CN107394138B - Lithium ion battery cathode material structure, lithium ion battery and preparation method thereof - Google Patents

Lithium ion battery cathode material structure, lithium ion battery and preparation method thereof Download PDF

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CN107394138B
CN107394138B CN201710537938.0A CN201710537938A CN107394138B CN 107394138 B CN107394138 B CN 107394138B CN 201710537938 A CN201710537938 A CN 201710537938A CN 107394138 B CN107394138 B CN 107394138B
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lithium ion
ion battery
negative electrode
silicon
electrode material
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CN107394138A (en
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方小红
尤莹
万吉祥
徐一麟
陈小源
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Pylon Technologies Co Ltd
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Shanghai Advanced Research Institute of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a lithium ion battery cathode material structure, a lithium ion battery and a preparation method thereof, wherein the preparation method comprises the following steps: 1) placing a silicon nano material, a carbon nano material and an additive in an organic solvent to prepare a dispersion liquid; 2) providing a metal catalytic substrate, and coating the dispersion on the upper surface of the metal catalytic substrate; 3) forming a graphene film on the upper surface of the structure obtained in the step 2). The battery cathode material structure not only retains the inherent characteristics of the silicon cathode material and the graphene, but also can exert the synergistic effect between the silicon cathode material and the graphene; meanwhile, the silicon nano material/carbon nano material composite film can be effectively contacted with a metal catalytic substrate current collector, so that high-efficiency lithium storage capacity can be provided, large volume change of the silicon nano material in the charging and discharging process is relieved, and internal stress of the negative electrode material is effectively inhibited and improved to avoid pulverization of the negative electrode material.

Description

Lithium ion battery cathode material structure, lithium ion battery and preparation method thereof
Technical Field
The invention belongs to the technical field of material preparation and processing, and particularly relates to a lithium ion battery cathode material structure, a lithium ion battery and a preparation method thereof.
Background
The first generation of lithium ion batteries successfully developed by the company sony, japan has become the preferred battery for most portable electronic devices due to their advantages of high energy density, long cycle life, and low environmental pollution. The lithium ion battery consists of a positive electrode, a negative electrode, electrolyte and a diaphragm. Typically, the positive electrode for lithium ions is made of a lithium-containing metal compound (e.g., lithium cobaltate (LiCoO)2) Iron phosphateLithium (LiFePO)4) And lithium manganate (LiMn)2O4) And (4) forming. And the negative electrode is composed of a material capable of storing lithium ions, such as carbon, transition metals, and other alloy materials (e.g., silicon, germanium). The selection of the negative electrode material has a great influence on both the electrochemical performance and the cycle stability of the lithium ion battery. Although graphite is widely applied to lithium ion battery cathode materials, the improvement of lithium ion battery lithium storage performance is limited due to the defects of low theoretical specific capacity, poor charging and discharging capacity and the like. In order to improve the energy density and the lithium storage capacity of the lithium ion battery, researchers are continuously exploring materials more suitable for the negative electrode of the lithium ion battery so as to develop the lithium ion battery with higher quality and good safety.
Silicon is considered to be one of the most promising anode materials due to its ultra-high theoretical specific capacity and ideal operating voltage. However, silicon has a disadvantage as the negative electrode of the lithium ion battery, namely, the volume of the material is greatly changed in the process of repeatedly removing and embedding lithium, and large stress is generated in the electrode, so that the negative electrode material is pulverized to cause structural damage, and the electrochemical cycle performance is poor. Meanwhile, due to the change of the volume of the silicon electrode, a solid electrolyte interface film (SEI) formed on the surface of the electrode is continuously broken, resulting in the loss of the function of preventing organic solvent molecules from entering the electrode material. Moreover, the re-exposed electrode surface reacts with the electrolyte to form a new SEI film, and thus the thickness of the SEI film increases repeatedly, which eventually results in a large degradation of lithium storage performance, and thus severely limits the application and development of silicon in lithium ion batteries.
