CN115188936A - Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof - Google Patents

Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof Download PDF

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CN115188936A
CN115188936A CN202210661740.4A CN202210661740A CN115188936A CN 115188936 A CN115188936 A CN 115188936A CN 202210661740 A CN202210661740 A CN 202210661740A CN 115188936 A CN115188936 A CN 115188936A
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phosphorus
carbon
lithium
source
binary
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孙洁
刘成
向黔新
周朝毅
李路
胡安生
武阳
王丽娟
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Guizhou Zhenhua Yilong E Chem Co ltd
Tianjin University
Guizhou Zhenhua New Material Co Ltd
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Guizhou Zhenhua Yilong E Chem Co ltd
Tianjin University
Guizhou Zhenhua New Material Co Ltd
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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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
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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 relates to a prelithiated binary topological structure phosphorus/carbon composite material and a preparation method and application thereof. The invention provides a prelithiation binary topological structure phosphorus/carbon composite material, which is lithiation x-dimensional phosphorus/y-dimensional carbon, wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 3, and y is more than or equal to 1 and less than or equal to 3. The invention also provides a preparation method of the prelithiation binary topological structure phosphorus/carbon composite material, which comprises the following steps: (a) Mixing a phosphorus source and a lithium source, and lithiating the phosphorus source by using the lithium source to obtain a lithium phosphide material; (b) And (b) mixing and heating the lithium phosphide material obtained in the step (a) and a carbon-based material to obtain the prelithiation binary topological structure phosphorus/carbon composite material. The pre-lithiation binary topological structure phosphorus/carbon composite material prepared by the method has high theoretical specific capacity and higher conductivity, and also ensures high first coulombic efficiency.

Description

Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof
The application is a divisional application of a parent application with the application number of 201911376368.7, the invention name of the parent application is 'prelithiated binary topological structure phosphorus/carbon composite material and a preparation method and application thereof', and the application date of the parent application is 2019, 12 months and 27 days.
Technical Field
The invention belongs to the field of lithium ion battery electrode materials, and particularly relates to a prelithiated phosphorus/carbon composite material with a binary topological structure, and a preparation method and application thereof.
Background
Lithium ion batteries have higher energy density and are used in numerous secondary battery systemsAnd has been successful in occupying the portable electronic device market for as little as twenty years. However, with the rise of new energy storage devices such as power batteries and stationary energy storage power stations, new requirements are placed on the development of secondary batteries. The power battery is required to have not only high energy density but also high rate performance and safety performance. However, the graphite which is a main commercialized lithium ion battery negative electrode material is low in electrode potential and is easy to form lithium dendrite under high current density, so that potential safety hazards are caused. While one kind of Li with "zero strain" spinel structure 4 Ti 5 O 12 Due to the higher electrode potential (1.5V vs Li/Li) + ) The characteristics of difficult formation of lithium dendrite in the charging and discharging process, high safety performance and the like attract people to pay attention. However, its low theoretical specific capacity (175 mAh/g) limits its wide application in lithium ion batteries. Phosphorus as a new cathode material has the advantages of low price, rich storage capacity, environmental friendliness, high specific capacity and the like, and gradually develops into the key point of cathode research. In addition, compared to silicon (0.4V vs Li/Li) + ) Graphite (0.1 Vvs Li/Li) + ) Negative electrode with higher electrode potential (0.7V vs Li/Li) + ) And the safety of the power battery under the condition of high-rate charge and discharge is facilitated. However, the development of phosphorus is limited by the problems of poor conductivity of phosphorus and large volume change during charge and discharge.
Phosphorus has a variety of allotropes: the application of white phosphorus, amorphous red phosphorus, purple phosphorus, fibrous phosphorus, black phosphorus and blue phosphorus in the lithium ion battery cathode material is proved experimentally or theoretically. In recent years, researchers have conducted a great deal of scientific research to take advantage of the high theoretical specific capacity of phosphorus, and mainly focus on the combination of red phosphorus or black phosphorus with a carbon-based material having good conductivity, and various phosphorus/carbon binary topological structures can be formed according to the difference in the dimension (D) and the combination mode of phosphorus and carbon. For example, liu cheng et al introduced phosphorus-carbon two-element topology in "phosphorus-carbon two-element topology design and its application in the field of energy storage" ("energy storage science and technology", volume seven, phase six) "includes red phosphorus/carbon two-element topology 0D/0D, 0D/1D, 1D/1D, 0D/2D, 2D/2D, 0D/3D and black phosphorus/carbon two-element topology 0D/0D, 0D/1D, 2D/2D, chinese patent publication No. CN109148870A takes surface oxidized, freeze dried graphite and nanotubes as base material, mixed with red phosphorus solid powder to seal the tube, high temperature baking, effectively filling red phosphorus into the interlayer spacing of the base material, forming 0D (red phosphorus)/2D (carbon) structure, these phosphorus-carbon two-element topologies can effectively improve the conductivity of the electrode material, alleviate its negative electrode and negative electrode stability and stability problems caused by volume change in the lithium ion process, but improve the stability of the phosphorus-carbon two-element topology, and further improve the charge and discharge efficiency, and further improve the charge-discharge efficiency.
