CN112164780A - Silicon-based negative electrode material, preparation method thereof and related product - Google Patents
Silicon-based negative electrode material, preparation method thereof and related product Download PDFInfo
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- CN112164780A CN112164780A CN202011056461.2A CN202011056461A CN112164780A CN 112164780 A CN112164780 A CN 112164780A CN 202011056461 A CN202011056461 A CN 202011056461A CN 112164780 A CN112164780 A CN 112164780A
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- 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
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- H01M4/386—Silicon or alloys based on silicon
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Abstract
The application provides a silicon-based anode material and a preparation method thereof, and a related product, the silicon-based anode material comprises a plurality of silicon-based composite particles, the silicon-based composite particles comprise a silicon-based material and a coating layer, the coating layer comprises a plurality of coating particles, and the coating particles are coated on at least part of the surface of the silicon-based material through atomic layer deposition. The coating layer can effectively coat the silicon-based material, and uniformly coats the coated particles on the surface of the silicon-based material, so that the effects of restricting the expansion of the silicon-based material and isolating the silicon-based material from contacting with the outside are realized, the cycling stability of the silicon-based negative electrode material is improved, when the silicon-based material is applied to a battery, the cycling performance of the battery can be improved, and the capacity retention rate of the battery can be high.
Description
Technical Field
The application relates to the technical field of electronics, in particular to a silicon-based negative electrode material, a preparation method thereof and a related product.
Background
At present, silicon has ultrahigh theoretical specific capacity (4200mAh/g) and lower lithium removal potential, and the voltage platform of silicon is slightly higher than that of graphite, so that surface lithium precipitation is difficult to cause during charging, and the safety performance is better. Silicon is becoming more and more popular as a carbon-based negative electrode of a lithium ion battery.
However, during the circulation process of the silicon-based negative electrode, lithium ions are continuously inserted and extracted to form a solid solution with silicon, which causes the silicon volume to be seriously expanded during the charging and discharging process, and also causes the continuous reaction with the electrolyte to cause the negative electrode to be continuously deteriorated, and the later decay rate of the negative electrode is higher than that of graphite. Therefore, how to solve the expansion of the silicon negative electrode in the recycling process so as to improve the cycle performance of the battery becomes a technical problem to be solved.
Disclosure of Invention
The application provides a silicon-based negative electrode material capable of improving the cycle performance of a battery, a preparation method thereof and a related product.
In a first aspect, an embodiment of the present application provides a silicon-based anode material, which includes a plurality of silicon-based composite particles, where the silicon-based composite particles include a silicon-based material and a coating layer, the coating layer includes a plurality of coating particles, and the coating particles are coated on at least a part of a surface of the silicon-based material through atomic layer deposition.
In a second aspect, the embodiment of the application provides a battery negative electrode plate, and the silicon-based negative electrode material is coated on a negative electrode current collector to obtain the battery negative electrode plate.
In a third aspect, an embodiment of the present application provides a battery, including the battery negative electrode tab.
In a fourth aspect, an embodiment of the present application provides an electronic device, including the battery.
In a fifth aspect, an embodiment of the present application provides a method for preparing a silicon-based anode material, including:
preparing a silicon-based material;
preparing a coated substrate, wherein the coated substrate comprises a plurality of coated particles;
depositing a number of the coating particles on the outer surface of the silicon-based material by atomic layer deposition to form a coating layer.
The embodiment of the application provides a silicon-based negative electrode material, through adopting nanometer cladding granule, mode through atomic layer deposition is with nanometer cladding granule cladding in the surface of silicon-based material, in order to form the thickness thinner and the even cladding coating, this coating can carry out effectual cladding to silicon-based material, with the even parcel of cladding granule on silicon-based material surface, thereby realize the effect of constraint silicon-based material expansion increase and isolated silicon-based material and external contact, silicon-based negative electrode material's cycle stability has been promoted, when silicon-based material is applied to the battery, can improve the discharge specific capacity of battery high, and improve the cycle performance of battery, still can make the capacity retention rate of battery high.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a negative electrode plate of a battery provided in an embodiment of the present application;
fig. 2 is a schematic structural diagram of an electronic device according to an embodiment of the present application;
FIG. 3 is an exploded view of the electronic device provided in FIG. 2;
fig. 4 is a schematic structural diagram of a first silicon-based anode material provided in an embodiment of the present application;
fig. 5 is a schematic structural diagram of a silicon-based material in a second silicon-based anode material provided in an embodiment of the present application;
FIG. 6 is a schematic structural diagram of a second silicon-based composite particle provided in an embodiment of the present application;
FIG. 7 is a schematic structural diagram of a third silicon-based composite particle provided in an example of the present application;
FIG. 8 is a schematic structural diagram of a fourth silicon-based composite particle provided in an embodiment of the present application;
FIG. 9 is a schematic structural diagram of a fifth silicon-based composite particle provided in embodiments of the present application;
fig. 10 is a flowchart of a method for preparing a silicon-based anode material according to an embodiment of the present disclosure;
fig. 11 is a flowchart of a method for preparing a silicon-based anode material provided in example two of the present application;
FIG. 12 is a surface topography of a silicon-based composite material provided in example two of the present application;
FIG. 13 is a surface topography of a silicon-based composite particle provided in example two of the present application;
FIG. 14 is a schematic thickness diagram of a coating layer of a silicon-based composite particle according to example II of the present application, which is detected by a transmission electron microscope;
FIG. 15 is a distribution diagram of surface carbon elements of a silicon-based composite material provided in example two of the present application;
FIG. 16 is a distribution diagram of surface silicon elements of a silicon-based composite material provided in example two of the present application;
FIG. 17 is a surface oxygen distribution diagram of a silicon-based composite material provided in example two of the present application;
fig. 18 is a flowchart of a method for preparing a silicon-based anode material provided in example three of the present application;
fig. 19 is a flowchart of a method for preparing a silicon-based anode material provided in example four of the present application;
fig. 20 is a flowchart of a method for preparing a silicon-based anode material provided in example five of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. The embodiments listed in the present application may be appropriately combined with each other.
Referring to fig. 1, an embodiment of the present application provides a silicon-based negative electrode material 11. The silicon-based negative electrode material 11 is used for preparing a battery negative electrode plate 1, specifically, the silicon-based negative electrode material 11 is uniformly mixed with a conductive agent and a binder to prepare a negative electrode slurry, and then the negative electrode slurry is coated on a negative electrode current collector 12. Referring to fig. 2 and 3, a plurality of single sheets are formed by rolling and slicing, and the plurality of single sheets are assembled into a battery cell by lamination, and then the battery cell is prepared into a battery 40. The battery 40 may be a lithium ion battery. The battery 40 is applied to the electronic apparatus 100. The electronic device 100 includes, but is not limited to, electronic products requiring a battery 40 for a laptop computer, a cell phone, a palmtop computer, a tablet computer, a wearable electronic device, and the like. The present embodiment is described by taking the electronic device 100 as a mobile phone as an example. The electronic device 100 includes a display screen 10, a middle frame 20 and a rear cover 30, which are sequentially covered, wherein the middle frame 20 has a battery compartment 210. The battery 40 is disposed in the battery compartment 210.
Referring to fig. 4, the silicon-based negative electrode material 11 includes a plurality of silicon-based composite particles 111. The silicon-based composite particles 111 may be nano-sized or micro-sized particles including silicon and other components combined. The number of the silicon-based composite particles 111 is plural, and the number of the silicon-based composite particles 111 is not specifically limited in the present application.
