CN109309198B - Preparation method of lithium ion battery cathode red phosphorus/graphene composite material - Google Patents
Preparation method of lithium ion battery cathode red phosphorus/graphene composite material Download PDFInfo
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- CN109309198B CN109309198B CN201710615622.9A CN201710615622A CN109309198B CN 109309198 B CN109309198 B CN 109309198B CN 201710615622 A CN201710615622 A CN 201710615622A CN 109309198 B CN109309198 B CN 109309198B
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- 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
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- 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
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
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- 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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- 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 a preparation method of a red phosphorus/graphene composite material for a lithium ion battery cathode. According to the method, red phosphorus and graphene are fully dispersed in a solvent through a low-temperature liquid phase method, and the surface electrical property difference of the red phosphorus and the graphene in the solvent is utilized, so that red phosphorus nanosheets are uniformly loaded on the surface of the graphene, and the uniform red phosphorus/graphene composite material is obtained. The method comprises the steps of purifying red phosphorus, preparing mixed dispersion liquid, centrifuging, freeze-drying and the like. The preparation method is simple, environment-friendly and low in cost; in the obtained red phosphorus/graphene composite material, the red phosphorus is in an amorphous nano flaky shape and is uniformly attached to the surface of the graphene, so that the utilization rate is high, and the specific capacity and the cyclic charge and discharge stability of the lithium ion battery are remarkably improved.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a preparation method for loading amorphous red phosphorus nanosheets on the surface of graphene, wherein the obtained red phosphorus/graphene composite material is used as a negative electrode material of a lithium ion battery.
Background
Lithium ion batteries are receiving attention due to their advantages of high specific energy, high voltage, and long life. The commercial lithium ion battery adopts a graphite material as a negative electrode, lithium-containing metal oxides such as lithium iron phosphate, lithium cobaltate, lithium manganate and the like as a positive electrode, and utilizes the rocking chair effect of lithium ions between the positive electrode and the negative electrode to contribute to capacity. However, the specific capacity of the graphite negative electrode is low, the rate capability is limited, and the higher and higher requirements of the current society on an energy storage system are difficult to meet, so that the search for a new negative electrode material with high capacity density becomes the key for improving the energy density of the lithium ion battery.
Among the many potential electrode materials, elemental phosphorus has its high specific capacity (2595mAh g)-1) More attention is gained. Elemental phosphorus has three allotropes: white phosphorus, black phosphorus and red phosphorus. Among them, white phosphorus is flammable and is not suitable as an electrode material from the viewpoint of safety. Black phosphorus has been widely studied for its high conductivity, however, its preparation process is complicated and harsh, and it needs to be synthesized by special equipment under the conditions of high temperature and high pressure and inert gas protection, which greatly increases its cost. In comparison, red phosphorus has the advantages of high specific capacity, low cost, good environmental compatibility and the like, and is expected to become a negative electrode material which has low cost and can replace graphite. At present, red phosphorus as a lithium ion battery cathode material has the problems that the red phosphorus has large volume expansion (490%) after lithium intercalation and has poor conductivity. Thus, it is desirable to complex it with other carbon materials, particularly carbon materials having a rich pore structure. On one hand, the high conductivity of the carbon material can improve the electron transmission efficiency of the composite material; on the other hand, the large amount of pore structure in the carbon material can sufficiently accommodate the volume expansion of red phosphorus in the electrochemical reaction, thereby maintaining a stable electrode structure. Based on the above considerations, graphene, which has high electrical conductivity, high mechanical strength and high flexibility, is considered as an ideal carbon support material. After the graphene is fully dispersed in the solvent, a continuous three-dimensional network can be formed, and more possibilities are provided for liquid phase synthesis of red phosphorus. The flexibility of the graphene can also effectively accommodate the volume expansion of the red phosphorus and buffer the stress in the electrode, so that the red phosphorus/graphene composite material with higher stability is obtained.
The existing red phosphorus and graphene compounding process generally sublimates red phosphorus at a temperature higher than 450 ℃ through high-temperature treatment, so that red phosphorus vapor is uniformly deposited in pores of a graphene network. The method has the disadvantages that the white phosphorus formed in the cooling process is inflammable and has certain danger, and toxic reagents such as carbon disulfide and the like are required for removing the white phosphorus, so that the potential safety hazard is large. And since red phosphorus is introduced by steam, the percentage of red phosphorus in the composite material is difficult to control. And high temperature heat treatment also consumes a large amount of energy, increasing the cost.