Disclosure of Invention
Aiming at the technical problems of high-rate charge-discharge cycle stability, low initial coulombic efficiency and the like of the conventional lithium ion battery phosphorus-based composite negative electrode material, the inventor designs a phosphorus-carbon binary topological structure with a confinement effect and a modification mode through long-term research, and aims to improve the initial coulombic efficiency and the high-rate charge-discharge performance of the phosphorus-based negative electrode material.
Therefore, the invention provides the following first technical scheme.
A pre-lithiated binary topological structure phosphorus/carbon composite material is lithiated x-dimensional phosphorus/y-dimensional carbon, wherein x and y are integers, x is more than or equal to 0 and less than or equal to 3, and y is more than or equal to 1 and less than or equal to 3.
Preferably, the pre-lithiated binary topology phosphorus/carbon composite material according to the above, wherein the phosphorus is amorphous red phosphorus, purple phosphorus, fibrous phosphorus, black phosphorus or blue phosphorus.
Preferably, the pre-lithiated binary topology phosphorus/carbon composite described above, wherein the carbon is a one-dimensional tubular carbon-based material, a two-dimensional layered carbon-based material, or a 3-dimensional porous carbon material.
The invention also provides a preparation method of the prelithiation binary topological structure phosphorus/carbon composite material, which comprises the following steps:
(a) Coating a phosphorus source by using a coating material, and then carrying out high-temperature carbonization to obtain x-dimensional phosphorus/y-dimensional carbon with a binary topological structure, wherein x and y are integers, x is more than or equal to 0 and less than or equal to 3, and y is more than or equal to 1 and less than or equal to 3;
(b) And (b) carrying out lithiation treatment on the binary topological structure x-dimensional phosphorus/y-dimensional carbon obtained in the step (a) by using a lithium source.
Preferably, according to the above production method, wherein the coating material is a substance that forms a carbon or nitrogen-doped carbon-based material after pyrolysis.
Preferably, according to the above preparation method, wherein the coating material is an organic amine compound.
Preferably, the preparation method is adopted, wherein the coating material is dopamine.
Preferably, according to the above preparation method, wherein the phosphorus source is elemental phosphorus or a compound that can form stable elemental phosphorus after pyrolysis.
Preferably, the production method described above, wherein the phosphorus source is a phosphorus-oxygen compound.
Preferably, according to the above production method, wherein the phosphorus source is phosphorus pentoxide.
Preferably, the preparation method is carried out at a carbonization temperature of 300-1000 ℃.
Preferably, the preparation method is carried out at a carbonization temperature of 350-800 ℃.
Preferably, the above production method, wherein the carbonization temperature is 500 to 700 ℃.
Preferably, the preparation method is characterized in that the mass ratio of the lithium source to the phosphorus source is 1.
Preferably, the above preparation method, wherein the lithium source is lithium foil, lithium powder, molten lithium, inorganic lithium salt or Li-organic complex solution.
Preferably, according to the above preparation method, wherein the lithiation treatment temperature is 180 to 400 ℃.
Preferably, according to the above preparation method, wherein the ratio of phosphorus source to coating material is 3.
The invention also provides a second preparation method of the prelithiation binary topological structure phosphorus/carbon composite material, which comprises the following steps:
(a) Placing a phosphorus source and a carbon-based material in two heating temperature areas of a tubular furnace chamber for heating to obtain x-dimensional phosphorus/y-dimensional carbon with a binary topological structure, wherein x and y are integers, x is more than or equal to 0 and less than 3, and y is more than or equal to 1 and less than or equal to 3;
(b) And (b) carrying out lithiation treatment on the binary topological structure x-dimensional phosphorus/y-dimensional carbon obtained in the step (a) by using a lithium source.
Preferably, according to the above preparation method, wherein the phosphorus source is elemental phosphorus or a compound that can form stable elemental phosphorus after pyrolysis.
Preferably, according to the above production method, wherein the phosphorus source is red phosphorus.
Preferably, according to the above production method, wherein the carbon-based material is graphite, expanded graphite, graphite acid, or porous carbon.
Preferably, according to the above production method, wherein the ratio of phosphorus source to carbon source by mass of phosphorus to carbon is 3.
Preferably, according to the above production method, wherein the heating temperature of the phosphorus source is 400 to 500 ℃, and the heating temperature of the carbon-based material is 200 to 350 ℃.
Preferably, the above preparation method, wherein the lithium source is lithium foil, lithium powder, molten lithium, inorganic lithium salt or Li-organic complex solution.
Preferably, according to the above preparation method, wherein the lithiation treatment temperature is 180 to 400 ℃.
Preferably, the preparation method is characterized in that the mass ratio of the lithium source to the phosphorus source is 1.
The invention also provides a third preparation method of the prelithiation binary topological structure phosphorus/carbon composite material, which comprises the following steps:
(a) Mixing the carbon-based material with a lithium source, and carrying out lithiation treatment on the carbon-based material by using the lithium source to obtain a lithiated carbon-based material;
(b) And (b) mixing and heating the lithiated carbon-based material obtained in the step (a) and a phosphorus source to obtain the pre-lithiated binary topological structure phosphorus/carbon composite material.
Preferably, according to the above production method, wherein the carbon-based material is graphite, expanded graphite, or porous carbon.
Preferably, the production method described above, wherein the carbon-based material is expanded graphite.
Preferably, the above preparation method, wherein the lithium source is lithium foil, lithium powder, molten lithium, inorganic lithium salt or Li-organic complex solution.
Preferably, according to the above preparation method, wherein the phosphorus source is elemental phosphorus or a compound that can form stable elemental phosphorus after pyrolysis.
Preferably, according to the above production method, wherein the phosphorus source is elemental phosphorus.
Preferably, according to the above preparation method, wherein the mass ratio of the phosphorus source to the carbon source is 1.
Preferably, according to the above preparation method, wherein the ratio of lithium source to phosphorus source by mass of lithium to phosphorus is 1.
Preferably, according to the above preparation method, wherein the lithiation treatment temperature is 200 to 800 ℃.
Preferably, according to the above preparation method, wherein the lithiation treatment temperature is 200 to 500 ℃.
Preferably, the above production method, wherein the heating temperature in the (b) step is 200 to 400 ℃.
Preferably, the preparation method is characterized in that the heating time in the step (b) is 1-4hr.
The invention also provides a fourth preparation method of the prelithiation binary topological structure phosphorus/carbon composite material, which comprises the following steps:
(a) Mixing a phosphorus source and a lithium source, and lithiating the phosphorus source by using the lithium source to obtain a lithium phosphide material;
(b) And (b) mixing and heating the lithium phosphide material obtained in the step (a) and a carbon-based material to obtain the prelithiation binary topological structure phosphorus/carbon composite material.
Preferably, according to the above preparation method, wherein the phosphorus source is elemental phosphorus or a compound that can form stable elemental phosphorus after pyrolysis.
Preferably, according to the above production method, wherein the phosphorus source is elemental phosphorus.
Preferably, the above preparation method, wherein the lithium source is lithium foil, lithium powder, molten lithium, inorganic lithium salt or Li-organic complex solution.
Preferably, the method of manufacturing above, wherein the lithium source is a lithium foil.
Preferably, the preparation method is characterized in that the mass ratio of the lithium source to the phosphorus source is 1.
Preferably, according to the above preparation method, wherein the lithiation treatment temperature is 200 to 800 ℃.
Preferably, according to the above preparation method, wherein the lithiation treatment temperature is 200 to 400 ℃.
Preferably, the production method as described above, wherein the heating temperature in the (b) step is 200 to 400 ℃.
Preferably, the preparation method is characterized in that the heating time in the step (b) is 1-4hr.
Preferably, the production method described above, wherein the carbon-based material is expanded graphite or graphite acid.
Preferably, the production method described above, wherein the carbon-based material is expanded graphite.
Preferably, the production method is carried out according to the above, wherein the ratio of phosphorus source to carbon source is 1.
The invention also provides a fifth preparation method of the prelithiated binary topological structure phosphorus/carbon composite material, which comprises the following steps:
(a) The phosphorus source and the conductive carbon material are directly mixed by ball milling or hand milling.
(b) And (b) mixing and heating the phosphorus-carbon composite material obtained in the step (a) with a lithium source to obtain the prelithiation binary topological structure phosphorus/carbon composite material.
Preferably, according to the above preparation method, wherein the phosphorus source is elemental phosphorus or a compound that can form stable elemental phosphorus after pyrolysis.
Preferably, according to the above production method, wherein the phosphorus source is elemental phosphorus.
Preferably, according to the above preparation method, wherein the carbon-based material is graphite, porous carbon, activated carbon, carbon nanotube.
Preferably, the method of manufacturing as described above, wherein the carbon-based material is carbon nanotubes.
Preferably, the production method described above, wherein the ratio of phosphorus source to carbon source by mass of phosphorus to carbon is 1.
Preferably, the above preparation method, wherein the lithium source is lithium foil, lithium powder, molten lithium, inorganic lithium salt or Li-organic complex solution.
Preferably, the method of manufacturing above, wherein the lithium source is a lithium foil.
Preferably, the preparation method is characterized in that the mass ratio of the lithium source to the phosphorus source is 1.
Preferably, according to the above preparation method, wherein the lithiation treatment temperature is 200 to 800 ℃.
Preferably, according to the above preparation method, wherein the lithiation treatment temperature is 300 to 500 ℃.
The invention also provides a lithium ion battery cathode, and the active substance of the lithium ion battery cathode is the pre-lithiation binary topological structure phosphorus/carbon composite material.
The invention also provides a lithium ion battery, which comprises the lithium ion battery cathode.
In addition, the present invention also provides a second technical solution to solve the above problems.
1. A pre-lithiation binary topological structure phosphorus/carbon composite material is lithiation x-dimensional phosphorus/y-dimensional carbon, wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 3, and y is more than or equal to 1 and less than or equal to 3; the preparation method comprises the following steps:
(a) Mixing a phosphorus source and a lithium source, and carrying out lithiation treatment on the phosphorus source by using the lithium source to obtain a lithium phosphide material;
(b) And (b) mixing and heating the lithium phosphide material obtained in the step (a) and a carbon-based material to obtain the prelithiation binary topological structure phosphorus/carbon composite material.
2. The preparation method according to claim 1, wherein the phosphorus source is elemental phosphorus or a compound capable of forming stable elemental phosphorus after pyrolysis; preferably, the phosphorus source is elemental phosphorus.
3. The preparation method according to claim 1 or 2, wherein the lithium source is lithium foil, lithium powder, molten lithium, inorganic lithium salt or Li-organic complex solution; preferably, the lithium source is lithium foil.
4. The production method according to any one of claims 1 to 3, wherein the ratio of the lithium source to the phosphorus source is 1.
5. The preparation method according to any one of claims 1 to 4, wherein the lithiation treatment temperature is 200 to 800 ℃; preferably, the lithiation treatment temperature is from 200 to 400 ℃.
6. The production method according to any one of claims 1 to 5, wherein the carbon-based material is expanded graphite or graphite acid; preferably, the carbon-based material is expanded graphite.
7. The production method according to any one of claims 1 to 6, wherein the ratio of the phosphorus source to the carbon source is 1 to 20 in terms of the mass ratio of phosphorus to carbon.
8. The preparation method of any one of technical schemes 1 to 7 is used for preparing the pre-lithiation phosphorus/carbon composite material with the binary topological structure.
9. The prelithiation binary topology phosphorus/carbon composite material of claim 8, wherein the phosphorus is amorphous red phosphorus, purple phosphorus, fibrous phosphorus, black phosphorus or blue phosphorus.
10. The prelithiation binary topology structure phosphorus/carbon composite material according to claim 8, wherein the carbon is a one-dimensional tubular carbon-based material, a two-dimensional layered carbon-based material, or a 3-dimensional porous carbon material.
11. An active material of the lithium ion battery cathode is a pre-lithiated binary topological structure phosphorus/carbon composite material prepared by the method in any one of technical schemes 1 to 7 or the pre-lithiated binary topological structure phosphorus/carbon composite material in any one of technical schemes 8 to 10.
12. A lithium ion battery comprising the lithium ion battery negative electrode of claim 11.
The invention has the following beneficial effects: (1) Compared with the phosphorus/carbon composite material with the binary topological structure, the pre-lithiated phosphorus/carbon composite material with the binary topological structure has high theoretical specific capacity and higher electrical conductivity. (2) In the pre-lithiation process, materials such as lithium phosphide, lithium oxide or lithium nitride with high ionic conductivity are formed on the surfaces of the elemental phosphorus and the carbon substrate material, so that the SEI film component is optimized. (3) Compared with a phosphorus/carbon composite material with a binary topological structure, the prelithiation is equivalent to a one-time lithium supplement process for a negative electrode, and high first coulombic efficiency is guaranteed.
Drawings
FIG. 1 is a TEM image (20 ten thousand times) of a binary topology phosphorus/carbon composite in example 1 of the present application;
fig. 2 is an XRD pattern of the prelithiated binary topology phosphorus/carbon composite obtained in example 3 of the present application;
fig. 3 is an SEM image (5 ten thousand times) of a prelithiated binary topology phosphorus/carbon composite obtained in example 3 of the present application;
fig. 4 is an SEM image (3 ten thousand times) of a prelithiated binary topology phosphorus/carbon composite obtained in example 4 of the present application;
fig. 5 is a schematic diagram of a prelithiated binary topology phosphorus/carbon composite obtained in example 7 of the present application.
Detailed Description
The invention firstly provides a pre-lithiation binary topological structure phosphorus/carbon composite material, which is lithiation x-dimensional phosphorus/y-dimensional carbon, wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 3, and y is more than or equal to 1 and less than or equal to 3. The phosphorus includes amorphous red phosphorus, purple phosphorus, fibrous phosphorus, black phosphorus, and blue phosphorus. The carbon includes a one-dimensional tubular carbon-based material, a two-dimensional layered carbon-based material, or a 3-dimensional porous carbon material.
The invention also provides four preparation methods of the prelithiation binary topological structure phosphorus/carbon composite material: (1) Elemental phosphorus is confined in a carbon-based material and then lithiated. (2) Lithiation of the carbon-based material is performed prior to the phosphorus being confined to the carbon-based material. (3) The phosphorus is lithiated and then confined to the carbon-based material. (4) Firstly, directly mixing a phosphorus source and a conductive carbon material in a ball milling or hand milling mode, and then carrying out lithiation treatment. In the preparation method of the (1), the method for confining elementary phosphorus into the carbon-based material to form a phosphorus-carbon binary topology comprises two ways: (I) in a 'top-down' mode, namely, firstly coating a phosphorus source and then carrying out high-temperature carbonization; (II) introducing elemental phosphorus into the carbon-based material in a bottom-up mode.
In the above method, the lithium source used for lithiation treatment is a lithium foil, lithium powder, molten lithium, inorganic lithium salt or Li-organic complex solution. The phosphorus source is elemental phosphorus or a compound that can form stable elemental phosphorus after pyrolysis. The carbon-based material is graphite, expanded graphite, graphite acid or porous carbon.
In the method (1) (I), the dosage ratio of the lithium source to the phosphorus source is that according to the mass ratio of lithium to phosphorus element of 1-1. The temperature of lithiation treatment is 180-400 ℃. The coating material is a substance which forms a carbon or nitrogen-doped carbon-based material after pyrolysis; the carbonization temperature is 300-1000 ℃.
Preferably, the phosphorus source is a phosphorus-oxygen compound, the coating material is one or more of organic amine compounds, and the carbonization temperature is 350-800 ℃.
More preferably, the phosphorus source is P 2 O 5 Or red phosphorus, the coating material is dopamine, and the carbonization temperature is 500-700 ℃.
In the method (1) and the method (II), a phosphorus source and a carbon-based material are placed in two heating temperature areas of the same tubular furnace chamber to be heated, the heating temperature of the phosphorus source is 400-500 ℃, the heating temperature of the carbon-based material is 200-350 ℃, the phosphorus source and the carbon-based material are reacted to obtain binary topological structure x-dimensional phosphorus/y-dimensional carbon, then the binary topological structure x-dimensional phosphorus/y-dimensional carbon is lithiated by a lithium source, and the lithiation treatment temperature is 180-400 ℃.
In the method (2), the carbon-based material is graphite, expanded graphite or porous carbon; the lithiation treatment temperature is 200-800 ℃; the phosphorus source is a compound of elemental phosphorus and elemental phosphorus or a phosphorus-oxygen compound which can be formed after pyrolysis.
Preferably, the carbon-based material is expanded graphite; the lithiation temperature is 200-500 ℃; the phosphorus source is elemental phosphorus.
In the method (3), the phosphorus source is simple substance phosphorus, the lithiation temperature is 200-800 ℃, and the carbon-based material is expanded graphite or graphite acid.
Preferably, the lithium source is lithium foil; the dosage ratio of the lithium source to the phosphorus source is that the mass ratio of lithium to phosphorus elements is 1-1; the carbon-based material is expanded graphite.
In the method (4), the phosphorus source is simple substance phosphorus or a compound capable of forming stable simple substance phosphorus after pyrolysis, preferably simple substance phosphorus; the carbon-based material is graphite, porous carbon, activated carbon and carbon nanotubes, and is preferably the carbon nanotubes; the lithium source is lithium foil, lithium powder, molten lithium, inorganic lithium salt or Li-organic compound solution, and preferably lithium foil; the mass ratio of the phosphorus source to the carbon source is (1-15); the lithiation treatment temperature is 200-800 ℃, preferably 300-500 ℃.
In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with the preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The instrument models and parameter conditions used in the following examples are as follows:
XRD: adopting a Brooks D8-Focus X-ray diffractometer, wherein the test range is 20-70 degrees, and the scanning speed is 5 degrees/min;
TEM: adopting a JEM-2100 type Transmission Electron Microscope (TEM);
SEM: hitachi S-4800 Scanning Electron Microscope (SEM) was used.
Example 1
1g of red phosphorus was put into a 250mL four-necked flask, 150mL of a 2mg/mL dopamine solution (Tris (hydroxymethyl) aminomethane buffer (Tris-HCl) as a solvent) was added thereto, and the mixture was stirred at room temperature for 72 hours, filtered, and dried. And (3) placing the obtained sample in a tube furnace, calcining at the high temperature of 500 ℃ for 3h under the inert atmosphere to obtain a binary topological structure of 0D phosphorus/3D carbon, wherein carbon formed by pyrolysis is coated on the surface of phosphorus in the composite material as shown in figure 1. Mixing 0.5g of 0D phosphorus/3D carbon and 0.02g of lithium foil, heating the mixture in an iron crucible at 300 ℃ for 1h in a glove box, naturally cooling the mixture, fully grinding the mixture, and heating the mixture at 300 ℃ for 1h to obtain a pre-lithiated binary topological structure of 0D phosphorus/3D carbon.
The composite material obtained in the embodiment is used as an active substance, and is pressed onto a foamed nickel substrate with the diameter of 12mm according to the weight ratio of 80. The assembled battery is a CR2032 type button cell battery which takes metal lithium as a negative electrode and a Cegard2300 microporous polypropylene film with the diameter of 16mm as a diaphragm.
And (3) cycle testing: when the blue light test system is used for testing, the temperature is room temperature, constant current charging and discharging are adopted, the voltage control range is 0.01-3V, and constant current charging and discharging are carried out at the current density of 100 mA/g.
Wherein the charge (discharge) specific capacity = charge (discharge) capacity/active material mass, and the above capacity test process is cycled to obtain n times of capacity retention = nth discharge specific capacity/first discharge specific capacity.
And (3) testing large multiplying power: when the test is carried out by using a blue electricity test system, the temperature is room temperature, constant current charging and discharging are adopted, the voltage control range is 0.01-3V, and the constant current charging and discharging are carried out at the current density of 1000 mA/g.
Example 2
1g of red phosphorus was put into a 250mL four-necked flask, 150mL of a 2mg/mL dopamine solution (solvent Tris (hydroxymethyl) aminomethane buffer (Tris-HCl)) was added thereto, and the mixture was stirred for 72 hours, filtered under suction, and dried. And placing the obtained sample in a tube furnace, and calcining for 3h at the high temperature of 600 ℃ under the inert atmosphere to obtain the binary topological structure of 0D phosphorus/3D carbon. And mixing 0.5g of 0D phosphorus/3D carbon and 0.02g of lithium foil, placing the mixture in an iron crucible, heating the mixture in a glove box at 300 ℃ for 1h, naturally cooling the mixture, fully grinding the mixture, and heating the mixture at 300 ℃ for 1h to obtain a pre-lithiated binary topological structure of 0D phosphorus/3D carbon.
The composite prepared in the embodiment is used as an active material, and the battery assembled by referring to the raw materials and the assembly process in the embodiment 1 has the advantages of reduced specific discharge capacity for the first time and improved rate capability, cycling stability and reversible capacity. The reason for this is presumably that the increase in the temperature increases phosphorus evaporated from the carbon core, the decrease in phosphorus in the composite material, and the decrease in the specific capacity. And with the increase of the temperature, the graphitization degree of the carbon material is increased, which is beneficial to the improvement of the conductivity of the material.
Example 3
Taking 0.9g of black phosphorus and 0.3g of carbon nano tube, mixing by ball milling, placing in an iron crucible, adding 0.6g of lithium foil, heating in a glove box at 300 ℃ for 1.5h, naturally cooling, fully grinding, and heating at 500 ℃ for 1h to obtain the pre-lithiated 0D phosphorus/1D carbon binary topological structure.
FIG. 2 is an XRD pattern of a binary topology of prelithiated 0D phosphorus/1D carbon, after prelithiation, conversion of phosphorus in the composite to lithium phosphide Li x P (x =1,3). Fig. 3 is an SEM image of the dual topology of pre-lithiated 0D phosphorous/1D carbon, from which it can be seen that the composite material after lithiation still exhibits the 0D/1D dual topology, and the surface of the carbon nanotubes becomes rough, which may be caused by the formation of lithium phosphide particles on the surface of the carbon nanotubes.
When the composite prepared in the embodiment is used as an active material and the battery is assembled by referring to the raw materials and the assembly process in the embodiment 1, the first-cycle specific discharge capacity can reach 1847.8 and the first-cycle coulombic efficiency can reach 87.2% under the current density of 100mA/g, and when the current density reaches 1000mA/g, the specific discharge capacity can still reach 667.3mAh/g after 1000 cycles.
Example 4
1g of red phosphorus and 1g of expanded graphite are respectively placed in two heating temperature areas of a tubular furnace chamber, the red phosphorus is heated at the temperature of 450 ℃, the temperature area of the expanded graphite is 300 ℃, and the binary topological structure of 0D phosphorus/2D carbon is obtained after the reaction for 4 hours. Mixing 0.5g of 0D phosphorus/2D carbon and 0.02g of lithium foil, putting the mixture in an iron crucible, heating the mixture for 1h at 300 ℃ in a glove box, fully grinding the mixture after natural cooling, and heating the mixture for 1h at 300 ℃ to obtain a pre-lithiated binary topological structure of 0D phosphorus/2D carbon (figure 4).
The rate performance of a battery assembled by using the composite prepared in the embodiment as an active material and referring to the raw materials and the assembly process in the embodiment 1 is greatly improved. It is presumed that the reason for this is that the abundant functional groups between the layers of the expanded graphite react with P to form a stable chemical force.
Example 5
Mixing 0.5g of expanded graphite with 0.02g of lithium foil, placing the mixture in an iron crucible, calcining the mixture in a glove box at 300 ℃ for 2 hours to obtain lithiated expanded graphite, adding 0.5g of red phosphorus, mixing, and heating the mixture at 300 ℃ for 2 hours to obtain a pre-lithiated 0D phosphorus/2D carbon binary topological structure.
When the composite prepared in the embodiment is used as an active material and the battery is assembled by referring to the raw materials and the assembly process in the embodiment 1, the first-cycle specific discharge capacity can reach 1698.6mAh/g, the capacity retention rate can reach 84.7% after the circulation is performed for 100 weeks, and the specific discharge capacity can still reach 512.4mAh/g after the circulation is performed for 1000 weeks under the current density of 1000 mA/g.
Example 6
0.5g of red phosphorus and 0.02g of lithium foil are mixed and placed in an iron crucible, calcined in a glove box at 300 ℃ for 2h and then calcined at 450 ℃ for 2h to obtain a lithium phosphide material, 0.5g of expanded graphite is added, mixed and heated at 300 ℃ for 3h to obtain a pre-lithiated 0D phosphorus/2D carbon binary topological structure.
When the composite prepared in this example is used as an active material and the battery is assembled by referring to the raw materials and assembly process in example 1, the specific capacity, rate capability and cycling stability are all reduced compared with example 4.
Example 7
Take 1.0g of P 2 O 5 Adding 120mL of hydrochloric acid with the molar concentration of 0.1mol/L into a four-neck flask, dropwise adding 480 mu L of aniline, stirring for 0.5h, dropwise adding 80mL of ammonium persulfate with the mass fraction of 1%, and stirring for 24h at the rotating speed of 600rpm in an ice-water bath to obtain polyaniline-coated P 2 O 5 And (3) placing the composite material in a tubular furnace, and calcining for 3h at 400 ℃ to obtain the composite material. Taking 0.5g of carbon-coated phosphorus porous composite material to be placed in an iron crucible, adding 0.05g of lithium foil, heating for 1.5h in a glove box at 300 ℃, fully grinding after natural cooling, and heating for 1h at 400 ℃ to obtain a pre-lithiated 0D phosphorus/3D carbon binary topological structure (figure 5).
When the compound prepared in the embodiment is used as an active material and the battery is assembled by referring to the raw materials and the assembly process in the embodiment 1, the first-cycle specific discharge capacity can reach 1804.3 and the first-cycle coulombic efficiency can reach 86.1 percent under the condition that the current density is 100mA/g, the first-cycle specific discharge capacity can reach 782.6mAh/g when the current density reaches 1000mA/g, and the discharge specific discharge capacity can still reach 645.2mAh/g after the battery is cycled for 1000 cycles.
Comparative example 1
The binary topology of 0D phosphorus/3D carbon was prepared the same as in example 1, except that a lithiation step was added in example 1, and no lithiation step was used in comparative example 1. The first discharge specific capacity of the comparative example 1 under the current density of 100mA/g can reach 1912.5mAh/g, but the first-week coulombic efficiency is only 52.4%, and when the current density is 1000mA/g, the discharge specific capacity of 289.8mAh/g can be only maintained after the circulation is 1000 weeks.
Comparative example 2
The binary topology of 0D phosphorus/2D carbon was prepared the same as example 4, except that example 4 had an additional lithiation step, whereas comparative example 2 had no lithiation step. When the current density is 100mA/g for charging and discharging, the first-cycle specific capacity obtained in the comparative example 2 is 1816.8mAh/g, the first-cycle coulombic efficiency is 61.2%, the capacity retention rate is 50.3% after the circulation is 100 weeks, and when the current density is 1000mA/g, the discharge specific capacity is 312.5mAh/g after the circulation is 1000 weeks.
TABLE 1 electrochemical Properties of each lithium cell in the examples
Figure BDA0003690786770000131
As can be seen from table 1, when the composite material prepared by the method of the present invention is used as an active material, the first coulombic efficiency and the high rate charge-discharge performance of the phosphorus-based negative electrode material can be significantly improved.
The present invention is described in detail with reference to the embodiments and the accompanying drawings, and the embodiments are only used to help understanding the method and the core idea of the present invention; also, it is to be understood that changes may be made in the particular embodiments and applications of the invention by those skilled in the art based on the concept and principles of the invention, and such changes are intended to be included within the scope of the invention.

Claims (12)

1. A method for preparing a pre-lithiation binary topological structure phosphorus/carbon composite material is lithiation x-dimensional phosphorus/y-dimensional carbon, wherein x and y are integers, and x is more than or equal to 0 and less than or equal to 3, and y is more than or equal to 1 and less than or equal to 3; the preparation method comprises the following steps:
(a) Mixing a phosphorus source and a lithium source, and carrying out lithiation treatment on the phosphorus source by using the lithium source to obtain a lithium phosphide material;
(b) And (b) mixing and heating the lithium phosphide material obtained in the step (a) and a carbon-based material to obtain the pre-lithiation binary topological structure phosphorus/carbon composite material.
2. The method of claim 1, wherein the phosphorus source is elemental phosphorus or a compound that forms stable elemental phosphorus after pyrolysis; preferably, the phosphorus source is elemental phosphorus.
3. The production method according to claim 1 or 2, wherein the lithium source is a lithium foil, lithium powder, molten lithium, inorganic lithium salt, or Li-organic complex solution; preferably, the lithium source is lithium foil.
4. The production method according to any one of claims 1 to 3, wherein the ratio of the lithium source to the phosphorus source is 1.
5. The production method according to any one of claims 1 to 4, wherein the lithiation treatment temperature is 200 to 800 ℃; preferably, the lithiation treatment temperature is 200 to 400 ℃.
6. The production method according to any one of claims 1 to 5, wherein the carbon-based material is expanded graphite or graphite acid; preferably, the carbon-based material is expanded graphite.
7. The production method according to any one of claims 1 to 6, wherein the ratio of the phosphorus source to the carbon source is 1.
8. The method of any one of claims 1-7, wherein a prelithiated binary topology phosphorus/carbon composite is prepared.
9. The prelithiated binary topology phosphorus/carbon composite of claim 8, wherein the phosphorus is amorphous red phosphorus, purple phosphorus, fibrous phosphorus, black phosphorus, or blue phosphorus.
10. The prelithiated binary topology phosphorus/carbon composite of claim 8, wherein carbon is a one-dimensional tubular carbon-based material, a two-dimensional layered carbon-based material, or a 3-dimensional porous carbon material.
11. A lithium ion battery negative electrode, the active material of which is the pre-lithiated binary topological structure phosphorus/carbon composite material prepared by the method of any one of claims 1 to 7 or the pre-lithiated binary topological structure phosphorus/carbon composite material of any one of claims 8 to 10.
12. A lithium ion battery comprising the lithium ion battery negative electrode of claim 11.
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