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Black phosphorus-based composite negative electrode material, preparation method thereof and application of black phosphorus-based composite negative electrode material in metal secondary battery

A technology of negative electrode materials and composite materials, applied in the fields of material chemistry and electrochemistry, can solve problems such as difficulty in realizing reversible capacity, and achieve the effect of improving service life and safety

Pending Publication Date: 2020-12-01
UNIV OF SCI & TECH OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, so far, it is still difficult to achieve reversible capacity under high current charge and discharge (for example, in lithium-ion batteries, it is necessary to achieve at least 5A / g current density and cycle more than 1000 cycles to maintain a reversible capacity of 350-400mAh / g)

Method used

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  • Black phosphorus-based composite negative electrode material, preparation method thereof and application of black phosphorus-based composite negative electrode material in metal secondary battery
  • Black phosphorus-based composite negative electrode material, preparation method thereof and application of black phosphorus-based composite negative electrode material in metal secondary battery
  • Black phosphorus-based composite negative electrode material, preparation method thereof and application of black phosphorus-based composite negative electrode material in metal secondary battery

Examples

Experimental program
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Effect test

Embodiment 1

[0063] Embodiment 1: the preparation of black phosphorus powder sample

[0064] Grind 500mg of black phosphorus block (prepared in the laboratory) into powder in a mortar, and then in a 50mL centrifuge tube, disperse it in 40mL of N,N-dimethylformamide (DMF) and heat at 600kW Ultrasonic treatment (Xinzhi Scientz-IID) under high power for 48 hours, suction filtration, washing and drying to obtain black phosphorus powder.

[0065] The black phosphorus powder that present embodiment 1 obtains is observed by scanning electron microscope (SEM), figure 1 Shown is a scanning electron microscope (SEM) photo of a black phosphorus powder sample obtained through ultrasonic treatment according to Example 1 of the present invention. Depend on figure 1 It can be seen that since black phosphorus is a layered two-dimensional material, its powder sample has a flake shape in the microscopic view, and the obtained black phosphorus powder has a uniform size of about 10 μm.

Embodiment 2

[0066] Embodiment 2: Preparation of black phosphorus-carbon modified material sample

[0067] In a ball mill (Fritcsh P7), 200 mg of the black phosphorus powder obtained in Example 1 and 50 mg of graphite powder (obtained from Alfa Aesar, 325 mesh) (the mass ratio of carbon to phosphorus is 4:1) were mixed under an argon atmosphere to Ball milling at a rotational speed of 550 rpm for 12 hours to obtain a black phosphorus-carbon modified composite material.

[0068] The black phosphorus-carbon modified composite material that present embodiment 2 obtains is observed by scanning electron microscope (SEM), figure 2 Shows a scanning electron microscope (SEM) photo of a black phosphorus-carbon modified composite material powder sample obtained through high-energy ball milling according to Example 2 of the present invention. The particle size ranges from 200 nm to 1 μm, and no layered The existence of black phosphorus indicates that the compounding is relatively uniform in ball mi...

Embodiment 3

[0070] Example 3: Preparation of black phosphorus-carbon modified composite material coated with conductive polymer

[0071] In a 20mL sample vial bottle, 50mg of the black phosphorus-carbon modified composite material powder obtained in Example 2 was dispersed in 3.6mL of aniline (obtained from Aladdin Company) with a concentration of 3mg / mL and phytic acid ( obtained from Aladdin) in an aqueous solution at a concentration of 4 mg / mL and sonicated for 1 min. Then, 1.2 mL of another aqueous solution of ammonium persulfate (obtained from Sinopharm Reagent) with a concentration of 5 mg / mL was added to the mixed solution, and sonicated for another 1 minute. Subsequently, it was stirred for 5 h under an ice bath to complete the in situ polymerization of aniline. Finally, the reaction solution was suction-filtered, washed with water, and dried in a vacuum oven at 100° C., thereby obtaining the desired black phosphorus-graphite modified composite material coated with polyaniline (t...

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Abstract

The invention relates to a black phosphorus-based composite negative electrode material, a preparation method thereof and an application of the black phosphorus-based composite negative electrode material in a metal secondary battery. The black phosphorus-based composite negative electrode material is composed of black phosphorus, a carbon material and a conductive polymer, wherein the carbon material and the black phosphorus are connected through covalent bonds through high-energy ball milling treatment, and therefore, a black phosphorus-carbon modified composite material is formed; the conductive polymer continuously or discontinuously coats the surface of the black phosphorus-carbon modified composite material through liquid phase in-situ polymerization, and therefore, the required black phosphorus-based composite negative electrode material is obtained; the coating amount of the conductive polymer is 0.01-50 wt% based on the total weight of the black phosphorus-based composite negative electrode material. The conditions of the high-energy ball milling treatment are as follows: the feeding mass ratio of the black phosphorus to the carbon material is (0.05-20): 1; the mass ratioof ball materials is (10-300): 1; the ball milling rotating speed ranges from 300 to 1,000 rpm; the ball milling time is 1-12 hours.

Description

technical field [0001] The invention belongs to the field of material chemistry and electrochemistry, and in particular relates to a black phosphorus-based composite negative electrode material, its preparation method and its application in metal secondary batteries (such as lithium ion batteries, sodium ion batteries, potassium ion batteries, etc.). Background technique [0002] At present, the power density of commercial lithium-ion batteries is mainly limited by the rate performance of negative electrode materials, and it is difficult for existing battery material systems to break through this bottleneck. Therefore, the key to breaking through this bottleneck is to develop a new generation of anode material system with high rate, high capacity and stable cycle. [0003] Because of its high theoretical specific capacity (2600mAh / g, much higher than the capacity of 370mAh / g of commercial graphite negative electrode), large layer spacing (0.53nm), and extremely low in-plane ...

Claims

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Application Information

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IPC IPC(8): H01M4/36H01M4/38H01M4/62H01M10/0525H01M10/054C08G73/02
CPCC08G73/0266H01M4/366H01M4/38H01M4/624H01M10/0525H01M10/054H01M2004/021H01M2004/027Y02E60/10
Inventor 季恒星金洪昌辛森
Owner UNIV OF SCI & TECH OF CHINA
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