CN110534712A - A kind of black phosphorus-titanium dioxide-carbon compound cathode materials and preparation method and application - Google Patents

Abstract

The invention discloses a black phosphorus-titanium dioxide-carbon composite negative electrode material and its preparation method and application. The preparation includes the following steps: under an inert gas protection atmosphere, red phosphorus is subjected to ball milling reaction to obtain nano-scale black phosphorus; Under an inert gas protection atmosphere, black phosphorus, titanium dioxide, and carbon materials are mixed to obtain a mixture, and the mixture is ball-milled to obtain a black phosphorus-titanium dioxide-carbon composite negative electrode material. Carbon and black phosphorus are linked by C-P bonds, which ensures the close contact between black phosphorus and carbon materials during charging and discharging, and alleviates the volume change during the process of black phosphorus intercalating lithium. There is a Ti-O-P bond between titanium dioxide and black phosphorus, which can effectively improve the utilization rate of the active material black phosphorus and increase the electron transfer rate at the interface. The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared by the invention is used as a lithium ion battery negative electrode material, and exhibits excellent cycle performance and high reversible capacity.

Description

A kind of black phosphorus-titanium dioxide-carbon composite negative electrode material and its preparation method and application

technical field

The invention relates to a battery material that can be used to prepare lithium ion batteries, in particular to a black phosphorus-titanium dioxide-carbon composite negative electrode material and its preparation method and application.

Background technique

Lithium-ion battery (LIB) is a relatively mature rechargeable battery at present. It not only has the characteristics of high specific capacity, long cycle life, no memory effect, low self-discharge rate, etc., but also has little pollution, meets environmental protection requirements, and can be widely used in Electric vehicles, aerospace, biomedical engineering and other fields. With the rapid development of science and technology around the world, the advancement of lithium-ion battery technology can no longer meet the growing needs of emerging energy applications, which usually require higher power/energy density and longer life, especially in power energy market as well as the grid energy storage market. Therefore, electrode materials with high specific capacity, long cycle life, and low cost play a key role in the energy storage market.

Compared with the low theoretical capacity (372mAh/g) of the traditional commercial graphite anode, the theoretical lithium storage capacity of elemental phosphorus is second only to silicon, about 2596mAh/g, which has aroused great interest of researchers. Black phosphorus is the most stable phosphorus allotrope at normal temperature and pressure. Compared with red phosphorus (10 ^-12 S/m), its electronic conductivity is as high as 10 ² S/m; secondly, it has a layered structure similar to graphite, and the layers are combined by van der Waals force, which can be peeled off into a single layer or a few layers of nanosheets. Its interlayer spacing is 5.4 Å (3.4 Å larger than that of graphite), which is much larger than the ionic radius of lithium ions (1.52 Å), which is conducive to the migration of Li ⁺ between its layers, so that high-rate cycle performance can be achieved. However, phosphorus materials have the following two key problems: (1) the poor electronic conductivity of phosphorus makes it difficult to carry out electrochemical redox reactions; (2) the volume expansion of phosphorus is large (>300%), resulting in the contact between phosphorus and conductive deterioration, particle pulverization, and continuous fragmentation and growth of the solid electrolyte membrane (SEI).

Contents of the invention

In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a black phosphorus-titanium dioxide-carbon composite negative electrode material with high reversible capacity and its preparation method and application. The preparation method uses red phosphorus, TiO ₂ , and carbon as raw materials through a solid-phase ball milling process, and is prepared by two-step ball milling. The preparation method has mild preparation conditions, simple process, and has a large-scale application prospect.

One of the objects of the present invention is to improve the conductivity of electrode materials by adding carbon to black phosphorus. Secondly, carbon and black phosphorus are linked by C-P bonds, which ensures the close contact between black phosphorus and carbon materials during charging and discharging, and alleviates the volume change during lithium intercalation of black phosphorus.

