CN108987733B - Preparation method of active porous carbon @ FeS of lithium ion battery cathode material - Google Patents

Preparation method of active porous carbon @ FeS of lithium ion battery cathode material Download PDF

Info

Publication number
CN108987733B
CN108987733B CN201811057809.2A CN201811057809A CN108987733B CN 108987733 B CN108987733 B CN 108987733B CN 201811057809 A CN201811057809 A CN 201811057809A CN 108987733 B CN108987733 B CN 108987733B
Authority
CN
China
Prior art keywords
fes
porous carbon
filter paper
carbon
treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811057809.2A
Other languages
Chinese (zh)
Other versions
CN108987733A (en
Inventor
张艳鸽
徐辉
李品将
杨晓刚
黄小龙
张庆波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhengzhou University
Xuchang University
Original Assignee
Zhengzhou University
Xuchang University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhengzhou University, Xuchang University filed Critical Zhengzhou University
Priority to CN201811057809.2A priority Critical patent/CN108987733B/en
Publication of CN108987733A publication Critical patent/CN108987733A/en
Application granted granted Critical
Publication of CN108987733B publication Critical patent/CN108987733B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of active porous carbon @ FeS of a lithium ion battery cathode material. The method mainly comprises the following steps: (1) cleaning qualitative filter paper, and drying for later use; (2) putting the dried filter paper in ZnCl2Soaking in water solution overnight, and drying; (3) will be soaked with ZnCl2Carrying out heat treatment on the dried filter paper of the activator to obtain a porous carbon material; (4) soaking the porous carbon material obtained after the treatment in an iron source substance solution overnight to obtain a precursor material, then placing the sublimed S powder and the precursor material in a closed container, and carrying out a vulcanization reaction in an incomplete vacuum environment to obtain the active porous carbon @ FeS. The synthetic method has the advantages of simple process, low price of the selected raw materials, environmental protection and wide application range.

