CN114899366A - Carbon-coated ferrosilicon negative electrode material and preparation method thereof - Google Patents

Carbon-coated ferrosilicon negative electrode material and preparation method thereof Download PDF

Info

Publication number
CN114899366A
CN114899366A CN202210297117.5A CN202210297117A CN114899366A CN 114899366 A CN114899366 A CN 114899366A CN 202210297117 A CN202210297117 A CN 202210297117A CN 114899366 A CN114899366 A CN 114899366A
Authority
CN
China
Prior art keywords
tin
ferrosilicon
carbon
conductive oxide
coated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210297117.5A
Other languages
Chinese (zh)
Inventor
王培初
邓明华
任建国
田立斌
黄浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huizhou Btr New Material Technology Co ltd
Dingyuan New Energy Technology Co Ltd
Original Assignee
Huizhou Btr New Material Technology Co ltd
Dingyuan New Energy Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huizhou Btr New Material Technology Co ltd, Dingyuan New Energy Technology Co Ltd filed Critical Huizhou Btr New Material Technology Co ltd
Priority to CN202210297117.5A priority Critical patent/CN114899366A/en
Publication of CN114899366A publication Critical patent/CN114899366A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application provides a carbon-coated ferrosilicon negative electrode material and a preparation method thereof. Foretell carbon-coated ferrosilicon negative pole material includes ferrosilicon alloy powder, tin base conductive oxide layer and carbon coating, and tin base conductive oxide layer cladding is in ferrosilicon alloy powder surface, and carbon coating cladding is in tin base conductive oxide layer surface. The carbon-coated ferrosilicon negative electrode material has high specific capacity, good cycle performance and low preparation cost.

Description

Carbon-coated ferrosilicon negative electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a carbon-coated ferrosilicon negative electrode material and a preparation method thereof.
Background
With the wider and wider application of lithium ion batteries, the requirements on the battery capacity and the preparation cost are higher and higher. At present, a graphite cathode material is mainly adopted in commercialization, and through the development of nearly thirty years, the energy density of the graphite cathode material is close to the theoretical value level (the theoretical specific capacity is 372mAh/g), so that the further improvement of the energy density of the lithium ion battery is limited. In recent years, high-capacity negative electrode materials are widely concerned, wherein the theoretical specific capacity of a silicon negative electrode material reaches 4200mAh/g due to high specific capacity, so that the silicon negative electrode material has a good development prospect, but the silicon negative electrode has poor cycle performance due to large volume expansion in the charging and discharging process, so that a silicon-based material is generally formed through nanocrystallization and carbon coating, the silicon-based material is compounded with graphite to prepare a silicon-carbon negative electrode material, the addition amount of silicon in the negative electrode material is limited, so that the high-capacity battery is difficult to prepare, the nanocrystallization cost of silicon is high, and the preparation cost of the battery is greatly increased.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the carbon-coated ferrosilicon negative electrode material which has higher specific capacity, better cycle performance and lower preparation cost and the preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
the utility model provides a carbon cladding ferrosilicon cathode material, includes ferrosilicon alloy powder, tin base conductive oxide layer and carbon coating, tin base conductive oxide layer cladding in ferrosilicon alloy powder surface, the carbon coating cladding in tin base conductive oxide layer surface.
In one embodiment, the ferrosilicon powder has a grain size of 1 μm to 10 μm.
In one embodiment, the ferrosilicon powder is industrial ferrosilicon with Si content not less than 75 wt%.
A preparation method of a carbon-coated ferrosilicon negative electrode material is used for preparing the carbon-coated ferrosilicon negative electrode material in any one of the embodiments, and the preparation method of the carbon-coated ferrosilicon negative electrode material comprises the following steps:
obtaining ferrosilicon alloy powder, lanthanum oxide and tin oxide;
carrying out jet milling treatment on the ferrosilicon powder;
calcining the tin oxide and the lanthanum oxide to obtain a tin-based conductive oxide precursor;
carrying out nano ball milling treatment on the tin-based conductive oxide precursor;
mixing and drying the ferrosilicon alloy powder and the tin-based conductive oxide precursor to obtain tin-based conductive oxide coated ferrosilicon alloy;
and carrying out carbon coating operation on the tin-based conductive oxide coated ferrosilicon alloy to obtain the carbon-coated ferrosilicon cathode material.
In one embodiment, the step of performing the carbon coating operation on the tin-based conductive oxide coated ferrosilicon alloy specifically comprises: and adding the tin-based conductive oxide coated ferrosilicon alloy into a CVD (chemical vapor deposition) gas phase coating furnace, introducing mixed gas of nitrogen and acetylene gas into the CVD gas phase coating furnace, and then carrying out gas phase chemical deposition to enable the tin-based conductive oxide coated ferrosilicon alloy to deposit carbon on the surface to form a carbon coating layer.
In one embodiment, the vapor phase chemical deposition is carried out at the temperature of 900-1000 ℃, and the deposition time is 2-3 h.
In one embodiment, the particle size of the tin-based conductive oxide precursor after nano ball milling treatment is less than 100 nm.
In one embodiment, the tin oxide and lanthanum oxide are subjected to a calcination operation at a temperature of 1000 ℃ to 1200 ℃.
In one embodiment, the content of the tin-based conductive oxide precursor in the tin-based conductive oxide-coated ferrosilicon alloy is 0.5 wt% to 3 wt%.