Another object of the present invention is to improve the electronic and ion conductivity of the material, improve the kinetics of the electrode reaction, and release the stress of the material by introducing titanium dioxide. Secondly, there is a Ti-O-P bond between titanium dioxide and black phosphorus, which can effectively improve the utilization rate of the active material black phosphorus and increase the electron transfer rate at the interface.

The purpose of the present invention is at least achieved by one of the following technical solutions.

The invention provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) Preparation of black phosphorus: In an inert gas protective atmosphere, add red phosphorus and ball milling beads into the ball milling tank to seal, and then perform ball milling reaction to obtain nano-scale black phosphorus;

(2) Preparation of black phosphorus-titanium dioxide-carbon composite negative electrode material: under an inert gas protective atmosphere, black phosphorus, titanium dioxide, and carbon materials were mixed to obtain a mixture, and the mixture was ball-milled to obtain black phosphorus-titanium dioxide-carbon composite negative electrode material.

Preferably, the ball milling in step (1) refers to high-energy pendulum ball milling, the ball milling speed is 800-1200rmp/min, the ball milling time is 1-10h, and the mass ratio of ball milling beads to red phosphorus, that is, the ball-to-material ratio is (20~ 100): 1. The ball milling method is intermittent operation, one-way operation for 10-30 minutes, and stop operation for 10-30 minutes.

Preferably, the ball milling in step (2) refers to high-energy pendulum ball milling, the rotational speed of the ball milling is 800-1200rmp/min, the milling time is 2-10h, and the mass ratio of ball milling beads to the mixture, that is, the ball-to-material ratio is (10- 100): 1. The ball milling method is intermittent operation, one-way operation for 10-30 minutes, and stop operation for 10-30 minutes.

Preferably, the ball mill in step (2) refers to a planetary ball mill, the speed of the ball mill is 300-500rmp/min, the milling time is 2-10h, and the mass ratio of ball milling beads to the mixture, that is, the ball-to-material ratio is (10-100) : 1. The way of ball milling is intermittent operation, one-way operation for 10-30min, and stop operation for 10-30min.

Preferably, the carbon material in step (2) is more than one of expanded graphite, graphite, carbon black, and Super P.

Preferably, in step (2), the mass ratio of black phosphorus to the mixture is 0.3-0.7, the mass ratio of titanium dioxide to the mixture is 0.1-0.3, and the rest is carbon materials.

Preferably, the inert gas is argon, and the pressure of the inert gas is 0.1 MPa.

Preferably, the ball milling beads are stainless steel balls.

The invention also provides the black phosphorus-titanium dioxide-carbon composite negative electrode material prepared by the preparation method.

The invention also provides the application of the black phosphorus-titanium dioxide-carbon composite negative electrode material in the preparation of lithium ion batteries.

Compared with the prior art, the present invention has the following beneficial effects and advantages:

1) In the black phosphorus-titanium dioxide-carbon composite negative electrode material prepared by the present invention, carbon and black phosphorus are linked by C-P bonds, which ensures the close contact between black phosphorus and carbon materials during charging and discharging, and alleviates the volume change in the process of black phosphorus intercalating lithium. There is a Ti-O-P bond between titanium dioxide and black phosphorus, which can effectively improve the utilization rate of the active material black phosphorus and increase the electron transfer rate at the interface;

2) The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared by the present invention, as a lithium ion battery negative electrode material, exhibits excellent cycle performance and high reversible capacity (the specific capacity after 300 cycles at a current density of 2A/g is 935.8 mAh/g, with a capacity retention rate of 83%) and excellent rate performance (the specific capacity is as high as 947.4mAh/g at a current density of 7A/g);

3) The preparation method of the black phosphorus-titanium dioxide-carbon composite negative electrode material provided by the present invention is simple and easy to operate, with a large amount of sample preparation, short time consumption, high yield, and no secondary pollution to the environment.

Description of drawings

Fig. 1 is the cycle performance curve of the lithium-ion battery assembled by the black phosphorus-titanium dioxide-carbon composite negative electrode material that embodiment 1 makes;

Figure 2 is the rate performance curve of the lithium ion battery assembled with the black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in Example 1.