Description

Preparation method of active porous carbon @ FeS of lithium ion battery cathode material
Technical Field
The invention belongs to the technical field of material chemistry, and relates to a preparation method of active porous carbon @ FeS of a lithium ion battery cathode material.
Background
At present, carbon-based negative electrode materials such as natural graphite and artificial graphite are still adopted for commercial lithium ion batteries, the graphite negative electrode materials have the advantages of large reversible capacity, stable structure, good conductivity and the like, but the potential of the graphite negative electrode materials is close to that of metallic lithium, and the battery overcharge can be separated out on the surface of an electrode to form lithium dendrites, so that the battery is pierced through a diaphragm to cause short circuit, and the battery has great potential safety hazard, and the reversible specific capacity of the carbon materials in practical use reaches 350mAh/g and is close to 372mAh/g of theoretical specific capacity. A large number of researchers have begun to focus on alternative negative electrode materials with high theoretical specific capacity, high safety performance. Because the volume expansion of the metal sulfide used as the lithium ion battery electrode material in the charging and discharging processes is smaller than that of the traditional metal oxide, compared with the traditional graphite material, the metal sulfide has higher theoretical specific capacity. FeS is used as a lithium ion battery cathode material, and the theoretical specific capacity of the FeS is 609 mAh/g. In addition to having some of the common advantages of transition metal sulfides, FeS (which has an electrode potential of about 1.3V compared to the standard lithium electrode potential (0.2V)) has a higher electrode potential. However, in the charging and discharging process, the volume expansion rate is as high as 200%, which causes the rapid decay of the battery performance. The main approach to solve these problems is to compound the carbon material, which not only has excellent conductivity and ductility, but also serves as a matrix for supporting the active material to stabilize its structure. The preparation of the FeS composite material with excellent performance and carbon load by combining the respective advantages of the carbon-based material and the metal sulfide material is a great hotspot in the field of materials science.
Lu Bian et al at university of Hunan adopts SiO2As a hard template, glucose is used as a carbon source to prepare a core-shell structure of FeS @ carbon. However, the preparation process is complex, for example, when the template is removed, the core-shell structure synthesized by adopting the template method may have a certain influence on a target product, and meanwhile, the overnight freeze drying process also wastes energy to a certain extent, which influences the further development of the core-shell structure in the research of the commercial lithium ion battery. Guo et al of Yangzhou university adopts a solid phase method to mix Fe powder, S powder and PAN (polyacrylonitrile) according to a certain proportion, and then the mixture is put into a vacuum tube furnace to obtain an N-doped FeS/PC composite material at high temperature. Fe synthesized by Yu et al of China university of science and technology through hydrothermal method2O3Precursor, which is then coated on Carbon Cloth and finally vulcanized in an argon atmosphere to produce FeS @ C/Carbon Cloth samples. Because the preparation method involves relatively complicated preparationThe process, and therefore, it is very important to find a simple preparation method.
The invention content is as follows:
the invention aims to solve the problems that: aiming at the defects of the prior art, the preparation method of the active porous carbon @ FeS of the lithium ion battery cathode material is provided.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the active porous carbon @ FeS of the lithium ion battery cathode material mainly comprises the following steps:
(1) cleaning qualitative filter paper, and drying for later use;
(2) putting the dried filter paper in ZnCl2Soaking in water solution overnight, and drying;
(3) will be soaked with ZnCl2Carrying out heat treatment on the dried filter paper of the activator to obtain a porous carbon material;
(4) and soaking the porous carbon material obtained after treatment in an iron source substance solution overnight to obtain a precursor material, then placing the sublimed S powder and the precursor material in a closed quartz tube, and carrying out a vulcanization reaction in an incomplete vacuum environment to obtain the active porous carbon @ FeS.
In the technical scheme of the invention, the selected qualitative filter paper is double-circle medium-speed qualitative filter paper for a commodity experiment;
in the technical scheme of the invention, the inert atmosphere in the step (3) is nitrogen, and N is2The air flow rate is 300-350 ml/min;
