CN108695505B - Lithium ion battery composite negative electrode material and preparation method thereof - Google Patents

Lithium ion battery composite negative electrode material and preparation method thereof Download PDF

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CN108695505B
CN108695505B CN201810540560.4A CN201810540560A CN108695505B CN 108695505 B CN108695505 B CN 108695505B CN 201810540560 A CN201810540560 A CN 201810540560A CN 108695505 B CN108695505 B CN 108695505B
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manganese
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CN108695505A (en
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郭华军
彭伟佳
李新海
王志兴
周玉
王接喜
彭文杰
胡启阳
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Central South University
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/62—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 discloses a lithium ion battery composite negative electrode material, wherein nano silicon coated by a conductive carbon network and a silicon-manganese alloy is used as an active substance, a manganese source is dispersed in a medium, is uniformly dispersed on the surface of silicon oxide by stirring, and is coated with a reticular conductive polymer in situ on the surface of particles, and the obtained precursor is subjected to high-temperature heat treatment to prepare the self-supporting material coated by the conductive carbon network and the silicon-manganese alloy. The invention also provides a preparation method of the nano silicon self-supporting cathode material with the carbon network and silicon-manganese alloy co-coated, which can effectively improve the cycle stability and rate capability of the cathode material.

Description

Lithium ion battery composite negative electrode material and preparation method thereof
Technical Field
The invention belongs to the field of lithium ion battery composite negative electrode materials, and particularly relates to a silicon-based composite material which is prepared by one-step reduction-carbonization of a silicon oxide, a manganese source and a conductive polymer and is coated by a conductive carbon net and a silicon alloy.
Background
With the development of human society, energy crisis and environmental problems become the focus of people's attention, and the clean and efficient utilization of traditional energy and the development of novel energy technology become the main trends at present. The lithium ion battery has high performance and safetyThe battery has the advantages of good performance, environmental friendliness and the like, and is a high-energy green secondary battery with the greatest development prospect and application prospect at present. However, in recent years, the demand for battery energy density has been rapidly increasing in various fields. Particularly, the popularization and application of new energy automobiles are accelerated in China, and novel high-energy-density batteries become a hot spot in research and development at present. The energy density of batteries depends mainly on electrode materials, and new electrode materials support the development of new generation chemical power sources. In the research of novel non-carbon negative electrode materials, the silicon-based materials have high theoretical specific capacity (3579mAh/g) and low lithium-intercalated/deintercalated potential (0.02-0.6V vs. Li) at room temperature+/Li), environment-friendly, abundant reserves and the like, and is considered to be the next generation of high energy density lithium ion battery cathode material with the most potential to replace graphite.
There are two key problems associated with the commercial use of silicon-based materials. Firstly, silicon belongs to an alloy type lithium storage material, and in the process of charging and discharging, the crystal structure of silicon expands and contracts to cause the electrode material to generate a huge volume effect, so that the electrode material is pulverized and falls off, the active material loses effective electric contact, and the poor cycle stability is shown. Second, the silicon material is in direct contact with the electrolyte and the interfacial SEI film is continuously broken and generated due to its volume change seriously. The continued formation of the SEI will consume electrolyte and lithium ions, reduce the conductivity of the material, increase irreversible capacity loss and cause the active material to fall off the current collector. To overcome these problems, researchers have adopted various strategies to alter the electrochemical properties of silicon-based materials. The research of modification can be mainly divided into four parts, including designing a new structure of a silicon-based material, selecting a novel strong adhesive, changing the composition of an electrolyte, and designing a new structure of a novel current collector and an electrode. Based on the volume expansion problem of nano silicon, silicon oxide, manganese metal oxide and polymer monomer are used as raw materials, and a silicon-based material which is coated by a conductive carbon net and a silicon-manganese alloy is generated through an in-situ chemical reaction. The silicon-manganese alloy coating layer can be effectively attached to the surface of the silicon material due to good adhesiveness, so that the volume expansion of the silicon material in the charging and discharging processes can be effectively relieved, the conductivity of the silicon material can be improved, and the oxidation resistance of the material can be enhanced. Meanwhile, a layer of carbon network is polymerized and coated outside the silicon alloy coating layer in situ, so that the mechanical strength of the material can be further improved, and the electronic conductivity can be improved. Compared with the traditional coating, the designed silicon-based composite material coated by the conductive carbon net and the silicon alloy is prepared by one-step reduction-carbonization, the preparation process is simple and controllable, and the main problem of the nano silicon material can be effectively solved.
