CN112397706A - Lithium ion battery cathode material structure, preparation method thereof and lithium ion battery - Google Patents
Lithium ion battery cathode material structure, preparation method thereof and lithium ion battery Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/386—Silicon or alloys based on silicon
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Abstract
The invention provides a lithium ion battery cathode material structure, a preparation method thereof and a lithium ion battery, wherein the preparation method comprises the following steps: 1) dispersing the nano silicon particles in an organic solvent to prepare a dispersion liquid; 2) providing a metal substrate, and coating the dispersion liquid on the upper surface of the metal substrate; 3) placing the structure obtained in the step 2) in a reaction device, introducing carbon source gas, and forming a three-dimensional graphene nano-silicon composite layer on the surface of the metal substrate by adopting a plasma enhanced chemical vapor deposition process, wherein the three-dimensional graphene nano-silicon composite layer comprises nano-silicon particles and a graphene layer positioned between the surfaces of the nano-silicon particles and the nano-silicon particles. The invention adopts the commercial nano silicon particles which are simple and easy to obtain as the effective lithium storage medium of the composite cathode; meanwhile, the plasma enhanced chemical vapor deposition method is adopted to realize the compounding of high-quality nano silicon and three-dimensional graphene, and the high-performance and high-stability lithium ion battery cathode material can be prepared.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a lithium ion battery cathode material structure, a preparation method thereof and a lithium ion battery based on the lithium ion battery cathode material.
Background
The lithium ion battery consists of a negative electrode, electrolyte, a diaphragm and a positive electrode. The negative electrode material is a very important part of the lithium ion battery, and the indexes for measuring the quality of the negative electrode material mainly comprise: the lithium ions can be reversibly inserted and extracted in the negative electrode; the negative electrode potential is lower after the lithium ions are embedded; the conductivity is good; in the charging and discharging process, the material can not be damaged and denatured; can form a better Solid Electrolyte Interface (SEI) film with an electrolyte solution; environment-friendly, low cost, easy preparation and the like.
Currently, negative electrode materials used for lithium ion batteries are roughly classified into carbon-based negative electrode materials, alloy-based negative electrode materials, and metal oxide-based negative electrode materials. The carbon negative electrode material is the best lithium ion battery negative electrode material commercialized at present and most applied at present, and can be divided into two types of graphitized carbon materials and amorphous carbon materials, wherein the graphitized carbon negative electrode material only comprises natural graphite, artificial graphite and modified graphite, and the material has a good layered structure and can form Li after lithium ions are inserted into the materialxC6Interlayer compound with theoretical specific capacity of 372mAhg-1And the charge-discharge potential is lower (0.01-0.2V vs Li)+/Li), no charging voltage hysteresis (see paper for details: dahn, J.R., et al, "Mechanisms for Lithium Insertion in Carbonic materials," Science 270.5236(1995): 590-. Amorphous carbon negative electrode materials can be divided into soft carbon and hard carbon according to the degree of graphitization difficulty, the lithium storage mechanism of the amorphous carbon negative electrode materials is different from that of graphite, the specific capacity of the amorphous carbon negative electrode materials is higher than that of graphite, such as carbon nano tubes, and the capacity of the amorphous carbon negative electrode materials can reach 650mAhg-1About twice as much as graphite and has good compatibility with electrolytes (see the article Schauerman, Christopher M., et al, "Recycling simple-wall carbon nanotubes elastomers from lithium batteries." Journal of Materials Chemistry 22.24(2012): 12008.). The metal oxide negative electrode materials can be classified into redox type, lithium intercalation type and alloy type according to the charging mechanism, and compared with graphite electrodes, the electrodes have higher discharge voltage,Good stability, low cost and good safety, but the specific capacity of the material is not high. The alloy type negative electrode material is a metal or semiconductor material capable of forming an alloy with lithium, mainly comprises silicon, tin, germanium, zinc and corresponding oxides thereof, lithium ions are inserted and removed through alloying and dealloying processes in