in the technical scheme of the invention, the treatment of the step (3) is as follows: raising the temperature from room temperature to 500-750 ℃ under inert atmosphere to perform pore-forming treatment, and then raising the temperature to 900-950 ℃ to perform graphitization treatment to obtain the graphitized porous carbon material.
In the technical scheme of the invention, the activation treatment time in the step (3) is 1-2h, and the graphitization treatment time is 2-4 h;
in the technical scheme of the invention, the heating rate in the step (3) is 4-5 ℃/min;
in the technical scheme of the invention, the incomplete vacuum environment in the step (4) refers to an environment with the relative pressure of nitrogen gas of-0.08 MPa to-0.03 MPa.
According to the technical scheme, in the step (4), the sublimed S powder and the precursor material are placed in a closed quartz tube for vulcanization, wherein the vulcanization temperature is 500-650 ℃, and the vulcanization time is 4-5 h.
According to the technical scheme, sublimed S is taken according to the stoichiometric ratio of the iron content of the iron source substance to S powder of 1: 1-2.
In the technical scheme of the invention, the iron source substance is Fe (NO)3)3·9H2O。
The method adopts qualitative filter paper as a carbon source, obtains the porous carbon material by carrying out heat treatment on the qualitative filter paper, preferably obtains the graphitized porous carbon material by a two-step heat treatment method, soaks the graphitized porous carbon material with an iron salt solution, and then carries out semi-vacuum vulcanization under certain nitrogen pressure to obtain the graphitized porous carbon @ FeS composite material with uniformly dispersed FeS. Due to ZnCl2Will overflow from the qualitative filter paper when heated to a certain temperature in an inert environment, leaving more active space for the FeS load, while ZnCl2The catalyst can be used in the subsequent graphitization heat treatment process to reduce the graphitization temperature of the carbon, so that the carbon material can be graphitized to a certain degree, the conductivity of the carbon material is increased, and Li is further used+The transmission between the electrolyte and the electrode material is quicker, and the cycling stability of the lithium ion battery in the charging and discharging process is improved.
The invention has the advantages that:
1. the synthetic method has simple preparation process. We adopt ZnCl2The solution is used as an activating agent, the qualitative filter paper is soaked in the iron source substance solution and then is activated through heat treatment to obtain a porous carbon material, and then the porous carbon @ FeS composite material is obtained through high-temperature semi-vacuum vulcanizationLow specific capacity when used as an electrode material, poor conductivity and high volume expansion when pure FeS is used as the electrode material, and the like.
2. The raw materials selected by the method are low in price, green and environment-friendly, and wide in application range. The substances generated in the reaction process have low toxicity, can reduce the environmental pollution and the harm to human bodies, and a surfactant is not used in the process, so that the industrial production and the technical popularization are facilitated. The method can also be applied to the synthesis of a series of graphitized porous carbon-based @ metal sulfides, and has popularization significance.
Description of the drawings:
FIG. 1-1, EXAMPLE 1X-ray powder diffractometer (XRD) pattern of two-step treatment of activated porous carbon @ FeS composite
FIG. 1-2, EXAMPLE 1 Raman diffraction (Raman) spectra of two-step treatment of activated porous carbon @ FeS composites
FIGS. 1-3, EXAMPLE 1 Scanning Electron Microscopy (SEM) micrographs of two-step treated activated porous carbon @ FeS composite
FIGS. 1-4, example 1 Charge-discharge cycle test chart of two-step processing of active porous carbon @ FeS composite material
FIGS. 1-5, EXAMPLE 1 Electrochemical Impedance Spectroscopy (EIS) plots of two-step processing of activated porous carbon @ FeS composites
FIG. 2-1, X-ray powder diffractometer (XRD) pattern of carbon @ FeS composite of control experiment of example
FIG. 2-2 Raman diffraction (Raman) spectra of carbon @ FeS composites of the control experiment of the example
FIGS. 2-3, Charge/discharge cycling test plots for two-step processed carbon @ FeS composites for comparative experiments of examples
FIG. 3-1, EXAMPLE 2X-ray powder diffractometer (XRD) pattern of one-step processing of carbon @ FeS composite
FIG. 3-2, example 2 Raman diffraction (Raman) spectra of one-step processing of carbon @ FeS composites
FIG. 3-3, Charge-discharge cycling test chart of one-step processing carbon @ FeS composite material of example 2
FIGS. 3-4, Electrochemical Impedance Spectroscopy (EIS) plots of one-step processing of carbon @ FeS composites in example 2
FIG. 4-1, COMPARATIVE EXAMPLE 1 Scanning Electron Microscopy (SEM) micrograph of two-step processed carbon @ FeS composite at a nitrogen pressure of-0.1 MPa
FIG. 4-2, comparative example 1 Charge-discharge cycle test chart for two-step processing of carbon @ FeS composite material under nitrogen pressure of-0.1 MPa
FIG. 5-1, comparative example 2 Scanning Electron Microscopy (SEM) picture of two-step processed carbon @ FeS composite at nitrogen pressure of-0.02 MPa.
The specific implementation mode is as follows:
the following examples further illustrate the performance optimization of the active porous C @ FeS composite as a negative electrode material for lithium ion batteries.
Example 1
1. Preparation work: putting the cut qualitative filter paper into absolute ethyl alcohol for ultrasonic cleaning for 30min, drying, and putting the filter paper into 1mol/L ZnCl2Soaking in water solution overnight, drying, treating at 750 deg.C for 2h in nitrogen flow of 350ml/min, and graphitizing at 905 deg.C for 4h (the mass of the active carbon is measured as m)1). Placing the filter paper after the two-step treatment in 3.4mol/L Fe (NO)3)3·9H2Soaking in O solution overnight, wiping off excessive solution on the surface of the activated carbon, and drying for later use (the weight of the activated carbon is recorded as m)2)。
2. The reaction steps are as follows: weighing sublimed S powder [ m ] according to the stoichiometric number of FeS(s)＝M(S)·(m2-m1)/M(Fe(NO3)3·9H2O)]And placing the sublimed S powder and the precursor material in a closed corundum crucible environment (so as to ensure that the precursor material can be more uniformly generated into FeS in the vulcanization reaction process). The sample was placed under nitrogen pressure at-0.05 MPa and incubated at 4 deg.C/min from room temperature to 650 deg.C for 4 h.
3. And (3) post-treatment: and after the reaction is finished, obtaining the active porous C @ FeS composite material, and determining that only FeS is contained in a sample and no other impurity peak appears when the sample is vulcanized at 650 ℃ by using an X-ray powder diffractometer (XRD). The characteristic peaks of carbon were found by analysis with Raman diffraction spectrometer (Raman): d and G peaks and ID/IGA ratio of less than 1 indicates that the composite contains graphitized carbon, and a characteristic raman peak of FeS. The microstructure of the activated carbon is observed under a Scanning Electron Microscope (SEM) to find that a large number of nano FeS particles are loaded on the surface of the activated carbon and in a micropore structure. And testing the electrochemical performance of the synthesized sample by a battery charge and discharge testing system. It was found that the specific capacity after charging and discharging 65 cycles was 591.9mAh/g when the charging and discharging current was 0.1C and the charging and discharging voltage ranged from 0.005v to 3 v. Its capacity fade was approximately 27.9%. The activated filter paper carbon @ FeS is subjected to frequency range of 0.01 HZ-10 by Electrochemical Impedance Spectroscopy (EIS)5Impedance analysis is carried out on HZ, and compared with filter paper carbon @ FeS (b) treated in one step (namely example 2 without graphitization treatment at 905 ℃), the filter paper carbon @ FeS (a) treated in two steps has a smaller arc radius than the filter paper carbon @ FeS treated in one step at high frequency, which indicates that the impedance for charge transfer between an electrode material and electrolyte is small, and the straight line of the filter paper carbon @ FeS treated in two steps at low frequency is steeper, which indicates that Li + diffuses in the electrolyte more rapidly. The XRD pattern of the sample is shown in figure 1-1, the Raman spectrum is shown in figure 1-2, the SEM scanning picture is shown in figure 1-3, the charge-discharge cycle test chart is shown in figure 1-4, and the Electrochemical Impedance Spectrum (EIS) is shown in figure 1-5 (the insets are impedance comparison graphs of one-step processed carbon @ FeS (b) and two-step processed carbon @ FeS (a)).
Control experiment:
1. preparation work: putting the cut qualitative filter paper into absolute ethyl alcohol for ultrasonic cleaning for 30min, drying, and putting the filter paper into 1mol/L ZnCl2Soaking in water solution overnight, drying, treating at 500 deg.C for 2 hr and carbonizing at 800 deg.C for 4 hr in nitrogen flow of 350ml/min (weighing activated carbon mass as m)1). Placing the filter paper after the two-step treatment in 3.4mol/L Fe (NO)3)3·9H2Soaking in O solution overnight, wiping off excessive solution on the surface of the activated carbon, and drying for later use (the weight of the activated carbon is recorded as m)2)。
2. The reaction steps are as follows: same as example 1
3. And (3) post-treatment: after the reaction is finished, the active porous C @ FeS composite material is obtained, and sulfur is determined to be 650 ℃ by an X-ray powder diffractometer (XRD)During chemical conversion, only FeS is contained in the sample, and no other impurity peaks appear. The characteristic peaks of carbon were found by analysis with Raman diffraction spectrometer (Raman): d and G peaks and ID/IGThe ratio of (A) to (B) is more than 1, which indicates that carbon in the composite material is mainly porous carbon and does not undergo graphitization; and the characteristic raman peak of FeS. And testing the electrochemical performance of the synthesized sample by a battery charge and discharge testing system. It was found that the specific capacity after charging and discharging 65 cycles was 424.3mAh/g when the charging and discharging current was 0.1C and the charging and discharging voltage ranged from 0.005v to 3 v. The XRD pattern of the sample is shown in figure 2-1, the Raman spectrum is shown in figure 2-2, and the charge-discharge cycle test pattern is shown in figure 2-3.