Detailed ways

The present invention will be described in further detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto.

Example 1

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 50:1, and perform high-energy pendulum ball milling for 2 hours. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 4 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.5g of black phosphorus, 0.2g of titanium dioxide, and 0.3g of expanded graphite at a mass ratio of 5:2:3, and then add it to a ball mill tank with a ball-to-material ratio of 50:1 , carry out high-energy pendulum ball milling, and the ball milling time is 5h. The specific operation mode is 30 minutes of one-way operation time, 30 minutes of stop operation time, 10 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out of the ball mill tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon composite anode material.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used for the negative electrode of lithium ion battery: the black phosphorus-titanium dioxide-carbon composite negative electrode material, conductive agent (Super-P) and binder (sodium carboxymethyl cellulose ) were mixed uniformly at a mass ratio of 70:15:15, coated on copper foil to make electrode sheets, and dried in vacuum; in an argon atmosphere glove box, metal lithium was used as a counter electrode to assemble a button battery for testing. The test conditions are that the charge and discharge current density is 200mA/g or 2A/g, and the charge and discharge cut-off voltage is 0.01~2.0V.

The lithium-ion battery assembled with the black phosphorus-titanium dioxide-carbon composite anode material prepared in this example had a specific discharge capacity of 1581.1 mAh/g for the first time, and a coulombic efficiency of 84.1% for the first time. Fig. 1 is the cycle performance curve of the lithium ion battery assembled with the black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example. It can be seen from the figure that the black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example shows a higher specific capacity and better cycle life, and the capacity is as high as 935.8mAh/g after 300 cycles at a current density of 2A/g , The capacity retention rate was 83%.

Fig. 2 is a rate performance curve of a lithium-ion battery assembled with the black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example. It can be seen from the figure that the black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example has a stable specific capacity contribution at different current densities. Even at 7A/g, the reversible capacity is still as high as 947.5mAh/g, showing Excellent rate capability.

Example 2

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 40:1, and perform high-energy pendulum ball milling for 5 hours. The specific operation mode is 30 minutes of one-way operation time, 30 minutes of stop operation time, 10 times of operation, and the ball milling speed is 1100rmp/min. After the ball milling is completed, the material is taken out from the ball milling tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.5g of black phosphorus, 0.1g of titanium dioxide, and 0.4g of expanded graphite in a mass ratio of 5:1:4, and then add it to a ball mill tank with a ball-to-material ratio of 50:1 , carry out high-energy pendulum ball milling, and the ball milling time is 5h. The specific operation mode is 30 minutes of one-way operation time, 30 minutes of stop operation time, 10 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out of the ball mill tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon Composite.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example had a first reversible specific capacity of 1097.1 mAh/g at a current density of 2 A/g, and after 200 cycles, the reversible specific capacity was still as high as 955.3 mAh/g.

Example 3

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 20:1, and perform high-energy pendulum ball milling for 10 hours. The specific operation mode is 30 minutes of one-way operation time, 30 minutes of stop operation time, 20 times of operation, and the ball milling speed is 1000rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.6g of black phosphorus, 0.2g of titanium dioxide, and 0.2g of expanded graphite at a mass ratio of 6:2:2, and then add it to a ball mill tank with a ball-to-material ratio of 50:1 , carry out high-energy pendulum ball milling, and the ball milling time is 5h. The specific operation mode is 30 minutes of one-way operation time, 30 minutes of stop operation time, 10 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out of the ball mill tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon composite anode material.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example had a first reversible specific capacity of 1072.4mAh/g at a current density of 2A/g, and after 250 cycles, the reversible specific capacity was 879mAh/g.

Example 4

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 100:1, and perform high-energy pendulum ball milling for 1 hour. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 2 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out of the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.5g of black phosphorus, 0.2g of titanium dioxide, and 0.3g of expanded graphite at a mass ratio of 5:2:3, and then add it to a ball mill tank with a ball-to-material ratio of 50:1 , carry out high-energy pendulum ball milling, and the ball milling time is 10h. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 20 times of operation, and the ball milling speed is 1100rmp/min. After the ball milling, the material is taken out from the ball milling tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon Composite.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example had a first reversible specific capacity of 1107mAh/g at a current density of 2A/g, and after 200 cycles, the reversible specific capacity was 948.3mAh/g.

Embodiment 5 (control)

This embodiment provides a method for preparing a black phosphorus-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 60:1, and perform high-energy pendulum ball milling for 2 hours. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 4 times of operation, and the ball milling speed is 1000rmp/min. After the ball milling is completed, the material is taken out of the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.5g of black phosphorus, 0g of titanium dioxide, and 0.5g of expanded graphite at a mass ratio of 5:0:5, and then add it to a ball mill tank with a ball-to-material ratio of 50:1. Carry out high-energy pendulum ball milling, and the ball milling time is 5 hours. The specific operation mode is 30 minutes of one-way operation time, 30 minutes of stop operation time, 10 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon glove box to obtain black phosphorus-carbon Composite anode materials.

The black phosphorus-carbon composite negative electrode material prepared in this example is used for the negative electrode of lithium ion battery: the preparation and testing method of the lithium ion battery are the same as in Example 1. The black phosphorus-carbon composite anode material prepared in this example has a reversible specific capacity of 1077mAh/g for the first time at a current density of 2A/g. After 200 cycles, the reversible specific capacity is only 480.3mAh/g. It can be found that TiO ₂ The addition of can significantly improve the electrochemical performance of phosphorus-based materials.

Example 6

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 50:1, and perform high-energy pendulum ball milling for 4 hours. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 8 times of operation, and the ball milling speed is 1100rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.5g of black phosphorus, 0.2g of titanium dioxide, and 0.3g of expanded graphite at a mass ratio of 5:2:3, and then add it to a ball mill tank with a ball-to-material ratio of 30:1 , carry out high-energy pendulum ball milling, and the ball milling time is 6h. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 12 times of operation, and the ball milling speed is 1000rmp/min. After the ball milling, the material is taken out from the ball milling tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon composite anode material.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example has a first discharge specific capacity of 1523.3mAh/g at a current density of 200mA/g, an initial charge specific capacity of 1255.2mAh/g, and an initial coulombic efficiency as high as 82.4%.

Example 7

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 50:1, and perform high-energy pendulum ball milling for 2 hours. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 4 times of operation, and the ball milling speed is 1100rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.5g of black phosphorus, 0.2g of titanium dioxide, and 0.3g of expanded graphite at a mass ratio of 5:2:3, and then add it to a ball mill tank with a ball-to-material ratio of 10:1 , carry out high-energy pendulum ball milling, and the ball milling time is 8h. The specific operation mode is 30 minutes of one-way operation time, 30 minutes of stop operation time, 16 times of operation, and the ball milling speed is 1100rmp/min. After the ball milling is completed, the material is taken out of the ball mill tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon composite anode material.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example has a first discharge specific capacity of 1578.3mAh/g at a current density of 200mA/g, an initial charge specific capacity of 1321.2mAh/g, and an initial coulombic efficiency as high as 83.7%.

Example 8

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 50:1, and perform high-energy pendulum ball milling for 2 hours. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 4 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.3g of black phosphorus, 0.3g of titanium dioxide, and 0.4g of expanded graphite at a mass ratio of 3:3:4, and then add them to a ball mill tank with a ball-to-material ratio of 50:1 , carry out high-energy pendulum ball milling, and the ball milling time is 5h. The specific operation mode is 30 minutes of one-way operation time, 30 minutes of stop operation time, 10 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out of the ball mill tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon composite anode material.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example has a first discharge specific capacity of 1142.6mAh/g at a current density of 200mA/g, an initial charge specific capacity of 937.6mAh/g, and an initial coulombic efficiency as high as 82.1%.

Example 9

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 50:1, and perform high-energy pendulum ball milling for 2 hours. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 4 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.5g of black phosphorus, 0.2g of titanium dioxide, and 0.3g of expanded graphite at a mass ratio of 5:2:3, and then add it to a ball mill tank with a ball-to-material ratio of 50:1 , carry out planetary ball milling, and the ball milling time is 10h. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 20 times of operation, and the ball milling speed is 500rmp/min. After the ball milling is over, the material is taken out of the ball mill tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon composite anode material.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example has a first discharge specific capacity of 1440.3mAh/g at a current density of 200mA/g, an initial charge specific capacity of 1134.3mAh/g, and an initial coulombic efficiency as high as 78.8%.

Example 10

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 40:1, and perform high-energy pendulum ball milling for 2 hours. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 4 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.5g of black phosphorus, 0.2g of titanium dioxide, and 0.3g of expanded graphite at a mass ratio of 5:2:3, and then add it to a ball mill tank with a ball-to-material ratio of 50:1 , carry out planetary ball milling, and the ball milling time is 5h. The specific operation mode is 30 minutes of one-way operation time, 30 minutes of stop operation time, 10 times of operation, and the ball milling speed is 500rmp/min. After the ball milling is completed, the material is taken out of the ball mill tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon composite anode material.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example has a first discharge specific capacity of 1432.5mAh/g at a current density of 200mA/g, an initial charge specific capacity of 1108.6mAh/g, and an initial coulombic efficiency as high as 77.4%.

Example 11

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 50:1, and perform high-energy pendulum ball milling for 2 hours. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 4 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.5g of black phosphorus, 0.2 of titanium dioxide, and 0.3g of expanded graphite at a mass ratio of 5:2:3, and then add them to a ball mill tank with a ball-to-material ratio of 50:1. Carry out planetary ball milling, the ball milling time is 10h. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 20 times of operation, and the ball milling speed is 300rmp/min. After the ball milling, the material is taken out from the ball milling tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon composite anode material.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example has a first discharge specific capacity of 1438.2mAh/g at a current density of 200mA/g, an initial charge specific capacity of 1123.7mAh/g, and an initial coulombic efficiency as high as 78.1%.

Example 12

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 50:1, and perform high-energy pendulum ball milling for 2 hours. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 4 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.5g of black phosphorus, 0.2g of titanium dioxide, and 0.3g of expanded graphite at a mass ratio of 5:2:3, and then add it to a ball mill tank with a ball-to-material ratio of 30:1 , carry out planetary ball milling, and the ball milling time is 10h. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 20 times of operation, and the ball milling speed is 500rmp/min. After the ball milling is over, the material is taken out of the ball mill tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon composite anode material.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example has a first discharge specific capacity of 1424.3mAh/g at a current density of 200mA/g, an initial charge specific capacity of 1071.8mAh/g, and an initial coulombic efficiency as high as 75.2%.

Example 13

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 50:1, and perform high-energy pendulum ball milling for 2 hours. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 4 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.6g of black phosphorus, 0.2g of titanium dioxide, and 0.2g of expanded graphite at a mass ratio of 6:2:2, and then add it to a ball mill tank with a ball-to-material ratio of 100:1 , carry out planetary ball milling, and the ball milling time is 2h. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 20 times of operation, and the ball milling speed is 500rmp/min. After the ball milling is over, the material is taken out of the ball mill tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon composite anode material.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example has an initial discharge specific capacity of 1830.2mAh/g at a current density of 200mA/g, an initial charge specific capacity of 1409.3mAh/g, and an initial coulombic efficiency as high as 76.9%.

Example 14

This embodiment provides a method for preparing a black phosphorus-titanium dioxide-carbon composite negative electrode material, comprising the following steps:

(1) In a 0.1MPa argon atmosphere glove box, add 1 g of original red phosphorus particles into a ball mill jar with a ball-to-material ratio of 50:1, and perform high-energy pendulum ball milling for 2 hours. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 4 times of operation, and the ball milling speed is 1200rmp/min. After the ball milling is completed, the material is taken out from the ball mill tank in an argon atmosphere glove box to obtain black phosphorus powder. .