the charging and discharging processes, and the material generally has a relatively high specific capacity, which is 783mAhg-1To 4200mAhg-1And not equal to, much higher than the graphite negative electrode commercialized today. Wherein, the theoretical specific capacity of the silicon material can reach 4200mAhg-1About ten times of the graphite electrode, which is the highest specific capacity of all the current cathode materials. However, the silicon negative electrode has large volume expansion and contraction in the charging and discharging processes, so that the negative electrode material is pulverized, and the reversible capacity is rapidly attenuated. On the other hand, the matching of silicon with the electrolyte solution is also poor, and it is difficult to maintain a stable solid electrolyte membrane. Currently, in order to better utilize silicon material in the negative electrode, various methods are used to improve the disadvantages of silicon material, and to make the cycling stability of the negative electrode better, including the Nano-silicon material, by reducing the silicon size to Nano-size to improve the problem of volume expansion (see paper: WuHui, and Yi Cui. "design nanostructured Si alloys for high energy consumption batteries." Nano Today 7.5(2012): 414) 429.); silicon thin film Materials and silicon-based Oxides, which are generally prepared by depositing a layer of silicon material on a current collector, can better release the volume effect during charging and discharging, and simultaneously realize good electrical contact between the silicon material and the current collector (see the paper: Poizot, P., et al. "ChemInform Abstract: Nano-Sized transformation-Metal Oxides as Negative-Electrode Materials for Lithium-Ion batteries." Nature 407.6803(2000):496 499.); the Silicon-carbon composite material uses a wrapping layer formed by a carbon material as a buffer layer to release volume change of the internal Silicon material during charging and discharging so as to achieve the purpose of inhibiting the volume change, and simultaneously utilizes good conductivity of the carbon material to improve the conductivity of the composite electrodebase lithium-ion base animals A chloride permanent review. "Nano Energy 31.Complete (2017): 113-143.). Among them, graphene materials are concerned about in the application of electrode materials of lithium ion batteries due to their unique advantages of electrical conductivity, chemical stability, specific surface area, etc., for example, patent publication No. CN109950544A describes that a graphene film is directly deposited on a substrate as a current collector of a lithium ion positive electrode material, but such materials still have the problems of insufficient adhesion between the graphene film and the substrate and process matching, and meanwhile, graphene is more applied to negative electrode materials in combination with silicon materials, but it is difficult to achieve a good balance in the aspects of preparation process, specific capacity, reversibility, safety, etc., and still has disadvantages.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a method for preparing a negative electrode material structure of a lithium ion battery with a relatively simple preparation process, and a negative electrode material structure of a lithium ion battery and a lithium ion battery thereof with high specific capacity, high reversible stability and the like.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing a negative electrode material structure of a lithium ion battery, the method comprising the steps of:
1) dispersing the nano silicon particles in an organic solvent to prepare a dispersion liquid;
2) providing a metal substrate, and coating the dispersion liquid on the upper surface of the metal substrate;
3) placing the structure obtained in the step 2) in a reaction device, introducing carbon source gas, and forming a three-dimensional graphene nano-silicon composite layer on the surface of the metal substrate by adopting a plasma enhanced chemical vapor deposition process, wherein the three-dimensional graphene nano-silicon composite layer comprises nano-silicon particles and a graphene layer positioned between the surfaces of the nano-silicon particles and the nano-silicon particles.
Optionally, the step 1) further comprises adding an auxiliary dispersant to prepare the dispersion liquid, wherein the auxiliary dispersant comprises carbon nanotubes; the method also comprises the step of carrying out ultrasonic treatment after the auxiliary dispersant is added.
Optionally, before applying the dispersion to the upper surface of the metal substrate, the method further includes a step of pretreating the metal substrate, where the pretreatment includes:
carrying out ultrasonic cleaning on the metal substrate in acetone and isopropanol in sequence;
polishing the metal substrate to improve the surface flatness of the metal substrate;
and cleaning and drying the metal substrate.