Example 2
1. Preparation work: putting the cut qualitative filter paper into absolute ethyl alcohol for ultrasonic cleaning for 30min, drying, and putting the filter paper into 1mol/L ZnCl2Soaking in the water solution overnight, drying, and treating at 750 deg.C for 2h in nitrogen flow of 350 ml/min. Placing the filter paper carbon after one-step treatment in 3.4mol/L Fe (NO)3)3·9H2Soaking in O solution overnight, wiping off excessive solution on the surface of the activated carbon, and drying for later use (the weight of the activated carbon is recorded as m)2)。
2. The reaction steps are as follows: same as example 1
3. And (3) post-treatment: and (3) obtaining the C @ FeS composite material after the reaction is finished, and determining that only FeS exists in the sample and no other impurity peaks appear in the sample when the sample is vulcanized at 650 ℃ by using an X-ray powder diffractometer (XRD). The characteristic peaks of carbon were found by analysis with Raman diffraction spectrometer (Raman): d and G peaks and ID/IGThe ratio of (A) to (B) is more than 1, which indicates that carbon in the composite material is mainly porous carbon and does not undergo graphitization; and the characteristic raman peak of FeS. And testing the electrochemical performance of the synthesized sample by a battery charge and discharge testing system. It was found that the specific capacity after charging and discharging 65 cycles was 338.6mAh/g when the charging and discharging current was 0.1C and the charging and discharging voltage ranged from 0.005v to 3 v. The activated filter paper carbon @ FeS is subjected to frequency range of 0.01 HZ-10 by Electrochemical Impedance Spectroscopy (EIS)5Impedance analysis is performed on HZ, XRD (X-ray diffraction) spectrum of the sample is shown in figure 3-1, Raman spectrum is shown in figure 3-2, charge-discharge cycle test is shown in figure 3-3, and electrochemical analysis is performedThe chemical impedance spectroscopy (EIS) is shown in fig. 3-4 (inset is a plot of impedance comparison for one-step processed carbon @ FeS (b) versus two-step processed carbon @ FeS (a), i.e., the active porous C @ FeS composite product of example 1).
Comparative example 1
1. Preparation work: same as example 1
2. The reaction steps are as follows: weighing sublimed S powder [ m ] according to the stoichiometric number of FeS(s)＝M(S)·(m2-m1)/M(Fe(NO3)3·9H2O)]And placing the sublimed S powder and the precursor material in a closed corundum crucible environment (so as to ensure that the precursor material can generate FeS more uniformly in the vulcanization reaction process). The sample was placed under nitrogen pressure at-0.1 MPa and incubated at 4 deg.C/min from room temperature to 650 deg.C for 4 h.
3. And (3) post-treatment: after the reaction is finished, the active porous C @ FeS composite material is obtained, and the microstructure of the composite material is observed under a Scanning Electron Microscope (SEM), and the FeS particles loaded on the carbon material are in a cross-linked block shape, which shows that the material is rapidly agglomerated in the growth process due to the reaction of the iron source and the sulfur source which are too high in vacuum. And testing the electrochemical performance of the synthesized sample by a battery charge and discharge testing system. It was found that the specific capacity after charging and discharging 65 cycles was 508mAh/g when the charging and discharging current was 0.1C and the charging and discharging voltage ranged from 0.005v to 3 v. The SEM scanning photograph is shown in FIG. 4-1, and the charge-discharge cycle test chart is shown in FIG. 4-2.
Comparative example 2
1. Preparation work: same as example 1
2. The reaction steps are as follows: weighing sublimed S powder [ m ] according to the stoichiometric number of FeS(s)＝M(S)·(m2-m1)/M(Fe(NO3)3·9H2O)]And placing the sublimed S powder and the precursor material in a closed corundum crucible environment (so as to ensure that the precursor material can generate FeS more uniformly in the vulcanization reaction process). The sample was placed under nitrogen pressure at-0.02 MPa and incubated at 4 deg.C/min from room temperature to 650 deg.C for 4 h.
3. And (3) post-treatment: and after the reaction is finished, obtaining the active porous C @ FeS composite material, observing the microstructure of the composite material under a Scanning Electron Microscope (SEM), and finding that FeS particles loaded on the carbon material are in an aggregated block shape, which indicates that the iron source and the sulfur source react slowly to enable the material to grow unevenly when the vacuum degree is too low. The SEM scan is shown in FIG. 5-1.