Disclosure of Invention
The invention designs a self-supporting nano-silicon cathode material which is based on silicon oxide, manganese source and mesh conductive polymer and is coated by a conductive carbon network and a silicon-manganese alloy through one-step reduction-carbonization by adopting an in-situ chemical reaction, in order to improve the interface stability of a nano-silicon material and an electrolyte, solve the problems of poor conductivity of the nano-silicon, volume expansion in the circulation process and active substance falling caused by the poor conductivity of the nano-silicon and the volume expansion in the circulation process. As a general design concept, a silicon oxide material is used as an active substance, a manganese source is dispersed in a medium, the mixture is stirred to be uniformly dispersed on the surface of the silicon oxide, meanwhile, a reticular conductive polymer is coated on the surface of particles in situ, and the obtained precursor is subjected to high-temperature heat treatment and one-step reduction-carbonization to prepare the self-supporting material co-coated by the reticular carbon network and the silicon-manganese alloy. The nano silicon negative electrode material coated by the silicon-manganese alloy and the carbon network has the advantages that the electrical conductivity and the mechanical strength of the nano silicon negative electrode material are enhanced due to the existence of the silicon-manganese alloy and the carbon network, the interface stability of an electrode/electrolyte in a battery is improved, and the electrochemical cycle stability is improved.
The invention also provides a preparation method of the carbon network and silicon-manganese alloy co-coated nano silicon negative electrode material, and the specific technical scheme comprises the following steps:
(1) dispersing a manganese source, silicon oxide and a surfactant in a medium, and uniformly dispersing by ultrasonic;
(2) adding an oxidant and a polymer monomer, stirring vigorously, and polymerizing the monomer to form a polymer conductive network to obtain an intermediate product;
(3) washing and drying the obtained intermediate product, and mixing the intermediate product with magnesium powder and sodium chloride to obtain a precursor;
(4) heating the precursor obtained in the step (3) in an inert protective gas to a certain temperature, decomposing a manganese source into a manganese metal compound, reducing silicon oxide and the manganese metal compound by magnesium powder, generating a silicon-manganese alloy on the surface of silicon by the obtained manganese metal and silicon, coating the silicon-manganese alloy on the surface of the silicon, and carbonizing a polymer conductive network at a high temperature;
(5) and (3) pickling the obtained silicon material, filtering and washing, and carrying out vacuum drying on the washed product to obtain the self-supporting silicon material co-coated by the carbon network and the silicon-manganese alloy.
The preparation method is preferably as follows:
in the step 1), the manganese source comprises one or more of manganese carbonate, manganese acetate, manganese oxalate, manganese nitrate and manganese phosphate; the silicon oxide is SiOX(x = 0-2); the added surfactant is one or more of CTAB and PVP; the molar ratio of the added manganese source to the silicon in the silicon oxide is 0.02-1; the mass ratio of the added surfactant to the polymer monomer is 0.2-0.6; the medium solution comprises one or more of water, absolute ethyl alcohol and hydrochloric acid solution with the concentration of 0.1-2 mol/L; the temperature of the medium is-10 to 10 ℃; in the ultrasonic dispersion process, the frequency is controlled to be 25-500 Hz, and the ultrasonic dispersion time is 10-100 min;
the oxidant added in the step 2) is one or more of ammonium peroxydisulfate, hydrogen peroxide and potassium permanganate, and the mass ratio of the oxidant to the polymer monomer is 0.4-1.2; the polymer monomer is one or more of pyrrole, thiophene, acetylene and aniline; the reaction time is 8-48 h;
the mass ratio of the magnesium powder to the precursor in the step 3) is controlled to be 0.2-10; the mass ratio of the sodium chloride to the precursor is 2-30; the mixing comprises one or more of solid-phase mixing and liquid-phase mixing, including grinding, high-energy ball milling and high-energy sanding;
the silicon-manganese alloy in the step 4) comprises MnSi and Mn5Si3、Mn27Si47、Mn6Si、Mn15Si26One or more of (a); in the step 4), the calcination temperature is divided into two sections, and the low-temperature calcination is controlled at 0-500 ℃, preferably at 100-400 ℃, more preferably at 150-300 DEG CThe low-temperature treatment time is controlled to be 1-24h, the low-temperature heating rate is controlled to be 1-10 ℃/min, the high-temperature calcination is controlled to be 500-.
The acid in the step 5) comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid and acetic acid; the concentration of the acid is 1-8 mol/L; the temperature of the acid is 10-90 ℃.
The invention has the beneficial effects that:
the invention utilizes the problems of serious volume expansion, poor conductivity, poor dispersibility and the like of the nano silicon material in the practical application process to prepare the nano silicon self-supporting material co-coated by the carbon network and the silicon-manganese alloy by one-step reduction-carbonization. The synthesized carbon network and the silicon-manganese alloy coating layer can be effectively attached to the surface of the silicon material due to good adhesiveness of the carbon network and the silicon-manganese alloy coating layer, so that the volume expansion of the silicon material in the charging and discharging processes is effectively relieved, and meanwhile, the carbon network and the silicon-manganese alloy can improve the conductivity of the silicon material and improve the high-temperature stability and the chemical stability of the material.
Compared with the prior art, the invention has the advantages that:
1) the nano silicon negative electrode material provided by the invention utilizes nano silicon oxide as a raw material, and can realize double-layer coating of silicon-manganese alloy and carbon network of the silicon material through in-situ chemical reaction and in-situ polymerization coating, thereby effectively improving the stability between the nano silicon and the air or electrolyte interface and improving the mechanical property of the material.
2) The invention adopts the manganese metal compound as a synthetic raw material, has lower cost compared with other materials, and can also play a role in inhibiting volume expansion.
3) The invention provides one-step reduction-carbonization, which fully utilizes the heat generated in the reduction process to carbonize the reticular polymer and further improves the conductivity of the material.
4) The self-supporting material co-coated by the tabular carbon network and the silicon-manganese alloy can be directly stamped to perform electrochemical test, and the operation process is simpler and more convenient.
5) The preparation process of the silicon negative electrode material provided by the invention is short, the controllability is high, the obtained nano silicon material is stable and high, the oxidation resistance is strong, the mechanical strength is high, the corrosion resistance is strong, and the silicon negative electrode material is more suitable for commercial application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed 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 invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is an XRD spectrum of a composite anode material of a lithium ion battery of the invention;
FIG. 2 is a scanning electron micrograph of the material obtained in preferred example 1 of the present invention;
FIG. 3 is a charge-discharge curve diagram of a lithium ion battery made of the material obtained in the preferred embodiment 1 of the present invention;
FIG. 4 is a graph of rate performance of lithium ion batteries prepared from the material obtained in preferred example 2 of the present invention;
FIG. 5 is a graph of the specific capacity of a lithium ion battery made of the material obtained in preferred embodiment 3 of the present invention.
In the figure: voltage, specific capacity, cycle number, capacity.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
Example 1:
dissolving 0.45g of hexadecyl trimethyl ammonium bromide particles in 100mL of hydrochloric acid solution with the concentration of 1mol/L at the temperature of 3 ℃, adding 0.5g of manganese acetate, and ultrasonically stirring and dispersing for 20min, wherein the ultrasonic frequency is 80 Hz. Then adding 0.2g of nano silicon dioxide, stirring uniformly, continuing ultrasonic dispersion for 30min, controlling the temperature to be constant in the process, then adding 0.8g of ammonium peroxodisulfate, stirring vigorously, dropwise adding 1mL of pyrrole after a white emulsion appears, and carrying out freeze drying on the obtained solution after 8h of reaction. Controlling the mass ratio of the obtained intermediate product to sodium chloride at 1:13, adding magnesium powder and sodium chloride, grinding, and obtaining a precursor after 20 min. And (2) carrying out two-stage sintering on the precursor in an inert atmosphere, reacting at 118 ℃ for 2h at a heating rate of 2 ℃/min, then reacting at 650 ℃ for 5h at a heating rate of 1 ℃/min, naturally cooling to room temperature, and then directly punching the obtained product into a battery pole piece for battery performance test.
The lithium ion battery cathode material of the example is prepared into a lithium ion battery for XRD test, and the XRD result in figure 1 shows that the processed silicon material is composed of Si, MnSi and Mn27Si47And amorphous carbon generated by ppy pyrolysis, no other hetero-phase peak exists, and the characteristic peak of silicon still keeps a better crystal form. From the SEM image of FIG. 2, it can be seen that the surface of the nano-silicon has a layer of MnSi and Mn with uniform thickness27Si47And it is uniformly coated by the carbon network. The obtained nano silicon material is assembled into a button cell to measure the cycle performance of the button cell, as shown in figure 3, the first discharge capacity of the cell is 3022mAh g from figure 3-1First charge capacity 1246mAh g-1First coulombic efficiency was 41.3%. 3 rd cycle discharge capacity 1424mAh g-1Charging capacity 1209mAh g-1(ii) a Coulombic efficiency 84.9% and no capacity fading. 1286mAh g of discharge capacity at 10 th cycle-11092mAh g charge capacity-1. The cycle performance can be seen, the cycle performance cycle stability of the treated material is greatly improved, which is attributed to the carbon network and the silicon-manganese alloy common coating layerThe stability of the interface of the silicon and the electrolyte is improved.
Example 2:
dissolving 0.35g of hexadecyl trimethyl ammonium bromide particles in 120mL of hydrochloric acid solution with the concentration of 3mol/L at the temperature of 2.5 ℃, adding 0.8g of manganese acetate, and ultrasonically stirring and dispersing for 20min at the ultrasonic frequency of 40 Hz. Then adding 2.0g of nano silicon dioxide, stirring uniformly, continuing ultrasonic dispersion for 45min, controlling the temperature to be constant in the process, then adding 1.0g of ammonium peroxodisulfate, stirring vigorously, dropwise adding 0.5mL of pyrrole after a white emulsion appears, and carrying out freeze drying on the obtained solution after reacting for 16 h. Controlling the mass ratio of the obtained intermediate product to sodium chloride at 1:10, adding magnesium powder and sodium chloride, grinding, and obtaining a precursor after 20 min. And (2) carrying out two-stage sintering on the precursor in an inert atmosphere, reacting at 158 ℃ for 2h at a heating rate of 1 ℃/min, then reacting at 700 ℃ for 5h at a heating rate of 2 ℃/min, naturally cooling to room temperature, and then directly punching the obtained product into a battery pole piece for battery performance test.
The lithium ion battery prepared from the lithium ion battery composite negative electrode material of the embodiment is subjected to performance test, the rate capability of the lithium ion battery is shown in fig. 4, and as seen from fig. 4, 100 mA g-1、200 mA g-1、500 mA g-1、1 A g-1、2 A g-1、3 A g-1、4 A g-1、5 A g-1、10 A g-1、100 mA g-1Rate capability at current density of (a). It can be seen that the composite material has a current density of 10A g-1While, reversible capacity-490 mA h g-1After a large current, the current density is 100 mA g-1The capacity still reaches 1091 mA h g-1The material returns to a small current after being charged and discharged by a large current, the lithium ion battery composite negative electrode material still shows good lithium releasing and embedding performance, and the structure of the lithium ion battery composite negative electrode material is stable.
Example 3:
dissolving 0.55g of hexadecyl trimethyl ammonium bromide particles in 200mL of hydrochloric acid solution with the concentration of 1.5mol/L at the temperature of 5 ℃, adding 0.5g of manganese acetate, and ultrasonically stirring and dispersing for 60min at the ultrasonic frequency of 20 Hz. Then adding 1.5g of nano silicon dioxide, stirring uniformly, continuing ultrasonic dispersion for 45min, controlling the ultrasonic frequency to be 120Hz, controlling the temperature to be constant in the process, then adding 1.0g of ammonium peroxodisulfate, stirring vigorously, dropwise adding 0.2mL of pyrrole after a white emulsion appears, and carrying out freeze drying on the obtained solution after 24h of reaction. Controlling the mass ratio of the obtained intermediate product to sodium chloride at 1:10, adding magnesium powder and sodium chloride, grinding, and obtaining a precursor after 20 min. And (2) carrying out two-stage sintering on the precursor in an inert atmosphere, reacting at 300 ℃ for 4h at a heating rate of 3 ℃/min, then reacting at 650 ℃ for 5h at a heating rate of 2.5 ℃/min, naturally cooling to room temperature, and then directly punching the obtained product into a battery pole piece for battery performance test.
The lithium ion battery composite negative electrode material of the embodiment is prepared into a lithium ion battery to be tested for the cycle performance, the cycle performance is shown as figure 5, and as shown in figure 5, the first discharge specific capacity of the material is 1988mAh g-1The first charging specific capacity is 994mAh g-1The first efficiency is 50.01%. After 190 times of circulation, the charging specific capacity is still 674mAh g-1The capacity retention rate was 67.8%. Therefore, the lithium ion battery composite negative electrode material prepared by the embodiment has high cycle stability.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (11)

1. The preparation method of the lithium ion battery composite negative electrode material is characterized in that the negative electrode material consists of a self-supporting silicon material which is coated by a carbon network and a silicon-manganese alloy;
the preparation method comprises the following steps of taking a silicon oxide material as a raw material, dispersing a manganese source in a medium to enable the manganese source to be uniformly coated on the surface of the silicon oxide, coating a reticular conducting polymer on the surface of particles in situ, and carrying out high-temperature heat treatment on an obtained precursor to prepare a self-supporting silicon material which is coated by a carbon network and a silicon-manganese alloy together;
the preparation method comprises the following steps of,
(1) dispersing a manganese source, silicon oxide and a surfactant in a medium, and uniformly dispersing by ultrasonic;
(2) adding an oxidant and a polymer monomer, stirring vigorously, and polymerizing the monomer to form a polymer conductive network to obtain an intermediate product;
(3) washing and drying the obtained intermediate product, and mixing the intermediate product with magnesium powder and sodium chloride to obtain a precursor;
(4) heating the precursor obtained in the step (3) in an inert protective gas to a certain temperature, decomposing a manganese source into a manganese metal compound, reducing silicon oxide and the manganese metal compound by magnesium powder, generating a silicon-manganese alloy on the surface of silicon by the obtained manganese metal and silicon, coating the silicon-manganese alloy on the surface of the silicon, and carbonizing a polymer conductive network at a high temperature;
(5) and (3) pickling the obtained silicon material, filtering and washing, and carrying out vacuum drying on the washed product to obtain the self-supporting silicon material co-coated by the carbon network and the silicon-manganese alloy.
2. The preparation method according to claim 1, wherein in the step (1), the manganese source comprises one or more of manganese carbonate, manganese acetate, manganese oxalate, manganese nitrate and manganese phosphate; the added surfactant is one or more of CTAB and PVP.
3. The method of claim 2, wherein the silicon oxide is SiOX，x=0~2。
4. The method according to claim 1, wherein in the step (1), the molar ratio of the added manganese source to silicon in the silicon oxide is 0.02 to 1; the mass ratio of the added surfactant to the polymer monomer is 0.2-0.6; the medium comprises one or more of water, absolute ethyl alcohol and hydrochloric acid solution with the concentration of 0.1-2 mol/L; the temperature of the medium is-10 to 10 ℃; in the ultrasonic dispersion process, the frequency is controlled to be 25-500 Hz, and the ultrasonic dispersion time is 10-100 min.
5. The preparation method according to claim 1, wherein in the step (2), the added oxidant is one or more of ammonium peroxodisulfate, hydrogen peroxide and potassium permanganate, and the mass ratio of the oxidant to the polymer monomer is 0.4-1.2; the polymer monomer is one or more of pyrrole, thiophene and aniline; the reaction time in the step (2) is 8-48 h.
6. The preparation method according to claim 1, wherein in the step (3), the mass ratio of the magnesium powder to the precursor is controlled to be 0.2-10; the mass ratio of the sodium chloride to the precursor is 2-30; the mixing includes one of solid phase mixing and liquid phase mixing.
7. The method of claim 1, wherein in step (4), the silicon-manganese alloy comprises MnSi and Mn5Si3、Mn27Si47、Mn6Si、Mn15Si26One or more of (a).
8. The method as claimed in claim 1, wherein in the step (4), the heating in the inert shielding gas is divided into two sections, the low-temperature calcination is controlled at 500 ℃ at 100-.
9. The method as claimed in claim 8, wherein the low temperature calcination is controlled at 400 ℃ and the high temperature calcination is controlled at 900 ℃ respectively.
10. The method as claimed in claim 8, wherein the low temperature calcination is controlled at 300 ℃ and the high temperature calcination is controlled at 800 ℃ and 150 ℃.
11. The method according to claim 1, wherein in the step (5), the acid comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid and acetic acid; the concentration of the acid is 1-8 mol/L; the temperature of the acid is 10-90 ℃.
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CN109286014A (en) * 2018-11-23 2019-01-29 浙江众泰汽车制造有限公司 A kind of Si-C composite material and its preparation method and application that surface is modified
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