Disclosure of Invention
In view of the above disadvantages of the prior art, an object of the present invention is to provide a negative electrode material structure of a lithium ion battery, a lithium ion battery and a preparation method thereof, which are used to solve the problems of low theoretical specific capacity and poor charge/discharge capacity of graphite as a negative electrode of a lithium ion battery in the prior art, and the problems of large mention variation and poor cycle stability of silicon as a negative electrode of a lithium ion battery.
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) placing a silicon nano material, a carbon nano material and an additive in an organic solvent to prepare a dispersion liquid;
2) providing a metal catalytic substrate, and coating the dispersion on the upper surface of the metal catalytic substrate;
3) forming a graphene film on the upper surface of the structure obtained in the step 2).
As a preferable embodiment of the preparation method of the negative electrode material structure of the lithium ion battery, in step 1), the silicon nanomaterial includes at least one of silicon nanoparticles, silicon nanowires, or silicon nanofibers.
As a preferable scheme of the preparation method of the lithium ion battery cathode material structure of the present invention, in step 1), the carbon nanomaterial includes at least one of a carbon nanotube, a carbon nanofiber, graphene powder, or fullerene.
As a preferable embodiment of the method for preparing the negative electrode material structure of the lithium ion battery, in the step 1), the additive includes at least one of a conductive additive, a stabilizer and a binder.
As a preferable embodiment of the preparation method of the negative electrode material structure of the lithium ion battery, the conductive additive includes at least one of acetylene black or graphite.
As a preferable embodiment of the preparation method of the negative electrode material structure of the lithium ion battery, in the step 1), the organic solvent includes at least one of N-methylpyrrolidone, ethanol, and isopropanol.
As a preferable scheme of the preparation method of the lithium ion battery cathode material structure, in the step 1), the concentration of the silicon nano material in the dispersion liquid is 3 mg/ml-300 mg/ml; the concentration of the carbon nano material in the dispersion liquid is 0.1 mg/ml-30 mg/ml.
As a preferable embodiment of the method for preparing the negative electrode material structure of the lithium ion battery, in the step 2), the material of the metal catalytic substrate is one or an alloy material of at least two of gold, platinum, palladium, iridium, ruthenium, nickel and copper, or another metal foil substrate material having the above metal plating layer or alloy plating layer.
As a preferable scheme of the preparation method of the lithium ion battery negative electrode material structure of the present invention, in the step 2), before coating the dispersion liquid on the upper surface of the metal catalytic substrate, the method further includes a step of cleaning and polishing the metal catalytic substrate.
As a preferred scheme of the preparation method of the lithium ion battery cathode material structure, the metal catalysis substrate is chemically polished by acetic acid, nitric acid or hydrochloric acid or electrochemically polished under the condition of phosphoric acid.
As a preferable embodiment of the preparation method of the lithium ion battery negative electrode material structure of the present invention, in the step 2), the dispersion liquid is coated on the upper surface of the metal catalytic substrate by using any one of dip-coating, spin coating, doctor blade, spray coating, wet coating, screen printing, roller coating, or plate coating.
As a preferable scheme of the preparation method of the lithium ion battery negative electrode material structure, a heat treatment step is further included between the step 2) and the step 3) to perform heat treatment on the structure obtained in the step 2) so as to cure the coated dispersion liquid.
As a preferable scheme of the preparation method of the lithium ion battery cathode material structure, the structure obtained in the step 2) is placed in a reducing atmosphere and heated to a reaction temperature, and a carbon source gas is introduced into the reducing atmosphere to form the graphene film on the upper surface of the structure obtained in the step 2).