(2) In a 0.1MPa argon atmosphere glove box, mix 0.5g of black phosphorus, 0.1g of titanium dioxide, and 0.4g of expanded graphite in a mass ratio of 5:1:4, and then add it to a ball mill tank with a ball-to-material ratio of 80:1 , carry out planetary ball milling, and the ball milling time is 8h. The specific operation mode is 30 minutes for one-way operation, 30 minutes for stop operation, 16 times of operation, and the ball milling speed is 500rmp/min. After the ball milling is over, the material is taken out from the ball mill tank in an argon glove box to obtain black phosphorus-titanium dioxide -Carbon composite anode material.

The black phosphorus-titanium dioxide-carbon composite negative electrode material prepared in this example is used as a lithium ion battery negative electrode: the preparation and testing methods of the lithium ion battery are the same as in Example 1. The black phosphorus-titanium dioxide-carbon composite anode material prepared in this example has an initial discharge specific capacity of 1488.3mAh/g at a current density of 200mA/g, an initial charge specific capacity of 1123.9mAh/g, and an initial Coulombic efficiency as high as 75.5%.

The above examples are only described as specific examples of the present invention, but the implementation of the present invention is not limited by the examples, and the carbon material can also be any one of graphite, carbon black, Super P, other Any changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the present invention shall be equivalent replacements and shall be included within the protection scope of the present invention.

Claims (10)

1. a kind of black phosphorus-titanium dioxide-carbon compound cathode materials preparation method, which comprises the following steps:

(1) it prepares black phosphorus: under inert gas shielding atmosphere, red phosphorus being added in ball grinder with ball milling pearl and is sealed, is then carried out Ball-milling reaction obtains nanoscale black phosphorus；

(2) black phosphorus-titanium dioxide-carbon compound cathode materials are prepared: under inert gas shielding atmosphere, by black phosphorus, titanium dioxide, Carbon material mixing, obtains mixture, by mixture ball milling, obtains black phosphorus-titanium dioxide-carbon compound cathode materials.

2. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that step Suddenly the ball milling in (1) refers to that high energy deploys formula ball milling, rotational speed of ball-mill 800-1200rmp/min, Ball-milling Time 1-10h, ball Mass ratio, that is, the ratio of grinding media to material for grinding pearl and red phosphorus is (20 ~ 100): 1, the mode of ball milling is intermittent duty, unidirectional operation 10-30min, 10-30min out of service.

3. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that step Suddenly the ball milling in (2) refers to that high energy deploys formula ball milling, and the revolving speed of ball milling is 800-1200rmp/min, Ball-milling Time 2-10h, Mass ratio, that is, ratio of grinding media to material of ball milling pearl and mixture is (10-100): 1, the mode of ball milling is intermittent duty, unidirectional operation 10- 30min, 10-30min out of service.

4. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that step Suddenly the ball milling in (2) refers to that planetary type ball-milling, the revolving speed of ball milling are 300-500rmp/min, Ball-milling Time 2-10h, ball milling pearl Mass ratio, that is, ratio of grinding media to material with mixture is (10-100): 1, the mode of ball milling is intermittent duty, and unidirectional operation 10-30min stops Only run 10-30min.

5. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that step Suddenly the carbon material in (2) is one or more of expanded graphite, graphite, carbon black, Super P.

6. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that step Suddenly the mass ratio that black phosphorus accounts for mixture in (2) is 0.3-0.7, and the mass ratio that titanium dioxide accounts for mixture is 0.1-0.3, remaining is Carbon material.

7. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that institute Stating inert gas is argon gas.

8. black phosphorus according to claim 1-titanium dioxide-carbon compound cathode materials preparation method, which is characterized in that ball Mill pearl is stainless steel ball.

9. black phosphorus-titanium dioxide-carbon compound cathode materials of any one of claim 1 to the 8 preparation method preparation.

10. application of the black phosphorus-titanium dioxide-carbon compound cathode materials as claimed in claim 9 in lithium ion battery preparation.