Referring to fig. 4, the silicon-based composite particle 111 includes a silicon-based material 112 and a coating layer 113. The silicon-based material 112 includes, but is not limited to, any one or combination of silicon-based particles, silicon-based nanowires, silicon-based nanotubes, and the like. Specifically, the silicon-based material 112 includes, but is not limited to, one or a combination of at least two of silicon nanowires, silicon magnesium material, silicon aluminum material, silicon magnesium-silicon aluminum, silicon carbon material, and silicon oxygen material.
This embodiment is exemplified by the silicon-based material 112 as silicon-based particles. The particle size of the silicon-based material 112 is 1 nm-50 um.
The coating layer 113 includes a plurality of coating particles 114. The coated particles 114 are nanoparticles. The particle size of the coated particles 114 may be 0.1 to 10 nm. The plurality of coating particles 114 are disposed on the surface of the silicon-based material 112 by atomic layer deposition, such that the plurality of coating particles 114 are attached to or embedded in the surface of the silicon-based material 112 to form the coating layer 113. The thickness of the coating layer 113 may be 0.1 to 10 nm. The coating layer 113 may be partially coated or completely coated, and may be continuously coated or intermittently coated. It will be appreciated that the particle size of the silicon-based particles is greater than the particle size of the coated particles 114.
The coated particles 114 include, but are not limited to, a composition that is one or at least two of carbon, graphite, graphene, carbon nanotubes, oxides, sulfides, fluorides.
According to the silicon-based anode material 11 provided by the embodiment of the application, the nanoscale coating particles 114 are adopted, the nanoscale coating particles 114 are coated on the surface of the silicon-based material 112 in an atomic layer deposition mode to form the coating layer 113 which is thin and uniform in coating, the thickness of the coating layer 113 can be 0.1-10 nm, the coating layer 113 can effectively coat the silicon-based material 112, and the coating particles 114 are uniformly coated on the surface of the silicon-based material 112, so that the effects of increasing the expansion of the silicon-based material 112 and isolating the silicon-based material 112 from being contacted with the outside are achieved, the circulation stability of the silicon-based anode material 11 is improved, when the silicon-based material 112 is applied to the battery 40, the discharge specific capacity of the battery 40 can be improved, the circulation performance of the battery 40 is improved, and the capacity retention rate of the battery 40 can.
Optionally, referring to fig. 5 and 6, the outer surface of the silicon-based material 112 has a plurality of first recesses 115. At least a portion of the cladding layer 113 is disposed within the first recess 115. In other words, the outer surface of the silicon-based material 112 may have micro-holes, which may be left by etching some of the components in the silicon-based material 112. The size of the micro-holes may be less than 1nm or several nanometers, when the coating particles 114 are disposed on the surface of the silicon-based material 112 by atomic layer deposition, a part of the coating particles 114 may be embedded or filled in the first recess hole 115, and another part of the coating particles 114 is disposed outside the first recess hole 115 and coated on the silicon-based material 112, so that a mutually embedded coating relationship is formed between the coating layer 113 and the silicon-based material 112, thereby improving the coating bonding performance between the coating layer 113 and the silicon-based material 112.
Optionally, the encapsulation layer 113 may fill at least a portion of the first recess 115. In one embodiment, referring to fig. 6, the cladding layer 113 fills the entire first recess 115 to improve the bonding strength between the cladding layer 113 and the silicon-based material 112. In another embodiment, referring to fig. 7, the cladding layer 113 may be filled in a portion of the first recess 115 to ensure that the cladding layer 113 and the si-based material 112 have a certain bonding strength, and another portion of the unfilled first recess 115 may absorb the expansion of the si-based material 112, so as to relatively reduce the expansion force of the si-based material 112 on the cladding layer 113, thereby improving the cycle stability of the si-based negative electrode material 11.
Alternatively, the first recess 115 may be formed by etching a portion of silicon on the surface of the silicon-based material 112. Specifically, the silicon-based material 112 is reacted with a reaction solution, and the concentration, reaction time, reaction temperature, and the like of the reaction solution are controlled, so that a plurality of first concave holes 115 are formed in the surface of the silicon-based material 112. Wherein the reaction solution can be hydrofluoric acid, alkali solution, etc.
Optionally, the composition of the silicon-based material 112 includes a metal. Specifically, the silicon-based material 112 may be a silicon-containing alloy or a silicon-containing alloy composite material. For example, the silicon-based material 112 includes, but is not limited to, a silicon-magnesium material, a silicon-aluminum material, a silicon-nickel material, a silicon-copper material, and the like. The first recess hole 115 may be formed by etching a portion of metal on the surface of the silicon-based material 112. By reacting the silicon-based material 112 with the reaction solution, the concentration, reaction time, reaction temperature, and the like of the reaction solution are controlled, so that a plurality of first concave holes 115 are formed on the surface of the silicon-based material 112. Wherein the reaction solution can be acid solution, alkali solution, etc.
In one embodiment, referring to fig. 8, the si-based material 112 includes a si-based core 116 and a metal shell or metal oxide shell 117 covering the si-based core 116. The first concave hole 115 is formed in the outer surface of the metal shell or the metal oxide shell 117.
Specifically, the silicon-based material 112 may include a silicon-based core 116, the silicon-based core 116 including, but not limited to, silicon nanowires, silicon carbon materials, silicon oxygen materials, and the like. The silicon-based material 112 may include a metal shell or metal oxide shell 117 encased in a silicon-based core 116. The thickness of the shell layer coated on the silicon-based core 116 can be 0.1-10 nm.
The material of the metal shell includes but is not limited to magnesium, aluminum, copper, tweezers and other materials. The material of the metal oxide shell 117 includes, but is not limited to, aluminum oxide, titanium oxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, tin oxide, silicon oxide, magnesium oxide, or a combination thereof.
The shell layer is arranged outside the silicon-based core 116 and can be metal or metal oxide, the shell layer of the silicon-based material 112 can react with the reaction liquid to form a plurality of first concave holes 115 on the outer surface of the shell layer, the coating particles 114 are arranged on the silicon-based material 112 in an atomic layer deposition mode to enable the coating particles 114 to coat the outer surface of the silicon-based material 112, and the coating layer 113 and the shell layer can separate the silicon-based core 116 from the electrolyte in the battery 40, so that the effects of restricting the expansion and increase of the silicon-based core 116 and isolating the silicon-based core 116 from contacting with the outside are achieved, the cycle stability of the silicon-based anode material 11 is improved, when the silicon-based material 112 is applied to the battery 40, the specific discharge capacity of the battery 40 can be improved, the cycle performance of the battery 40 is improved, and the capacity retention rate of the battery.
In one embodiment, referring to fig. 9, the cladding layer 113 includes a first cladding layer 118 and a second cladding layer 119. The first cladding layer 118 is coated on the outer surface of the silicon-based material 112. The outer surface of the first cladding layer 118 has a plurality of second recesses 120, and the second cladding layer 119 is at least partially disposed within the second recesses 120.
Specifically, the materials of the first cladding layer 118 and the second cladding layer 119 may be the same or different. Optionally, the material of the first cladding layer 118 is different from that of the second cladding layer 119. For example, the material of the first coating layer 118 is metal oxide or metal, and the material of the second coating layer 119 is carbon, graphite, graphene, carbon nanotube, sulfide, fluoride, or the like.
In one embodiment, the first cladding layer 118 is formed by atomic layer deposition to cover the outer surface of the silicon-based material 112, so as to form a thin and uniform film for first layer protection of the silicon-based material 112. The first coating layer 118 is made of metal oxide or metal, a plurality of second concave holes 120 can be formed in the outer surface of the first coating layer 118 in a reaction liquid corrosion mode, and then the second coating layer 119 is coated on the outer surface of the silicon-based material 112 in an atomic layer deposition mode to form a thin and uniform coating film layer so as to perform second-layer protection on the silicon-based material 112. The second cladding layer 119 may be at least partially embedded in the second recess 120 of the first cladding layer 118, so that the bonding strength between the first cladding layer 118 and the second protective layer is good, and the protection performance for the silicon-based material 112 is further improved.
Of course, in other embodiments, the first recess hole 115 may be further disposed on the surface of the silicon-based material 112, so that the first cladding layer 118 is disposed in the first recess hole 115, and the bonding strength between the first cladding layer 118 and the silicon-based material 112 is improved, thereby improving the binding strength of the first cladding layer 118 to the silicon-based material 112 and the protection performance of the silicon-based material 112 from contacting the outside.
Referring to fig. 1, a battery negative electrode sheet 1 provided in the embodiment of the present application is prepared by coating a silicon-based negative electrode material 11 according to any one of the above embodiments on a negative electrode current collector 12. Specifically, a silicon-based negative electrode material 11 is uniformly mixed with a conductive agent and a binder to prepare a negative electrode slurry, and then the negative electrode slurry is coated on a negative electrode current collector 12 and rolled and sliced to form a plurality of battery negative electrode plates 1. The battery negative pole piece 1 is made of a silicon-based negative pole material 11, and the battery negative pole piece 1 has good cycling stability.
The battery 40 provided by the embodiment of the application comprises the battery negative pole piece 1. The battery 40 is prepared by assembling a plurality of battery negative pole pieces 1 into the battery core through lamination, and then packaging the battery core, so that the discharge specific capacity of the battery 40 can be improved, the cycle performance of the battery 40 can be improved, and the capacity retention rate of the battery 40 can be high.
Referring to fig. 2 and fig. 3, an electronic device 100 according to an embodiment of the present disclosure includes the battery 40.
Referring to fig. 10, an embodiment of the present application further provides a method for preparing a silicon-based negative electrode material 11, and the method for preparing a silicon-based negative electrode material 11 includes, but is not limited to, the following embodiments.
The first embodiment is as follows: the preparation method of the silicon-based anode material 11 at least comprises the following steps. It is to be understood that the present application is not limited to the specific order of the steps.
110: referring collectively to fig. 4, a silicon-based material 112 is prepared.
Specifically, the silicon-based material 112 includes, but is not limited to, any one or combination of silicon-based particles, silicon-based nanowires, silicon-based nanotubes, and the like. Specifically, the silicon-based material 112 includes, but is not limited to, one or a combination of at least two of silicon nanowires, silicon magnesium material, silicon aluminum material, silicon magnesium-silicon aluminum, silicon carbon material, and silicon oxygen material.
In the present embodiment, the silicon-based material 112 is in the form of particles. The particle size of the silicon-based material 112 is 1 nm-50 um.
In preparing the silicon-based material 112, a powder or a solution of the silicon-based material 112, including a plurality of silicon-based materials 112, may be prepared.
120: a coated substrate is prepared such that the coated substrate includes a plurality of coated particles 114.
The coating layer 113 includes a plurality of coating particles 114. The coated particles 114 are nanoparticles. The particle size of the coated particles 114 may be 0.1 to 10 nm. The coated particles 114 include, but are not limited to, a composition that is one or at least two of carbon, graphite, graphene, carbon nanotubes, oxides, sulfides, fluorides.
130: depositing a plurality of coating particles 114 on the outer surface of the silicon-based material 112 by an atomic layer deposition process to form a coating layer 113, wherein the thickness of the coating layer 113 is 0.1-10 nm to form the silicon-based composite particles 111. The plurality of silicon-based composite particles 111 form the silicon-based anode material 11.
The plurality of coating particles 114 are disposed on the surface of the silicon-based material 112 by atomic layer deposition, such that the plurality of coating particles 114 are attached to or embedded in the surface of the silicon-based material 112 to form the coating layer 113. The thickness of the coating layer 113 may be 0.1 to 10 nm. The coating layer 113 may be partially coated or completely coated, and may be continuously coated or intermittently coated. It will be appreciated that the particle size of the silicon-based particles is greater than the particle size of the coated particles 114.
According to the preparation method of the silicon-based anode material 11 provided by the embodiment of the application, the nanoscale coating particles 114 are adopted, the nanoscale coating particles 114 are coated on the surface of the silicon-based material 112 in an atomic layer deposition mode to form the coating layer 113 which is thin and uniform in coating, the thickness of the coating layer 113 can be 0.1-10 nm, the coating layer 113 can effectively coat the silicon-based material 112, and the coating particles 114 are uniformly coated on the surface of the silicon-based material 112, so that the effects of restricting the expansion and increase of the silicon-based material 112 and isolating the silicon-based material 112 from being contacted with the outside are achieved, the cycle stability of the silicon-based anode material 11 is improved, when the silicon-based material 112 is applied to the battery 40, the specific discharge capacity of the battery 40 can be improved, the cycle performance of the battery 40 is improved, and the capacity retention rate of the.
Example two: referring to fig. 11, the steps of the method for preparing the silicon-based anode material 11 at least include the following steps. It is to be understood that the present application is not limited to the specific order of the steps.
210: referring collectively to fig. 4, a silicon-based material 112 is prepared.
Specifically, the silicon-based material 112 includes, but is not limited to, any one or combination of silicon-based particles, silicon-based nanowires, silicon-based nanotubes, and the like. Specifically, the silicon-based material 112 includes, but is not limited to, one or a combination of at least two of silicon nanowires, silicon magnesium material, silicon aluminum material, silicon magnesium-silicon aluminum, silicon carbon material, and silicon oxygen material.
In the present embodiment, the silicon-based material 112 is in the form of particles. The particle size of the silicon-based material 112 is 1 nm-50 um.
In preparing the silicon-based material 112, a powder or a solution of the silicon-based material 112, including a plurality of silicon-based materials 112, may be prepared.
220: a coated substrate is prepared such that the coated substrate includes a plurality of coated particles 114.
The coating layer 113 includes a plurality of coating particles 114. The coated particles 114 are nanoparticles. The particle size of the coated particles 114 may be 0.1 to 10 nm. The coated particles 114 include, but are not limited to, a composition that is one or at least two of carbon, graphite, graphene, carbon nanotubes, oxides, sulfides, fluorides. The material of the oxide includes, but is not limited to, alumina, titania, zinc oxide, iron oxide, zirconia, ceria, tin oxide, silica, magnesia, or combinations thereof. Fluoride materials include, but are not limited to, aluminum fluoride, lithium fluoride, iron fluoride, or combinations thereof.
Optionally, after preparing the coated substrate, the method further includes dissolving the coated substrate in a solvent to form a coated substrate solution.
Specifically, the nano-coated substrate is dispersed in a solvent to prepare a precursor, wherein the nano-coated substrate is one or more of carbon, graphite, graphene, a carbon nanotube, an oxide, a sulfide, a fluoride and the like. Solvents include, but are not limited to, deionized water, alcohols, acetone, and the like. The dispersion means includes but is not limited to physical stirring, ultrasonic dispersion, ball milling, etc.
230: depositing a plurality of coating particles 114 on the outer surface of the silicon-based material 112 by an atomic layer deposition process to form a coating layer 113, wherein the thickness of the coating layer 113 is 0.1-10 nm to form the silicon-based composite particles 111. The plurality of silicon-based composite particles 111 form the silicon-based anode material 11.
Depositing a plurality of the coating particles 114 on the outer surface of the silicon-based material 112 by an atomic layer deposition process to form a coating layer 113, including: arranging the silicon-based material 112 in a reaction chamber of an atomic layer deposition device, raising the temperature of the reaction chamber to a preset temperature, raising the pressure of the reaction chamber to a first preset pressure, arranging the coated substrate solution in the reaction chamber, and maintaining the first preset pressure; raising the pressure of the reaction chamber to a second preset pressure so as to remove the solvent in the coating substrate solution; a plurality of the coating particles 114 are deposited on the outer surface of the silicon-based material 112 to form a coating layer 113.
Specifically, the silicon-based material 112 is placed in a reaction chamber of a dry atomic layer deposition device, the temperature of the reaction chamber is raised to a specified temperature, and the temperature of the reaction chamber is kept within a set range; wherein the specified temperature range is 50-300 ℃, and can be selected as 100-200 ℃. The temperature rising speed is 1-50 ℃/min, and 10-20 ℃/min can be selected. The selected silicon-based material 112 can be a silicon nanowire, a silicon magnesium-silicon aluminum, a silicon carbon material, a silicon oxygen material, etc., and the size of the silicon-based material is 1nm to 50 um.
Specifically, the reaction chamber is sealed, and a precursor for coating the substrate is introduced into the reaction chamber, wherein the precursor is a coating substrate solution. For a certain time, the precursor of the coated substrate reacts with the silicon-based material 112. And (4) boosting the pressure to remove the solvent in the precursor, so as to obtain the silicon-based negative electrode material 11. Wherein, before the precursor is introduced, the pressure in the reaction chamber is kept to 2-50 atmospheric pressures, and 5-20 atmospheric pressures can be selected. And keeping the time for 5-300 min, optionally 30-90 min after the precursor is introduced. The pressure of the precursor removing solvent can be selected to be 10-30 atmospheric pressures.
Specifically, the silicon-based anode material 11 is taken out. Introducing inert gas, and further cleaning the reaction chamber; wherein the inert gas can be Ar (argon) or N2 (nitrogen); the cleaning time is 1-30 min.
Specifically, the silicon-based negative electrode material 11 with the required thickness of the cladding layer 113 can be obtained by repeating the atomic layer deposition times according to the required thickness of the cladding layer 113. In this embodiment, the thickness of the cladding layer 113 is 0.1 to 10 nm.
Referring to fig. 12 and 13, fig. 12 and 13 are a first surface topography diagram and a second surface topography diagram of a silicon oxygen material (i.e., a silicon-based composite particle) coated with carbon by atomic layer deposition, respectively. As can be seen from fig. 13, after coating, a uniform coating layer 113 can be seen on the surface of the silicon-based anode material 11. The block of the clad layer 113 in fig. 13 is a structure in which a silicon oxide material is clad with carbon. The cover 113 is a pile-like structure on the surface of the block.
Referring to fig. 14, fig. 14 is a schematic diagram of the thickness of the coating layer detected by transmission electron microscopy using atomic layer deposition of a silicon oxygen material coated with carbon. It can be seen from fig. 14 that the thickness of the cladding layer is about 5 nm.
Referring to fig. 15 to 17, fig. 15 to 17 are graphs showing the distribution of carbon, silicon and oxygen on the surface of a silicon oxygen material coated with carbon by atomic layer deposition. The elemental distribution pattern shows that the surface of the silicon oxygen material is uniformly coated with a layer of carbon.
According to the preparation method of the silicon-based anode material 11 provided by the embodiment of the application, the nanoscale coating particles 114 are adopted, the nanoscale coating particles 114 are coated on the surface of the silicon-based material 112 in an atomic layer deposition mode to form the coating layer 113 which is thin and uniform in coating, the thickness of the coating layer 113 can be 0.1-10 nm, the coating layer 113 can effectively coat the silicon-based material 112, and the coating particles 114 are uniformly coated on the surface of the silicon-based material 112, so that the effects of restricting the expansion and increase of the silicon-based material 112 and isolating the silicon-based material 112 from being contacted with the outside are achieved, the cycle stability of the silicon-based anode material 11 is improved, when the silicon-based material 112 is applied to the battery 40, the specific discharge capacity of the battery 40 can be improved, the cycle performance of the battery 40 is improved, and the capacity retention rate of the.
Example three: referring to fig. 18, the steps of the method for preparing the silicon-based anode material 11 at least include the following steps. It is to be understood that the present application is not limited to the specific order of the steps.
310: referring collectively to fig. 4, a silicon-based material 112 is prepared.
Specifically, the silicon-based material 112 includes, but is not limited to, any one or combination of silicon-based particles, silicon-based nanowires, silicon-based nanotubes, and the like. Specifically, the silicon-based material 112 includes, but is not limited to, one or a combination of at least two of silicon nanowires, silicon magnesium material, silicon aluminum material, silicon magnesium-silicon aluminum, silicon carbon material, and silicon oxygen material.
In the present embodiment, the silicon-based material 112 is in the form of particles. The particle size of the silicon-based material 112 is 1 nm-50 um.
In preparing the silicon-based material 112, a powder or a solution of the silicon-based material 112, including a plurality of silicon-based materials 112, may be prepared.
320: the silicon-based material 112 is subjected to dispersion treatment.
When the silicon-based material 112 is not dispersed, the particles are agglomerated to form large particles, and in the charging and discharging process, the particles can be subjected to corresponding agglomeration stress, the larger the large particle group is, the larger the stress is, and meanwhile, the corresponding volume expansion effect of the silicon-based material 112 is, so that the electrode structure is damaged, and the specific capacity irreversible loss is large. This step is to perform dispersion treatment on the silicon-based material 112 in the following manner.
Optionally, the silicon-based material 112 is dispersed in a solvent, and after 30-180min of ultrasonic treatment, a uniformly dispersed silicon-based material 112 solution can be prepared. Solvents include, but are not limited to, deionized water, alcohols, acetone, and the like.
Optionally, the silicon-based material 112 with better dispersibility and concentrated particle size distribution can be prepared by fully grinding the silicon-based material 112, sieving the silicon-based material with a large mesh screen and the like, so that the volume expansion effect of silicon is relieved, the lithium ion transmission path is shortened, and the electrochemical cycle performance of the silicon-based material 112 is improved.
Optionally, the silicon-based material 112 is dispersed in a solvent, and a uniformly dispersed silicon-based material 112 solution can be prepared by ball milling for 0.5-10 hours. Solvents include, but are not limited to, deionized water, alcohols, acetone, and the like.
The dispersing agent can effectively reduce the interaction among particles, reduce the degree of adhesion of fine particles of the silicon-based material 112 on a grinding medium, promote the flow of the grinding material, reduce the energy consumption of ball milling, and improve the product quality and the production efficiency.
Further, a dispersing agent may be added to the silicon-based material 112, followed by ball milling. Dispersants include, but are not limited to, triamines citrate, oleic acid, cetyltrimethylammonium bromide, polyvinyl alcohol, sodium hexametaphosphate, and the like.
When the silicon-based material 112 particles are scattered, on one hand, the particle size of the silicon-based material 112 can be reduced, thereby increasing the coverage area for the silicon-based material 112, so that the cladding layer 113 can clad more silicon-based material 112, and the cladding and protection for more silicon-based material 112 can be improved; on the other hand, the stress on the small silicon-based material 112 particles is relatively isolated, and the electrode structure is difficult to damage, so that the amount of lithium source for the cycling reaction in the electrochemical reaction is more, and the cycling efficiency is higher, so that the electrochemical performance of the silicon-based material 112 can be effectively improved by performing the dispersant treatment on the silicon-based material, the specific capacity of the battery 40 is improved, and the cycling performance of the battery 40 is improved.
Optionally, 0.5-2.5% hexadecyl trimethyl ammonium bromide ion dispersant can be selected as the dispersant, and the silicon-based material 112 body can be obtained after ball milling. The hexadecyl trimethyl ammonium bromide ion dispersing agent can be adsorbed on the surfaces of the particles, so that mutual adsorption among the particles is hindered, and the growth of the particles is prevented.
330: a coated substrate is prepared such that the coated substrate includes a plurality of coated particles 114.
The coating layer 113 includes a plurality of coating particles 114. The coated particles 114 are nanoparticles. The particle size of the coated particles 114 may be 0.1 to 10 nm. The coated particles 114 include, but are not limited to, a composition that is one or at least two of carbon, graphite, graphene, carbon nanotubes, oxides, sulfides, fluorides. The material of the oxide includes, but is not limited to, alumina, titania, zinc oxide, iron oxide, zirconia, ceria, tin oxide, silica, magnesia, or combinations thereof. Fluoride materials include, but are not limited to, aluminum fluoride, lithium fluoride, iron fluoride, or combinations thereof.
Optionally, after preparing the coated substrate, the method further includes dissolving the coated substrate in a solvent to form a coated substrate solution.
Specifically, the nano-coated substrate is dispersed in a solvent to prepare a precursor, wherein the nano-coated substrate is one or more of carbon, graphite, graphene, a carbon nanotube, an oxide, a sulfide, a fluoride and the like. Solvents include, but are not limited to, deionized water, alcohols, acetone, and the like. The dispersion means includes but is not limited to physical stirring, ultrasonic dispersion, ball milling, etc.
Further, the coated substrate may be subjected to a dispersion process, and the specific embodiment may refer to step 320, which is not described herein again. By dispersing the coating base material, the agglomeration of the coating particles 114 can be reduced, the particle size of the coating particles 114 can be reduced, and the coating layer 113 having a small thickness can be further formed.
340: depositing a plurality of coating particles 114 on the outer surface of the silicon-based material 112 by an atomic layer deposition process to form a coating layer 113, wherein the thickness of the coating layer 113 is 0.1-10 nm to form the silicon-based composite particles 111. The plurality of silicon-based composite particles 111 form the silicon-based anode material 11. Step 230 can be referred to in this step, and is not described in detail in this embodiment.
According to the preparation method of the silicon-based anode material 11, after the silicon-based material 112 is prepared, the silicon-based material 112 is subjected to dispersion treatment to obtain the silicon-based material 112 with good dispersibility, the nanoscale coating particles 114 are coated on the surface of the silicon-based material 112 in an atomic layer deposition mode to form the coating layer 113 which is thin in thickness and uniform in coating, the thickness of the coating layer 113 can be 0.1-10 nm, the coating layer 113 can effectively coat the silicon-based material 112, the coating particles 114 are uniformly coated on the surface of the silicon-based material 112, and therefore the effects of restraining the silicon-based material 112 to expand and increase and isolating the silicon-based material 112 from contacting with the outside are achieved, and the circulation stability of the silicon-based anode material 11 is improved; the silicon-based material 112 may be subjected to a dispersion treatment to reduce the grain size of the silicon-based material 112, thereby increasing the coverage area for the silicon-based material 112, so that the cladding layer 113 may clad more of the silicon-based material 112, and thus, the cladding and protection for more of the silicon-based material 112 may be improved.
Example four: referring to fig. 19, the steps of the method for preparing the silicon-based anode material 11 at least include the following steps. It is to be understood that the present application is not limited to the specific order of the steps.
410: referring to fig. 4, a silicon-based material 112 is prepared.
Specifically, the silicon-based material 112 includes, but is not limited to, any one or combination of silicon-based particles, silicon-based nanowires, silicon-based nanotubes, and the like. Specifically, the silicon-based material 112 includes, but is not limited to, one or a combination of at least two of silicon nanowires, silicon magnesium material, silicon aluminum material, silicon magnesium-silicon aluminum, silicon carbon material, and silicon oxygen material.
In the present embodiment, the silicon-based material 112 is in the form of particles. The particle size of the silicon-based material 112 is 1 nm-50 um.
In preparing the silicon-based material 112, a powder or a solution of the silicon-based material 112, including a plurality of silicon-based materials 112, may be prepared.
420: a coated substrate is prepared such that the coated substrate includes a plurality of coated particles 114. Step 330 can be referred to in this step, and is not described in detail in this embodiment.
430: the silicon-based material 112 and the clad substrate are subjected to a surface active treatment.
The silicon-based material 112 is mixed with a first surfactant so that the surface of the silicon-based material 112 is positively or negatively charged.
After the preparing the clad substrate, comprising: the coated particles 114 are mixed with a second surfactant to charge the surface of the coated particles 114 with a charge having a polarity opposite to that of the surface of the silicon-based material 112.
Alternatively, the first surfactant may be a positively charged surfactant to impart a positive charge to the surface of the silicon-based material 112; the second surfactant may be a negatively charged surfactant to negatively charge the surface of the coated particles 114. Specifically, the solution of the silicon-based material 112 may be mixed with a first surfactant aqueous solution, and after ultrasonic oscillation for 1 to 30 minutes, the silicon-based material 112 with positive charges may be obtained after washing and drying with deionized water. The coated substrate solution may be mixed with a second surfactant aqueous solution, ultrasonically oscillated for 1-30min, washed with deionized water, and dried to obtain negatively charged coated particles 114.
Alternatively, the first surfactant may be a negatively charged surfactant to negatively charge the surface of the silicon-based material 112; the second surfactant may be a positively charged surfactant to impart a positive charge to the surface of the coated particles 114.
The positive charge surfactant includes, but is not limited to, one or more of cetyltrimethylammonium bromide, dimethylbenzyldodecylammonium bromide, benzyltriethylammonium chloride, octadecyltrimethylammonium chloride, benzalkonium bromide, N-dimethyldodecylamine, 3-aminopropyltrimethoxysiloxane, 3-aminopropyltriethoxysiloxane, silicone quaternary ammonium salts, bisimidazoline quaternary ammonium salts, lauramidopropyl sulfate ammonium, cationic polyacrylamide, PVP-Q cationic copolymer, polyethylene imine quaternary ammonium salts, aliphatic triethanolamine acetate, dodecylamine acetate, quaternized panthenol, polydiallyldimethylammonium chloride, diethylaminoethyl acrylate ammonium chloride, dimethyldiallylammonium chloride, and ammonium chloride.
Negatively charged surfactants include, but are not limited to, one or more of p-methylstyrene sulfonate, polystyrene sulfonate, dodecyl diphenyl oxide disulfonate, sodium 3-chloro-2-hydroxypropanesulfonate, polyether carboxylic acid surfactants, carboxymethylcellulose salts, fatty carboxylates, alkyl phosphate hydroxyethyl ethers, alkoxy phosphates, allyl alcohol ether phosphates, dialkyl phosphates, alkyl sulfonated succinic acid monoester disodium salt, sodium hexanyl succinic amide sulfonate, acrylic acid-propylene sulfonic acid-isopropenyl phosphoric acid copolymer, polyacrylamide.
One surfactant is arranged on the surface of the silicon-based material 112, so that the adjacent silicon-based material 112 particles cannot be agglomerated due to charge repulsion, the other surfactant is arranged on the surface of the coating particle 114, so that the adjacent coating particles 114 cannot be agglomerated due to charge repulsion, the charges on the surface of the silicon-based material 112 particles and the charges on the surface of the coating particle 114 attract each other, so that the coating particle 114 can be more easily coated on the surface of the silicon-based material 112 due to charge attraction in the subsequent process, and the coating rate of the coating particle 114 on the silicon-based material 112 is higher.
440: depositing a plurality of coating particles 114 on the outer surface of the silicon-based material 112 by an atomic layer deposition process to form a coating layer 113, wherein the thickness of the coating layer 113 is 0.1-10 nm to form the silicon-based composite particles 111. The plurality of silicon-based composite particles 111 form the silicon-based anode material 11. Step 230 can be referred to in this step, and is not described in detail in this embodiment.
In the preparation method of the silicon-based anode material 11 provided by the embodiment of the application, after the silicon-based material 112 is prepared, the surface active treatment is performed on the silicon-based material 112 to obtain the silicon-based material 112 with good dispersibility and small particle size, the surface active treatment is performed on the coating substrate to obtain the coating particles 114 with good dispersibility and small particle size, when the nanoscale coating particles 114 are coated on the surface of the silicon-based material 112 in an atomic layer deposition manner, charges on the surface of the coating particles 114 are attracted to charges on the surface of the silicon-based material 112, so that the coating particles 114 can more easily form a uniform and thin coating layer 113 on the surface of the silicon-based material 112, the thickness of the coating layer 113 can be 0.1-10 nm, the coating layer 113 can effectively coat the silicon-based material 112, and the coating particles 114 are uniformly coated on the surface of the silicon-based material 112, thereby realizing the effects of restraining the silicon-based material 112 from expanding and isolating, the cycling stability of the silicon-based anode material 11 is improved.
Example five: referring to fig. 20, the steps of the method for preparing the silicon-based anode material 11 at least include the following steps. It is to be understood that the present application is not limited to the specific order of the steps.
510: referring collectively to fig. 4, a silicon-based material 112 is prepared.
Specifically, the silicon-based material 112 includes, but is not limited to, any one or combination of silicon-based particles, silicon-based nanowires, silicon-based nanotubes, and the like. Specifically, the silicon-based material 112 includes, but is not limited to, one or a combination of at least two of silicon nanowires, silicon magnesium material, silicon aluminum material, silicon magnesium-silicon aluminum, silicon carbon material, and silicon oxygen material.
In the present embodiment, the silicon-based material 112 is in the form of particles. The particle size of the silicon-based material 112 is 1 nm-50 um.
In preparing the silicon-based material 112, a powder or a solution of the silicon-based material 112, including a plurality of silicon-based materials 112, may be prepared.
520: a coated substrate is prepared such that the coated substrate includes a plurality of coated particles 114. Step 330 can be referred to in this step, and is not described in detail in this embodiment.
530: referring to fig. 5 and 6 in combination, the surface roughness treatment is performed on the silicon-based material 112. The silicon-based material 112 is reacted with a reaction solution, so that a part of the surface of the silicon-based material 112 is corroded to form a plurality of first concave holes 115.
540: depositing a plurality of coating particles 114 on the outer surface of the silicon-based material 112 by an atomic layer deposition process to form a coating layer 113, wherein the thickness of the coating layer 113 is 0.1-10 nm to form the silicon-based composite particles 111. The plurality of silicon-based composite particles 111 form the silicon-based anode material 11.
Depositing a plurality of the coated particles 114 on the outer surface of the silicon-based material 112 by an atomic layer deposition process, including: a plurality of the coating particles 114 are deposited on the outer surface of the silicon-based material 112 by an atomic layer deposition process, so that at least part of the coating particles 114 are embedded in the first concave hole 115.
When the coating particles 114 are disposed on the surface of the silicon-based material 112 by atomic layer deposition, a portion of the coating particles 114 may be embedded or filled in the first recess hole 115, and another portion of the coating particles 114 is disposed outside the first recess hole 115 and coated on the silicon-based material 112, so that a mutually embedded coating relationship is formed between the coating layer 113 and the silicon-based material 112, thereby improving the coating bonding performance between the coating layer 113 and the silicon-based material 112.
The first recess hole 115 of the outer surface of the silicon-based material 112 may be a micro-hole. The size of the micropores may be 1nm or less or several nanometers. Alternatively, the first recess 115 may be formed by etching a portion of silicon on the surface of the silicon-based material 112. Specifically, the silicon-based material 112 is reacted with a reaction solution, and the concentration, reaction time, reaction temperature, and the like of the reaction solution are controlled, so that a plurality of first concave holes 115 are formed in the surface of the silicon-based material 112. Wherein the reaction solution can be hydrofluoric acid, alkali solution, etc.
Optionally, the composition of the silicon-based material 112 includes a metal. Specifically, the silicon-based material 112 may be a silicon-containing alloy or a silicon-containing alloy composite material. For example, the silicon-based material 112 includes, but is not limited to, a silicon-magnesium material, a silicon-aluminum material, a silicon-nickel material, a silicon-copper material, and the like. The first recess hole 115 may be formed by etching a portion of metal on the surface of the silicon-based material 112. By reacting the silicon-based material 112 with the reaction solution, the concentration, reaction time, reaction temperature, and the like of the reaction solution are controlled, so that a plurality of first concave holes 115 are formed on the surface of the silicon-based material 112. Wherein the reaction solution can be acid solution, alkali solution, etc.
In one embodiment, with reference to fig. 8 in combination, the silicon-based material 112 includes a silicon-based core 116 and a metal or metal oxide shell 117 encasing the silicon-based core 116. The first concave hole 115 is formed in the outer surface of the metal shell or the metal oxide shell 117.
Specifically, the silicon-based material 112 may include a silicon-based core 116, the silicon-based core 116 including, but not limited to, silicon nanowires, silicon carbon materials, silicon oxygen materials, and the like. The silicon-based material 112 may include a metal shell or metal oxide shell 117 encased in a silicon-based core 116. The thickness of the shell layer coated on the silicon-based core 116 can be 0.1-10 nm.
The material of the metal shell includes but is not limited to magnesium, aluminum, copper, tweezers and other materials. The material of the metal oxide shell 117 includes, but is not limited to, aluminum oxide, titanium oxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, tin oxide, silicon oxide, magnesium oxide, or a combination thereof. The concentration, reaction time, reaction temperature, and the like of the reaction liquid are controlled by reacting the metal shell of the silicon-based material 112 with the reaction liquid, so that a plurality of first recesses 115 are formed on the surface of the metal shell. Wherein the reaction solution can be acid solution, alkali solution, etc.
The shell layer is arranged outside the silicon-based core 116 and can be metal or metal oxide, the shell layer of the silicon-based material 112 can react with the reaction liquid to form a plurality of first concave holes 115 on the outer surface of the shell layer, the coating particles 114 are arranged on the silicon-based material 112 in an atomic layer deposition mode to enable the coating particles 114 to coat the outer surface of the silicon-based material 112, and the coating layer 113 and the shell layer can separate the silicon-based core 116 from the electrolyte in the battery 40, so that the effects of restricting the expansion and increase of the silicon-based core 116 and isolating the silicon-based core 116 from contacting with the outside are achieved, the cycle stability of the silicon-based anode material 11 is improved, when the silicon-based material 112 is applied to the battery 40, the specific discharge capacity of the battery 40 can be improved, the cycle performance of the battery 40 is improved, and the capacity retention rate of the battery.
Further, referring to fig. 9 in combination, the clad layer 113 includes a first clad layer 118 and a second clad layer 119. The first cladding layer 118 is coated on the outer surface of the silicon-based material 112. The first concave hole 115 can be formed in the surface of the silicon-based material 112, so that the first coating layer 118 is arranged in the first concave hole 115, the bonding strength between the first coating layer 118 and the silicon-based material 112 is improved, and the binding strength of the first coating layer 118 to the silicon-based material 112 and the protection performance of blocking the silicon-based material 112 from contacting with the outside are improved.
The outer surface of the first cladding layer 118 has a plurality of second recesses 120, and the second cladding layer 119 is at least partially disposed within the second recesses 120.
Specifically, the materials of the first cladding layer 118 and the second cladding layer 119 may be the same or different. Optionally, the material of the first cladding layer 118 is different from that of the second cladding layer 119. For example, the material of the first coating layer 118 is metal oxide or metal, and the material of the second coating layer 119 is carbon, graphite, graphene, carbon nanotube, sulfide, fluoride, or the like.
In one embodiment, the first cladding layer 118 is formed by atomic layer deposition to cover the outer surface of the silicon-based material 112, so as to form a thin and uniform film for first layer protection of the silicon-based material 112. The first coating layer 118 is made of metal oxide or metal, a plurality of second concave holes 120 can be formed in the outer surface of the first coating layer 118 in a reaction liquid corrosion mode, and then the second coating layer 119 is coated on the outer surface of the silicon-based material 112 in an atomic layer deposition mode to form a thin and uniform coating film layer so as to perform second-layer protection on the silicon-based material 112. The second cladding layer 119 may be at least partially embedded in the second recess 120 of the first cladding layer 118, so that the bonding strength between the first cladding layer 118 and the second protective layer is good, and the protection performance for the silicon-based material 112 is further improved.
According to the preparation method of the silicon-based anode material 11 provided by the embodiment of the application, after the silicon-based material 112 is prepared, the first concave hole 115 is formed in the surface of the silicon-based material 112, the nanoscale coating particles 114 are coated on the surface of the silicon-based material 112 in an atomic layer deposition mode, so that the coating particles 114 are at least partially arranged in the first concave hole 115, the bonding force between the coating layer 113 and the silicon-based material 112 is further improved, the coating layer 113 can effectively coat the silicon-based material 112, the coating particles 114 are uniformly coated on the surface of the silicon-based material 112, the effects of restricting the expansion of the silicon-based material 112 and isolating the silicon-based material 112 from being contacted with the outside are achieved, and the circulation stability of the silicon-based anode.
While the foregoing is directed to embodiments of the present application, it will be appreciated by those skilled in the art that various changes and modifications may be made without departing from the principles of the application, and it is intended that such changes and modifications be covered by the scope of the application.
Claims (16)
1. The silicon-based anode material is characterized by comprising a plurality of silicon-based composite particles, wherein the silicon-based composite particles comprise a silicon-based material and a coating layer, the coating layer comprises a plurality of coating particles, and the coating particles are coated on at least part of the surface of the silicon-based material through atomic layer deposition.
2. The silicon-based negative electrode material as claimed in claim 1, wherein the outer surface of the silicon-based material has a plurality of first recesses, and at least a portion of the cladding layer is disposed in the first recesses.
3. The silicon-based negative electrode material as claimed in claim 2, wherein the composition of the silicon-based material comprises metal, and the first recess is formed by etching a part of the metal or silicon on the surface of the silicon-based material.
4. The silicon-based negative electrode material as claimed in claim 2 or 3, wherein the silicon-based material comprises a silicon-based core and a metal shell or a metal oxide shell covering the silicon-based core, and the first recess is formed in an outer surface of the metal shell or the metal oxide shell.
5. The silicon-based negative electrode material of claim 1 or 2, wherein the cladding layer comprises a first cladding layer and a second cladding layer, the first cladding layer is clad on the silicon-based material, the outer surface of the first cladding layer is provided with a plurality of second concave holes, and the second cladding layer is at least partially arranged in the second concave holes.
6. The silicon-based negative electrode material of claim 1, wherein the silicon-based material is in a granular form, and the particle size of the silicon-based material is 1nm to 50 um; the thickness of the coating layer is 0.1-10 nm.
7. The silicon-based anode material of claim 1, wherein the silicon-based material comprises one or a combination of at least two of silicon nanowires, silicon magnesium-silicon aluminum, silicon carbon material, and silicon oxygen material.
8. The silicon-based anode material of claim 1, wherein the coating particles comprise one or a combination of at least two of carbon, graphite, graphene, carbon nanotubes, oxides, sulfides, fluorides.
9. A battery negative pole piece is characterized in that the silicon-based negative pole material of any one of claims 1 to 8 is coated on a negative pole current collector to obtain the battery negative pole piece.
10. A battery comprising the negative electrode tab of claim 9.
11. An electronic device characterized by comprising the battery of claim 10.
12. A preparation method of a silicon-based negative electrode material is characterized by comprising the following steps:
preparing a silicon-based material;
preparing a coated substrate, wherein the coated substrate comprises a plurality of coated particles;
depositing a number of the coating particles on the outer surface of the silicon-based material by atomic layer deposition to form a coating layer.
13. The method of claim 12, further comprising, after said preparing the silicon-based material:
and carrying out surface active treatment and/or surface roughness treatment on the silicon-based material.
14. The method according to claim 13, wherein the subjecting the silicon-based material to a surface activation treatment and/or a surface roughness treatment comprises:
mixing the silicon-based material with a first surfactant to make the surface of the silicon-based material have positive or negative charges;
after the preparing the clad substrate, comprising:
mixing the coated particles with a second surfactant to charge the surface of the coated particles with a charge having a polarity opposite to the charge of the surface of the silicon-based material.
15. The method according to claim 13 or 14, wherein the subjecting the silicon-based material to a surface activation treatment and/or a surface roughness treatment comprises:
reacting the silicon-based material with a reaction solution to corrode part of the surface of the silicon-based material to form a plurality of concave holes;
depositing a plurality of the coated particles on the outer surface of the silicon-based material by an atomic layer deposition process, comprising:
and depositing a plurality of coating particles on the outer surface of the silicon-based material by an atomic layer deposition process, so that at least part of the coating particles are embedded in the concave hole.
16. The method of claim 12, wherein the preparing the clad substrate further comprises, after:
dissolving the coated substrate in a solvent to form a coated substrate solution;
depositing a plurality of the coating particles on an outer surface of the silicon-based material by an atomic layer deposition process to form a coating layer, comprising:
arranging the silicon-based material in a reaction chamber of atomic layer deposition equipment, raising the temperature of the reaction chamber to a preset temperature, and raising the pressure of the reaction chamber to a first preset pressure;
arranging the coating substrate solution in the reaction chamber, and maintaining the first preset pressure;
raising the pressure of the reaction chamber to a second preset pressure so as to remove the solvent in the coating substrate solution;
depositing a plurality of the coating particles on an outer surface of the silicon-based material to form a coating.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112978803A (en) * | 2021-02-23 | 2021-06-18 | 四川大学 | Preparation method of water-soluble superparamagnetic ferroferric oxide microspheres with positively charged surfaces |
| CN114503305A (en) * | 2021-03-31 | 2022-05-13 | 宁德新能源科技有限公司 | Negative electrode active material, electrochemical device and electronic device |
| CN117476920A (en) * | 2023-12-28 | 2024-01-30 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| WO2024098352A1 (en) * | 2022-11-11 | 2024-05-16 | 宁德时代新能源科技股份有限公司 | Negative electrode active material and preparation method therefor, secondary battery and preparation method therefor, and electrical device |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101849306A (en) * | 2007-09-06 | 2010-09-29 | 佳能株式会社 | Method for producing lithium ion storage/release material, lithium ion storage/release material, electrode structure using the material, and electricity storage device |
| CN103151503A (en) * | 2012-12-10 | 2013-06-12 | 昆明理工大学 | Lithium ion battery silicon substrate composite negative electrode materials and preparation method thereof |
| CN104521036A (en) * | 2012-06-18 | 2015-04-15 | 斯拉纳米技术有限公司 | Multi-shell structures for battery active materials with expansion properties |
| KR20150098453A (en) * | 2014-02-20 | 2015-08-28 | 주식회사 엘지화학 | Surface coated porous silicon based anode active material, preparation method thereof, and lithium secondary battery comprising the same |
| CN106784763A (en) * | 2016-12-03 | 2017-05-31 | 合肥国轩高科动力能源有限公司 | Preparation method of porous oxide coated battery silicon negative electrode material |
| CN106876687A (en) * | 2017-04-28 | 2017-06-20 | 无锡德碳科技股份有限公司 | A kind of preparation method of carbon coating silicon quantum dot composite lithium ion battery cathode material |
| CN107623104A (en) * | 2017-09-25 | 2018-01-23 | 常州市宇科不绣钢有限公司 | A kind of structure silicon-based negative material of multi-buffer and preparation method thereof |
| CN108023074A (en) * | 2017-11-29 | 2018-05-11 | 上海汽车集团股份有限公司 | A kind of silicon based composite material with nanometer hierarchical structure and its preparation method and application |
| CN108232141A (en) * | 2017-12-21 | 2018-06-29 | 中国科学院化学研究所 | A kind of silicon-carbon composite cathode material of lithium ion battery of high-pressure solid and preparation method thereof |
| CN109285994A (en) * | 2017-07-21 | 2019-01-29 | 天津大学 | The preparation method of lithium ion battery silicon-carbon cathode material |
| CN109616623A (en) * | 2018-10-31 | 2019-04-12 | 深圳市德方纳米科技股份有限公司 | A kind of silicon-based anode material and preparation method thereof |
| CN109686942A (en) * | 2018-12-21 | 2019-04-26 | 东北大学 | A kind of preparation method of silicon based anode material |
| CN109817949A (en) * | 2019-03-11 | 2019-05-28 | 清华大学 | Silicon or its oxide@titanium dioxide@carbon core-shell structure composite particles and preparation |
| CN109950515A (en) * | 2019-04-23 | 2019-06-28 | 清华大学 | A kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method thereof |
| CN110635115A (en) * | 2018-06-22 | 2019-12-31 | 东莞东阳光科研发有限公司 | Nano-silicon/graphite phase carbon nitride/graphite composite negative electrode material and preparation method thereof |
| CN111048756A (en) * | 2019-12-04 | 2020-04-21 | 兰溪致德新能源材料有限公司 | High-conductivity silica negative electrode material and application thereof |
-
2020
- 2020-09-29 CN CN202011056461.2A patent/CN112164780B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101849306A (en) * | 2007-09-06 | 2010-09-29 | 佳能株式会社 | Method for producing lithium ion storage/release material, lithium ion storage/release material, electrode structure using the material, and electricity storage device |
| CN104521036A (en) * | 2012-06-18 | 2015-04-15 | 斯拉纳米技术有限公司 | Multi-shell structures for battery active materials with expansion properties |
| CN103151503A (en) * | 2012-12-10 | 2013-06-12 | 昆明理工大学 | Lithium ion battery silicon substrate composite negative electrode materials and preparation method thereof |
| KR20150098453A (en) * | 2014-02-20 | 2015-08-28 | 주식회사 엘지화학 | Surface coated porous silicon based anode active material, preparation method thereof, and lithium secondary battery comprising the same |
| CN106784763A (en) * | 2016-12-03 | 2017-05-31 | 合肥国轩高科动力能源有限公司 | Preparation method of porous oxide coated battery silicon negative electrode material |
| CN106876687A (en) * | 2017-04-28 | 2017-06-20 | 无锡德碳科技股份有限公司 | A kind of preparation method of carbon coating silicon quantum dot composite lithium ion battery cathode material |
| CN109285994A (en) * | 2017-07-21 | 2019-01-29 | 天津大学 | The preparation method of lithium ion battery silicon-carbon cathode material |
| CN107623104A (en) * | 2017-09-25 | 2018-01-23 | 常州市宇科不绣钢有限公司 | A kind of structure silicon-based negative material of multi-buffer and preparation method thereof |
| CN108023074A (en) * | 2017-11-29 | 2018-05-11 | 上海汽车集团股份有限公司 | A kind of silicon based composite material with nanometer hierarchical structure and its preparation method and application |
| CN108232141A (en) * | 2017-12-21 | 2018-06-29 | 中国科学院化学研究所 | A kind of silicon-carbon composite cathode material of lithium ion battery of high-pressure solid and preparation method thereof |
| CN110635115A (en) * | 2018-06-22 | 2019-12-31 | 东莞东阳光科研发有限公司 | Nano-silicon/graphite phase carbon nitride/graphite composite negative electrode material and preparation method thereof |
| CN109616623A (en) * | 2018-10-31 | 2019-04-12 | 深圳市德方纳米科技股份有限公司 | A kind of silicon-based anode material and preparation method thereof |
| CN109686942A (en) * | 2018-12-21 | 2019-04-26 | 东北大学 | A kind of preparation method of silicon based anode material |
| CN109817949A (en) * | 2019-03-11 | 2019-05-28 | 清华大学 | Silicon or its oxide@titanium dioxide@carbon core-shell structure composite particles and preparation |
| CN109950515A (en) * | 2019-04-23 | 2019-06-28 | 清华大学 | A kind of Silicon Based Anode Materials for Lithium-Ion Batteries and preparation method thereof |
| CN111048756A (en) * | 2019-12-04 | 2020-04-21 | 兰溪致德新能源材料有限公司 | High-conductivity silica negative electrode material and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JAEWOOK SHIN: "Agglomeration Mechanism and a Protective Role of Al2O3 for Prolonged Cycle Life of Si Anode in Lithium-Ion Batteries", 《CHEMISTRY OF MATERIALS》 * |
| JAEWOOK SHIN: "Agglomeration Mechanism and a Protective Role of Al2O3 for Prolonged Cycle Life of Si Anode in Lithium-Ion Batteries", 《CHEMISTRY OF MATERIALS》, vol. 30, no. 10, 25 April 2018 (2018-04-25), pages 3233 * |
Cited By (5)
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|---|---|---|---|---|
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| CN114503305A (en) * | 2021-03-31 | 2022-05-13 | 宁德新能源科技有限公司 | Negative electrode active material, electrochemical device and electronic device |
| WO2022205151A1 (en) * | 2021-03-31 | 2022-10-06 | 宁德新能源科技有限公司 | Negative electrode active material, electrochemical apparatus, and electronic apparatus |
| WO2024098352A1 (en) * | 2022-11-11 | 2024-05-16 | 宁德时代新能源科技股份有限公司 | Negative electrode active material and preparation method therefor, secondary battery and preparation method therefor, and electrical device |
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