CN111697215A - Antimony/carbon fiber composite material and preparation method and application thereof - Google Patents
Antimony/carbon fiber composite material and preparation method and application thereof Download PDFInfo
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- CN111697215A CN111697215A CN202010388877.8A CN202010388877A CN111697215A CN 111697215 A CN111697215 A CN 111697215A CN 202010388877 A CN202010388877 A CN 202010388877A CN 111697215 A CN111697215 A CN 111697215A
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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
- H01M4/362—Composites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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 discloses an antimony/carbon fiber composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) soaking carbon fibers in an antimonate solution, and drying to obtain an antimonate/carbon fiber precursor; 2) and connecting the antimonate/carbon fiber precursor with a power supply to form a closed loop, wherein in the closed loop, the current is 1-8A, the voltage is 35-38V, and the loop is disconnected after the closed loop is electrified for 0.1-3s, so that the antimonate/carbon fiber composite material is obtained. In the composite material, Sb nano particles with the size of 20-50nm are uniformly dispersed and combined on the surface of a carbon fiber carrier, so that the Sb nano particles have more sufficient contact area with an electrolyte, and meanwhile, the carbon fiber substrate material can provide a conductive network structure for superfine Sb nano particles. The antimony/carbon fiber composite material has excellent cycling stability when being used as a potassium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of nano materials and electrochemistry, in particular to an antimony/carbon fiber composite material and a preparation method and application thereof.
Background
Electrode materials have been the subject of intense research in batteries. Like lithium and sodium metals, potassium metal can be alloyed with a variety of elements (e.g., Si, Sn, Sb, etc.). For example, Si alloys for lithium ion battery negative electrodes with theoretical capacities as high as 4200mAh g-1The Sn alloy can reach 990mAh g-1. Initially, there was little research on alloy negative electrodes for potassium ion batteries, and as of 2015 Wu et al, application of Sb-C nanocomposites in potassium ion batteries formed K3Sb alloy providing 650mAh g-1The reversible capacity of (a). Although the theoretical specific capacity of such negative electrode materials is generally higher, K is+A large volume change occurs after embedding. The volume expansion problem of the alloying reaction is serious, and the pulverization of the material is still a key factor which causes the alloy cathode to be difficult to meet the requirements of people. The measures that can be taken to solve the above problems are:
(1) designing and synthesizing the nano material with novel micro-morphology, structure and porous characteristic. The nano material has the characteristics of many surface active sites, large specific surface area, high reaction activity and the like, so the construction of the nano structure is also regarded as an effective means of the electrode material of the potassium ion battery with high safety, high energy density and long cycle life. In addition, the negative electrode material with the nano structure can relieve the influence of the volume expansion effect on the electrode structure, and inhibit the electrode from collapsing and crushing, so that the activity of the electrochemical reaction is obviously improved, and the potassium storage property of the electrode material is improved.
(2) A carbon-based material is introduced. The compound material is compounded with the high-conductivity carbon material, the carbon material with good conductivity can play a dual role, not only can be used as a conductive agent to improve the conductivity of the whole compound and accelerate the transmission rate of ions and electrons, but also can be used as a buffer layer or a support matrix to maintain the structure of the compound material stable, and the improvement of the electrochemical performance is realized.
The common methods for synthesizing the nano material at present comprise a hydrothermal method, a solvothermal method, a ball milling method, high-temperature sintering and the like, the methods can well control the size, the phase and the structure of the nano material, and can also prepare nano particles distributed on a substrate. Although these methods have met with some success in the preparation of nanomaterials, in the solvothermal process, environmentally unfriendly solvents and dispersants, and the continuous thermodynamic atmosphere in a high temperature route, can have a negative impact on the production of high performance, high energy nanoparticles, and designing and preparing good dispersibility of supporting nanomaterials remains a significant challenge; the synthesis of the nano particles by using a ball milling method is more uniform, but the required time is longer; the high-temperature sintering method has slow heating and cooling rates (up to 40 ℃/min).
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a simple and efficient preparation method of an antimony/carbon fiber composite material and application of the prepared antimony/carbon fiber composite material as a potassium ion battery cathode material.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the antimony/carbon fiber composite material is characterized by comprising the following steps of:
1) soaking the carbon fiber in an antimonate solution to enable antimonate to be attached to the carbon fiber, taking out and drying to remove the solvent on the carbon fiber, and obtaining an antimonate/carbon fiber precursor;
2) and connecting the antimonate/carbon fiber precursor with a power supply to form a closed loop, wherein in the closed loop, the current is 1-8A, the voltage is 35-38V, and the loop is disconnected after the closed loop is electrified for 0.1-3s, so that the antimonate/carbon fiber composite material is obtained.
According to the invention, a power supply is switched on by utilizing a Joule heating principle, when current passes through the carbon fiber attached with the antimonate, electric energy is converted into heat energy by resistance loss in the material, and due to the fact that the ultra-high temperature generated by thermal shock is higher than the decomposition temperature (more than 1000K) of the metal salt, the metal salt precursor is firstly decomposed and then is cooled and solidified into Sb nano particles with strong interface bonding strength with the carbon fiber within milliseconds, so that the nanoscale ultrafine particles are successfully and firmly fixed on the surface of the carbon fiber. Moreover, the whole high-temperature superconducting process is continued within millisecond-level time, and the ultra-fast heating/cooling rate can prevent the migration and agglomeration of the nano particles, so that the uniformly dispersed Sb nano particles on the carbon carrier are obtained, and further, the Sb nano particles have more sufficient contact area with the electrolyte, and meanwhile, the carbon fiber substrate material can provide a conductive network structure for the ultrafine Sb nano particles.
Preferably, the preparation method of the antimony/carbon fiber composite material further comprises, before the step 1): and (3) carrying out carbonization pretreatment on the carbon fiber.
In the preparation method of the antimony/carbon fiber composite material, the preferable carbonization pretreatment process comprises the following specific steps: the carbon fiber is kept warm for 1-3h under the inert atmosphere and the temperature of 750-850 ℃. The purpose of the pretreatment is to remove volatile substances from the carbon fibers and to increase their strength.
In the preparation method of the antimony/carbon fiber composite material, preferably, the antimony salt is soluble in water or alcohol. More preferably, the antimony salt is SbCl3、SbBr3、Sb(CH3COO)3One or more of (a).
In the preparation method of the antimony/carbon fiber composite material, preferably, the concentration of the antimony salt solution is 0.03-0.07M, and the impregnation time of the carbon fiber is 10-14 h.
As a general inventive concept, the invention also provides an antimony/carbon fiber composite material prepared by the preparation method, which comprises carbon fibers and antimony ultrafine nanoparticles uniformly dispersed and fixed on the surfaces of the carbon fibers, wherein the size of the antimony ultrafine nanoparticles in the antimony ultrafine nanoparticles is 20-50 nm.
As a general inventive concept, the invention also provides an application of the antimony/carbon fiber composite material as a negative electrode material of a potassium ion battery.
Compared with the prior art, the invention has the advantages that:
1. the preparation method of the antimony/carbon fiber composite material is simple, rapid and efficient, and the time of the whole synthesis process is very short.
2. The nano composite material prepared by the invention has strong interface bonding strength and is an important component of various energy conversion devices.
3. The ultra-fast heating/cooling rate of the invention can prevent the migration and agglomeration of Sb nanoparticles.
4. The invention can control and reduce the size of the nano material, thereby improving the activity of the nano particle and increasing the specific surface area of the total nano particle.
5. The antimony/carbon fiber composite material prepared by the invention has excellent cycling stability when being used as a potassium ion battery cathode material.
Drawings
Fig. 1 is an SEM image of antimony/carbon fiber composites (Sb-CNFs) prepared according to an example of the present invention, wherein a is an SEM image of 5 μm antimony/carbon fiber composites on a scale, b is an enlarged view of a, and b is an SEM image of 1 μm antimony/carbon fiber composites on a scale.
Fig. 2 is an EDX-mapping diagram of antimony/carbon fiber composites (Sb-CNFs) prepared according to examples of the present invention (where, a is an SEM diagram of the antimony/carbon fiber composites, b is a carbon element distribution of the antimony/carbon fiber composites in the a, and c is an antimony element distribution of the antimony/carbon fiber composites in the a).
Fig. 3 is a cycle curve diagram of the antimony/carbon fiber composite material (Sb-CNFs) prepared in the embodiment of the present invention after being assembled into a potassium ion battery as a negative electrode material.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
Example 1:
the preparation method of the antimony/carbon fiber composite material (Sb-CNFs) of the embodiment is as follows:
firstly, carbon fibers (CNFs) are carbonized, namely: and (3) carrying out heat preservation treatment for 2h at 800 ℃ in an inert gas atmosphere. Simultaneously weighing a certain amount of SbCl3Salt, which was added to absolute ethanol and stirred to be completely dissolved to prepare 0.05M concentration of SbCl3Salt solutionAnd (4) liquid. Soaking carbonized CNFs in SbCl3The salt solution is taken out for 12h and then is dried in an oven at 60 ℃ for 8h to obtain SbCl3-CNFs composite materials. Reacting SbCl3Two ends of the CNFs composite material are fixed on a conductive copper foil through silver glue to manufacture a conductive device, then the conductive copper foil is connected with a direct current power supply in an inert gas glove box to form a closed loop, the range of direct current is 6A, the range of voltage is 37V, the electrifying time is 1s, the whole high-temperature superconducting process is continued within millisecond-level time, and due to the ultra-high temperature (more than 1000K) generated by thermal shock, a metal salt precursor is firstly decomposed to form a metal molten state. After the circuit was broken, the metal melted cooled and solidified into nanoparticles within a few milliseconds, so that the nanoparticles on the carbon support were uniformly dispersed. As shown in FIG. 1, the Sb ultrafine nanoparticles which are uniformly distributed are rapidly synthesized on a carbon fiber (CNFs) substrate by using the Joule heating principle high HTS technology, and the size range of the Sb ultrafine nanoparticles is 20-50 nm. Referring to fig. 2, as can be seen from fig. 2b and 2c, carbon element and antimony element are uniformly distributed in the antimony/carbon fiber composite material.
The synthesized superfine nano particles can be in more sufficient area contact with the electrolyte, and meanwhile, the carbon fiber substrate material can provide a conductive network structure for the superfine nano particles.
Electrochemical performance test of antimony/carbon fiber composite material (Sb-CNFs) as potassium ion battery negative electrode material
The antimony/carbon fiber composite material (Sb-CNFs) prepared by the embodiment is used as a negative electrode material of a potassium ion battery, metal potassium is used as a counter electrode, glass fiber is used as a diaphragm, 3M potassium difluorosulfonimide (KFSI) -dimethyl ether (DME) solution is used as an electrolyte, and the current density is 0.05A g-1The measured cycle curve is shown in fig. 3, and it can be seen that the antimony/carbon fiber composite (Sb-CNFs) electrode material has excellent cycle stability during charge and discharge.
Comparative example 2:
the preparation method of the antimony/carbon fiber composite material (Sb-CNFs) of the comparative example is as follows:
firstly, carbon fibers (CNFs) are carbonized, namely: keeping at 800 deg.C in inert gas atmosphereAnd (5) warming for 2 h. Simultaneously weighing a certain amount of SbCl3Salt, which was added to absolute ethanol and stirred to be completely dissolved to prepare 0.05M concentration of SbCl3A salt solution. Soaking carbonized CNFs in SbCl3The salt solution is taken out for 12h and then is dried in an oven at 60 ℃ for 8h to obtain SbCl3-CNFs composite materials. Reacting SbCl3Fixing two ends of the CNFs composite material on a conductive copper foil by using silver adhesive to manufacture a conductive device, and then connecting the conductive copper foil with a direct current power supply in an inert gas glove box to form a closed loop, wherein the range of direct current is 8A, the range of voltage is 40V, and the electrifying time is 5 s. The invention utilizes the Joule heating principle HTS technology to rapidly synthesize the antimony/carbon fiber composite material, the carbon fiber of the antimony/carbon fiber composite material has no obvious Sb ultrafine nano particles, and the diameter of the carbon fiber tube is 200nm larger than that of the pure carbon fiber. Indicating that the Sb volatilizes and the joints among the carbon fibers are bonded when the temperature is too high.
The above description is only for the preferred embodiment of the present application and should not be taken as limiting the present application in any way, and although the present application has been disclosed in the preferred embodiment, it is not intended to limit the present application, and those skilled in the art should understand that they can make various changes and modifications within the technical scope of the present application without departing from the scope of the present application, and therefore all the changes and modifications can be made within the technical scope of the present application.
Claims (7)
1. The preparation method of the antimony/carbon fiber composite material is characterized by comprising the following steps of:
1) soaking the carbon fiber in an antimonate solution to enable antimonate to be attached to the carbon fiber, taking out and drying to remove the solvent on the carbon fiber, and obtaining an antimonate/carbon fiber precursor;
2) and connecting the antimonate/carbon fiber precursor with a power supply to form a closed loop, wherein in the closed loop, the current is 1-8A, the voltage is 35-38V, and the loop is disconnected after the closed loop is electrified for 0.1-3s, so that the antimonate/carbon fiber composite material is obtained.
2. The method for preparing antimony/carbon fiber composite material according to claim 1, further comprising, before the step 1): and (3) carrying out carbonization pretreatment on the carbon fiber.
3. The preparation method of the antimony/carbon fiber composite material as claimed in claim 2, wherein the carbonization pretreatment comprises the following specific steps: the carbon fiber is kept warm for 1-3h under the inert atmosphere and the temperature of 750-850 ℃.
4. The method of claim 1, wherein the antimony salt is SbCl3、SbBr3、Sb(CH3COO)3One or more of (a).
5. The method of claim 4, wherein the concentration of the antimony salt solution is 0.03-0.07M, and the impregnation time of the carbon fiber is 10-14 h.
6. An antimony/carbon fiber composite material prepared by the preparation method according to any one of claims 1 to 5, comprising carbon fibers and antimony ultrafine nanoparticles uniformly dispersed and fixed on the surfaces of the carbon fibers, wherein the size of the antimony ultrafine nanoparticles is 20 to 50 nm.
7. Use of the antimony/carbon fiber composite material as claimed in claim 6 as a negative electrode material for a potassium ion battery.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526565A (en) * | 2021-07-09 | 2021-10-22 | 天津大学 | Method for rapidly synthesizing lithium cobaltate cathode material and application |
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| CN104934581A (en) * | 2015-06-03 | 2015-09-23 | 武汉理工大学 | Three-dimensional-antimony/carbon network structure composite material, preparation method and application thereof |
| US20150311515A1 (en) * | 2012-03-28 | 2015-10-29 | Sharp Laboratories Of America, Inc. | Antimony and Layered Carbon Network Battery Anode |
| CN109768238A (en) * | 2018-12-24 | 2019-05-17 | 肇庆市华师大光电产业研究院 | A kind of Sb-C/S nano-fiber composite material, preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150311515A1 (en) * | 2012-03-28 | 2015-10-29 | Sharp Laboratories Of America, Inc. | Antimony and Layered Carbon Network Battery Anode |
| CN104934581A (en) * | 2015-06-03 | 2015-09-23 | 武汉理工大学 | Three-dimensional-antimony/carbon network structure composite material, preparation method and application thereof |
| CN109768238A (en) * | 2018-12-24 | 2019-05-17 | 肇庆市华师大光电产业研究院 | A kind of Sb-C/S nano-fiber composite material, preparation method and application |
Non-Patent Citations (2)
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| CHUNPENG YANG ET AL.: ""Ultrafine Silver Nanoparticles for Seeded Lithium Deposition toward Stable Lithium Metal Anode"", 《ADV. MATER.》 * |
| DANYANG LIU ET AL.: ""Ultra-stable Sb confined into N-doped carbon fibers anodes for high-performance potassium-ion batteries"", 《SCIENCE BULLETIN》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526565A (en) * | 2021-07-09 | 2021-10-22 | 天津大学 | Method for rapidly synthesizing lithium cobaltate cathode material and application |
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