As a preferable scheme of the preparation method of the lithium ion battery cathode material structure, the step of placing the structure obtained in the step 2) in a reducing atmosphere and heating the structure to a reaction temperature, and introducing a carbon source gas into the reducing atmosphere to form the graphene film on the upper surface of the structure obtained in the step 2) specifically includes the following steps:
3-1) placing the structure obtained in the step 2) in a tube furnace;
3-2) introducing reducing gas into the tubular furnace, heating the structure obtained in the step 2) to the reaction temperature, preserving the temperature, and introducing carbon source gas into the tubular furnace in the heat preservation process so as to form the graphene film on the upper surface of the structure obtained in the step 2).
As a preferable scheme of the preparation method of the lithium ion battery cathode material structure, a step of cleaning a reducing gas pipeline is further included between the step 3-1) and the step 3-2).
As a preferable scheme of the preparation method of the lithium ion battery cathode material structure of the present invention, in the step 3-2), the reducing gas introduced into the tube furnace includes hydrogen, a mixed gas of hydrogen and nitrogen, or a mixed gas of hydrogen and argon.
As a preferable embodiment of the method for preparing the negative electrode material structure of the lithium ion battery, in the step 3-2), the carbon source gas introduced into the tube furnace includes at least one of methane, ethylene, acetylene, ethanol, and cyclohexane.
As a preferable scheme of the preparation method of the lithium ion battery cathode material structure, in the step 3-2), the reaction temperature is 500-1000 ℃.
As a preferable scheme of the preparation method of the lithium ion battery cathode material structure, in the step 3-2), the heat preservation time is 5-30 min.
The invention also provides a lithium ion battery cathode material structure, which comprises the following components:
a metal-catalyzed substrate;
a layer of solidified material on the upper surface of the metal catalyzed substrate; the curing material layer is a composite material layer comprising a silicon nano material, a carbon nano material and an additive;
and the graphene film is positioned on the upper surface of the solidified material layer.
In a preferred embodiment of the structure of the negative electrode material for lithium ion batteries according to the present invention, the material of the metal catalyst substrate is one or an alloy of at least two of gold, platinum, palladium, iridium, ruthenium, nickel, and copper, or another metal foil substrate material having the above metal plating layer or alloy plating layer.
As a preferable scheme of the negative electrode material structure of the lithium ion battery, the silicon nanomaterial comprises at least one of silicon nanoparticles, silicon nanowires, or silicon nanofibers.
As a preferable scheme of the negative electrode material structure of the lithium ion battery, the carbon nanomaterial includes at least one of a carbon nanotube, a carbon nanofiber, graphene powder, or fullerene.
As a preferable aspect of the structure of the negative electrode material for a lithium ion battery of the present invention, the additive includes at least one of a conductive additive, a binder, and a stabilizer.
As a preferable scheme of the structure of the lithium ion battery negative electrode material of the present invention, the conductive additive includes at least one of acetylene black or graphite.
The invention also provides a lithium ion battery cathode which comprises the lithium ion battery cathode material structure in any one of the above schemes.
The invention also provides a lithium ion battery, which comprises the lithium ion battery cathode in the scheme.
As described above, the lithium ion battery cathode material structure, the lithium ion battery and the preparation method thereof of the invention have the following beneficial effects: according to the preparation method, the silicon nanomaterial is selected as an active material in the preparation process, the carbon nanomaterial is used as a conductive additive and a dispersing agent, and the chemical vapor deposition method is adopted to prepare the composite negative electrode material which can directly grow the graphene film on the surface of the metal catalytic substrate coated with the silicon nanomaterial/carbon nanomaterial composite film so as to form the composite negative electrode material, so that the inherent characteristics of the silicon negative electrode material and the graphene are retained, the synergistic effect between the silicon negative electrode material and the graphene is exerted, and the application value is wider; meanwhile, the silicon nanomaterial/carbon nanomaterial composite film can be effectively contacted with a metal catalytic substrate current collector, high-efficiency lithium storage capacity can be provided, the graphene film is a flexible grid substrate, large volume change of the silicon nanomaterial in the charging and discharging process is relieved, internal stress of the negative electrode material is effectively inhibited and improved, pulverization of the negative electrode material is avoided, the preparation process is simple, industrial production is facilitated, and electrochemical stability and performance of the lithium ion battery can be effectively improved.
Drawings
Fig. 1 is a flowchart illustrating a method for manufacturing a negative electrode material structure of a lithium ion battery according to a first embodiment of the present invention.
Fig. 2 to fig. 4 are schematic structural diagrams of the method for preparing the negative electrode material structure of the lithium ion battery according to the first embodiment of the present invention in each step.
Fig. 5 shows a cyclic voltammetry test chart of a lithium ion battery negative electrode material structure prepared by the preparation method of the lithium ion battery negative electrode material structure provided in the first embodiment of the present invention, for a lithium ion battery negative electrode.
Description of the element reference numerals
1 Metal catalyzed substrate
2 layer of solidified material
3 graphene thin film
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 5. It should be noted that the drawings provided in the present embodiment are only schematic and illustrate the basic idea of the present invention, and although the drawings only show the components related to the present invention and are not drawn according to the number, shape and size of the components in actual implementation, 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.
Example one
Referring to fig. 1, the present invention provides a method for preparing a negative electrode material structure of a lithium ion battery, where the method for preparing the negative electrode material structure of the lithium ion battery includes the following steps:
1) placing a silicon nano material, a carbon nano material and an additive in an organic solvent to prepare a dispersion liquid;
2) providing a metal catalytic substrate, and coating the dispersion on the upper surface of the metal catalytic substrate;
3) forming a graphene film on the upper surface of the structure obtained in the step 2).
In step 1), referring to step S1 in fig. 1, a silicon nanomaterial, a carbon nanomaterial, and an additive are placed in an organic solvent to prepare a dispersion.
By way of example, the silicon nanomaterial may include at least one of silicon nanoparticles, silicon nanowires, or silicon nanofibers, that is, the silicon nanomaterial may be silicon nanoparticles, silicon nanowires, or silicon nanofibers, or a mixture of any two or three of silicon nanoparticles, silicon nanowires, or silicon nanofibers. Preferably, in this embodiment, the silicon nanomaterial is a silicon nanoparticle.
As an example, the size of the silicon nanomaterial can be set according to actual needs, and preferably, in this embodiment, the particle diameter of the silicon nanomaterial is 15nm to 300 nm.
As an example, the carbon nanomaterial includes at least one of a carbon nanotube, a carbon nanofiber, a graphene powder, or a fullerene, that is, the carbon nanomaterial may be a carbon nanotube, a carbon nanofiber, a graphene powder, or a fullerene, or a mixture of any two, three, or four of a carbon nanotube, a carbon nanofiber, a graphene powder, or a fullerene. Preferably, in this embodiment, the carbon nanomaterial is a carbon nanotube.
As an example, the additive may include at least one of a conductive additive, a stabilizer and a binder, and preferably, the conductive additive includes at least one of acetylene black or graphite, that is, the conductive additive may be acetylene black or graphite, or a mixture of acetylene black and graphite.
As an example, the organic solvent may include at least one of N-methylpyrrolidone, ethanol, or isopropanol. Preferably, in this embodiment, the organic solvent is N-methylpyrrolidone.
For example, the silicon nanomaterial, the carbon nanomaterial, and the additive may be mixed and dissolved in the organic solvent at any ratio to prepare a dispersion liquid with a desired concentration, and preferably, in this embodiment, the concentration of the silicon nanomaterial in the dispersion liquid is 3mg/ml to 300 mg/ml; the concentration of the carbon nano material in the dispersion liquid is 0.1 mg/ml-30 mg/ml.
In step 2), referring to step S2 in fig. 1 and fig. 2 to 3, a metal catalytic substrate 1 is provided, and the dispersion is coated on the upper surface of the metal catalytic substrate 1.
As an example, providing the metal catalytic substrate 1, as shown in fig. 2, the material of the metal catalytic substrate 1 may be one or an alloy material of at least two of gold, platinum, palladium, iridium, ruthenium, nickel, and copper, or other metal foil substrate materials with the above metal plating layer or alloy plating layer; preferably, in this embodiment, the metal catalyst substrate 1 is a copper foil substrate.
As an example, before applying the dispersion to the upper surface of the metal-catalyzed substrate 1, the method further includes the step of cleaning and polishing the metal-catalyzed substrate 1.
As an example, the metal catalytic substrate 1 may be placed in deionized water or an organic solvent for cleaning, and preferably, in this embodiment, the metal catalytic substrate 1 is respectively placed in acetone and ethanol for ultrasonic cleaning
As an example, the metal-catalyzed substrate 1 is chemically polished by acetic acid, nitric acid or hydrochloric acid or the metal-catalyzed substrate 1 is electrochemically polished under phosphoric acid condition, and preferably, in the present embodiment, the cleaned metal-catalyzed substrate 1 is placed in an orthophosphoric acid solution and electrochemically polished under 5V voltage condition. The time for performing the electrochemical polishing on the metal-catalyzed substrate 1 may be set according to actual needs, and preferably, in this embodiment, the time for performing the electrochemical polishing on the metal-catalyzed substrate 1 may be 5min to 15 min.
As an example, after polishing the metal catalytic substrate 1, rinsing the polished metal catalytic substrate 1 with deionized water, and blow-drying with nitrogen.
As an example, the dispersion may be applied to the upper surface of the metal catalytic substrate 1 using any one of dip-coating, spin-coating, doctor-blading, spray-coating, wet-coating, screen-printing, roll-coating, or plate-coating. Preferably, in the present embodiment, the dispersion is applied to the upper surface of the metal catalytic substrate 1 by a spin coating process.
As an example, between step 2) and step 3), a step of heat-treating the structure obtained in step 2) is further included, so as to cure the applied dispersion, so as to obtain a cured material layer 2, as shown in fig. 3.
In step 3), referring to step S3 in fig. 1 and fig. 4, the graphene film 3 is formed on the upper surface of the structure obtained in step 2).
As an example, the structure obtained in step 2) is placed in a reducing atmosphere and heated to a reaction temperature, and a carbon source gas is introduced into the reducing atmosphere to form the graphene film 3 on the upper surface of the structure obtained in step 2).
Specifically, the step of placing the structure obtained in the step 2) in a reducing atmosphere and heating the structure to a reaction temperature, and introducing a carbon source gas into the reducing atmosphere to form the graphene film 3 on the upper surface of the structure obtained in the step 2) specifically includes the following steps:
3-1) placing the structure obtained in the step 2) in a tube furnace;
3-2) introducing reducing gas into the tubular furnace, heating the structure obtained in the step 2) to the reaction temperature, preserving the temperature, and introducing carbon source gas into the tubular furnace in the heat preservation process so as to form the graphene film 3 on the upper surface of the structure obtained in the step 2).
As an example, a step of cleaning the reducing gas pipeline is further included between the step 3-1) and the step 3-2).
As an example, in the step 3-2), the reducing gas introduced into the tube furnace includes hydrogen, a mixed gas of hydrogen and nitrogen, or a mixed gas of hydrogen and argon. Preferably, in this embodiment, the reducing gas is hydrogen.
As an example, in step 3-2), the carbon source gas introduced into the tubular furnace includes at least one of methane, ethylene, acetylene, ethanol or cyclohexane, that is, the carbon source gas introduced into the tubular furnace may be methane, ethylene, acetylene, ethanol or cyclohexane, or may be a mixed gas of any two or more of methane, ethylene, acetylene, ethanol or cyclohexane. Preferably, in this embodiment, the carbon source gas is methane.
As an example, in step 3-2), the reaction temperature is 500 ℃ to 1000 ℃, i.e., the temperature to which the structure obtained in step 2) is heated is 500 ℃ to 1000 ℃.
As an example, in the step 3-2), the holding time is 5min to 30 min.
Specifically, in one example, the metal catalytic substrate coated with the dispersion liquid is placed in a tube furnace system, after a reducing gas conveying pipeline is cleaned, the air pressure in the tube furnace is pumped to be below 5Pa by using a mechanical pump, hydrogen is introduced, the temperature is kept at 1000 ℃, and a methane carbon source is introduced in the heat preservation process.
With reference to fig. 3, the present invention further provides a lithium ion battery cathode material structure, which is prepared by the above preparation method in this embodiment, and the lithium ion battery cathode material structure includes: a metal-catalyzed substrate 1; a solidified material layer 2, wherein the solidified material layer 2 is positioned on the upper surface of the metal catalytic substrate 1; the curing material layer 2 is a composite material layer comprising a silicon nano material, a carbon nano material and an additive; and the graphene film 3 is positioned on the upper surface of the solidified material layer 2.
As an example, the material of the metal catalytic substrate 1 may be one or an alloy material of at least two of gold, platinum, palladium, iridium, ruthenium, nickel and copper, or other metal foil substrate materials with the above metal plating layers or alloy plating layers; preferably, in this embodiment, the metal catalytic substrate 1 is a copper foil substrate.
By way of example, the silicon nanomaterial may include at least one of silicon nanoparticles, silicon nanowires, or silicon nanofibers, that is, the silicon nanomaterial may be silicon nanoparticles, silicon nanowires, or silicon nanofibers, or a mixture of any two or three of silicon nanoparticles, silicon nanowires, or silicon nanofibers. Preferably, in this embodiment, the silicon nanomaterial is a silicon nanoparticle.
As an example, the carbon nanomaterial includes at least one of a carbon nanotube, a carbon nanofiber, a graphene powder, or a fullerene, that is, the carbon nanomaterial may be a carbon nanotube, a carbon nanofiber, a graphene powder, or a fullerene, or a mixture of any two, three, or four of a carbon nanotube, a carbon nanofiber, a graphene powder, or a fullerene. Preferably, in this embodiment, the carbon nanomaterial is a carbon nanotube.
As an example, the additive may include at least one of a conductive additive, a binder and a stabilizer, and preferably, the conductive additive includes at least one of acetylene black or graphite, that is, the conductive additive may be acetylene black or graphite, or a mixture of acetylene black and graphite.
Compared with silicon with large particle size, the silicon nano material has higher cycle stability and reversible capacity; the carbon nano material has excellent electrical and mechanical properties, and the structure advantage of the carbon nano material and the lithium storage capacity of the silicon nano material can be combined to prepare the cathode material structure of the lithium ion battery by compounding the silicon nano material and the carbon nano material; the carbon nano material can buffer the volume expansion of the silicon nano material in the circulation process, effectively improve the agglomeration phenomenon among the silicon nano materials and increase the conductivity of the material; the silicon nano material can greatly improve the cycle specific capacity of the lithium ion battery due to the lithium storage specific capacity of the silicon nano material, so that the lithium storage capacity of the lithium ion battery is obviously improved.
According to the invention, the silicon nanomaterial is selected as an active material in the preparation process, the carbon nanomaterial is used as a conductive additive and a dispersing agent, and the chemical vapor deposition method is adopted to prepare the composite negative electrode material which can directly grow the graphene film on the surface of the metal catalytic substrate coated with the silicon nanomaterial/carbon nanomaterial composite film so as to form the composite negative electrode material, so that the inherent characteristics of the silicon negative electrode material and the graphene are retained, the synergistic effect between the silicon negative electrode material and the graphene can be exerted, and the application value is wider; meanwhile, the silicon nanomaterial/carbon nanomaterial composite film can be effectively contacted with a metal catalytic substrate current collector, high-efficiency lithium storage capacity can be provided, the graphene film is a flexible grid substrate, large volume change of the silicon nanomaterial in the charging and discharging process is relieved, internal stress of the negative electrode material is effectively inhibited and improved, pulverization of the negative electrode material is avoided, the preparation process is simple, industrial production is facilitated, and electrochemical stability and performance of the lithium ion battery can be effectively improved.
Fig. 5 is a voltammetry test chart of the lithium ion battery cathode material structure prepared by the preparation method of the lithium ion battery cathode material structure in the embodiment, which is used for 6 times of lithium ion battery cathode cycle, as can be seen from fig. 5, in the first discharge process, an obvious discharge peak appears on the electrode and disappears in the subsequent cycle, which corresponds to the irreversible decomposition process of the electrolyte and the formation of the solid electrolyte interface; from 2 cycles, the cyclic voltammetry characteristics of the two electrodes almost remained consistent in shape, indicating that a stable solid electrolyte interface had been formed on the electrode surface and had a relatively stable structure with good reversibility.
Example two
The invention also provides a lithium ion battery cathode, which comprises the lithium ion battery cathode material structure in the embodiment I.
EXAMPLE III
The invention also provides a lithium ion battery, which comprises the lithium ion battery cathode in the embodiment II.
In summary, the invention provides a lithium ion battery cathode material structure, a lithium ion battery and a preparation method thereof, wherein the preparation method comprises the following steps: 1) placing a silicon nano material, a carbon nano material and an additive in an organic solvent to prepare a dispersion liquid; 2) providing a metal catalytic substrate, and coating the dispersion on the upper surface of the metal catalytic substrate; 3) forming a graphene film on the upper surface of the structure obtained in the step 2). According to the invention, the silicon nanomaterial is selected as an active material in the preparation process, the carbon nanomaterial is used as a conductive additive and a dispersing agent, and the chemical vapor deposition method is adopted to prepare the composite negative electrode material which can directly grow the graphene film on the surface of the metal catalytic substrate coated with the silicon nanomaterial/carbon nanomaterial composite film so as to form the composite negative electrode material, so that the inherent characteristics of the silicon negative electrode material and the graphene are retained, the synergistic effect between the silicon negative electrode material and the graphene can be exerted, and the application value is wider; meanwhile, the silicon nanomaterial/carbon nanomaterial composite film can be effectively contacted with a metal catalytic substrate current collector, high-efficiency lithium storage capacity can be provided, the graphene film is a flexible grid substrate, large volume change of the silicon nanomaterial in the charging and discharging process is relieved, internal stress of the negative electrode material is effectively inhibited and improved, pulverization of the negative electrode material is avoided, the preparation process is simple, industrial production is facilitated, and electrochemical stability and performance of the lithium ion battery can be effectively 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 (19)

1. The preparation method of the lithium ion battery cathode material structure is characterized by comprising the following steps:
1) placing a silicon nano material, a carbon nano material and an additive into an organic solvent to prepare a dispersion liquid, wherein the organic solvent comprises at least one of N-methyl pyrrolidone, ethanol or isopropanol, and the additive comprises at least one of a conductive additive, a stabilizer and a binder;
2) providing a metal catalytic substrate, and coating the dispersion liquid on the upper surface of the metal catalytic substrate, wherein the metal catalytic substrate is made of one or at least two alloy materials of gold, platinum, palladium, iridium, ruthenium, nickel and copper, or other metal foil substrate materials with the metal coating or the alloy coating;
3) placing the structure obtained in the step 2) in a reducing atmosphere, heating to 500-1000 ℃, and introducing a carbon source gas into the reducing atmosphere to form a graphene film on the upper surface of the structure obtained in the step 2), wherein the reducing atmosphere comprises hydrogen, a mixed gas of hydrogen and nitrogen, or a mixed gas of hydrogen and argon.
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: in step 1), the silicon nanomaterial comprises at least one of silicon nanoparticles, silicon nanowires, or silicon nanofibers.
3. 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 carbon nano material comprises at least one of carbon nano tube, carbon nano fiber, graphene powder or fullerene.
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: the conductive additive includes at least one of acetylene black or graphite.
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 concentration of the silicon nano material in the dispersion liquid is 3 mg/ml-300 mg/ml; the concentration of the carbon nano material in the dispersion liquid is 0.1 mg/ml-30 mg/ml.
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), before the dispersion is coated on the upper surface of the metal catalytic substrate, the method further comprises the step of cleaning and polishing the metal catalytic substrate.
7. The method for preparing the negative electrode material structure of the lithium ion battery according to claim 6, wherein the method comprises the following steps: and chemically polishing the metal catalytic substrate by adopting acetic acid, nitric acid or hydrochloric acid or electrochemically polishing the metal catalytic substrate under the phosphoric acid condition.
8. 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), the dispersion liquid is coated on the upper surface of the metal catalytic substrate by any one of dip-coating, spin-coating, doctor-blading, spray-coating, wet-coating, screen-printing, roller-coating or plate-coating.
9. 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 2) and the step 3) are also carried out by carrying out a heat treatment step on the structure obtained in the step 2) so as to cure the coated dispersion liquid.
10. 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: placing the structure obtained in the step 2) in a reducing atmosphere, heating to a reaction temperature, and introducing a carbon source gas into the reducing atmosphere to form the graphene film on the upper surface of the structure obtained in the step 2), wherein the method specifically comprises the following steps:
3-1) placing the structure obtained in the step 2) in a tube furnace;
3-2) introducing reducing gas into the tubular furnace, heating the structure obtained in the step 2) to the reaction temperature, preserving the temperature, and introducing carbon source gas into the tubular furnace in the heat preservation process so as to form the graphene film on the upper surface of the structure obtained in the step 2).
11. The method for preparing the negative electrode material structure of the lithium ion battery according to claim 10, wherein the method comprises the following steps: a step of cleaning the reducing gas pipeline is also included between the step 3-1) and the step 3-2).
12. The method for preparing the negative electrode material structure of the lithium ion battery according to claim 10, wherein the method comprises the following steps: in the step 3-2), the carbon source gas introduced into the tubular furnace comprises at least one of methane, ethylene, acetylene, ethanol or cyclohexane.
13. The method for preparing the negative electrode material structure of the lithium ion battery according to claim 10, wherein the method comprises the following steps: in the step 3-2), the heat preservation time is 5min to 30 min.
14. A lithium ion battery negative electrode material structure is characterized by comprising:
the metal catalytic substrate is made of one or at least two alloy materials of gold, platinum, palladium, iridium, ruthenium, nickel and copper or other metal foil substrate materials with the metal plating layers or the alloy plating layers;
a layer of solidified material on the upper surface of the metal catalyzed substrate; the curing material layer is a composite material layer comprising a silicon nano material, a carbon nano material and an additive, wherein the additive comprises at least one of a conductive additive, a stabilizer and a binder;
and the graphene film is positioned on the upper surface of the solidified material layer.
15. The lithium ion battery negative electrode material structure of claim 14, wherein: the silicon nanomaterial includes at least one of a silicon nanoparticle, a silicon nanowire, or a silicon nanofiber.
16. The lithium ion battery negative electrode material structure of claim 14, wherein: the carbon nano material comprises at least one of carbon nano tube, carbon nano fiber, graphene powder or fullerene.
17. The lithium ion battery negative electrode material structure of claim 14, wherein: the conductive additive includes at least one of acetylene black or graphite.
18. A lithium ion battery negative electrode, characterized in that it comprises a lithium ion battery negative electrode material structure according to any one of claims 14 to 17.
19. A lithium ion battery comprising the lithium ion battery negative electrode of claim 18.
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