According to the invention, graphene is fully dispersed in a solvent through a low-temperature liquid phase method, and the surface electrical property difference of red phosphorus and graphene in the solvent is utilized to uniformly load red phosphorus nanosheets on the surface of the graphene, so that the uniform red phosphorus/graphene composite material is obtained. The prepared composite material has higher specific capacity and superior cycle performance when being used as a negative electrode material of a lithium ion battery.
Disclosure of Invention
In order to solve the problems of the existing red phosphorus and graphene composite process, the invention provides a preparation method of a lithium ion battery cathode red phosphorus/graphene composite material. According to the method, red phosphorus and graphene are fully dispersed in a solvent through a low-temperature liquid phase method, and the surface electrical property difference of the red phosphorus and the graphene in the solvent is utilized, so that red phosphorus nanosheets are uniformly loaded on the surface of the graphene, and the uniform red phosphorus/graphene composite material is obtained. The composite material prepared by the method has higher specific capacity and superior cycle performance when being used as a negative electrode material of a lithium ion battery.
In order to achieve the aim, the invention adopts the following technical scheme:
according to the method, red phosphorus and graphene are fully dispersed in a solvent through a low-temperature liquid phase method, and red phosphorus nanosheets are uniformly loaded on the surface of the graphene by virtue of surface electrical property difference of the red phosphorus and the graphene in the solvent, so that the uniform red phosphorus/graphene composite material is obtained.
The method comprises the following steps:
1) purifying red phosphorus: carrying out ball milling on commercial red phosphorus in deionized water, carrying out hydrothermal treatment at 200 ℃ for 12h, and then carrying out vacuum drying;
2) preparing a mixed dispersion liquid: dispersing the purified red phosphorus and graphene in a mixed solvent of ethanol/deionized water, and performing ultrasonic dispersion for 5-120 min to obtain a uniform mixed dispersion liquid;
3) and (3) centrifugal treatment: centrifuging the mixed dispersion liquid obtained in the step 2) for multiple times, wherein the exchange solvent is deionized water to obtain a pure mixture;
4) and (3) freeze drying: freezing the mixture obtained in the step 3) at-80 ℃, and freeze-drying by a freeze dryer to obtain the red phosphorus/graphene composite material.
Preferably, the mixed solvent in the step 2) is an ethanol-water mixed solvent, wherein the volume ratio of ethanol to water is 1:5-1: 1.
Preferably, the concentration of the graphene in the mixed dispersion liquid is 0.1-10 g/L.
Preferably, the mass ratio of the red phosphorus to the graphene in the mixed dispersion liquid is 1: 2-4: 1.
The zeta potential of the red phosphorus in the mixed solvent is negative, and the zeta potential of the graphene in the mixed solvent is positive, so that the red phosphorus and the graphene are mutually adsorbed in the solution to form a stable composite structure.
The invention has the advantages and beneficial effects that: the preparation method is simple and environment-friendly; in the obtained red phosphorus/graphene composite material, the red phosphorus is in an amorphous nano flaky shape and is uniformly attached to the surface of the graphene, so that the utilization rate is high, and the specific capacity and the cyclic charge and discharge stability of the lithium ion battery are remarkably improved.
Drawings
The invention is further illustrated by the following figures and examples.
Fig. 1 is an XRD pattern of the red phosphorus/graphene composite material prepared in example 1.
Fig. 2 is an SEM image and corresponding phosphorus and carbon element distribution diagram of the red phosphorus/graphene composite material prepared in example 1.
Fig. 3 is a TEM image of the red phosphorus/graphene composite material and the graphene material prepared in example 1.
Fig. 4 is a high power TEM image of the red phosphorus/graphene composite material prepared in example 1.
Fig. 5 is a cycle curve of the red phosphorus/graphene composite material prepared in example 1 and a red phosphorus material.
Detailed Description
Example 1
1) Purifying red phosphorus: ball milling commercial red phosphorus in deionized water for 6h at the rotating speed of 300rpm, carrying out hydrothermal treatment at 200 ℃ for 12h, and then carrying out vacuum drying to obtain purified red phosphorus powder;
2) preparing a mixed dispersion liquid: ultrasonically dispersing 80mg of red phosphorus powder and 20mg of graphene in 50mL of ethanol/deionized water (volume ratio is 1:3) mixed solution for 30min to obtain graphene-red phosphorus mixed dispersion liquid;
3) and (3) centrifugal treatment: centrifuging the mixed dispersion liquid for several times, and exchanging a solvent by using deionized water to obtain a pure mixture;
4) and (3) freeze drying: freezing the mixture obtained in the step 3) at-80 ℃, and freeze-drying by a freeze dryer to obtain the red phosphorus/graphene composite material.