In one embodiment, the method for preparing the carbon-coated silicon-iron anode material further comprises, after the step of subjecting the tin oxide and the lanthanum oxide to the calcination operation and before the step of subjecting the silicon-iron alloy powder, the lanthanum oxide, and the tin oxide to the mixing and drying operation, the steps of:
and carrying out nano ball milling treatment on the tin-based conductive oxide precursor by adopting a dispersing agent.
Compared with the prior art, the invention has at least the following advantages:
according to the carbon-coated ferrosilicon negative electrode material, ferrosilicon alloy powder is used for replacing a silicon-based material, and the ferrosilicon alloy powder has small expansion degree in the lithium desorption process and stable structure, and tin-based conductive oxide coating and carbon coating are sequentially carried out on the ferrosilicon alloy powder, so that a tin-based conductive oxide layer and a carbon coating layer are sequentially formed on the surface of the ferrosilicon alloy powder, the expansion degree of the carbon-coated ferrosilicon negative electrode material in the charging and discharging processes is better reduced, the cycle performance and the electrochemical performance of the carbon-coated ferrosilicon negative electrode material are improved, the content of the carbon-coated ferrosilicon negative electrode material in the negative electrode material is increased, namely the specific capacity of a battery is improved, the problem of nanocrystallization is avoided, and the preparation cost of the carbon-coated ferrosilicon negative electrode material is reduced; in addition, the ferrosilicon alloy powder has better conductivity, and the tin-based conductive oxide layer and the carbon coating layer which are sequentially formed on the surface of the ferrosilicon alloy powder further improve the conductivity of the ferrosilicon alloy powder, so that the conductivity of the carbon-coated ferrosilicon negative electrode material is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 is a flowchart of a method for preparing a carbon-coated ferrosilicon negative electrode material according to an embodiment of the present invention;
fig. 2 is a graph of cycle performance for the carbon-coated ferrosilicon anode material of example 5.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The application provides a carbon-coated ferrosilicon negative electrode material. Foretell carbon-coated ferrosilicon negative pole material includes ferrosilicon alloy powder, tin base conductive oxide layer and carbon coating, and tin base conductive oxide layer cladding is in ferrosilicon alloy powder surface, and carbon coating cladding is in tin base conductive oxide layer surface.
According to the carbon-coated ferrosilicon negative electrode material, ferrosilicon alloy powder is used for replacing a silicon-based material, and the ferrosilicon alloy powder has small expansion degree in the lithium desorption process and stable structure, and tin-based conductive oxide coating and carbon coating are sequentially carried out on the ferrosilicon alloy powder, so that a tin-based conductive oxide layer and a carbon coating layer are sequentially formed on the surface of the ferrosilicon alloy powder, the expansion degree of the carbon-coated ferrosilicon negative electrode material in the charging and discharging processes is better reduced, the cycle performance and the electrochemical performance of the carbon-coated ferrosilicon negative electrode material are improved, the content of the carbon-coated ferrosilicon negative electrode material in the negative electrode material is increased, the specific capacity of a battery is improved, the problem of nanocrystallization treatment is avoided, and the preparation cost of the carbon-coated ferrosilicon negative electrode material is reduced; in addition, the ferrosilicon alloy powder has better conductivity, and the tin-based conductive oxide layer and the carbon coating layer which are sequentially formed on the surface of the ferrosilicon alloy powder further improve the conductivity of the ferrosilicon alloy powder, so that the conductivity of the carbon-coated ferrosilicon negative electrode material is improved.
It should be noted that, tin-based conductive oxide coating has been carried out to ferrosilicon alloy powder and has formed tin-based conductive oxide layer, tin-based conductive oxide layer has the effect of lithium desorption, the specific capacity of carbon-coated ferrosilicon negative electrode material has further been increased, and tin-based conductive oxide layer self has the expanded ability of buffer volume, including tin-based conductive oxide layer surface cladding has the carbon coating, carbon-coated ferrosilicon negative electrode material's expansibility has been reduced effectively, carbon-coated ferrosilicon negative electrode material's cyclicity performance has been improved.
It should be further noted that the tin-based conductive oxide layer is attached to the ferrosilicon alloy powder, so that the tin-based conductive oxide is dispersed on the surface of the ferrosilicon alloy powder, the dispersity of the tin-based conductive oxide is improved, namely, the mutual contact of the tin-based conductive oxide is reduced, further, the surface of the tin-based conductive oxide layer is coated with the carbon coating layer, the mutual contact of the tin-based conductive oxide is further effectively reduced by the carbon coating layer, further, the agglomeration of tin formed by the tin-based conductive oxide in the lithium desorption and insertion process is effectively reduced, and the cycle performance of the carbon-coated ferrosilicon negative electrode material is effectively improved under the condition that the specific capacity of the carbon-coated ferrosilicon negative electrode material is further improved.
In one embodiment, the tin-based conductive oxide layer is a lanthanum oxide doped tin-based conductive oxide layer. The lanthanum oxide-doped tin-based conductive oxide layer is a layer structure formed by doping the lanthanum oxide with the tin-based oxide, the lanthanum oxide-doped tin-based oxide is a substance formed by doping and heat treating the lanthanum oxide and the tin-based oxide, and the lanthanum oxide doping can effectively improve the cycle performance of the tin-based conductive oxide layer, so that the cycle performance of the carbon-coated silicon-iron cathode material is further improved.