Optionally, in step 1), the organic solvent comprises one or more of N-methylpyrrolidone, ethanol and isopropanol; in the step 2), the metal substrate is made of one or at least two alloy materials of gold, platinum, palladium, iridium, ruthenium, nickel and copper, or a metal foil substrate material with the metal plating layer or the alloy plating layer; the carbon source gas in the step 3) comprises one or more of methane, ethylene, acetylene, ethanol and cyclohexane.
Optionally, in the step 1), the diameter of the nano silicon particles is 30-200 nm.
Optionally, in the step 2), after the dispersion liquid is coated on the upper surface of the metal substrate, a step of placing the metal substrate coated with the dispersion liquid in an oven for drying is further included, and the drying time is 5-10 min.
Optionally, the reaction device comprises a radio frequency plasma vapor deposition device, a direct current discharge plasma vapor deposition device or a microwave plasma vapor deposition device.
Optionally, in the chemical vapor deposition process in the step 3), the plasma power is 100-500W, the process temperature is 600-1000 ℃, and the process time is 30 s-60 min.
Optionally, the vapor deposition process is performed under a reducing gas atmosphere, and the reducing gas is hydrogen, a mixed gas of hydrogen and nitrogen, or a mixed gas of hydrogen and argon.
The invention also provides a lithium ion battery cathode material structure which is prepared based on the preparation method in any one of the schemes, the lithium ion battery cathode material comprises a metal substrate and a three-dimensional graphene nano-silicon composite layer, the three-dimensional graphene nano-silicon composite layer is positioned on the surface of the metal substrate, and the three-dimensional graphene nano-silicon composite layer comprises nano-silicon particles and a graphene layer positioned between the surface of the nano-silicon particles and the nano-silicon particles.
The invention also provides a lithium ion battery, which comprises the lithium ion battery negative electrode material in the scheme.
As mentioned above, the preparation method of the lithium ion battery cathode material of the invention adopts the simple and easily obtained commercialized nano silicon particles as the effective lithium storage medium of the composite cathode, and the nano silicon particle material has high-capacity lithium storage capacity and can effectively resist the volume change generated by the silicon material in the charging and discharging process; meanwhile, the invention adopts a Plasma-Enhanced Chemical Vapor Deposition (PECVD) method to realize the compounding of high-quality nano silicon and three-dimensional graphene, the graphene grows on the surface of the nano silicon particles, the nano silicon particles are coated, the graphene continues to grow to be expanded from the surface of the nano silicon particles to the space and is mutually branched to form a three-dimensional graphene framework, the stable preparation of the composite cathode can be realized through the regulation and control of process conditions, and the preparation method is simple and efficient. The lithium ion battery cathode material prepared based on the preparation method provided by the invention has high-capacity lithium storage capacity and also has extremely high stability and ultrastrong reversibility. The capacity and the safety performance of the lithium ion battery prepared based on the lithium ion electrode cathode material can be obviously improved.
Drawings
Fig. 1 shows a flow chart of a method for preparing a structure of a lithium ion battery negative electrode material according to the present invention.
Fig. 2 is a scanning electron microscope image of nano silicon particles after the dispersion liquid is coated on the surface of the metal substrate in the preparation method according to the present invention.
FIG. 3 is a scanning electron microscope image of the structure of the lithium ion battery cathode material prepared by the preparation method of the invention.
Fig. 4 is a raman spectrum of three-dimensional graphene in a three-dimensional graphene nano-silicon composite layer of a lithium ion battery negative electrode material structure prepared according to the preparation method of the present invention.