Referring to fig. 1, this figure is an XRD pattern of the red phosphorus/graphene composite material prepared in this example, and it can be seen that red phosphorus has an amorphous structure.
Referring to fig. 2, which is an SEM image and a corresponding phosphorus and carbon distribution diagram of the red phosphorus/graphene composite material prepared in this example, it can be seen that the prepared red phosphorus/graphene composite material forms a uniform composite material structure.
Referring to fig. 3, this figure is a TEM image of the red phosphorus/graphene composite material and the graphene material prepared in this embodiment, and it can be seen from this figure that in the prepared red phosphorus/graphene composite material, red phosphorus is uniformly attached to the surface of graphene.
Referring to fig. 4, this figure is a high-power TEM image of the red phosphorus/graphene composite material and the graphene material prepared in this example, and it can be seen from this figure that in the prepared red phosphorus/graphene composite material, the red phosphorus has a lamellar structure.
Referring to fig. 5, the cycle curve of the red phosphorus/graphene composite material prepared in this example and the red phosphorus material is shown, and it can be seen from the figure that the prepared red phosphorus/graphene composite material shows good cycle performance. PreparedUnder the current of 200mA/g, the red phosphorus/graphene composite material still maintains 1286mAh g after 100 cycles-1The specific capacity of the material is obviously higher than that of red phosphorus material.
Example 2
1) Purifying red phosphorus: ball milling commercial red phosphorus in deionized water for 6h at the rotating speed of 300rpm, then carrying out hydrothermal treatment at 200 ℃ for 12h, washing with water, and then drying in vacuum to obtain purified red phosphorus powder;
2) preparing a mixed dispersion liquid: ultrasonically dispersing 10mg of red phosphorus powder and 20mg of graphene in 50mL of ethanol/deionized water (volume ratio is 1:3) mixed solution for 30min to obtain graphene-red phosphorus mixed dispersion liquid;
3) and (3) centrifugal treatment: centrifuging the mixed dispersion liquid for several times, and exchanging a solvent by using deionized water to obtain a pure mixture;
4) and (3) freeze drying: freezing the mixture obtained in the step 3) at-80 ℃, and freeze-drying by a freeze dryer to obtain the red phosphorus/graphene composite material.
Example 3
1) Purifying red phosphorus: ball milling commercial red phosphorus in deionized water for 6h at the rotating speed of 300rpm, carrying out hydrothermal treatment at 200 ℃ for 12h, washing with water, and carrying out vacuum drying to obtain purified red phosphorus powder;
2) preparing a mixed dispersion liquid: ultrasonically dispersing 60mg of red phosphorus powder and 20mg of graphene in 50mL of ethanol/deionized water (volume ratio is 1:3) mixed solution for 30min to obtain graphene-red phosphorus mixed dispersion liquid;
3) and (3) centrifugal treatment: centrifuging the mixed dispersion liquid for several times, and exchanging a solvent by using deionized water to obtain a pure mixture;
4) and (3) freeze drying: freezing the mixture obtained in the step 3) at-80 ℃, and freeze-drying by a freeze dryer to obtain the red phosphorus/graphene composite material.
Finally, it should be noted that: the above examples are merely illustrative for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.
Claims (1)
1. A preparation method of a lithium ion battery cathode red phosphorus/graphene composite material is characterized by comprising the following steps: according to the method, red phosphorus and graphene are fully dispersed in a solvent through a low-temperature liquid phase method, and red phosphorus nanosheets are uniformly loaded on the surface of the graphene by virtue of surface electrical property difference of the red phosphorus and the graphene in the solvent, so that a uniform red phosphorus/graphene composite material is obtained;
the method comprises the following steps:
1) purifying red phosphorus: carrying out ball milling on commercial red phosphorus in deionized water, carrying out hydrothermal treatment at 200 ℃ for 12h, and then carrying out vacuum drying;
2) preparing a mixed dispersion liquid: dispersing the purified red phosphorus and graphene in a mixed solvent of ethanol/deionized water, and performing ultrasonic dispersion for 5-120 min to obtain a uniform mixed dispersion liquid, wherein the zeta potential of the red phosphorus in the mixed solvent is negative, and the zeta potential of the graphene in the mixed solvent is positive, so that the red phosphorus and the graphene are mutually adsorbed in the solution to form a stable composite structure;
3) and (3) centrifugal treatment: centrifuging the mixed dispersion liquid obtained in the step 2) for multiple times, wherein the exchange solvent is deionized water to obtain a pure mixture;
4) and (3) freeze drying: freezing the mixture obtained in the step 3) at-80 ℃, and freeze-drying the mixture by a freeze dryer to obtain the red phosphorus/graphene composite material;
the mixed solvent in the step 2) is an ethanol-water mixed solvent, wherein the volume ratio of ethanol to water is 1:5-1: 1;
the concentration of the graphene in the mixed dispersion liquid is 0.1-10 g/L;
the mass ratio of the red phosphorus to the graphene in the mixed dispersion liquid is 1: 2-4: 1.
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| CN110212185B (en) * | 2019-06-04 | 2021-01-05 | 中国地质大学（北京） | Sn-P-CNT composite material and application thereof in preparation of lithium ion battery negative electrode material |
| CN113023713A (en) * | 2021-02-02 | 2021-06-25 | 厦门大学 | Preparation method of red phosphorus/graphene composite roll |
| CN116111223B (en) * | 2023-02-20 | 2023-11-07 | 东莞理工学院 | Method for preparing ternary composite material by recycling waste lithium battery negative electrode and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101604752A (en) * | 2009-07-22 | 2009-12-16 | 北京化工大学 | A kind of lithium ion battery phosphorus/carbon compound cathode materials and preparation method thereof |
| CN103296261A (en) * | 2012-02-24 | 2013-09-11 | 清华大学 | Preparation method of lithium ion battery cathode material |
| KR20140103376A (en) * | 2013-02-15 | 2014-08-27 | 서울대학교산학협력단 | Nagative active material for sodium ion battery, method of preparing elecrode using thereof and sodium ion battery comprising same |
| CN104966826A (en) * | 2015-07-09 | 2015-10-07 | 天津工业大学 | Preparation method for graphene-coated inorganic nanoparticle cathode material of ion battery |
| CN105098154A (en) * | 2015-07-09 | 2015-11-25 | 天津工业大学 | Preparation method for anode material of red phosphorous cladding carbon nano tube composite ion battery |
| CN105702939A (en) * | 2016-04-27 | 2016-06-22 | 中国科学院化学研究所 | Phosphorus-carbon composite material and preparation method and application thereof |
| CN105845906A (en) * | 2016-04-08 | 2016-08-10 | 清华大学 | Phosphorus-contained negative electrode composite material and preparation method therefor, and lithium ion battery |
| CN106299292A (en) * | 2016-09-12 | 2017-01-04 | 三峡大学 | A kind of phosphorus/carbon compound cathode materials and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100788487B1 (en) * | 2006-08-08 | 2007-12-24 | 재단법인서울대학교산학협력재단 | Method for preparing black phosphorus and black phosphorus-carbon composites, the prepared black phosphorus and black phosphorus-carbon composites and lithium rechargeable battery comprising the same and method for using the rechargeable battery |
-
2017
- 2017-07-26 CN CN201710615622.9A patent/CN109309198B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101604752A (en) * | 2009-07-22 | 2009-12-16 | 北京化工大学 | A kind of lithium ion battery phosphorus/carbon compound cathode materials and preparation method thereof |
| CN103296261A (en) * | 2012-02-24 | 2013-09-11 | 清华大学 | Preparation method of lithium ion battery cathode material |
| KR20140103376A (en) * | 2013-02-15 | 2014-08-27 | 서울대학교산학협력단 | Nagative active material for sodium ion battery, method of preparing elecrode using thereof and sodium ion battery comprising same |
| CN104966826A (en) * | 2015-07-09 | 2015-10-07 | 天津工业大学 | Preparation method for graphene-coated inorganic nanoparticle cathode material of ion battery |
| CN105098154A (en) * | 2015-07-09 | 2015-11-25 | 天津工业大学 | Preparation method for anode material of red phosphorous cladding carbon nano tube composite ion battery |
| CN105845906A (en) * | 2016-04-08 | 2016-08-10 | 清华大学 | Phosphorus-contained negative electrode composite material and preparation method therefor, and lithium ion battery |
| CN105702939A (en) * | 2016-04-27 | 2016-06-22 | 中国科学院化学研究所 | Phosphorus-carbon composite material and preparation method and application thereof |
| CN106299292A (en) * | 2016-09-12 | 2017-01-04 | 三峡大学 | A kind of phosphorus/carbon compound cathode materials and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Phosphorus Nanoparticles Encapsulated in Graphene Scrolls as a High‐Performance Anode for Sodium‐Ion Batteries;Longkai Pei;《ChemElectroChem》;20150717(第6期);补充材料实验部分，摘要，附图1 * |
| 过渡金属磷化物Co2P与Fe2P纳米颗粒水热合成及表征;黄河;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140330;第16-18页 * |
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