Claims (8)

1. The preparation method of the active porous carbon @ FeS of the lithium ion battery cathode material is characterized by comprising the following steps of: the method mainly comprises the following steps:
(1) cleaning qualitative filter paper, and drying for later use;
(2) putting the dried filter paper in ZnCl2Soaking in water solution overnight, and drying;
(3) will be soaked with ZnCl2And (3) carrying out heat treatment on the dried filter paper of the activator to obtain the porous carbon material, wherein the heat treatment comprises the following steps: heating from room temperature to 750 ℃ under an inert atmosphere to carry out activation pore-forming treatment, then heating to 950 ℃ to carry out graphitization treatment, wherein the graphitization treatment time is 2-4h, so as to obtain a graphitized porous carbon material;
(4) soaking the porous carbon material obtained after treatment in an iron source substance solution overnight to obtain a precursor material, then placing the sublimation S powder and the precursor material in a closed quartz tube, and carrying out a vulcanization reaction in an incomplete vacuum environment to obtain the active porous carbon @ FeS, wherein the incomplete vacuum environment in the step (4) refers to an environment with the relative pressure of nitrogen gas of-0.08 MPa to-0.03 MPa.
2. The method of claim 1, wherein: the selected qualitative filter paper is double-circle medium-speed qualitative filter paper.
3. The method of claim 1, wherein: the inert atmosphere in the step (3) is nitrogen, N2The gas flow rate was 300-350 ml/min.
4. The method of claim 1, wherein: the activation treatment time in the step (3) is 1-2 h.
5. The method of claim 1, wherein: the temperature rise rate in the step (3) is 4-5 ℃ per min.
6. The method of claim 1, wherein: in the step (4), the sublimed S powder and the precursor material are placed in a sealed quartz tube for vulcanization, wherein the vulcanization temperature is 500 ℃ and 650 ℃, and the vulcanization time is 4-5 h.
7. The method of claim 1, wherein: taking sublimed S according to the stoichiometric ratio of the iron content of the iron source substance to the S powder of 1: 1-2.
8. The method of claim 1, wherein: the iron source substance is Fe (NO)3)3·9H2O。
CN201811057809.2A 2018-09-11 2018-09-11 Preparation method of active porous carbon @ FeS of lithium ion battery cathode material Active CN108987733B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811057809.2A CN108987733B (en) 2018-09-11 2018-09-11 Preparation method of active porous carbon @ FeS of lithium ion battery cathode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811057809.2A CN108987733B (en) 2018-09-11 2018-09-11 Preparation method of active porous carbon @ FeS of lithium ion battery cathode material