In one embodiment, the ferrosilicon powder has a grain size of 1 μm to 10 μm. It can be understood that when the grain size of the ferrosilicon powder is 1-10 μm, the carbon coating layer can better buffer the expansion of the ferrosilicon powder, and further ensure the cycle performance of the carbon-coated ferrosilicon negative electrode material.
In one embodiment, the ferrosilicon powder has a grain size of 3 μm to 5 μm. It can be understood that when the grain size of the ferrosilicon powder is 1 μm to 10 μm, the carbon coating layer can buffer the expansion of the ferrosilicon powder more sufficiently, thereby ensuring the cycle performance of the carbon-coated ferrosilicon negative electrode material.
In one embodiment, the silicon-iron alloy powder is industrial silicon-iron alloy, the Si content of the industrial silicon-iron alloy is more than or equal to 75 wt%, and due to the existence of the tin-based conductive oxide layer and the carbon coating layer, when the Si content of the industrial silicon-iron alloy is more than or equal to 75 wt%, the expansion of the silicon-iron alloy powder can be well buffered, and the specific capacity of the carbon-coated silicon-iron negative electrode material is well improved.
The application also provides a preparation method of the carbon-coated ferrosilicon negative electrode material, which is used for preparing the carbon-coated ferrosilicon negative electrode material in any embodiment. The preparation method of the carbon-coated ferrosilicon negative electrode material comprises the following steps: obtaining ferrosilicon alloy powder, lanthanum oxide and tin oxide; carrying out jet milling treatment on the ferrosilicon powder; calcining the tin oxide and the lanthanum oxide to obtain a tin-based conductive oxide precursor; carrying out nano ball milling treatment on the tin-based conductive oxide precursor; mixing and drying the ferrosilicon alloy powder and the tin-based conductive oxide precursor to obtain tin-based conductive oxide coated ferrosilicon alloy; and carrying out carbon coating operation on the ferrosilicon alloy coated with the tin-based conductive oxide to obtain the carbon-coated ferrosilicon cathode material.
The preparation method of the carbon-coated ferrosilicon negative electrode material selects ferrosilicon alloy powder, lanthanum oxide and tin oxide to prepare the carbon-coated ferrosilicon negative electrode material, is favorable for realizing the high rate capability and high specific capacity of the carbon-coated ferrosilicon negative electrode material, and performs mixing and drying operation on the ferrosilicon alloy powder and a tin-based conductive oxide precursor to form a tin-based conductive oxide layer on the surface of the ferrosilicon alloy powder, further performs carbon coating operation on the tin-based conductive oxide coated ferrosilicon alloy to form a carbon coating layer on the surface of the ferrosilicon alloy coated by the tin-based conductive oxide, under the condition that the dispersity of the tin-based conductive oxide is effectively improved by coating the tin-based conductive oxide on the surface of the ferrosilicon alloy, the carbon coating layer further effectively reduces the mutual contact of the tin-based conductive oxide, and further effectively reduces the agglomeration of tin formed by the tin-based conductive oxide in the lithium extraction process, under the condition of further improving the specific capacity of the carbon-coated ferrosilicon negative electrode material, the cycle performance and the conductivity of the carbon-coated ferrosilicon negative electrode material are effectively improved.
For better understanding of the method for preparing the carbon-coated ferrosilicon negative electrode material of the present application, the following further explains the method for preparing the carbon-coated ferrosilicon negative electrode material of the present application:
referring to fig. 1, a method for preparing a carbon-coated ferrosilicon negative electrode material according to an embodiment includes the following steps:
s100, obtaining the silicon-iron alloy powder, lanthanum oxide and tin oxide. It can be understood that the ferrosilicon alloy powder and the lanthanum oxide-doped tin-based conductive oxide both have higher specific capacities, and the lanthanum oxide-doped tin-based conductive oxide also has better conductivity, so that the ferrosilicon alloy powder, the lanthanum oxide and the tin oxide are selected to prepare the carbon-coated ferrosilicon anode material in order to better realize the high rate performance and the high specific capacity of the carbon-coated ferrosilicon anode material.
S200, carrying out jet milling treatment on the ferrosilicon powder, and ensuring that the grain diameter of the ferrosilicon powder has higher consistency.
S300, calcining the tin oxide and the lanthanum oxide to obtain the tin-based conductive oxide precursor. It can be understood that the tin-based conductive oxide precursor obtained by calcining the tin oxide and the lanthanum oxide, that is, the obtained lanthanum oxide-doped tin-based conductive oxide, that is, the tin-based conductive oxide precursor is obtained, so that the lanthanum oxide doping of the tin oxide is better realized, and the tin-based conductive oxide precursor has better void structure and structural stability.
S400, carrying out nano ball milling treatment on the tin-based conductive oxide precursor.