Description of the element reference numerals
S1-S3
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1 to 4. It should be noted that the drawings provided in the present embodiment are only schematic and illustrative of the basic idea of the present invention, and only the components related to the present invention are shown in the drawings rather than being drawn according to the number, shape and size of the components in actual implementation, and the form, quantity and proportion of the components in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
Referring to fig. 1, the present invention provides a method for preparing a negative electrode material structure of a lithium ion battery, including the following steps:
s1: dispersing the nano silicon particles in an organic solvent to prepare a dispersion liquid;
s2: providing a metal substrate, and coating the dispersion liquid on the upper surface of the metal substrate;
s3: and (4) placing the structure obtained in the step (S2) in a reaction device, introducing carbon source gas, and forming a three-dimensional graphene nano-silicon composite layer on the surface of the metal substrate by adopting a plasma enhanced chemical vapor deposition process, wherein the three-dimensional graphene nano-silicon composite layer comprises the nano-silicon particles and a graphene layer positioned between the surface of the nano-silicon particles and the nano-silicon particles.
The preparation method of the lithium ion battery cathode material adopts the simple and easily obtained commercialized nano silicon particles as the effective lithium storage medium of the composite cathode, and the nano silicon particle material has high-capacity lithium storage capacity and can effectively resist the volume change generated by the silicon material in the charging and discharging process; meanwhile, the invention adopts a Plasma-Enhanced Chemical Vapor Deposition (PECVD) method to realize the compounding of high-quality nano silicon and three-dimensional graphene, the graphene grows on the surface of the nano silicon particles, the nano silicon particles are coated, the graphene continues to grow to be expanded from the surface of the nano silicon particles to the space and is mutually branched to form a three-dimensional graphene framework, the stable preparation of the composite cathode can be realized through the regulation and control of process conditions, and the preparation method is simple and efficient. The preparation method can be used for preparing the lithium ion battery cathode material with high performance and high stability.
Illustratively, the diameter of the nano silicon particles is 30 to 200nm, preferably 30 to 100nm, and more preferably 30 to 50nm, so that the nano silicon particles can be more uniformly dispersed in the organic solvent.
As an example, the organic solvent includes one or more of N-methylpyrrolidone, ethanol, and isopropanol, and when the organic solvent is a mixed solvent of a plurality of chemical solvents, the plurality of chemical solvents are mutually soluble with each other to maximally ensure uniform dispersion of the nano silicon particles. A single solvent, such as N-methyl pyrrolidone, is preferred in this embodiment, because N-methyl pyrrolidone is a colorless transparent oily liquid, and has the advantages of low volatility, good thermal stability and chemical stability, and the like, and is suitable for uniform dispersion of the nano silicon particles.
In order to enable the nano silicon particles to be dispersed more uniformly, as an example, an auxiliary dispersant is further added in the step 1) to prepare the dispersion liquid, the auxiliary dispersant includes a carbon nanotube, or two or more of a carbon nanotube, a carbon nanofiber, a graphene powder or a fullerene, and after the auxiliary dispersant is added, ultrasonic treatment can be performed until a stable and uniform dispersion liquid is formed. The content of the auxiliary dispersant in the dispersion liquid is less than that of the nano silicon particles, for example, the mass percentage of the auxiliary dispersant in the dispersion liquid is less than 10% of that of the nano silicon particles, so as to ensure that the finally prepared lithium ion battery negative electrode material structure has good specific capacity.
The material of the metal substrate is, for example, one or an alloy material of at least two of gold, platinum, palladium, iridium, ruthenium, nickel, and copper, or a metal foil substrate material having the above metal plating layer or alloy plating layer, for example, the metal substrate may be a copper foil with good conductivity, or a composite base structure with a metal copper layer plated on the surface of another metal base.
As an example, the dispersion may be applied to the upper surface of the metal substrate using one or more of dip-coating, spin-coating, doctor-blading, spray-coating, wet-coating, screen-printing, roll-coating, or plate-coating.
As an example, before the dispersion is coated on the upper surface of the metal substrate, the method further includes a step of pretreating the metal substrate, and the pretreatment includes:
carrying out ultrasonic cleaning on the metal substrate in acetone and isopropanol in sequence;
polishing the metal substrate to remove the surface roughness of the metal substrate and improve the surface flatness of the metal substrate; for example, putting the mixture into an orthophosphoric acid solution, and carrying out electrochemical polishing under the condition of 2-5V voltage for 3-10 min; alternatively, the chemical polishing may be performed by using acetic acid, nitric acid or hydrochloric acid, which is not limited in this embodiment.