Publications (2)

Publication Number Publication Date
CN108987733A CN108987733A (en) 2018-12-11
CN108987733B true CN108987733B (en) 2021-04-27

Family

ID=64546119

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811057809.2A Active CN108987733B (en) 2018-09-11 2018-09-11 Preparation method of active porous carbon @ FeS of lithium ion battery cathode material

Country Status (1)

Country Link
CN (1) CN108987733B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110171828B (en) * 2019-06-14 2021-02-09 陕西科技大学 FeS nano material based on carbon cloth directional growth and preparation method and application thereof
CN111217355B (en) * 2020-01-16 2021-06-01 中南大学 Preparation and application of iron sulfide @ sulfur hybrid porous carbon anode precursor material and sulfur-carrying anode active material thereof
CN111498842A (en) * 2020-04-20 2020-08-07 辽宁科技大学 Preparation method of ferrous sulfide asphalt-based composite spherical activated carbon
CN113130924B (en) * 2021-04-20 2022-09-06 中国科学技术大学 Metal-air battery catalyst, preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106478100A (en) * 2016-10-14 2017-03-08 中国石油大学(华东) A kind of preparation method of the adjustable flexible, porous C film in aperture
CN107715836A (en) * 2017-09-27 2018-02-23 洛阳师范学院 A kind of preparation method based on biomass iron-based porous carbon composite adsorbing material
CN108198696A (en) * 2017-12-28 2018-06-22 青岛大学 The preparation method and applications of porous carbon materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106478100A (en) * 2016-10-14 2017-03-08 中国石油大学(华东) A kind of preparation method of the adjustable flexible, porous C film in aperture
CN107715836A (en) * 2017-09-27 2018-02-23 洛阳师范学院 A kind of preparation method based on biomass iron-based porous carbon composite adsorbing material
CN108198696A (en) * 2017-12-28 2018-06-22 青岛大学 The preparation method and applications of porous carbon materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FeS2 nanocrystals prepared in hierarchical porous carbon for lithium-ion battery;Xin Xu et al.;《Journal of Power Sources》;20161130;第331卷;第366-372页 *

Also Published As

Publication number Publication date
CN108987733A (en) 2018-12-11

Similar Documents

Publication Publication Date Title
CN108987733B (en) Preparation method of active porous carbon @ FeS of lithium ion battery cathode material
CN107331867B (en) Preparation method of nitrogen-doped porous carbon material used as negative electrode of sodium-ion battery
CN111146424B (en) Metal sulfide/carbon composite material, and preparation method and application thereof
CN112349899B (en) Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery
CN110518213A (en) A kind of porous silicon-carbon nano tube compound material and its preparation method and application
CN108123110A (en) A kind of preparation method and application of nitrogenous big pore volume porous carbon materials
CN111153448A (en) Preparation method and application of bamboo/wood-based nano-cellulose limited transition metal oxide electrode material
CN107732209B (en) Method for preparing lithium ion carbon negative electrode material from mixed bacteria residue waste
CN109686941A (en) A method of preparing lithium-ion-power cell silicon-carbon cathode material
CN112174119B (en) Method for preparing graphene foam from antibiotic fungi residues
CN110729478B (en) Antimony trisulfide nano-dot/sulfur-doped carbon composite material, preparation method thereof and application thereof in sodium/potassium ion battery
CN111653774A (en) Method for preparing biomass carbon lithium ion battery cathode material
CN109786709B (en) Ferroferric oxide/carbon composite negative electrode material and preparation method and application thereof
CN110600710B (en) Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery
CN111106321B (en) Nitrogen-doped molybdenum disulfide/three-dimensional graphene composite material
CN116854075A (en) Chemical surface modified biomass hard carbon material and preparation method and application thereof
CN111952569B (en) Silicon oxide-based negative electrode material for lithium ion battery and preparation method thereof
CN111799458B (en) Tin elemental composite tungsten disulfide/reduced graphene oxide composite electrode material and preparation method and application thereof
CN110518194B (en) Method for preparing core-shell silicon/carbon composite material by in-situ carbon coating and application thereof
CN111106320B (en) Nitrogen-doped molybdenum disulfide/C/three-dimensional graphene composite material
CN112310371A (en) Iron oxyhydroxide/biomass charcoal composite material and preparation method thereof
CN111653735A (en) Low-temperature carbon-coated porous silicon composite negative electrode material and preparation method thereof
CN114956035B (en) Ultra-microporous carbon material, sulfur positive electrode material and application research of ultra-microporous carbon material and sulfur positive electrode material in lithium sulfur battery
CN114649533B (en) Silicon-based heterostructure material and preparation and application thereof
CN114613982B (en) Carbon-coated silicon oxide material for doping induced disproportionation and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant