CN108311100B - Preparation method of magnetic carbon material - Google Patents
Preparation method of magnetic carbon material Download PDFInfo
- Publication number
- CN108311100B CN108311100B CN201810057310.5A CN201810057310A CN108311100B CN 108311100 B CN108311100 B CN 108311100B CN 201810057310 A CN201810057310 A CN 201810057310A CN 108311100 B CN108311100 B CN 108311100B
- Authority
- CN
- China
- Prior art keywords
- carbon material
- magnetic carbon
- heating
- temperature
- preparation
- 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
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
Abstract
A preparation method of a magnetic carbon material belongs to the technical field of carbon materials and can solve the problems of wastewater generated in the preparation process of the existing magnetic carbon material taking ferroferric oxide as a magnetic component, complex preparation process and expensive equipment, and specifically, ferrocene and red phosphorus are used as raw materials, are uniformly mixed according to a feeding ratio of 0.5-3:1 by mass, and are placed in a closed reaction kettle with the oxygen content of 5-25% for heating treatment. The temperature raising mechanism is as follows: firstly, heating to 400-500 ℃ at the speed of 1-5 ℃/min, keeping the temperature for 1-5h, and then naturally cooling to room temperature. And opening the kettle, taking out the reaction product, heating at the temperature of 40-80 ℃ to initiate combustion, and collecting the black fluffy combustion product, namely the magnetic carbon material. The preparation method of the magnetic carbon material has the advantages of simple and reliable process route, large-scale preparation and the like.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a preparation method of a magnetic carbon material.
Background
The magnetic carbon material is an important functional carbon material, and has wide application and development prospects in the aspects of microwave absorption, sewage treatment, catalyst carriers, biomedicine, energy storage and the like. The nanoscale uniform dispersion of the magnetic components in the carbon material is the key for the material to have high performance and excellent stability. On one hand, the nanocrystallization fully exerts the functions of the magnetic components; on the other hand, the existence of the carbon carrier or the carbon coating plays an anchoring role on the nano particles, thereby avoiding or greatly eliminating the agglomeration phenomenon of the nano particles in the using process and further improving the operation stability. For example, ferroferric oxide as a typical magnetic material has potential application value in the aspect of secondary lithium ion batteries. The theoretical lithium storage capacity is as high as 924 mA.h/g, which is far higher than that of the current commercial lithium battery cathode product. However, like other metal oxides, the biggest problems of application of ferrosoferric oxide to lithium battery negative electrode materials are the huge volume expansion and low electrical conductivity during lithium intercalation/deintercalation, ultimately resulting in rapid decay of reversible capacity during cycling and extremely poor rate performance. The nano-preparation of ferroferric oxide and the uniform compounding of ferroferric oxide and carbon materials are widely proved to be the most effective way for solving the problems.
At present, many reports have been made on magnetic carbon materials containing ferroferric oxide as a magnetic component. The present invention is mainly focused on the compounding with a carrier-type carbon such as graphene, carbon nanotubes, or activated carbon, and the coating of a carbon layer, in which an organic substance such as resin or glucose is a precursor, on the surface of a ferroferric oxide nanoparticle. The corresponding preparation methods are mainly liquid phase methods, such as coprecipitation method, sol-gel method, hydrothermal method, electrophoretic deposition method, and the like. In addition, spray pyrolysis methods, electrospinning methods, and chemical vapor deposition methods have been reported in a small amount. In view of the above current situation, the liquid phase method can generate a large amount of industrial wastewater in the actual production process, and has a certain environmental protection pressure, and the existing non-liquid phase preparation technology faces the problems of expensive equipment, complex process, difficulty in stable amplification or high energy consumption in the actual implementation process to different degrees.
Disclosure of Invention
The invention provides a preparation method of a magnetic carbon material, which is simple and stable in process route and easy for large-scale production, aiming at the problems of wastewater generated in the preparation process of the existing magnetic carbon material taking ferroferric oxide as a magnetic component, complex preparation process and expensive equipment.
The invention adopts the following technical scheme:
a preparation method of a magnetic carbon material comprises the following steps:
firstly, weighing ferrocene and red phosphorus according to the mass ratio of 0.5-3:1, uniformly mixing, and placing in a closed reaction kettle with oxygen content of 5-25% for heating treatment, wherein the heating treatment process comprises the following steps: heating to 400-500 ℃ at the speed of 1-5 ℃/min, keeping the temperature for 1-5h, and cooling to room temperature;
and secondly, taking out a product in the reaction kettle, heating and initiating combustion at the temperature of 40-80 ℃, and obtaining a black fluffy combustion product, namely the magnetic carbon material.
Preferably, the mass ratio of the ferrocene to the red phosphorus is 1-2.5: 1.
Preferably, the oxygen content is 10-21%.
Preferably, the heat treatment process is as follows: heating to 400-500 ℃ at the speed of 2-4 ℃/min, keeping the temperature for 3-5h, and cooling to room temperature.
The magnetic component in the magnetic carbon material is ferroferric oxide nano-particles.
The invention has the following beneficial effects:
the preparation method of the magnetic carbon material provided by the invention has the advantages of simple process route, easiness in implementation of large-scale production, high operation stability and feasibility and small environmental pollution. The magnetic carbon material prepared has nanometer particle with magnetic component below 10nm and dispersed homogeneously in carbon matrix. The performance evaluation shows that the lithium storage battery has excellent lithium storage performance.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product of example 1 of the present invention; the main components in the product can be proved to be amorphous carbon and ferroferric oxide.
FIG. 2 is a graph showing the cycling performance of the product of example 1 of the present invention at a current density of 100 mA/g. The figure shows that the product has higher storage capacity and excellent long-range cycle stability when being used as the negative electrode material of the lithium ion battery.
Detailed Description
Example 1
Ferrocene and red phosphorus are used as raw materials, the ferrocene and the red phosphorus are uniformly mixed according to the feeding ratio of 1.5:1 by mass ratio, and then the mixture is placed in a closed reaction kettle with the oxygen content of 21% for heating treatment. The temperature raising mechanism is as follows: heating to 450 ℃ at the speed of 3 ℃/min, keeping the temperature for 4h, and naturally cooling to room temperature. And opening the kettle, taking out the reaction product, heating at 50 ℃ to initiate combustion, and collecting the black fluffy combustion product, namely the magnetic carbon material. When the material is used as a lithium ion battery cathode material, the reversible capacity of 554 mAh/g can be maintained after 500 charge-discharge cycles under the current density of 100 mA/g.
Example 2
Taking ferrocene and red phosphorus as raw materials, uniformly mixing the ferrocene and the red phosphorus according to the feeding ratio of 0.5:1 by mass ratio, and placing the mixture in a closed reaction kettle with the oxygen content of 5% for heating treatment. The temperature raising mechanism is as follows: firstly heating to 400 ℃ at the speed of 5 ℃/min, keeping the temperature for 1h, and then naturally cooling to room temperature. And opening the kettle, taking out the reaction product, heating at the temperature of 40 ℃ to initiate combustion, and collecting the obtained black fluffy combustion product, namely the magnetic carbon material. The material is used as a lithium ion battery cathode material, and can maintain the reversible capacity of 502 mAh/g after 500 charge-discharge cycles under the current density of 100 mA/g.
Example 3
Taking ferrocene and red phosphorus as raw materials, uniformly mixing the ferrocene and the red phosphorus according to the feeding ratio of 2:1 by mass ratio, and then placing the mixture in a closed reaction kettle with 15 percent of oxygen content for heating treatment. The temperature raising mechanism is as follows: firstly heating to 500 ℃ at the speed of 2 ℃/min, keeping the temperature for 4h, and then naturally cooling to room temperature. And opening the kettle, taking out the reaction product, heating at the temperature of 80 ℃ to initiate combustion, and collecting the obtained black fluffy combustion product, namely the magnetic carbon material. The material is used as a lithium ion battery cathode material, and can maintain the reversible capacity of 529 mAh/g after 500 charge-discharge cycles under the current density of 100 mA/g.
Example 4
Uniformly mixing ferrocene and red phosphorus serving as raw materials according to a mass ratio of 3:1, and then placing the mixture in a closed reaction kettle with oxygen content of 25% for heating treatment. The temperature raising mechanism is as follows: firstly heating to 500 ℃ at the speed of 1 ℃/min, keeping the temperature for 5h, and then naturally cooling to room temperature. And opening the kettle, taking out the reaction product, heating at the temperature of 80 ℃ to initiate combustion, and collecting the obtained black fluffy combustion product, namely the magnetic carbon material. When the material is used as a lithium ion battery cathode material, the reversible capacity of 486 mAh/g can be maintained after 500 charge-discharge cycles under the current density of 100 mA/g.
Claims (5)
1. A method for preparing a magnetic carbon material is characterized in that: the method comprises the following steps:
firstly, weighing ferrocene and red phosphorus according to the mass ratio of 0.5-3:1, uniformly mixing, and placing in a closed reaction kettle with oxygen content of 5-25% for heating treatment, wherein the heating treatment process comprises the following steps: heating to 400-500 ℃ at the speed of 1-5 ℃/min, keeping the temperature for 1-5h, and cooling to room temperature;
and secondly, taking out a product in the reaction kettle, heating and initiating combustion at the temperature of 40-80 ℃, and obtaining a black fluffy combustion product, namely the magnetic carbon material.
2. The method according to claim 1, wherein the step of preparing the magnetic carbon material comprises: the mass ratio of the ferrocene to the red phosphorus is 1-2.5: 1.
3. The method according to claim 1, wherein the step of preparing the magnetic carbon material comprises: the oxygen content is 10-21%.
4. The method according to claim 1, wherein the step of preparing the magnetic carbon material comprises: the heating treatment process comprises the following steps: heating to 400-500 ℃ at the speed of 2-4 ℃/min, keeping the temperature for 3-5h, and cooling to room temperature.
5. The method according to claim 1, wherein the step of preparing the magnetic carbon material comprises: the magnetic component in the magnetic carbon material is ferroferric oxide nano-particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810057310.5A CN108311100B (en) | 2018-01-22 | 2018-01-22 | Preparation method of magnetic carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810057310.5A CN108311100B (en) | 2018-01-22 | 2018-01-22 | Preparation method of magnetic carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108311100A CN108311100A (en) | 2018-07-24 |
| CN108311100B true CN108311100B (en) | 2020-11-06 |
Family
ID=62886842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810057310.5A Active CN108311100B (en) | 2018-01-22 | 2018-01-22 | Preparation method of magnetic carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108311100B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004352592A (en) * | 2003-05-30 | 2004-12-16 | Canon Inc | Method for manufacturing coil shape carbon material |
| CN101234751A (en) * | 2008-03-05 | 2008-08-06 | 中国科学院化学研究所 | Method for preparing nano material by flame combustion |
| CN101794652A (en) * | 2010-03-10 | 2010-08-04 | 中国科学技术大学 | Method for preparing carbon-coated superparamagnetic ferroferric oxide gel |
| CN101954480A (en) * | 2010-11-08 | 2011-01-26 | 华东理工大学 | Method for preparing carbon-coated core-shell nanoparticles continuously |
| CN103236547A (en) * | 2013-04-26 | 2013-08-07 | 中国东方电气集团有限公司 | Lithium ion battery iron-carbon composite negative material and preparation method thereof |
| WO2014009952A2 (en) * | 2012-07-09 | 2014-01-16 | Yeda Research And Development Co. Ltd | Logic circuits with plug and play solid-state molecular chips |
| CN103647041A (en) * | 2013-12-10 | 2014-03-19 | 浙江大学 | Carbon-covering ferroferric oxide nanowire as well as preparation method thereof and application in preparation of lithium ion battery |
| CN104525069A (en) * | 2015-01-01 | 2015-04-22 | 陈红 | Preparation method of carbon-loaded iron-based magnetic microsphere material |
| CN104953103A (en) * | 2015-07-09 | 2015-09-30 | 山西大学 | Method for preparing Fe2O3 and expanded graphite composite material of lithium ion battery |
| CN107069031A (en) * | 2016-11-08 | 2017-08-18 | 天津理工大学 | The preparation method and applications of ferroso-ferric oxide carbon core shell nanoparticles in situ |
-
2018
- 2018-01-22 CN CN201810057310.5A patent/CN108311100B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004352592A (en) * | 2003-05-30 | 2004-12-16 | Canon Inc | Method for manufacturing coil shape carbon material |
| CN101234751A (en) * | 2008-03-05 | 2008-08-06 | 中国科学院化学研究所 | Method for preparing nano material by flame combustion |
| CN101794652A (en) * | 2010-03-10 | 2010-08-04 | 中国科学技术大学 | Method for preparing carbon-coated superparamagnetic ferroferric oxide gel |
| CN101954480A (en) * | 2010-11-08 | 2011-01-26 | 华东理工大学 | Method for preparing carbon-coated core-shell nanoparticles continuously |
| WO2014009952A2 (en) * | 2012-07-09 | 2014-01-16 | Yeda Research And Development Co. Ltd | Logic circuits with plug and play solid-state molecular chips |
| CN103236547A (en) * | 2013-04-26 | 2013-08-07 | 中国东方电气集团有限公司 | Lithium ion battery iron-carbon composite negative material and preparation method thereof |
| CN103647041A (en) * | 2013-12-10 | 2014-03-19 | 浙江大学 | Carbon-covering ferroferric oxide nanowire as well as preparation method thereof and application in preparation of lithium ion battery |
| CN104525069A (en) * | 2015-01-01 | 2015-04-22 | 陈红 | Preparation method of carbon-loaded iron-based magnetic microsphere material |
| CN104953103A (en) * | 2015-07-09 | 2015-09-30 | 山西大学 | Method for preparing Fe2O3 and expanded graphite composite material of lithium ion battery |
| CN107069031A (en) * | 2016-11-08 | 2017-08-18 | 天津理工大学 | The preparation method and applications of ferroso-ferric oxide carbon core shell nanoparticles in situ |
Non-Patent Citations (1)
| Title |
|---|
| "Facile solution-free preparation of a carbon coated Fe3O4 nanoparticles/expanded graphite composite with outstanding Li-storage performances";Yun Zhao et al.;《Materials Letters》;20160414;第177卷;摘要、第149页2节、左栏第4段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108311100A (en) | 2018-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Advances in new cathode material LiFePO4 for lithium-ion batteries | |
| CN101728526B (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN102169986B (en) | Preparation method of lithium ferric phosphate / grapheme composite positive electrode material | |
| CN113104828B (en) | Preparation method of porous carbon modified sodium iron pyrophosphate phosphate/sodium carbonate ion battery positive electrode material | |
| CN107394180B (en) | Two-dimensional transition group metal carbide (nitride) -nano silicon particle composite material, preparation and application | |
| CN108155353B (en) | Graphitized carbon coated electrode material, preparation method thereof and application of graphitized carbon coated electrode material as energy storage device electrode material | |
| CN103794760B (en) | A kind of lithium ferrous phosphate composite material of ternary carbon source cladding and preparation method thereof | |
| CN107464938B (en) | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery | |
| CN106571465A (en) | Hydrotalcite precursor technique nitrogen-sulfur co-doped carbon loaded transition metal sulfide solid solution, preparation method and application thereof | |
| CN105390674A (en) | Iron diselenide/sulfur-doped graphene anode composite material for sodium-ion battery and preparation method of iron diselenide/sulfur-doped graphene anode composite material | |
| CN102104143A (en) | Hydrothermal synthesis method of composite material for high-performance power battery | |
| CN105702958B (en) | Preparation method and application of tin dioxide quantum dot solution and composite material thereof | |
| CN105271176A (en) | Mesoporous carbon material and manufacturing method thereof | |
| CN105047919B (en) | Preparation method of lithium iron phosphate battery positive electrode material | |
| CN108172770A (en) | Carbon coating NiP with monodisperse structure featurexNanometer combined electrode material and preparation method thereof | |
| CN107611359A (en) | The preparation method of lithium ion battery Ni NiO/ graphene composite negative poles | |
| CN105428618A (en) | Preparation method for shell-core type carbon-coated metal sulfide nano-composite particles and application of particles | |
| CN109473643B (en) | CoSe2Preparation method and application of graphene composite material | |
| CN105000545A (en) | Method for preparing lithium ion battery artificial graphite/coke anode material | |
| CN103887081B (en) | Nanocomposite material of nitrogen doped with graphene/zinc ferrite and preparation method thereof | |
| CN102347477B (en) | Method for preparing high-performance lithium iron phosphate / carbon anode material by microwave method | |
| CN113451570A (en) | MOF-derived core-shell-structured lithium ion battery negative electrode material and preparation method thereof | |
| CN106169567B (en) | A kind of carbon-coated lithium iron phosphate positive material and preparation method thereof | |
| CN106430306A (en) | Preparation method for vanadium dioxide micro-nanometer structure material | |
| CN113054170B (en) | Preparation method of nickel-nickel molybdenum oxide-graphene composite material and application of nickel-nickel molybdenum oxide-graphene composite material in lithium ion battery |
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 |