The metal substrate is cleaned and dried, such as by rinsing with deionized water, and then blown dry with nitrogen or other inert gas to ensure cleanliness of the metal substrate surface.
As an example, in step S2, after the dispersion liquid is coated on the upper surface of the metal substrate, the method further includes a step of drying the metal substrate coated with the dispersion liquid in an oven, wherein the drying time is 5-10 min, so as to accelerate the volatilization of the organic solvent, so that the nano silicon particles can be uniformly fixed on the surface of the metal substrate, and after the treatment, a scanning electron microscope image of the nano silicon particles on the surface of the metal substrate is shown in fig. 2. As can be seen from the figure, the nano silicon particles are uniformly dispersed on the surface of the metal substrate, and no agglomeration phenomenon occurs, which lays a solid foundation for the subsequent growth of three-dimensional graphene and the formation of a stable structure.
The carbon source gas in step S3 includes one or more of methane, ethylene, acetylene, ethanol, and cyclohexane, and in order to prevent impurity gases such as oxygen from being mixed into the chemical vapor deposition process to cause oxidation contamination, the chemical vapor deposition process is performed under a reducing gas atmosphere, and the reducing gas is hydrogen, a mixed gas of hydrogen and nitrogen, or a mixed gas of hydrogen and argon, for example. Meanwhile, in the process of introducing the carbon source gas to carry out the chemical deposition process, the introduced reducing gas can also be used as a carrier gas, so that the carbon source gas is more uniformly distributed in the reaction device.
As an example, the reaction apparatus includes a radio frequency plasma vapor deposition apparatus, a direct current discharge plasma vapor deposition apparatus, or a microwave plasma vapor deposition apparatus, and the reaction apparatus may be a plasma reaction apparatus having a dual temperature zone. Before the chemical vapor deposition process, the reaction apparatus is usually cleaned, for example, the pipes and the reaction chamber of the reaction apparatus are cleaned with hydrogen, after cleaning, the metal substrate is placed in the reaction apparatus, and the reducing gas is introduced before the formal chemical vapor deposition process is started to keep the reaction chamber in the reducing gas atmosphere. And then heating the metal substrate, introducing the carbon source gas after heating to 600-1000 ℃, carrying out plasma transformation on the carbon source gas by adopting the radio frequency power supply power of the reaction device so as to carry out a plasma enhanced chemical vapor deposition process on the surface of the metal substrate to form the three-dimensional graphene nano-silicon composite layer, and stopping heating after a preset process time so as to naturally cool the metal substrate. In the chemical vapor deposition process, the plasma power is 100-500W, the process temperature is 600-1000 ℃, and the process time is 30 s-60 min. In the chemical vapor deposition process, ionized carbon atoms are not only gathered on the surface of the nano silicon particles to generate graphene to coat the nano silicon particles, but also continuously penetrate into gaps of the nano silicon particles to be expanded from the surface of the nano silicon particles to the space and are mutually branched to form a three-dimensional graphene skeleton. This is different from the structure in which the graphene layer formed by the conventional atmospheric pressure chemical vapor deposition process is only located on the surface of the nano-silicon particles. Fig. 3 illustrates a scanning electron microscope structure of the three-dimensional graphene nano-silicon composite layer prepared by the preparation method of the invention. As can be seen from fig. 3, the nano silicon particles are not visible on the surface of the metal substrate, but only graphene with a three-dimensional structure is present, and the three-dimensional graphene is interconnected to form a three-dimensional skeleton network, so as to fully cover the nano silicon particles therein, and meanwhile, the three-dimensional skeleton network is helpful for absorbing the volume expansion of the nano silicon particles at the bottom during the charging and discharging processes, so as to maintain the structural integrity of the lithium ion battery cathode, and is beneficial for forming a stable SEI layer (solid electrolyte interface (film)), so as to improve the long-term cycling stability of the lithium ion battery cathode. On the other hand, graphene is also a good lithium storage medium as a two-dimensional carbon material, so that the three-dimensional graphene skeleton forms a large specific surface area while stabilizing the negative electrode structure, and has a certain lithium storage capacity, which further increases the negative electrode capacity of the lithium ion battery. Fig. 4 is a raman spectrum of three-dimensional graphene in the three-dimensional graphene nano-silicon composite layer of the lithium ion battery anode material prepared by the present invention, and it can be seen from fig. 4 that three characteristic peaks of graphene are obvious. The D peak represents the defect of the graphene, and the higher D peak in the invention comes from a large number of edge structures in the three-dimensional graphene structure; the intensity ratio of the 2D peak to the G peak is 1.71, which indicates that the prepared graphene has good quality.
The invention further provides a lithium ion battery cathode material structure, which is prepared based on any one of the preparation methods, so that the content related to the lithium ion battery cathode material structure is completely applicable to the structure. The lithium ion battery cathode material comprises a metal substrate and a three-dimensional graphene nano silicon composite layer positioned on the surface of the metal substrate, wherein the three-dimensional graphene nano silicon composite layer comprises nano silicon particles and a graphene layer positioned between the surfaces of the nano silicon particles and the nano silicon particles, and the nano silicon particles are positioned on the surface of the metal substrate. The lithium ion battery cathode material prepared based on the preparation method provided by the invention has high-capacity lithium storage capacity and also has extremely high stability and ultrastrong reversibility.
The present invention also provides a lithium ion battery, which includes the lithium ion battery negative electrode material as described in the foregoing scheme, besides, the lithium ion battery of the present application has no great difference in structure from the lithium ion battery of the prior art, and since the specific structure of the lithium ion battery is well known to those skilled in the art, the detailed description of the lithium ion battery is omitted here. The capacity and the safety performance of the lithium ion battery prepared based on the lithium ion electrode cathode material can be obviously improved.
As described above, the present invention provides a negative electrode material structure of a lithium ion battery, a method for preparing the same, and a lithium ion battery. The preparation method comprises the following steps: 1) dispersing the nano silicon particles in an organic solvent to prepare a dispersion liquid; 2) providing a metal substrate, and coating the dispersion liquid on the upper surface of the metal substrate; 3) placing the structure obtained in the step 2) in a reaction device, introducing carbon source gas, and forming a three-dimensional graphene nano-silicon composite layer on the surface of the metal substrate by adopting a plasma enhanced chemical vapor deposition process, wherein the three-dimensional graphene nano-silicon composite layer comprises nano-silicon particles and a graphene layer positioned between the surfaces of the nano-silicon particles and the nano-silicon particles. The preparation method of the lithium ion battery cathode material adopts the simple and easily obtained commercialized nano silicon particles as the effective lithium storage medium of the composite cathode, and the nano silicon particle material has high-capacity lithium storage capacity and can effectively resist the volume change generated by the silicon material in the charging and discharging process; meanwhile, the invention adopts a Plasma-Enhanced Chemical Vapor Deposition (PECVD) method to realize the compounding of high-quality nano-silicon and three-dimensional graphene, the graphene is grown on the surface of the nano-silicon particles, the nano-silicon is coated, the graphene is continuously grown to be expanded from the surface of the nano-silicon particles to the space and is mutually branched to form a three-dimensional graphene framework, the stable preparation of the composite cathode can be realized through the regulation and control of process conditions, and the preparation method is simple and efficient. The lithium ion battery cathode material prepared based on the preparation method provided by the invention has high-capacity lithium storage capacity and also has extremely high stability and ultrastrong reversibility. The capacity and the safety performance of the lithium ion battery prepared based on the lithium ion electrode cathode material can be obviously improved.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (11)
1. The preparation method of the lithium ion battery cathode material structure is characterized by comprising the following steps:
1) dispersing the nano silicon particles in an organic solvent to prepare a dispersion liquid;
2) providing a metal substrate, and coating the dispersion liquid on the upper surface of the metal substrate;
3) placing the structure obtained in the step 2) in a reaction device, introducing carbon source gas, and forming a three-dimensional graphene nano-silicon composite layer on the surface of the metal substrate by adopting a plasma enhanced chemical vapor deposition process, wherein the three-dimensional graphene nano-silicon composite layer comprises nano-silicon particles and a graphene layer positioned between the surfaces of the nano-silicon particles and the nano-silicon particles.
2. The method for preparing the negative electrode material structure of the lithium ion battery according to claim 1, wherein the method comprises the following steps: the step 1) further comprises adding an auxiliary dispersing agent to prepare the dispersion liquid, wherein the auxiliary dispersing agent comprises carbon nano tubes; the method also comprises the step of carrying out ultrasonic treatment after the auxiliary dispersant is added.
3. The method for preparing the negative electrode material structure of the lithium ion battery according to claim 1, wherein before the dispersion liquid is coated on the upper surface of the metal substrate, the method further comprises a step of pretreating the metal substrate, and the pretreatment comprises the following steps:
carrying out ultrasonic cleaning on the metal substrate in acetone and isopropanol in sequence;
polishing the metal substrate to improve the surface flatness of the metal substrate;
and cleaning and drying the metal substrate.
4. The method for preparing the negative electrode material structure of the lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step 1), the organic solvent comprises one or more of N-methyl pyrrolidone, ethanol and isopropanol; in the step 2), the metal substrate is made of one or at least two alloy materials of gold, platinum, palladium, iridium, ruthenium, nickel and copper, or a metal foil substrate material with the metal plating layer or the alloy plating layer; the carbon source gas in the step 3) comprises one or more of methane, ethylene, acetylene, ethanol and cyclohexane.
5. The method for preparing the negative electrode material structure of the lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step 1), the diameter of the nano silicon particles is 30-200 nm.
6. The method for preparing the negative electrode material structure of the lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step 2), after the dispersion liquid is coated on the upper surface of the metal substrate, the step of drying the metal substrate coated with the dispersion liquid in a drying oven is further included, and the drying time is 5-10 min.
7. The method for preparing the negative electrode material structure of the lithium ion battery according to claim 1, wherein the method comprises the following steps: the reaction device comprises a radio frequency plasma vapor deposition device, a direct current discharge plasma vapor deposition device or a microwave plasma vapor deposition device.
8. The method for preparing the negative electrode material structure of the lithium ion battery according to any one of claims 1 to 7, wherein:
in the chemical vapor deposition process in the step 3), the plasma power is 100-500W, the process temperature is 600-1000 ℃, and the process time is 30 s-60 min.
9. The method for preparing the negative electrode material structure of the lithium ion battery according to claim 8, wherein the method comprises the following steps: the vapor deposition process is carried out in a reducing gas atmosphere, wherein the reducing gas is hydrogen, a mixed gas of hydrogen and nitrogen or a mixed gas of hydrogen and argon.
10. A lithium ion battery negative electrode material structure is characterized in that the lithium ion battery negative electrode material structure is prepared based on the preparation method of any one of claims 1 to 9, and the lithium ion battery negative electrode material structure comprises:
a metal substrate;
the three-dimensional graphene nano-silicon composite layer is positioned on the surface of the metal substrate and comprises nano-silicon particles and a graphene layer positioned between the surface of the nano-silicon particles and the nano-silicon particles.
11. A lithium ion battery, characterized in that the lithium ion battery comprises the lithium ion battery negative electrode material according to claim 10.
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| US11633785B2 (en) | 2019-04-30 | 2023-04-25 | 6K Inc. | Mechanically alloyed powder feedstock |
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