S500, mixing and drying the ferrosilicon alloy powder and the tin-based conductive oxide precursor to obtain the tin-based conductive oxide coated ferrosilicon alloy. It can be understood that the tin-based conductive oxide precursor is a tin-based conductive oxide, because the tin-based conductive oxide expands in the process of lithium deintercalation and generates Sn in the process of lithium deintercalation, Sn is easy to agglomerate to affect the cycle performance of the negative electrode material, if the ferrosilicon alloy powder and the tin-based conductive oxide are directly mixed and doped, although the tin-based conductive oxide is diluted, the agglomeration of Sn can be reduced, and the conductivity of the ferrosilicon alloy powder can be improved, but the effect is limited, and the agglomeration of Sn and the conductivity of the ferrosilicon alloy powder are difficult to further reduce, therefore, in the application, a mode of mixing and drying the ferrosilicon alloy powder and the tin-based conductive oxide precursor is adopted, so that a tin-based conductive oxide layer is formed on the surface of the ferrosilicon alloy powder, and the ferrosilicon alloy coated with the tin-based conductive oxide is obtained, make tin base conductive oxide highly disperse in ferrosilicon alloy powder surface, further improved tin base conductive oxide dispersion degree, further reduced tin base conductive oxide contact each other promptly, and then played the effect that reduces the reunion of Sn better, and tin base conductive oxide cladding in the surface of ferrosilicon alloy powder, further improved the electric conductivity of ferrosilicon alloy powder effectively, realized the cycling performance and the electric conductivity of carbon cladding ferrosilicon negative pole material promptly effectively.
S600, carrying out carbon coating operation on the ferrosilicon alloy coated with the tin-based conductive oxide to obtain the carbon-coated ferrosilicon cathode material. It can be understood that the mode of carrying out carbon coating operation on the tin-based conductive oxide coated silicon iron alloy is adopted, so that a carbon coating layer is formed on the surface of the tin-based conductive oxide coated silicon iron alloy, and the carbon-coated silicon iron negative electrode material is obtained.
The preparation method of the carbon-coated ferrosilicon negative electrode material selects ferrosilicon alloy powder, lanthanum oxide and tin oxide to prepare the carbon-coated ferrosilicon negative electrode material, is favorable for realizing the high rate capability and high specific capacity of the carbon-coated ferrosilicon negative electrode material, and performs mixing and drying operation on the ferrosilicon alloy powder and a tin-based conductive oxide precursor to form a tin-based conductive oxide layer on the surface of the ferrosilicon alloy powder, further performs carbon coating operation on the tin-based conductive oxide coated ferrosilicon alloy to form a carbon coating layer on the surface of the ferrosilicon alloy coated by the tin-based conductive oxide, under the condition that the dispersity of the tin-based conductive oxide is effectively improved by coating the tin-based conductive oxide on the surface of the ferrosilicon alloy, the carbon coating layer further effectively reduces the mutual contact of the tin-based conductive oxide, and further effectively reduces the agglomeration of tin formed by the tin-based conductive oxide in the lithium extraction process, under the condition of further improving the specific capacity of the carbon-coated ferrosilicon negative electrode material, the cycle performance and the conductivity of the carbon-coated ferrosilicon negative electrode material are effectively improved.
In one embodiment, the content of the tin-based conductive oxide precursor in the tin-based conductive oxide-coated ferrosilicon alloy is 0.5 wt% -3 wt%, so that effective coating of ferrosilicon alloy powder is effectively ensured, high dispersion of the generated tin-based conductive oxide is effectively ensured, and the cycle performance and the conductivity of the carbon-coated ferrosilicon negative electrode material are effectively improved under the condition of improving the specific capacity of the carbon-coated ferrosilicon negative electrode material.
In one embodiment, the step of performing the carbon coating operation on the tin-based conductive oxide coated ferrosilicon alloy specifically comprises: the tin-based conductive oxide coated silicon-iron alloy is added into a CVD gas phase coating furnace, mixed gas of nitrogen and acetylene gas is introduced into the CVD gas phase coating furnace, and then, gas phase chemical deposition is carried out, so that carbon is deposited on the surface of the tin-based conductive oxide coated silicon-iron alloy to form a carbon coating layer, and the carbon coating of the tin-based conductive oxide coated silicon-iron alloy is effectively realized.
In one embodiment, the carbon coating of the tin-based conductive oxide coated ferrosilicon alloy is better realized by performing vapor phase chemical deposition at the temperature of 900-1000 ℃ for 2-3 h.
In one embodiment, the tin oxide is SnO 2 (ii) a The lanthanum oxide is La 2 O 3 ；SnO 2 And La 2 O 3 The molar ratio of (A) to (B) is 0.01-0.10, so that the cycle performance and specific capacity of the tin-based conductive oxide are better ensured.
In one embodiment, the tin oxide and the lanthanum oxide are calcined at the temperature of 1000-1200 ℃, so that the tin-based conductive oxide has a better void structure and structural stability.
In one embodiment, the tin oxide and the lanthanum oxide are calcined at the temperature of 1000-1200 ℃, the calcination time is 2-3 h, the full doping, calcination and molding of the tin oxide and the lanthanum oxide are ensured, and the tin-based conductive oxide is further ensured to have a better void structure and structural stability.
In one embodiment, the method for preparing the carbon-coated ferrosilicon anode material, after the step of subjecting the tin oxide and the lanthanum oxide to the calcination operation and before the step of subjecting the ferrosilicon alloy powder and the tin-based conductive oxide precursor to the mixing and drying operation, further includes the steps of: and carrying out nano ball milling treatment on the tin-based conductive oxide precursor by adopting a dispersing agent. It can be understood that, in order to make tin-based conductive oxide fully and uniformly adhere to the surface of silicon-iron alloy powder better, in this application, adopt the dispersant to carry out dispersion grinding to tin-based conductive oxide precursor for tin-based conductive oxide's particle size reduces, and utilize the dispersant to support tin-based conductive oxide to disperse more evenly in the surface of silicon-iron alloy powder, and further, dry the dispersant, realized forming the silicon-based oxide layer of highly even dispersion on silicon-iron alloy powder surface.
