CN111519075B - Lithium composite material, lithium composite target material, and preparation method and application thereof - Google Patents

Lithium composite material, lithium composite target material, and preparation method and application thereof Download PDF

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CN111519075B
CN111519075B CN202010237314.9A CN202010237314A CN111519075B CN 111519075 B CN111519075 B CN 111519075B CN 202010237314 A CN202010237314 A CN 202010237314A CN 111519075 B CN111519075 B CN 111519075B
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lithium
lithium composite
composite material
molten
oxygen
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CN111519075A (en
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张艳芳
谭志
虞文韬
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Vitalink Industry Shenzhen Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C24/00—Alloys based on an alkali or an alkaline earth metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00—Casting in, on, or around objects which form part of the product
    • B22D19/08—Casting in, on, or around objects which form part of the product for building-up linings or coverings, e.g. of anti-frictional metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • H01M4/134—Electrodes based on metals, Si 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
    • H01M4/36—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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a lithium composite material, a lithium composite target material, a preparation method and application thereof, wherein the preparation method of the lithium composite material comprises the steps of introducing nitrogen and oxygen into molten lithium under a vacuum condition to obtain molten reaction liquid, and cooling the molten reaction liquid to obtain the lithium composite material; when the lithium-containing compound is applied to the preparation of a lithium ion battery, the growth of dendritic crystals in the charging and discharging processes of the lithium ion battery can be effectively inhibited, so that the cycle performance and the safety of the lithium ion battery are improved.

Description

Lithium composite material, lithium composite target material, and preparation method and application thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium composite material, a lithium composite target material, and a preparation method and application thereof.
Background
The lithium ion battery has the characteristics of high specific capacity, high voltage platform and the like, and is widely applied to the fields of portable electronic 3C equipment, electric automobiles, ships, space technology, biomedical engineering, logistics, national defense and military industry and the like. With the development of science and technology, the development and application of lithium ion batteries are raised to a brand new height, at present, the specific capacity of a lithium ion battery system taking graphite as a negative electrode reaches the bottleneck (372mAh/g), lithium intercalation and lithium deintercalation cannot be completed due to the structural change of a positive electrode or the damage of the negative electrode in the process of charging and discharging, particularly, the negative electrode structure is seriously damaged after circulating for hundreds of times and cannot receive lithium ions provided by the positive electrode so as to separate lithium, the capacity is reduced too early, and the recycling performance of the lithium ion battery system can not meet the requirements of the modern society.
In recent years, researchers have found that the theoretical specific capacity of the battery using lithium metal as the negative electrode vegetation is high, reaching 3860mAh/g, but there are two fatal problems: firstly, due to the high activity of the metal lithium, the metal lithium is very easy to generate irreversible reaction with the electrolyte in the circulation process, the electrolyte is consumed, the coulomb efficiency is reduced, and the service life of the battery is further influenced; on the other hand, in the process of cyclic charge and discharge of the battery, metal lithium is easy to form dendrite and 'dead lithium', the cyclic performance of the lithium electrode is also reduced, and the continuous growth of lithium dendrite can pierce through a diaphragm to cause a series of problems such as short circuit and even explosion. Therefore, how to improve the cycle performance of the lithium ion battery is a difficult problem for those skilled in the art to overcome.
Disclosure of Invention
Based on the above, the invention provides a lithium composite material, a lithium composite target material, a preparation method and an application thereof, wherein the lithium composite material can inhibit the growth of lithium dendrites, and further can improve the cycle performance of a battery; the invention further provides an electrode plate and a battery containing the lithium composite material.
The technical scheme of the invention is as follows.
In one aspect, the present invention provides a method for preparing a lithium composite material, comprising the steps of:
introducing nitrogen and oxygen into molten lithium to react under a vacuum condition to obtain molten reaction liquid;
and cooling the molten reaction liquid to obtain the lithium composite material.
In the method for producing the lithium composite material, the molar ratio of the molten lithium to the introduced nitrogen and oxygen is (4-8): (1-4): (1-3).
In the above method for preparing a lithium composite material, the reaction conditions are as follows: reacting for 4-8 h at 180-1000 ℃.
In the method for preparing the lithium composite material, the nitrogen gas and the oxygen gas are introduced at a flow rate of 150sccm to 300 sccm.
In the preparation method of the lithium composite material, the dosage of the raw materials is controlled within a reasonable range, so that nitrogen, oxygen and lithium are reacted with each other to form the lithium composite with the laminated crystal structure of LiO-LiON-LiN.
Further, the invention also provides a lithium composite material prepared by the preparation method of the lithium composite material.
The invention also provides a lithium composite material prepared by the preparation method of the lithium composite material or an application of the lithium composite material in preparation of a lithium battery.
The lithium composite material is a lithium composite with a laminated crystal structure of LiO-LiON-LiN, and the lithium composite can effectively inhibit the growth of dendritic crystals in the charging and discharging processes of the lithium ion battery, so that the cycle performance and the safety of the lithium ion battery are improved.
In the process of preparing the lithium ion battery, the battery obtained from material to assembly is subjected to a plurality of processes including preparation of a target material, preparation of positive and negative electrode plates and the like, so that the lithium composite material prepared by the preparation method of the lithium composite material or the application of the lithium composite material in the preparation of the lithium ion battery comprises the application of the lithium material in each process of preparing the lithium ion battery, such as the application in the preparation of the lithium target material.
The invention also provides a lithium composite target material, which comprises a target tube and a lithium composite material coated on the target tube, wherein the lithium composite material is the lithium composite material.
The invention further provides a preparation method of the lithium composite target material, which comprises the following steps:
introducing nitrogen and oxygen into molten lithium to react under a vacuum condition to obtain molten reaction liquid;
arranging a target tube in a mould, and forming a forming cavity for forming between the target tube and the inner wall of the mould;
pouring the molten reaction liquid into the molding cavity for cooling and molding;
and removing the mold.
In the preparation method of the lithium composite target material, the outer wall of the target tube is provided with a concave part, and/or the outer wall of the target tube is provided with grains.
The nitrogen and the oxygen are fully contacted with the molten lithium and then react to generate the lithium-containing compound with a laminated crystal structure of LiO-LiON-LiN, and the lithium-containing compound can effectively inhibit the growth of lithium dendrites in the charging and discharging processes of the lithium ion battery, so that the cycle use performance and the safety of the lithium ion battery are improved.
Further, the invention also provides an electrode plate, which contains the lithium composite material.
Still further, the present invention also provides a battery comprising the electrode tab as described above.
The lithium-containing compound in the electrode plate of the battery can effectively inhibit the growth of lithium dendrite in the charging and discharging processes of the lithium ion battery, thereby improving the cycle performance and safety of the lithium ion battery.
Advantageous effects
According to the preparation method, under the vacuum condition, nitrogen and oxygen are introduced into molten lithium to obtain molten reaction liquid, and the molten reaction liquid is cooled to obtain the lithium composite material; the nitrogen and the oxygen are fully contacted with the molten lithium and then react to generate a lithium-containing compound with a laminated crystal structure of LiO-LiON-LiN, and the lithium-containing compound can effectively inhibit the growth of lithium dendrites in the charging and discharging processes of the lithium ion battery, so that the cycle performance and the safety of the lithium ion battery are improved.
Drawings
FIG. 1 is a schematic view of a cast target according to an embodiment of the present invention;
FIG. 2 is a schematic view of a target tube in accordance with one embodiment of the present invention;
FIG. 3 is a schematic view of a target tube according to another embodiment of the present invention.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
An embodiment of the present invention provides a method of preparing a lithium composite material, including the following steps S1-S2.
And S1, introducing nitrogen and oxygen into the molten lithium to react under the vacuum condition to obtain molten reaction liquid.
And S2, cooling the molten reaction liquid to obtain the lithium composite material.
In the prior art, metal lithium in a lithium ion battery and most of electrolyte can not stably coexist for a long time, and the metal lithium is easy to have irreversible reaction with the electrolyte in the cyclic charge and discharge process of the lithium ion battery, so that the service life of the battery is reduced; meanwhile, the growth of lithium dendrites is often accompanied in the charging and discharging processes of the lithium ion battery, the cycle performance of the lithium ion battery can be reduced, and the lithium dendrites can easily puncture the diaphragm to cause short circuit and even explosion. The skilled in the art is always searching for a method for improving the cycle life and safety of a lithium ion battery, and currently, the most common means for improving the cycle performance of a lithium ion battery is to improve an electrolyte, such as a solid electrolyte, a high-salt-concentration electrolyte, or a nano electrolyte. However, the low ionic conductivity of solid electrolytes limits their applications; the preparation process of the high-salt-concentration electrolyte and the nano electrolyte is complex, the cost is high, and large-scale application cannot be realized at all. How to improve the cycle performance of the lithium ion battery is still a difficult problem for the technicians in the field to overcome.
The technical personnel of the invention develops a new way on the basis of the research of the predecessor, starts with the improvement of the electrode material, and finds out after a large amount of creative experiments that: the lithium-containing compound with the laminated crystal structure of LiO-LiON-LiN can effectively inhibit the growth of lithium dendrites in the charging and discharging processes of the lithium ion battery, thereby improving the cycle performance and safety of the lithium ion battery.
In one embodiment, the molar ratio of the molten lithium to the nitrogen to the oxygen is (4-8) to (1-4) to (1-3).
In one embodiment, the molar ratio of the molten lithium to the nitrogen to the oxygen is (5-7) to (2-3) to (1-2).
Further preferably, in one embodiment, the molar ratio of molten lithium, nitrogen and oxygen is 7: 2: 1.
In one embodiment, the preparation of molten lithium comprises the following steps: under the protection of inert gas, heating the lithium ingot to 180-500 ℃ to form molten lithium.
It is understood that other methods may be used for the preparation of molten lithium, as long as liquid molten lithium is obtained.
In one embodiment, in step S1, the molten lithium is stirred while nitrogen and oxygen are introduced into the molten lithium until the reaction is completed, and the stirring is stopped.
In the preparation method of the lithium composite material, the dosage of the raw materials is controlled within a reasonable range, so that nitrogen, oxygen and lithium are reacted with each other to form the lithium composite with the laminated crystal structure of LiO-LiON-LiN.
In one embodiment, the reaction conditions are: reacting for 4-8 h at 180-1000 ℃.
In one embodiment, the vacuum conditions are: 10-3Pa～10-1Pa。
In one embodiment, the nitrogen and oxygen are introduced at a rate of 150sccm to 300 sccm.
During the reaction, the molten lithium may cause a change in gas pressure when heated, and the unstable gas pressure may cause the reaction to proceed in an undesired direction, thereby failing to obtain a desired product. Therefore, the nitrogen and the oxygen react with the molten lithium under the same pressure condition by controlling the feeding speed of the nitrogen and the oxygen to ensure that the vacuum condition is kept stable and unchanged, so as to form the compound with the laminated crystal structure of LiO-LiON-LiN.
Further, the invention also provides a lithium composite material prepared by the preparation method of the lithium composite material.
According to the invention, nitrogen and oxygen are introduced into molten lithium to obtain molten reaction liquid, and the molten reaction liquid is cooled to obtain the lithium composite material. The nitrogen and the oxygen are fully contacted with the molten lithium and then react to generate the lithium compound with the laminated crystal structure of LiO-LiON-LiN, and the lithium compound can effectively inhibit the growth of lithium dendrites in the charging and discharging processes of the lithium ion battery, so that the cycle use performance and the safety of the lithium ion battery are improved.
The invention also provides a lithium composite material prepared by the preparation method of the lithium composite material or an application of the lithium composite material in preparation of a lithium battery.
In one embodiment, the lithium battery is a lithium ion battery.
The lithium composite material is a lithium composite with a laminated crystal structure of LiO-LiON-LiN, and the lithium composite can effectively inhibit the growth of lithium dendrites in the charging and discharging processes of the lithium ion battery, so that the cycle performance and the safety of the lithium ion battery are improved.
It can be understood that in the process of preparing the lithium ion battery, the battery from the material to the final assembly is subjected to a plurality of processes including the preparation of the target material, the preparation of the positive and negative electrode plates, and the like, and therefore, the lithium composite material prepared by the preparation method of the lithium composite material or the application of the lithium composite material in the preparation of the lithium ion battery includes the application of the lithium material in each process of preparing the lithium ion battery, such as the application in the preparation of the lithium target material.
One embodiment of the present invention provides a lithium composite target, which includes a target tube and a lithium composite material coated on the target tube, wherein the lithium composite material is the above-mentioned lithium composite material.
In the lithium composite target material, the lithium composite material coated on the target tube is a lithium composite with a laminated crystal structure of LiO-LiON-LiN, and the lithium composite can effectively inhibit the growth of dendritic crystals in the charge and discharge processes of the lithium ion battery, so that the cycle performance and the safety of the lithium ion battery are improved.
An embodiment of the present invention provides a method for preparing the lithium composite target, including the following steps S10-S40.
And S10, introducing nitrogen and oxygen into the molten lithium to react under the vacuum condition to obtain molten reaction liquid.
In one embodiment, the molar ratio of the molten lithium to the nitrogen to the oxygen is (4-8) to (1-4) to (1-3).
In one embodiment, the molar ratio of the molten lithium to the nitrogen to the oxygen is (5-7) to (2-3) to (1-2).
Further preferably, in one embodiment, the molar ratio of molten lithium, nitrogen and oxygen is 7: 2: 1.
In one embodiment, in step S10, the molten lithium is stirred while nitrogen and oxygen are introduced into the molten lithium until the reaction is completed, and the stirring is stopped.
In the preparation method of the lithium composite target material, the dosage of the raw materials is controlled within a reasonable range, so that nitrogen, oxygen and lithium are interacted and reacted to form a molten reaction liquid, the molten reaction liquid is a lithium composite with a layered crystal structure of LiO-LiON-LiN, and the lithium composite can effectively inhibit the growth of lithium dendrites in the charging and discharging processes of a lithium ion battery, so that the cycle performance and the safety of the lithium ion battery are improved, and the requirements of lithium ion batteries with different types of anodes can be met.
In one embodiment, the reaction conditions are: reacting for 4-8 h at 180-1000 ℃.
In one embodiment, the reaction conditions are: reacting for 4-8 h at 180-600 ℃.
In one embodiment, the vacuum conditions are: 10-3Pa～10-1Pa。
In one embodiment, the nitrogen and oxygen are introduced at a rate of 150sccm to 300 sccm.
During the reaction, the molten lithium may cause a change in gas pressure when heated, and the unstable gas pressure may cause the reaction to proceed in an undesired direction, thereby failing to obtain a desired product. Therefore, the nitrogen and the oxygen react with the molten lithium under the same pressure condition by controlling the feeding speed of the nitrogen and the oxygen to ensure that the vacuum condition is kept stable and unchanged, so as to form the compound with the laminated crystal structure of LiO-LiON-LiN.
And S20, arranging the target tube in the mold, and forming a molding cavity for molding between the target tube and the inner wall of the mold.
In one embodiment, the bottom of the mold is provided with a fixing thread groove, and the target tube is fixed in the mold through the fixing thread groove.
It will be appreciated that the mold and target tube are detachable from each other.
In one embodiment, the material of the mold is at least one of stainless steel, aluminum, iron, graphite, or copper.
In one embodiment, the inner wall of the mold is covered with a metal foil, and further, the metal foil is selected from any one of aluminum foil, copper foil, iron foil, and graphite foil.
It will be appreciated that after the subsequent step of removing the mould, the metal foil is removed.
It will be appreciated that the shape and size of the mold may be determined based on the shape and size of the target to be ultimately formed, for example, in embodiments of the invention where the final target is cylindrical, the mold is cylindrical.
In one embodiment, the outer wall of the target tube has a recess and/or the outer wall of the target tube has a texture.
Generally, in the casting process, the molten reaction liquid is not completely attached to the target tube due to shrinkage in the cooling process, so that the formed lithium composite material may have problems of local foaming, bulging and the like, and further the quality and performance of the target material are affected. Therefore, the contact area between the surface of the target tube and the molten reaction liquid can be increased by arranging the concave parts or the lines on the outer wall of the target tube, so that stress release when the molten reaction liquid is cooled and shrunk firstly appears at the concave parts, and the molten reaction liquid can be tightly attached to the target tube in the cooling process.
Further, the recess is an annular structure around the circumference of the target tube.
It should be noted that the concave part on the target tube can be arranged at any position on the target tube, except two ends of the target tube, it can also be in the middle of the target tube; the number of the recesses may be one or more, and the size of each recess may be the same or different.
In one embodiment, the concave parts are arranged at two ends of the outer wall of the target tube, further, the depth of the concave parts is 1 mm-10 mm, the width of the concave parts is 1 mm-20 cm, and the gradient of the concave parts is 5-85 degrees.
The slope of the concave part is an included angle between an oblique line formed by directly connecting the point at the bottommost end of the concave part and any point on the edge of the concave part and a horizontal line where the point at the bottommost end of the concave part is located.
Referring to fig. 2, in a specific example, the depressions are provided at both ends of the outer wall of the target tube, and the depressions have a depth of 5mm, a width of 5cm, and a slope of 30 °.
Providing the outer wall of the target tube with the recessed portion increases the contact area of the surface of the target tube with the molten reaction liquid, so that stress relaxation at the time of cooling shrinkage of the molten reaction liquid occurs first in the recessed portion.
In some embodiments, the texture may be a convex texture or a concave texture. It should be noted that the outer protrusion or inner recess is referred to herein as an outer wall of the target tube that is not textured.
In one embodiment, the outer wall of the target tube has an inner concave texture, further, the depth of the inner concave texture is 0.01 mm-20 mm, and further, the depth of the texture is 1 mm.
The depth here refers to the maximum distance that the concave texture is recessed inwardly relative to the surface of the outer wall where the texture is not provided.
The concave grains are arranged on the outer wall of the target tube, so that the contact area between the surface of the target tube and the molten reaction liquid can be increased, and stress release during cooling and shrinkage of the molten reaction liquid is firstly found in the concave grains.
In one embodiment, the outer wall of the target tube has convex grains, further, the convex height is 0.01 mm-20 mm, and further, the height of the grains is 1 mm.
It should be noted that, the height of the convex vein is relative to the outer wall without vein, which means the maximum distance of the convex vein protruding outwards relative to the outer wall surface without vein.
The outer wall of the target pipe is provided with the convex grains, so that the contact area between the surface of the target pipe and the molten reaction liquid can be increased, and at the moment, the outer wall without the convex grains is an inward concave part relative to the convex grains, so that the stress release when the molten reaction liquid is cooled and contracted is firstly carried out at the outer wall without the convex grains.
It should be noted that the outer wall of the target tube may have a plurality of lines, and the depth or height of each line may be the same or different, and the depth or height of different parts of the same line may also be the same or different, and the lines may be criss-cross lines with irregular shapes.
In some of these embodiments, the texture is a criss-cross wavy texture.
Referring to fig. 3, in a specific example, the outer wall of the target tube is provided with a plurality of concave grains, the depth of the grains is 0.01 mm-20 mm, and the grains are in a criss-cross wavy shape.
In one embodiment, the material of the target tube is stainless steel.
In one of the embodiments, the target tube may be solid or hollow. In the subsequent cooling step, a cooling liquid can be injected into the hollow target tube to assist the cooling of the molten reaction liquid.
If necessary, step S10 and step S20 do not have a specific priority.
S30, pouring the molten reaction liquid prepared in the step S10 into the molding cavity prepared in the step S20, cooling and molding.
Referring to FIG. 1, in one embodiment, a casting process is shown in FIG. 1. The prepared molten reaction liquid is poured into a molding cavity 3 formed between the target tube 1 and the inner wall of the mold 2 for cooling and molding.
In one embodiment, in step S30, the molten reaction solution is cooled by natural cooling or by the action of a cooling liquid.
Further, in one embodiment, the molten reaction liquid is poured into the molding cavity, a cooling liquid is added into the hollow target tube, and the molten reaction liquid is rapidly cooled under the action of the cooling liquid.
The cooling liquid mode can accelerate the cooling speed of the molten reaction liquid, and is favorable for eliminating air holes and shrinkage cavities in the molten reaction liquid.
The cooling liquid can be water or any other liquid capable of accelerating the cooling speed of the solution.
And S40, removing the die.
Specifically, the mold is removed to obtain the lithium composite target material.
In one embodiment, after step S40, the method further includes a step of polishing the prepared lithium composite target material.
The invention also provides an electrode plate, which contains the lithium composite material prepared by the preparation method or the lithium composite material.
In one embodiment, the electrode sheet is a negative electrode sheet of a lithium ion battery.
The nitrogen and the oxygen are fully contacted with the molten lithium and then react to generate the lithium-containing compound with a laminated crystal structure of LiO-LiON-LiN, and the lithium-containing compound can effectively inhibit the growth of lithium dendrites in the charging and discharging processes of the lithium ion battery, so that the cycle use performance and the safety of the lithium ion battery are improved.
In the electrode sheet, the lithium composite material includes, but is not limited to, an electrode material or a lithium supplement material as an electrode material in the electrode sheet.
The invention also provides a battery, which comprises the electrode plate.
In one embodiment, the battery is a lithium ion battery, and further, the electrode plate is used as a negative electrode plate of the battery.
The lithium-containing compound in the electrode plate can effectively inhibit the growth of lithium dendrite in the charging and discharging process of the lithium ion battery, thereby improving the cycle performance and safety of the lithium ion battery.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The preparation method of the lithium composite material according to the present invention is exemplified herein, but the present invention is not limited to the following examples.
The concrete steps of the embodiments 1-4 are as follows:
1) putting metallic lithium into a heating tank with a stirring device, heating and melting into molten lithium, and vacuumizing the heating tank to 10 DEG-1Pa。
2) Controlling the temperature of the heating tank at the reaction temperature (as shown in Table 1), introducing oxygen and nitrogen while stirring, monitoring the vacuum degree in the heating tank at any time, and controlling the introduction speed of nitrogen and oxygen to maintain the vacuum degree in the tank at 10-1And Pa, introducing nitrogen and oxygen, and reacting for 5 hours to obtain a molten reaction solution.
3) Pouring the molten reaction liquid into a mold (shown in figure 2) through a pipeline, injecting cooling liquid water into a hollow target tube in the mold, cooling, taking down the mold to obtain the lithium composite target material, and polishing the target material.
4) And 3) preparing an electrode plate by taking the lithium composite material on the lithium composite target material prepared in the step 3) as an electrode material.
5) And (3) assembling the electrode slice prepared in the step (4) as a negative electrode of the battery to obtain the lithium ion battery, wherein the parts for assembling the lithium ion battery are not different from the lithium ion battery sold in the market except for the negative electrode slice.
Note: the target tube shown in figure 2 is a hollow stainless steel cylindrical target tube, the depressed parts are arranged at two ends of the outer wall of the target tube, the depth of the depressed parts is 5mm, the width of the depressed parts is 5cm, and the gradient of the depressed parts is 30 degrees.
The charge ratio and reaction temperature of the raw materials in examples 1 to 4 are shown in Table 1.
TABLE 1
Figure BDA0002431425640000101
Figure BDA0002431425640000111
Note: the molar ratio in table 1 refers to the molar ratio of molten lithium, nitrogen and oxygen.
Comparative example 1
Comparative example 1 is substantially the same as example 4 except that oxygen is not fed in step 2) of comparative example 1 and the molar amount of nitrogen fed in comparative example 1 is the sum of the molar amounts of nitrogen and oxygen fed in example 4, to obtain a lithium nitride target.
Comparative example 2
Comparative example 2 a lithium ion battery was assembled by using elemental lithium as an electrode material of an electrode tab and using the prepared electrode tab as a negative electrode of the battery, wherein the other parts except the negative electrode tab among the parts for assembling the lithium ion battery were the same as those of example 1
Comparative example 3
A commercially available lithium ion battery, referred to as a Maxell Cr2032 rechargeable and dischargeable button cell.
Example 5
Example 5 the cycle life of the batteries prepared in examples 1 to 4 and comparative examples 1 to 3 was tested.
1) And (3) testing the cycle service life of the battery: charging for 150 minutes under the condition of room temperature at 25 ℃ by a constant-current constant-voltage mode 1C charging system, discharging to 2.75V by a constant-current 1C discharging system, stopping the discharging for one cycle, finishing the test when one discharging time is less than 36 minutes, and recording the cycle number. The specific steps refer to GB-T18287-2000.
Specific results are shown in table 2.
TABLE 2
Number of cycles Volume (diameter X height)
Example 1 120 φ20mm x 3.2mm
Example 2 150 φ20mm x 3.2mm
Example 3 180 φ20mm x 3.2mm
Example 4 220 φ20mm x 3.2mm
Comparative example 1 80 φ20mm x 3.2mm
Comparative example 2 10 φ20mm x 3.2mm
Maxell ML2032 110 φ20mm x 3.2mm
From the results in table 1, it can be seen that the lithium composite target material prepared by the method for preparing a lithium composite target material of the present invention in examples 1 to 4 can effectively inhibit the growth of lithium dendrites during the charging and discharging processes of the lithium ion battery, thereby improving the cycle performance and safety of the lithium ion battery.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (11)

1. A method for preparing a lithium composite material, comprising the steps of:
introducing nitrogen and oxygen into molten lithium to react under a vacuum condition to obtain molten reaction liquid;
cooling the molten reaction liquid to obtain a lithium composite material;
wherein the molar ratio of the molten lithium to the introduced nitrogen and oxygen is (4-8): 1-4): 1-3;
the introducing speed of the nitrogen and the oxygen is 150 sccm-300 sccm.
2. The method of claim 1, wherein the molar ratio of the molten lithium to the nitrogen and the oxygen introduced is (5-7): (2-3): (1-2).
3. The method of preparing a lithium composite material according to claim 1, wherein the reaction conditions are: reacting for 4-8 h at 180-1000 ℃.
4. The method of preparing the lithium composite material according to claim 1, wherein the molar ratio of the molten lithium to the nitrogen gas and the oxygen gas introduced is 7: 2: 1.
5. The lithium composite material manufactured by the method of manufacturing the lithium composite material according to any one of claims 1 to 4.
6. Use of a lithium composite produced by the method of any one of claims 1 to 4 for the production of a lithium battery.
7. A lithium composite target comprising a target tube and a lithium composite material coated on the target tube, wherein the lithium composite material is the lithium composite material according to claim 5.
8. The preparation method of the lithium composite target material is characterized by comprising the following steps:
introducing nitrogen and oxygen into molten lithium to react under a vacuum condition to obtain molten reaction liquid;
arranging a target tube in a mold, wherein a molding cavity for molding is formed between the target tube and the inner wall of the mold;
pouring the molten reaction liquid into the molding cavity for cooling and molding;
removing the mold;
wherein the molar ratio of the molten lithium to the introduced nitrogen and oxygen is (4-8): 1-4): 1-3;
the introducing speed of the nitrogen and the oxygen is 150 sccm-300 sccm.
9. The method of claim 8, wherein the outer wall of the target tube has a recess and/or the outer wall of the target tube has a texture.
10. An electrode sheet comprising the lithium composite material according to claim 5.
11. A battery comprising the electrode tab of claim 10.
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