a cathode material, and the cathode material comprises the carbon nanomaterial obtained by the preparation method in the embodiment of the invention and selenium disulfide loaded in the carbon nanomaterial.
The positive electrode material provided by the invention contains the carbon nano material obtained by the preparation method special for the embodiment of the invention, the carbon nano material has a controllable carbon structure and a larger specific surface area, simultaneously realizes Co/N double doping, and can be favorable for preventing loss of polyselenium/polysulfide compound, so that the carbon nano material can be well applied to Li-SeS2The positive electrode of the battery.
Specifically, in the positive electrode material, the mass percentage content of selenium disulfide is 70-73%; at this ratio the active substance SeS2To be effectively supported in the carbon matrix and on the carbon surface).
Finally, an embodiment of the present invention further provides a preparation method of the foregoing positive electrode material, including the following steps: mixing the carbon nano material with selenium disulfide, heating at 140 ℃ and 200 ℃ (160 ℃ in one embodiment), and cooling to obtain the cathode material (namely carbon/SeS)2Composite materials).
The preparation method of the cathode material comprises the carbon nano material obtained by the preparation method special in the embodiment of the invention and selenium disulfide (SeS)2) Fully mixing, heating the mixed sample at 140-200 ℃ to melt the selenium disulfide and fully infiltrate the selenium disulfide into the carbon nano material, and effectively preventing the loss of the selenium/polysulfide compound in the finally obtained anode material in Li-SeS2Has good application in batteriesAnd 4, application prospect.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
(1) Preparation of carbon nanomaterials
Weighing benzimidazole (0.29539g), 2-methylbenzimidazole (0.26432g) and cobalt chloride (0.03399) and placing the weighed materials in a beaker, adding 40ml of DMF solution, placing the beaker on a magnetic stirrer, stirring for 20min to form a solution A, weighing zinc acetate (0.49394) and placing the weighed materials in the beaker, adding 30ml of DMF solution, placing the beaker on the magnetic stirrer, stirring for 20min to form a solution B, slowly adding the solution B into the solution A, stirring strongly for 24h at room temperature, filtering, washing with ethanol for three times, and drying at 70 ℃ overnight to obtain cobalt-doped Zn-MOF, namely CMJ-0.03.
And (3) placing the CMJ-0.03 into a tube furnace, heating at 900 ℃, wherein the heating rate is 5 ℃/min, the constant temperature time is 5h, naturally cooling to room temperature after the constant temperature is finished, placing the obtained black powder sample into a hydrochloric acid solution (10 wt%), carrying out ultrasonic treatment for 30min, washing with ethanol and deionized water, and drying in a 70 ℃ oven to obtain the Co/N Co-doped carbon material CMC-0.03.
(2) Preparation of cathode material
According to CMC-0.03 and selenium disulfide (SeS)2) Is mixed sufficiently at a mass ratio of 27:73, the mixed sample is kept at a constant temperature of 160 ℃ for 12 hours, and then is naturally cooled to room temperature. Determination of SeS2The loading was measured by thermogravimetric analysis (TGA). The obtained composite anode material is named as CMC-0.03/SeS2。
Example 2
(1) Preparation of carbon nanomaterials
Weighing benzimidazole (0.29539), 2-methylbenzimidazole (0.26432g) and cobalt chloride (0.05558g) and placing the mixture in a beaker, adding 40ml of DMF solution, placing the beaker on a magnetic stirrer, stirring for 20min to form a solution A, weighing zinc acetate (0.49407g) and placing the mixture in the beaker, adding 30ml of DMF solution, placing the beaker on the magnetic stirrer, stirring for 20min to form a solution B, slowly adding the solution B into the solution A, and stirring strongly at room temperature for 24 h; after filtration, it was washed three times with ethanol and dried overnight at 70 ℃ to give cobalt doped Zn-MOF, CMJ-0.05.
And (3) placing the CMJ-0.05 into a tube furnace, heating at 900 ℃, wherein the heating rate is 5 ℃/min, the constant temperature time is 5h, naturally cooling to room temperature after the constant temperature is finished, placing the obtained black powder sample into a hydrochloric acid solution (10 wt%), carrying out ultrasonic treatment for 30min, washing with ethanol and deionized water, and drying in a 70 ℃ oven to obtain the Co/N Co-doped carbon material CMC-0.05.
(2) Preparation of cathode material
According to CMC-0.05 and selenium disulfide (SeS)2) Is mixed sufficiently at a mass ratio of 27:73, the mixed sample is kept at a constant temperature of 160 ℃ for 12 hours, and then is naturally cooled to room temperature. The obtained composite anode material is named as CMC-0.05/SeS2。
Example 3
(1) Preparation of carbon nanomaterials
Weighing benzimidazole (0.29539g), 2-methylbenzimidazole (0.26432g) and cobalt chloride (0.07131g) and placing the mixture in a beaker, adding 40ml of DMF solution, placing the beaker on a magnetic stirrer, stirring for 20min to form a solution A, weighing zinc acetate (0.49394g) and placing the solution in the beaker, adding 30ml of DMF solution, placing the beaker on the magnetic stirrer, stirring for 20min to form a solution B, slowly adding the solution B into the solution A, and stirring strongly at room temperature for 24 h; after filtration, it was washed three times with ethanol and dried overnight at 70 ℃ to give cobalt doped Zn-MOF, CMJ-0.07.
And (2) placing the CMJ-0.07 into a tube furnace, heating at a certain temperature of 900 ℃, with the heating rate of 5 ℃/min and the constant temperature time of 5h, naturally cooling to room temperature after the constant temperature is finished, placing the obtained black powder sample into a hydrochloric acid solution (10 wt%), performing ultrasonic treatment for 30min, washing with ethanol and deionized water, and drying in a 70 ℃ oven to obtain the Co/N Co-doped carbon material CMC-0.07.
(2) Preparation of cathode material
According to the formula of CMC-0.07 and selenium disulfide (SeS)2) In a mass ratio of 27:73The mixture was mixed well, and the mixed sample was allowed to stand at 160 ℃ for 12 hours and then cooled naturally to room temperature. The obtained composite anode material is named as CMC-0.07/SeS2。
Example 4
(1) Preparation of carbon nanomaterials
Zn-MOF (0.5g) and cobalt chloride (0.06g) were added to 120mL of ethanol solution, stirred vigorously at room temperature for 24h, and dried to remove ethanol, to obtain cobalt-doped Zn-MOF, i.e., PCMJ-0.5/0.06.
And (2) placing the PCMJ-0.5/0.06 into a tube furnace, heating at a certain temperature of 900 ℃, with the heating rate of 5 ℃/min and the constant temperature time of 5h, naturally cooling to room temperature after the constant temperature is finished, placing the obtained black powder sample into a hydrochloric acid solution (10 wt%), performing ultrasonic treatment for 30min, washing with ethanol and deionized water, and drying in a 70 ℃ oven to obtain the Co/N Co-doped carbon material PCMC-0.5/0.06.
(2) Preparation of cathode material
According to the ratio of PCMC-0.5/0.06 to selenium disulfide (SeS)2) Is mixed fully according to the mass ratio of 3:7, the mixed sample needs to be kept at the constant temperature of 160 ℃ for 12 hours, and then is naturally cooled to the room temperature. The obtained composite anode material is named as PCMC-0.5/0.06-SeS2(or abbreviated as PCMC-0.5/SeS)2)。
Example 5
(1) Preparation of carbon nanomaterials
Zn-MOF (0.8g) and cobalt chloride (0.06g) were added to 120mL of an ethanol solution, stirred vigorously at room temperature for 24h, and dried to remove ethanol, to obtain Co-doped Zn-MOF, i.e., PCMJ-0.8/0.06.
And (2) placing the PCMJ-0.8/0.06 into a tube furnace, heating at a certain temperature of 900 ℃, with the heating rate of 5 ℃/min and the constant temperature time of 5h, naturally cooling to room temperature after the constant temperature is finished, placing the obtained black powder sample into a hydrochloric acid solution (10 wt%), performing ultrasonic treatment for 30min, washing with ethanol and deionized water, and drying in a 70 ℃ oven to obtain the Co/N Co-doped carbon material PCMC-0.8/0.06.
(2) Preparation of cathode material
According to the ratio of PCMC-0.8/0.06 to selenium disulfide (SeS)2) Mass ratio ofThe mixture was mixed sufficiently at a ratio of 3:7, and the mixed sample was allowed to stand at 160 ℃ for 12 hours and then cooled naturally to room temperature. The obtained composite anode material is named as PCMC-0.8/0.06-SeS2(or abbreviated as PCMC-0.8/SeS)2)。
Example 6
(1) Preparation of carbon nanomaterials
Zn-MOF (1.1g) and cobalt chloride (0.06g) were added to 120mL of an ethanol solution, stirred vigorously at room temperature for 24h, and dried to remove ethanol, to obtain cobalt-doped Zn-MOF, i.e., PCMJ-1.1/0.06.
Placing the PCMJ-1.1/0.06 into a tube furnace, heating at a certain temperature of 900 ℃, wherein the heating rate is 5 ℃/min, the constant temperature time is 5h, naturally cooling to room temperature after the constant temperature is finished, placing the obtained black powder sample into a hydrochloric acid solution (10 wt%), performing ultrasonic treatment for 30min, washing with ethanol and deionized water, and drying in a 70 ℃ oven to obtain the Co/N Co-doped carbon material PCMC-1.1/0.06.
(2) Preparation of cathode material
According to the ratio of PCMC-1.1/0.06 to selenium disulfide (SeS)2) Is mixed fully according to the mass ratio of 3:7, the mixed sample needs to be kept at the constant temperature of 160 ℃ for 12 hours, and then is naturally cooled to the room temperature. The obtained composite anode material is named as PCMC-1.1/0.06-SeS2(or abbreviated as PCMC-1.1/SeS)2)。
And (3) performance testing:
firstly, the elemental analysis of each precursor and the Co/N Co-doped carbon nanomaterial are respectively shown in table 1 and table 2 (wherein, CMC-0 is a carbon material prepared by carbonizing Zn-based MOF without doping cobalt, and the size characterization of the Co/N Co-doped carbon nanomaterial is shown in table 3.
TABLE 1
Figure RE-GDA0002428782240000131
Figure RE-GDA0002428782240000141
TABLE 2
Figure RE-GDA0002428782240000142
TABLE 3
Figure RE-GDA0002428782240000151
Relevant test data for the cobalt doped Zn-MOF precursors of the above examples are as follows: FIG. 2 is (a, d) CMJ-0.03, (b, e) CMJ-0.05, (c, f) CMJ-0.07; (g) electron micrographs of PCMJ-0.5/0.06, (h) PCMJ-0.8/0.06, and (i) PCMJ-1.1/0.06. FIG. 3: (a, b) XRD, (c) DR-UV-Vis spectra, (d) FT-IR spectra, (e, f) TGA thermogravimetric analysis of the precursor. FIG. 4 is an optical photograph of powder samples of (a) CMJ-0, (b) CMJ-0.03, (c) CMJ-0.05and (d) CMJ-0.07: as can be seen from the figure, as the doping amount of cobalt increases, the prepared cobalt-doped zinc-based metal organic framework changes from white at the beginning to darker color.
The relevant test data for the Co/N Co-doped carbon material in the above example are as follows: FIG. 5 is (a, d) CMC-0.03, (b, e) CMC-0.05 and (c, f) CMC-0.07; (g) electron micrographs of (z) XRD and (k, l) BET and pore size distribution of PCMC-0.5/0.06, (h) PCMC-0.8/0.06 and (i) PCMC-1.1/0.06. FIG. 6 is a transmission electron micrograph of CMC-0.03(A1-A3), CMC-0.05(B1-B3), CMC-0.07(C1-C3) and PCMC-0.8(D1-D3), showing that the resulting carbon structure is hollow bamboo joint-shaped, and has more holes exposed, thus facilitating the loading of active substances and realizing cobalt doping; FIG. 7 is EDS photographs of (A) CMJ-0.03, (B) CMJ-0.05and (C) CMJ-0.07.
carbon/SeS in the above example2The relevant test data for the composite are as follows: FIG. 8 shows thermogravimetric curves (a, b), (c, d) XRD curves, (e, f) CMC-n/SeS2The raman curve of (1). FIG. 9 shows CMJ-0.07/SeS2EDS photograph of (a). FIG. 10 shows CMJ-0.05/SeS2EDS photograph of (a). FIG. 11 shows CMJ-0.03/SeS2EDS photograph of (a).
FIG. 12 shows CMC-n/SeS2And PCMC-m/SeS2(ii) the magnification test result of (1) (wherein, the curve is PCMC-1.1/SeS)2The curve 2 is PCMC-0.8/SeS2The curve 3 is PCMC-0.5/SeS2Curve 4 is CMC-0/SeS2Curve 5 is CMC-0.03/SeS2Curve 6 shows CMC-0.05/SeS2Curve 7 is CMC-0.07/SeS2). FIG. 13 shows CMC-n/SeS2And PCMC-m/SeS2Resistance test of electrode (wherein, curve 1 is CMC-0.03/SeS2Curve 2 shows CMC-0.05/SeS2Curve 3 shows CMC-0.07/SeS2Curve 4 is CMC-0/SeS2The curve 5 is PCMC-0.5/SeS2The curve 6 is PCMC-0.8/SeS2The curve 7 is PCMC-1.1/SeS2)。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A preparation method of a carbon nano material is characterized by comprising the following steps:
providing a cobalt-doped zinc-based metal organic framework, wherein the organic framework in the cobalt-doped zinc-based metal organic framework contains nitrogen elements;
and sequentially carrying out carbonization treatment and acid treatment on the cobalt-doped zinc-based metal organic framework, and then drying to obtain the Co/N Co-doped carbon nano material.
2. The method of preparing a carbon nanomaterial of claim 1, wherein the method of preparing the cobalt-doped zinc-based metal-organic framework comprises:
dissolving benzimidazole, 2-methylbenzimidazole and a cobalt source in a first solvent to obtain a first solution;
dissolving a zinc source in a second solvent to obtain a second solution;
and mixing the first solution and the second solution, and then carrying out solid-liquid separation to obtain the cobalt-doped zinc-based metal organic framework.
3. The method for producing a carbon nanomaterial according to claim 2, wherein the molar ratio of the zinc element in the zinc source to the cobalt element in the cobalt source is 1 (0.07-0.2); and/or the presence of a gas in the gas,
the zinc source is at least one selected from zinc acetate, zinc sulfate and zinc chloride; and/or the presence of a gas in the gas,
the cobalt source is selected from at least one of cobalt acetate, cobalt sulfate, cobalt nitrate and cobalt chloride; and/or the presence of a gas in the gas,
the first solvent and the second solvent are both N, N-dimethylformamide.
4. The method of preparing a carbon nanomaterial of claim 1, wherein the method of preparing the cobalt-doped zinc-based metal-organic framework comprises:
dissolving cobalt salt and a zinc-based metal organic framework containing nitrogen elements in an alcohol solvent, and then drying and removing the alcohol solvent to obtain the cobalt-doped zinc-based metal organic framework.
5. The method according to claim 4, wherein the molar ratio of the zinc element in the nitrogen-containing zinc-based metal-organic framework to the cobalt element in the cobalt source is 1 (0.07-0.2); and/or the presence of a gas in the gas,
the cobalt source is selected from at least one of cobalt acetate, cobalt sulfate, cobalt nitrate and cobalt chloride; and/or the presence of a gas in the gas,
the alcohol solvent is at least one selected from methanol, ethanol and propanol.
6. The method for preparing carbon nanomaterial of any of claims 1-5, wherein the temperature of the carbonization treatment is 600-; and/or the presence of a gas in the gas,
the carbonization time is 4-6 h; and/or the presence of a gas in the gas,
the temperature rise rate of the carbonization treatment is 5 ℃/min.
7. The method for producing a carbon nanomaterial according to any one of claims 1 to 5, wherein the acid treatment comprises: and (3) placing the carbonized product in an acid solution for ultrasonic treatment.
8. A positive electrode material, characterized in that the positive electrode material comprises the carbon nanomaterial obtained by the production method according to any one of claims 1 to 7, and selenium disulfide supported in the carbon nanomaterial.
9. The positive electrode material according to claim 8, wherein the content of selenium disulfide in the positive electrode material is 70 to 73% by mass.
10. A method for producing a positive electrode material according to claim 8 or 9, comprising the steps of: and mixing the carbon nano material with selenium disulfide, then heating at 140-200 ℃, and cooling to obtain the cathode material.
CN201911258768.8A 2019-12-10 2019-12-10 Preparation method of carbon nano material, positive electrode material and preparation method thereof Pending CN111106332A (en)

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CN113979425A (en) * 2021-10-21 2022-01-28 河北中煤旭阳能源有限公司 Co/N double-doped carbon nanoribbon and Li-SeS2Battery positive electrode material, preparation method thereof and secondary battery
CN115050943A (en) * 2022-07-12 2022-09-13 北京北化工程技术有限公司 Selenium-doped thiotrithiocyanuric acid material with high compaction density, preparation method thereof and battery positive plate

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CN113381120A (en) * 2021-06-11 2021-09-10 中国科学院兰州化学物理研究所 Preparation method of nitrogen-doped clay mineral-loaded cobalt hybrid material modified lithium-sulfur battery diaphragm
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CN113979425A (en) * 2021-10-21 2022-01-28 河北中煤旭阳能源有限公司 Co/N double-doped carbon nanoribbon and Li-SeS2Battery positive electrode material, preparation method thereof and secondary battery
CN115050943A (en) * 2022-07-12 2022-09-13 北京北化工程技术有限公司 Selenium-doped thiotrithiocyanuric acid material with high compaction density, preparation method thereof and battery positive plate

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