In one embodiment, the particle size of the tin-based conductive oxide precursor after the nano ball milling treatment is less than 100nm, so that the dispersibility of the tin-based conductive oxide is improved, and the adhesion effect of the tin-based conductive oxide layer is ensured.
In one embodiment, the particle size of the tin-based conductive oxide precursor after the nano ball milling treatment is less than 20nm, so that the dispersibility of the tin-based conductive oxide is improved, and the adhesion effect of the tin-based conductive oxide layer is ensured.
In one embodiment, the dispersing agent is an NMP solution, ensuring the dispersing effect of the tin-based conductive oxide.
In one embodiment, after the step of performing the carbon coating operation on the tin-based conductive oxide coated silicon-iron alloy, the method for preparing the carbon-coated silicon-iron negative electrode material further comprises the following steps: and cooling the carbon-coated ferrosilicon negative electrode material.
In one embodiment, the carbon-coated ferrosilicon negative electrode material is cooled at room temperature to cool the carbon-coated ferrosilicon negative electrode material to room temperature.
Compared with the prior art, the invention has at least the following advantages:
according to the carbon-coated ferrosilicon negative electrode material, ferrosilicon alloy powder is used for replacing a silicon-based material, and the ferrosilicon alloy powder has small expansion degree in the lithium desorption process and stable structure, and tin-based conductive oxide coating and carbon coating are sequentially carried out on the ferrosilicon alloy powder, so that a tin-based conductive oxide layer and a carbon coating layer are sequentially formed on the surface of the ferrosilicon alloy powder, the expansion degree of the carbon-coated ferrosilicon negative electrode material in the charging and discharging processes is better reduced, the cycle performance and the electrochemical performance of the carbon-coated ferrosilicon negative electrode material are improved, the content of the carbon-coated ferrosilicon negative electrode material in the negative electrode material is increased, namely the specific capacity of a battery is improved, the problem of nanocrystallization is avoided, and the preparation cost of the carbon-coated ferrosilicon negative electrode material is reduced; in addition, the ferrosilicon alloy powder has better conductivity, and the tin-based conductive oxide layer and the carbon coating layer which are sequentially formed on the surface of the ferrosilicon alloy powder further improve the conductivity of the ferrosilicon alloy powder, so that the conductivity of the carbon-coated ferrosilicon negative electrode material is improved.
For further understanding of the present invention, the present invention is further illustrated by the following examples, but it should be understood that the embodiments are carried out under the premise of technical solution of the present invention, and the detailed embodiments and specific operation procedures are given only for further illustrating the features and advantages of the present invention, not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
Taking ferrosilicon powder, and carrying out jet milling on the ferrosilicon powder to obtain ferrosilicon powder with the average grain diameter of 3 mu m; lanthanum oxide and tin oxide are mixed according to a molar ratio of 0.01: 1, and reacting the mixture at 1000 ℃ for 2.5 hours to obtain a tin-based conductive oxide; adding tin-based conductive oxide into NMP solution, and performing ball milling in a sand mill to obtain tin-based nano oxide conductive slurry; uniformly mixing the ferrosilicon alloy powder with the tin-based conductive oxide conductive slurry, and drying to obtain a tin-based conductive oxide coated ferrosilicon alloy material, wherein the content of tin-based conductive oxide in the tin-based conductive oxide coated ferrosilicon alloy material is 0.5 wt%; adding the ferrosilicon alloy material coated by the tin-based conductive oxide into a CVD (chemical vapor deposition) gas phase coating furnace, introducing nitrogen and acetylene mixed gas, heating to 1000 ℃, carrying out gas phase chemical deposition, carrying out heat preservation reaction for 2h, depositing a carbon coating layer on the surface of ferrosilicon alloy particles coated by the tin-based conductive oxide, naturally cooling to room temperature, and taking out to obtain the carbon-coated ferrosilicon cathode material.
Example 2
Taking ferrosilicon powder, and carrying out jet milling on the ferrosilicon powder to obtain ferrosilicon powder with the average grain diameter of 3 mu m; lanthanum oxide and tin oxide are mixed according to a molar ratio of 0.025: 1, and reacting the mixture at 1100 ℃ for 2 hours to obtain a tin-based conductive oxide; adding tin-based conductive oxide into NMP solution, and performing ball milling in a sand mill to obtain tin-based nano oxide conductive slurry; uniformly mixing the ferrosilicon alloy powder with the tin-based conductive oxide conductive slurry, and drying to obtain a tin-based conductive oxide coated ferrosilicon alloy material, wherein the tin-based conductive oxide content in the tin-based conductive oxide coated ferrosilicon alloy material is 1.5 wt%; adding the ferrosilicon alloy material coated by the tin-based conductive oxide into a CVD (chemical vapor deposition) gas phase coating furnace, introducing nitrogen and acetylene mixed gas, heating to 900 ℃, carrying out gas phase chemical deposition, carrying out heat preservation reaction for 2h, depositing a carbon coating layer on the surface of ferrosilicon alloy particles coated by the tin-based conductive oxide, naturally cooling to room temperature, and taking out to obtain the carbon-coated ferrosilicon cathode material.
Example 3
Taking ferrosilicon powder, and carrying out jet milling on the ferrosilicon powder to obtain ferrosilicon powder with the average grain diameter of 3 mu m; lanthanum oxide and tin oxide are mixed according to a molar ratio of 0.05: 1, and reacting the mixture at 1100 ℃ for 2 hours to obtain a tin-based conductive oxide; adding tin-based conductive oxide into an NMP solution, and performing ball milling in a sand mill to obtain tin-based nano oxide conductive slurry; uniformly mixing the ferrosilicon alloy powder with the tin-based conductive oxide conductive slurry, and drying to obtain a tin-based conductive oxide coated ferrosilicon alloy material, wherein the tin-based conductive oxide content in the tin-based conductive oxide coated ferrosilicon alloy material is 1.5 wt%; adding the ferrosilicon alloy material coated by the tin-based conductive oxide into a CVD (chemical vapor deposition) gas phase coating furnace, introducing nitrogen and acetylene mixed gas, heating to 900 ℃, carrying out gas phase chemical deposition, carrying out heat preservation reaction for 2h, depositing a carbon coating layer on the surface of ferrosilicon alloy particles coated by the tin-based conductive oxide, naturally cooling to room temperature, and taking out to obtain the carbon-coated ferrosilicon cathode material.
Example 4
Taking ferrosilicon powder, and carrying out jet milling on the ferrosilicon powder to obtain ferrosilicon powder with the average grain diameter of 3 mu m; lanthanum oxide and tin oxide are mixed according to a molar ratio of 0.1: 1, and reacting the mixture at 1100 ℃ for 2 hours to obtain a tin-based conductive oxide; adding tin-based conductive oxide into NMP solution, and performing ball milling in a sand mill to obtain tin-based nano oxide conductive slurry; uniformly mixing the ferrosilicon alloy powder with the tin-based conductive oxide conductive slurry, and drying to obtain a tin-based conductive oxide coated ferrosilicon alloy material, wherein the tin-based conductive oxide content in the tin-based conductive oxide coated ferrosilicon alloy material is 1.5 wt%; adding the ferrosilicon alloy material coated by the tin-based conductive oxide into a CVD (chemical vapor deposition) gas phase coating furnace, introducing nitrogen and acetylene mixed gas, heating to 900 ℃, carrying out gas phase chemical deposition, carrying out heat preservation reaction for 2h, depositing a carbon coating layer on the surface of ferrosilicon alloy particles coated by the tin-based conductive oxide, naturally cooling to room temperature, and taking out to obtain the carbon-coated ferrosilicon cathode material.
Example 5
Taking ferrosilicon powder, and carrying out jet milling on the ferrosilicon powder to obtain ferrosilicon powder with the average grain diameter of 3 mu m; lanthanum oxide and tin oxide are mixed according to a molar ratio of 0.025: 1, and reacting the mixture at 1100 ℃ for 2 hours to obtain a tin-based conductive oxide; adding tin-based conductive oxide into NMP solution, and performing ball milling in a sand mill to obtain tin-based nano oxide conductive slurry; uniformly mixing the ferrosilicon alloy powder with the tin-based conductive oxide conductive slurry, and drying to obtain a tin-based conductive oxide coated ferrosilicon alloy material, wherein the content of tin-based conductive oxide in the tin-based conductive oxide coated ferrosilicon alloy material is 3.0 wt%; (ii) a Adding the ferrosilicon alloy material coated by the tin-based conductive oxide into a CVD (chemical vapor deposition) gas phase coating furnace, introducing nitrogen and acetylene mixed gas, heating to 900 ℃, carrying out gas phase chemical deposition, carrying out heat preservation reaction for 2h, depositing a carbon coating layer on the surface of ferrosilicon alloy particles coated by the tin-based conductive oxide, naturally cooling to room temperature, and taking out to obtain the carbon-coated ferrosilicon cathode material.
Example 6
Taking ferrosilicon powder, and carrying out jet milling on the ferrosilicon powder to obtain ferrosilicon powder with the average grain diameter of 3 mu m; lanthanum oxide and tin oxide are mixed according to a molar ratio of 0.05: 1, and reacting the mixture at 1100 ℃ for 2 hours to obtain a tin-based conductive oxide; adding tin-based conductive oxide into NMP solution, and performing ball milling in a sand mill to obtain tin-based nano oxide conductive slurry; uniformly mixing the ferrosilicon alloy powder with the tin-based conductive oxide conductive slurry, and drying to obtain a tin-based conductive oxide coated ferrosilicon alloy material, wherein the content of tin-based conductive oxide in the tin-based conductive oxide coated ferrosilicon alloy material is 3.0 wt%; adding the ferrosilicon alloy material coated by the tin-based conductive oxide into a CVD (chemical vapor deposition) gas phase coating furnace, introducing nitrogen and acetylene mixed gas, heating to 900 ℃, carrying out gas phase chemical deposition, carrying out heat preservation reaction for 2h, depositing a carbon coating layer on the surface of ferrosilicon alloy particles coated by the tin-based conductive oxide, naturally cooling to room temperature, and taking out to obtain the carbon-coated ferrosilicon cathode material.
Example 7
Taking ferrosilicon powder, and carrying out jet milling on the ferrosilicon powder to obtain ferrosilicon powder with the average grain diameter of 3 mu m; lanthanum oxide and tin oxide are mixed according to a molar ratio of 0.01: 1, and reacting the mixture at 1100 ℃ for 2 hours to obtain a tin-based conductive oxide; adding tin-based conductive oxide into an NMP solution, and performing ball milling in a sand mill to obtain tin-based nano oxide conductive slurry; uniformly mixing the ferrosilicon alloy powder with the tin-based conductive oxide conductive slurry, and drying to obtain a tin-based conductive oxide coated ferrosilicon alloy material, wherein the content of tin-based conductive oxide in the tin-based conductive oxide coated ferrosilicon alloy material is 3.0 wt%; adding the ferrosilicon alloy material coated by the tin-based conductive oxide into a CVD (chemical vapor deposition) gas phase coating furnace, introducing nitrogen and acetylene mixed gas, heating to 900 ℃, carrying out gas phase chemical deposition, carrying out heat preservation reaction for 2h, depositing a carbon coating layer on the surface of ferrosilicon alloy particles coated by the tin-based conductive oxide, naturally cooling to room temperature, and taking out to obtain the carbon-coated ferrosilicon cathode material.
Comparative example 1
Taking ferrosilicon alloy powder, and carrying out jet milling on the ferrosilicon alloy powder to obtain ferrosilicon alloy powder with the average grain size of 3 mu m; adding ferrosilicon powder into a CVD (chemical vapor deposition) gas phase coating furnace, introducing nitrogen and acetylene mixed gas, heating to 900 ℃, carrying out gas phase chemical deposition, carrying out heat preservation reaction for 2 hours, depositing a carbon coating layer on the surface of ferrosilicon particles coated by tin-based conductive oxide, naturally cooling to room temperature, and taking out to obtain the carbon-coated ferrosilicon cathode material.
The carbon-coated ferrosilicon negative electrode materials prepared in examples 1 to 11 and comparative example 1 were mixed with acetylene black, CMC, and SBR at a mass ratio of 8: 1: 0.5: 0.5, adding a proper amount of deionized water, uniformly stirring to prepare slurry, coating the obtained viscous slurry on a circular copper foil with the diameter of 10mm to prepare a pole piece, and then drying the pole piece in a vacuum drying oven at 80 ℃ for 12 hours to remove water. In a glove box filled with argon, a metal lithium sheet is taken as a counter electrode, Celgard2500 polypropylene porous membrane is taken as a diaphragm, and 1mol/L LiPF 6 And the solution of/EC-EMC-DMC (volume ratio is 1: 1: 1) is used as electrolyte to assemble the CR2032 button half-cell.
Each CR2032 button half cell was subjected to constant current charge and discharge performance testing on a battery test system (LAND CTR 2001A). The voltage range is 0.01-1.5V, the specific capacity of the carbon-coated ferrosilicon negative electrode material is tested by 100mA/g charging and discharging, and the cycle performance of the carbon-coated ferrosilicon negative electrode material is tested by 100mA/g charging and discharging. Test of electrochemical properties of the carbon-coated ferrosilicon negative electrode material electrochemical properties are shown in table 1, and fig. 2 is a graph showing cycle performance of the carbon-coated ferrosilicon negative electrode material of example 5.
Table 1: electrochemical performance of carbon-coated ferrosilicon negative electrode material
Sample (I) Specific capacity (mAh/g) First charge-discharge efficiency (%) Capacity retention ratio (%) at 100 cycles
Example 1 749 80 75
Example 2 756 81 82
Example 3 829 81 81
Example 4 798 80 76
Example 5 825 82 85
Example 6 748 79 77
Example 7 694 76 63
Comparative example 1 729 74 57
As can be seen from table 1 and fig. 2, the carbon-coated ferrosilicon negative electrode materials of examples 1 to 7 all have better electrochemical cycle performance and higher specific capacity than comparative example 1, particularly, the specific capacities of the carbon-coated ferrosilicon negative electrode materials of example 5 can reach 825mAh/g, and the capacity retention rate after 100 cycles can reach 85%, and the carbon-coated ferrosilicon negative electrode materials of examples 1 to 7 all have higher first charge and discharge efficiency than comparative example 1, particularly, the carbon-coated ferrosilicon negative electrode material of example 5 can reach 85%, which indicates that the carbon-coated ferrosilicon negative electrode material prepared from the carbon-coated ferrosilicon negative electrode material of the present application has better cycle performance and specific capacity.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The utility model provides a carbon cladding ferrosilicon cathode material which characterized in that, includes ferrosilicon alloy powder, tin base conductive oxide layer and carbon cladding layer, tin base conductive oxide layer cladding in ferrosilicon alloy powder surface, the carbon cladding in tin base conductive oxide layer surface.
2. The carbon-coated ferrosilicon negative electrode material according to claim 1, wherein the ferrosilicon powder has a particle size of 1 to 10 μm.
3. The carbon-coated ferrosilicon negative electrode material according to claim 1, wherein the ferrosilicon powder is an industrial ferrosilicon alloy having an Si content of not less than 75 wt%.
4. A method for producing a carbon-coated ferrosilicon negative electrode material, for use in producing the carbon-coated ferrosilicon negative electrode material according to any one of claims 1 to 3, comprising the steps of:
obtaining ferrosilicon alloy powder, lanthanum oxide and tin oxide;
carrying out jet milling treatment on the ferrosilicon powder;
calcining the tin oxide and the lanthanum oxide to obtain a tin-based conductive oxide precursor;
carrying out nano ball milling treatment on the tin-based conductive oxide precursor;
mixing and drying the ferrosilicon alloy powder and the tin-based conductive oxide precursor to obtain tin-based conductive oxide coated ferrosilicon alloy;
and carrying out carbon coating operation on the tin-based conductive oxide coated ferrosilicon alloy to obtain the carbon-coated ferrosilicon cathode material.
5. The method for preparing a carbon-coated ferrosilicon anode material according to claim 4, wherein the step of performing the carbon-coating operation on the tin-based conductive oxide-coated ferrosilicon alloy specifically comprises: and adding the tin-based conductive oxide coated ferrosilicon alloy into a CVD (chemical vapor deposition) gas phase coating furnace, introducing mixed gas of nitrogen and acetylene gas into the CVD gas phase coating furnace, and then carrying out gas phase chemical deposition to enable the tin-based conductive oxide coated ferrosilicon alloy to deposit carbon on the surface to form a carbon coating layer.
6. The method for preparing a negative electrode material of silicon-iron coated with carbon as claimed in claim 5, wherein the vapor-phase chemical deposition is carried out at a temperature of 900-1000 ℃ for a deposition time of 2-3 hours.
7. The method for preparing the carbon-coated ferrosilicon anode material of claim 4, wherein the grain size of the tin-based conductive oxide precursor subjected to nano ball milling is less than 100 nm.
8. The method for producing a carbon-coated ferrosilicon anode material according to claim 4, wherein the tin oxide and the lanthanum oxide are subjected to a calcination operation at a temperature of 1000 ℃ to 1200 ℃.
9. The method for producing a carbon-coated ferrosilicon anode material according to claim 4, wherein the content of the tin-based conductive oxide precursor in the tin-based conductive oxide-coated ferrosilicon alloy is 0.5 to 3 wt%.
10. The method of producing a carbon-coated ferrosilicon negative electrode material according to claim 4, wherein the method of producing a carbon-coated ferrosilicon negative electrode material further includes, after the step of subjecting the tin oxide and the lanthanum oxide to the calcination operation and before the step of subjecting the ferrosilicon alloy powder and the tin-based conductive oxide precursor to the mixing and drying operation, the steps of:
and carrying out nano ball milling treatment on the tin-based conductive oxide precursor by adopting a dispersing agent.
CN202210297117.5A 2022-03-24 2022-03-24 Carbon-coated ferrosilicon negative electrode material and preparation method thereof Pending CN114899366A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210297117.5A CN114899366A (en) 2022-03-24 2022-03-24 Carbon-coated ferrosilicon negative electrode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210297117.5A CN114899366A (en) 2022-03-24 2022-03-24 Carbon-coated ferrosilicon negative electrode material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN114899366A true CN114899366A (en) 2022-08-12

Family

ID=82715894

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210297117.5A Pending CN114899366A (en) 2022-03-24 2022-03-24 Carbon-coated ferrosilicon negative electrode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114899366A (en)

Similar Documents

Publication Publication Date Title
CN102479948B (en) Negative active core-shell material of a kind of lithium ion battery and preparation method thereof and a kind of lithium ion battery
CN111146416B (en) Nitrogen-doped silicon-based material, preparation method thereof and application thereof in battery
CN111463419B (en) Silicon-based @ titanium niobium oxide core-shell structure anode material and preparation method thereof
CN108682833B (en) Preparation method of lithium iron phosphate-based modified cathode material
WO2022002057A1 (en) Silicon-oxygen composite negative electrode material, negative electrode, lithium-ion battery, and preparation methods therefor
CN111342031B (en) Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof
CN115954443B (en) Preparation method of carbon-coated silicon-copper alloy negative electrode material of lithium ion battery
CN110854373B (en) Composite negative electrode material and preparation method thereof
CN114314564B (en) Carbon nanotube conductive network coated SiO@C composite material and preparation method and application thereof
CN112289985B (en) C @ MgAl2O4Composite coating modified silicon-based negative electrode material and preparation method thereof
CN114242961A (en) Graphene/silicon oxide-coated nano-silicon composite material, and preparation method and application thereof
CN114105149B (en) Carbon-coated nitrogen-phosphorus double-doped silicon oxide composite material, preparation method thereof and application thereof in lithium ion battery
WO2022042266A1 (en) Silicon-oxygen composite negative electrode material, preparation method therefor, and lithium ion battery
CN114497507A (en) Quick-filling graphite composite material and preparation method thereof
CN114678502A (en) Graphene-based nitride negative electrode material and preparation method thereof
CN114899366A (en) Carbon-coated ferrosilicon negative electrode material and preparation method thereof
CN109962232B (en) Positive electrode active material, preparation method, positive electrode and battery
CN112968155A (en) Composite negative electrode material for lithium ion battery and preparation method thereof
CN111403725A (en) Aluminum oxide coated hafnium/nitrogen co-doped lithium iron phosphate cathode material and preparation method thereof
CN108305992B (en) Carbon-coated lithium ion battery electrode material and preparation method thereof
CN114583137B (en) Method for modifying carbon surface by sulfur doped phosphorus and application thereof
CN116190660B (en) Adhesive, preparation method and application thereof, silicon-based negative electrode and preparation method thereof
CN114335457B (en) Preparation method and application of monoclinic-phase molybdenum dioxide/nitrogen-doped carbon nanotube three-dimensional nanocomposite
CN114864915B (en) Preparation method of porous silicon/carbon nano tube composite material
CN113948686A (en) Porous spherical silicon-based composite anode material, preparation method thereof and battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication