CN111170364A - Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery - Google Patents

Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery Download PDF

Info

Publication number
CN111170364A
CN111170364A CN201911405060.0A CN201911405060A CN111170364A CN 111170364 A CN111170364 A CN 111170364A CN 201911405060 A CN201911405060 A CN 201911405060A CN 111170364 A CN111170364 A CN 111170364A
Authority
CN
China
Prior art keywords
silicon
carbon
source
niobium
titanium
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
CN201911405060.0A
Other languages
Chinese (zh)
Inventor
杜孟衣
赵晓磊
雷磊
高学华
李盼
高学博
成信刚
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.)
Yinlong New Energy Co Ltd
Northern Altair Nanotechnologies Co Ltd
Original Assignee
Yinlong New Energy Co Ltd
Northern Altair Nanotechnologies 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 Yinlong New Energy Co Ltd, Northern Altair Nanotechnologies Co Ltd filed Critical Yinlong New Energy Co Ltd
Priority to CN201911405060.0A priority Critical patent/CN111170364A/en
Publication of CN111170364A publication Critical patent/CN111170364A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a carbon-coated silicon-based titanium-niobium composite material, a preparation method thereof and a lithium ion battery. The preparation method comprises the following steps: carrying out a first calcination process by taking a titanium source and a niobium source as raw materials to obtain a first calcination product, wherein the temperature of the first calcination process is 800-1200 ℃; performing a second calcination process on a silicon source, the first calcination product and a carbon source to obtain a carbon-coated silicon-based titanium-niobium composite material, wherein the temperature of the first calcination process is 500-1000 ℃; wherein the titanium source is selected from one or more of anatase titanium dioxide, anatase titanium dioxide hydrate silicon powder and silicon oxide, the niobium source is niobium pentoxide, the silicon source is silicon powder or silicon oxide, and the carbon source is hydrocarbon. The carbon-coated silicon-based titanium-niobium composite material prepared by the method has smaller volume effect and higher cycle performance in the charging and discharging processes, and meanwhile, the preparation method also has the advantages of simple process, no pollution, high repeatability, large-scale production and the like.

Description

Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery
Technical Field
The invention relates to the field of lithium ion battery preparation, in particular to a carbon-coated silicon-based titanium-niobium composite material, a preparation method thereof and a lithium ion battery.
Background
Silicon is the lithium ion battery negative electrode material with the highest specific capacity (4200mAh/g) known at present. Compared with the traditional graphite cathode material, the silicon has extremely high gravimetric specific capacity which is more than ten times that of the natural graphite; compared with metal lithium, the bulk density of silicon in the alloy material is similar to that of lithium, so that the silicon also has high volume specific capacity; compared with carbon materials, silicon has higher lithium-releasing and-inserting potential, and effectively avoids the precipitation of lithium in the process of high-rate charge and discharge, thereby improving the safety of the battery. Based on the above advantages, silicon materials are considered as a new generation of high energy lithium ion battery cathode materials with the most application potential.
Because silicon shows a severe volume effect (more than 300%) in the charging and discharging processes, the silicon electrode material is pulverized and peeled off from the current collector, so that the active material and the active material, and the active material and the current collector lose electric contact, and simultaneously a new solid electrolyte layer (SEI) is continuously formed, and finally the electrochemical performance is deteriorated, which is the biggest obstacle of the silicon material becoming a commercial negative electrode material.
In view of the above problems, there is a need to provide a method for improving the stability of silicon material in lithium ion battery during charging and discharging.
Disclosure of Invention
The invention mainly aims to provide a carbon-coated silicon-based titanium-niobium composite material, a preparation method thereof and a lithium ion battery, so as to solve the problem of poor stability of a silicon material in the lithium ion battery in the charging and discharging processes.
In order to achieve the above object, one aspect of the present invention provides a method for preparing a carbon-coated silicon-based titanium-niobium composite material, the method comprising: carrying out a first calcination process by taking a titanium source and a niobium source as raw materials to obtain a first calcination product, wherein the temperature of the first calcination process is 800-1200 ℃; performing a second calcination process on a silicon source, the first calcination product and a carbon source to obtain a carbon-coated silicon-based titanium-niobium composite material, wherein the temperature of the second calcination process is 500-1000 ℃; wherein the titanium source is selected from one or more of anatase titanium dioxide, anatase titanium dioxide hydrate silicon powder and silicon oxide, the niobium source is niobium pentoxide, the silicon source is silicon powder or silicon oxide, and the carbon source is hydrocarbon.
Furthermore, in the first calcination process, the molar ratio of the titanium element in the titanium source to the niobium element in the niobium source is 1 (0.5-6), preferably 1 (1-5).
Further, before the first calcination process, the preparation method further includes: mixing the raw materials with a first solvent in an inert atmosphere, and then carrying out first wet grinding to obtain first slurry; after the first slurry is subjected to first drying, a first calcining process is carried out to obtain a first calcined product; preferably, in the first wet grinding process, the solid content of the first slurry is 10-30%, the particle size D50 of solid particles in the first slurry is not more than 0.8 μm, and the grinding electric quantity is 5-15 kwh/kg.
Further, a drying device adopted in the first drying process is selected from oven drying or spray drying, preferably, the drying process is carried out in the spray drying device, the inlet temperature of the spray drying device is 200-300 ℃, the outlet temperature of the spray drying device is 60-150 ℃, and the air flow is 4.8-8.8 mL/min.
Further, the temperature of the first calcining process is 900-1100 ℃, and the calcining time is 4-16 h.
Further, the carbon source is selected from one or more of glucose, sucrose, citric acid and phenolic resin.
Further, the preparation method also comprises the following steps: carrying out second wet grinding on a silicon source and a second solvent to obtain second slurry; sequentially performing ball milling and second drying processes on the mixture of the second slurry, the first calcined product and the carbon source, and then performing a second calcining process to obtain the carbon-coated silicon-based titanium-niobium composite material; preferably, the second solvent is selected from one or more of ethanol, ethylene glycol, isopropanol, and methanol; preferably, in the second wet grinding process, the solid content of the second slurry is 10-30%, the particle size D50 of solid particles in the second slurry is not more than 0.5 μm, and the grinding electric quantity is 5-15 kwh/kg; preferably, in the ball milling process, the carbon element coating amount is 3-10% and the silicon element doping amount is 30-80% in terms of weight percentage of the first calcined product.
Further, the temperature of the second calcining process is 600-800 ℃, and the calcining time is 2-10 h.
Further, the preparation method also comprises the following steps: screening the product of the second calcining process to obtain the carbon-coated silicon-based titanium-niobium composite material; preferably, the screening treatment process adopts a screen of 200-300 meshes.
The carbon-coated silicon-based titanium-niobium composite material is prepared by the preparation method.
The application further provides a lithium ion battery, which comprises a negative plate coated with a negative electrode material, wherein the negative electrode material comprises the carbon-coated silicon-based titanium-niobium composite material.
By applying the technical scheme of the invention, the titanium niobium oxide (first calcined product) can be prepared by carrying out the first calcination process by taking the titanium source and the niobium source as raw materials. Because silicon and oxygen have good affinity, in the second calcining process of the titanium niobium oxide, a silicon source and a carbon source, the silicon and the metal oxide titanium niobium oxide are compounded, the silicon is used as a reinforcement, the titanium niobium oxide is used as a matrix, and a stress buffer layer and an ion exchange layer are constructed around silicon particles, so that the volume effect of the silicon in the charging and discharging process can be buffered, the electrical contact of the silicon particles is improved, and the cycle stability of the material is improved. The silicon-based titanium niobium oxide composite material is coated with carbon, which is beneficial to improving the cycle performance of the silicon material. In addition, the preparation method has simple process, no pollution, high repeatability and large-scale production. On the basis, the carbon-coated silicon-based titanium-niobium composite material prepared by the method has smaller volume effect and higher cycle performance in the charging and discharging processes, and meanwhile, the preparation method has the advantages of simple process, no pollution, high repeatability, large-scale production and the like.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows an XRD pattern of a carbon-coated silicon-based titanium-niobium composite material prepared in example 1 of the present invention;
FIG. 2 shows an SEM spectrum of a carbon-coated silicon-based titanium-niobium composite material prepared in example 1 of the present invention;
FIG. 3 is a graph showing the first charging and discharging curves of the carbon-coated silicon-based titanium-niobium composite material prepared in example 1 of the present invention;
fig. 4 shows the charge-discharge curve after 50 cycles of the carbon-coated silicon-based titanium-niobium composite material prepared in example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the silicon material in the existing lithium ion battery has a problem of poor stability during charging and discharging processes. In order to solve the technical problem, the application provides a preparation method of a carbon-coated silicon-based titanium-niobium composite material, which comprises the following steps: carrying out a first calcination process by taking a titanium source and a niobium source as raw materials to obtain a first calcination product, wherein the temperature of the first calcination process is 800-1200 ℃; performing a second calcination process on a silicon source, the first calcination product and a carbon source to obtain a carbon-coated silicon-based titanium-niobium composite material, wherein the temperature of the second calcination process is 500-1000 ℃; wherein the titanium source is selected from one or more of anatase titanium dioxide, anatase titanium dioxide hydrate silicon powder and silicon oxide, the niobium source is niobium pentoxide, the silicon source is silicon powder or silicon oxide, and the carbon source is hydrocarbon.
The titanium niobium oxide (first calcined product) can be produced by performing the first calcination process using a titanium source and a niobium source as raw materials. Because silicon and oxygen have good affinity, in the second calcining process of the titanium niobium oxide, a silicon source and a carbon source, the silicon and the metal oxide titanium niobium oxide are compounded, the silicon is used as a reinforcement, the titanium niobium oxide is used as a matrix, and a stress buffer layer and an ion exchange layer are constructed around silicon particles, so that the volume effect of the silicon in the charging and discharging process can be buffered, the electrical contact of the silicon particles is improved, and the cycle stability of the material is improved. The silicon-based titanium niobium oxide composite material is coated with carbon, which is beneficial to improving the cycle performance of the silicon material. In addition, the preparation method has simple process, no pollution, high repeatability and large-scale production. On the basis, the carbon-coated silicon-based titanium-niobium composite material prepared by the method has smaller volume effect and higher cycle performance in the charging and discharging processes, and meanwhile, the preparation method has the advantages of simple process, no pollution, high repeatability, large-scale production and the like.
Compared with a silicon-carbon composite material, the combination of silicon and titanium niobium oxide has a higher lithium-releasing and-inserting potential different from that of a silicon material, a voltage platform of the silicon-titanium niobium oxide is between 1.5 and 2V, and a voltage platform of the silicon is under 0.6V, so that when the composite material is subjected to an electrochemical lithium-releasing and-inserting reaction under a voltage window of 0 to 1.5V, only silicon with higher capacity participates in a lithium-releasing and-inserting treatment process, and a matrix material does not generate a lithium-releasing and-inserting process.
In a preferred embodiment, the molar ratio of the titanium element in the titanium source to the niobium element in the niobium source in the first calcination process is 1 (0.5-6). The mole ratio of the titanium element in the titanium source and the niobium element in the niobium source includes but is not limited to the above range, and the limitation of the mole ratio in the above range is beneficial to further improving the mechanical property of the carbon-coated silicon-based titanium niobium composite material, so that the volume effect of the carbon-coated silicon-based titanium niobium composite material is further reduced, and the stability of the carbon-coated silicon-based titanium niobium composite material in the charging and discharging processes is improved. More preferably, the molar ratio of the titanium element in the titanium source to the niobium element in the niobium source is 1 (1 to 5).
In a preferred embodiment, before the first calcination process, the preparation method further comprises: mixing the raw materials with a first solvent in an inert atmosphere, and then carrying out first wet grinding to obtain first slurry; and after the first slurry is subjected to first drying, a first calcining process is carried out to obtain a first calcined product. Before the first calcining process, the raw materials are subjected to first grinding and first drying, so that the stability of the performance of a first calcined product is improved, and further the comprehensive performance of the carbon-coated silicon-based titanium-niobium composite material is improved. More preferably, in the first wet grinding process, the solid content of the first slurry is 10-30%, the particle size D50 of solid particles in the first slurry is not more than 0.8 μm, and the grinding electric quantity is 5-15 kwh/kg.
It should be noted that the particle size D50 in the solid particles refers to the particle size corresponding to the cumulative percentage of particle size distribution of the sample reaching 50%.
In a preferred embodiment, the drying device used in the first drying process includes, but is not limited to, oven drying or spray drying. More preferably, the drying process is carried out in a spray drying device, the inlet temperature of the spray drying device is 200-300 ℃, the outlet temperature of the spray drying device is 60-150 ℃, and the air flow is 4.8-8.8 mL/min. Limiting the inlet and outlet temperatures of the spray drying device within the above ranges is advantageous for further improving the drying efficiency.
In a preferred embodiment, the temperature of the first calcination process is 900-1100 ℃, and the calcination time is 4-16 h. The temperature and the calcination time of the first calcination process include, but are not limited to, the above ranges, and it is advantageous to further increase the conversion of the first calcination product by limiting it to the above ranges.
The carbon source may be a hydrocarbon commonly used in the art. In a preferred embodiment, the carbon source includes, but is not limited to, one or more of glucose, sucrose, citric acid, and phenolic resin. Compared with other carbon sources, the raw materials can obtain more carbon elements in the calcining process, and the price is low, so that the adoption of the raw materials as the carbon source is beneficial to further improving the electrical cycle performance of the carbon-coated silicon-based titanium-niobium composite material.
In a preferred embodiment, the preparation method further comprises: carrying out second wet grinding on a silicon source and a second solvent to obtain second slurry; and performing ball milling and second drying processes on the mixture of the second slurry, the first calcined product and the carbon source in sequence, and then performing a second calcining process to obtain the carbon-coated silicon-based titanium-niobium composite material. Before the second calcining process, the silicon source is subjected to second wet grinding, and then ball milling and second drying processes are sequentially performed on the silicon source and other materials, so that the comprehensive performance of the carbon-coated silicon-based titanium-niobium composite material is improved. More preferably, in the second wet grinding process, the solid content of the second slurry is 10-30%, the particle size D50 of solid particles in the second slurry is not more than 0.5 μm, and the grinding electric quantity is 5-15 kwh/kg;
preferably, the second solvent includes, but is not limited to, one or more of ethanol, ethylene glycol, isopropanol, and methanol. Compared with other solvents, the adoption of the solvents is also beneficial to reducing the silicon source oxidation in the second wet grinding process, so that the stability of the finally prepared carbon-coated silicon-based titanium-niobium composite material in the charging and discharging processes is improved. Meanwhile, the solvents are easy to remove in the drying process.
In a preferred embodiment, during the ball milling process, the coating amount of the carbon element is 3 to 10 percent and the doping amount of the silicon element is 30 to 80 percent based on the weight percentage of the first calcined product. The carbon element coating amount and the silicon element doping amount include, but are not limited to, the above ranges, and are limited to the above ranges, so that the carbon-coated silicon-based titanium niobium composite material is beneficial to further reducing the volume reduction in the charge and discharge processes, and improving the electrical cycle performance.
In a preferred embodiment, the temperature of the second calcination process is 600-800 ℃, and the calcination time is 2-10 h. The temperature and the calcination time of the second calcination process include, but are not limited to, the above ranges, and it is advantageous to further increase the yield of the carbon-coated silicon-based titanium niobium composite material by limiting the temperature and the calcination time to the above ranges.
In order to improve the uniformity of the carbon-coated silicon-based titanium-niobium composite material and further improve the comprehensive performance of the lithium ion battery in the subsequent application process, in a preferred embodiment, the preparation method further comprises the following steps: screening the product of the second calcining process to obtain the carbon-coated silicon-based titanium-niobium composite material; more preferably, a screen mesh of 200-300 meshes is adopted in the screening treatment process.
The carbon-coated silicon-based titanium-niobium composite material is prepared by the preparation method.
The titanium niobium oxide (first calcined product) can be produced by performing the first calcination process using a titanium source and a niobium source as raw materials. Because silicon and oxygen have good affinity, in the second calcining process of the titanium niobium oxide, a silicon source and a carbon source, the silicon and the metal oxide titanium niobium oxide are compounded, the silicon is used as a reinforcement, the titanium niobium oxide is used as a matrix, and a stress buffer layer and an ion exchange layer are constructed around silicon particles, so that the volume effect of the silicon in the charging and discharging process can be buffered, the electrical contact of the silicon particles is improved, and the cycle stability of the material is improved. The silicon-based titanium niobium oxide composite material is coated with carbon, which is beneficial to improving the cycle performance of the silicon material. In addition, the preparation method has simple process, no pollution, high repeatability and large-scale production. On the basis, the carbon-coated silicon-based titanium-niobium composite material prepared by the method has a small volume effect and high cycle performance in the charging and discharging processes.
Still another aspect of the present application further includes a lithium ion battery comprising a negative electrode sheet coated with a negative electrode material, the negative electrode material comprising the above carbon-coated silicon-based titanium niobium composite material.
The carbon-coated silicon-based titanium-niobium composite material prepared by the method has small volume effect and high cycle performance in the charging and discharging processes. Therefore, when the lithium ion battery is prepared by using the negative plate coated with the carbon-coated silicon-based titanium-niobium composite material, the electrical cycle performance and the cycle stability of the lithium ion battery can be greatly improved.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
A preparation method of a carbon-coated silicon-based titanium-niobium composite material comprises the following steps:
weighing deionized water, 400gNb2O5(1.50mol) and 139.57gTiO2·2H2Mixing O (1.20mol) to prepare slurry with the solid content of 13%; carrying out first wet grinding on the slurry to obtain first slurry, wherein the grinding electric quantity is 10kwh/kg, and the particle size D50 is less than or equal to 0.2 mu m; the first slurry was subjected to a first spray-drying using a spray-drying apparatus having an inlet temperature of 220 ℃ and an outlet temperature of 100 ℃.
And (3) carrying out a first calcining process on the spray-dried material in air, wherein the temperature of the first calcining process is 1100 ℃, and the sintering time is 6 h. The product of the first calcination process was subjected to a sieving treatment using a 200-mesh sieve to obtain a first calcined product (titanium niobium oxide material).
Mixing 400g of silicon powder with absolute ethyl alcohol to prepare silicon slurry with the solid content of 13%, and then carrying out second wet ball milling on the silicon slurry in a circulating closed ball mill to obtain second slurry, wherein the grinding electric quantity is 8kwh/kg, and the particle size D50 is less than or equal to 0.5 mu m; (ii) a
And (3) mixing the second slurry subjected to ball milling, 400g of titanium niobium oxide and 50% of silicon, adding 109.9964g of glucose into the mixture, wherein the carbon coating amount is 5%, and finally preparing the mixed slurry with the solid content of 18%. Carrying out ultrasonic and high-speed stirring on the mixed slurry with the solid content of 18% for 4 hours, and then carrying out second spray drying in a closed spray drying device, wherein the spray drying environment is an inert environment protected by Ar gas, the inlet temperature of the adopted spray drying device is 200 ℃, the outlet temperature of the adopted spray drying device is 90 ℃, and the gas flow is 5.2 mL/min; carrying out a second calcining process on the powder obtained in the spray drying process in an atmosphere tube furnace, wherein the atmosphere is argon atmosphere, the temperature of the second calcining process is 750 ℃, and the sintering time is 4 h; and sieving the material obtained in the second calcining process by using a 200-mesh screen to obtain the carbon-coated silicon-based titanium-niobium composite material.
An X-ray radiation instrument is adopted to test the carbon-coated silicon-based titanium-niobium composite material prepared in the example 1, and XRD is shown in figure 1; the microscopic morphology of the carbon-coated silicon-based titanium-niobium composite material prepared in example 1 was observed by scanning electron microscopy, and the SEM thereof is shown in fig. 2.
The material prepared in example 1, superconducting carbon black and a binder are mixed uniformly according to a ratio of 90:5:5 to prepare a negative electrode diaphragm, a lithium sheet is used as a positive electrode to prepare a half cell, and a cell tester is used for testing gram capacity and cycle performance. The charge and discharge multiplying power is 0.1C, the first discharge gram capacity reaches 1450.2mAh/g, as shown in figure 3, and the gram capacity can still be stabilized at 400mAh/g after 50 cycles, as shown in figure 4.
Example 2
The differences from example 1 are: the temperature of the first calcination process was 800 deg.c, the temperature of the second calcination process was 1000 deg.c, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the first discharge gram capacity reaches 1030.2mAh/g, and the gram capacity after 50 cycles is 308 mAh/g.
Example 3
The differences from example 1 are: the temperature of the first calcination process was 1200 c, the temperature of the second calcination process was 500 c, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the first discharge gram capacity reaches 1137.5mAh/g, and the gram capacity after 50 cycles is 326.5 mAh/g.
Example 4
The differences from example 1 are: the temperature of the first calcination process was 900 deg.c, the temperature of the second calcination process was 800 deg.c, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the first discharge gram capacity reaches 1294.5mAh/g, and the gram capacity after 50 cycles is 368.6 mAh/g.
Example 5
The differences from example 1 are: the temperature of the first calcination process was 1100 deg.c, the temperature of the second calcination process was 600 deg.c, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the first discharge gram capacity reaches 1290.6mAh/g, and the gram capacity after 50 cycles is 371.5 mAh/g.
Example 6
The differences from example 1 are: in the first calcination process, the molar ratio of the titanium element in the titanium source to the niobium element in the niobium source was 1:0.5, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the first discharge gram capacity reaches 1169.5mAh/g, and the gram capacity after 50 cycles is 305.2 mAh/g.
Example 7
The differences from example 1 are: in the first calcination process, the molar ratio of the titanium element in the titanium source to the niobium element in the niobium source was 1:6, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the gram capacity of the lithium ion battery reaches 1158.5mAh/g after the lithium ion battery is discharged for the first time, and the gram capacity of the lithium ion battery is 298.6mAh/g after 50 cycles.
Example 8
The differences from example 1 are: in the first calcination process, the molar ratio of the titanium element in the titanium source to the niobium element in the niobium source was 1:1, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the first discharge gram capacity reaches 1385.7mAh/g, and the gram capacity after 50 cycles is 361.2 mAh/g.
Example 9
The differences from example 1 are: in the first calcination process, the molar ratio of the titanium element in the titanium source to the niobium element in the niobium source was 1:5, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the gram capacity of the lithium ion battery reaches 1398.6.mAh/g in the first discharge, and the gram capacity of the lithium ion battery is 360.8mAh/g after 50 cycles.
Example 10
The differences from example 1 are: the coating amount of carbon element was 3% and the doping amount of silicon element was 80% in terms of the weight percentage of the first calcined product, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the first discharge gram capacity reaches 1385.6mAh/g, and the gram capacity after 50 cycles is 206.7 mAh/g.
Example 11
The differences from example 1 are: the coating amount of the carbon element was 10% and the doping amount of the silicon element was 30% in terms of the weight percentage of the first calcined product, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the gram capacity of the lithium ion battery reaches 1379.2mAh/g after the lithium ion battery is discharged for the first time, and the gram capacity of the lithium ion battery is 225.9mAh/g after 50 cycles.
Example 12
The differences from example 1 are: the coating amount of carbon element was 6% and the doping amount of silicon element was 50% in terms of the weight percentage of the first calcined product, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the gram capacity of the lithium ion battery reaches 1432.8mAh/g after the lithium ion battery is discharged for the first time, and the gram capacity of the lithium ion battery is 395.6mAh/g after 50 cycles.
Comparative example 1
The differences from example 1 are: the temperature of the first calcination process was 700 deg.c, the temperature of the second calcination process was 1100 deg.c, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the first discharge gram capacity reaches 850.9mAh/g, and the gram capacity after 50 cycles is 169.5 mAh/g.
Comparative example 2
The differences from example 1 are: the temperature of the first calcination process was 1300 c, the temperature of the second calcination process was 400 c, and the performance test method was the same as in example 1.
The charge and discharge multiplying power is 0.1C, the first gram capacity of the lithium ion battery is 769.6 mAh/g, and the gram capacity after 50 cycles is 126.3 mAh/g.
Comparative example 3
A preparation method of a carbon-coated silicon-based titanium-niobium composite material comprises the following steps:
weighing the deionized water, 109.9964g of glucose, 400g of silicon powder and 400gNb2O5(1.50mol) and 139.57gTiO2·2H2Mixing O (1.20mol) to prepare slurry with the solid content of 13%; carrying out wet grinding on the slurry, wherein the grinding electric quantity is 10kwh/kg, and the particle size D50 is not more than 0.2 mu m; and (3) carrying out spray drying on the slurry obtained after the wet grinding, wherein the inlet temperature of a spray drying device is 220 ℃, and the outlet temperature of the spray drying device is 100 ℃.
And (3) calcining the spray-dried material in air, wherein the temperature of the calcining process is 800 ℃, and the sintering time is 6 h. And sieving the product of the calcination process by using a 200-mesh sieve to obtain the calcined product.
The charge and discharge multiplying power is 0.1C, the first discharge gram capacity reaches 699.8mAh/g, and the gram capacity after 50 cycles is 106.8 mAh/g.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
comparing examples 1 to 5 and comparative examples 1 to 2, it can be seen that limiting the temperature of the first calcination process and the temperature of the second calcination process within the preferred ranges of the present application is advantageous to further improve the electrical properties of the carbon-coated silicon-based titanium niobium composite material.
Comparing examples 1 to 12 and comparative examples 1 to 3, it can be seen that the carbon-coated silicon-based titanium-niobium composite material prepared by the method provided by the present application has more excellent electrical properties.
Comparing examples 1, 6 to 9, it is found that limiting the molar ratio of the titanium element in the titanium source and the niobium element in the niobium source in the first calcination process to the preferred range in the present application is advantageous for further improving the electrical properties of the carbon-coated silicon-based titanium niobium composite.
Comparing examples 1, 10 to 12, it can be seen that limiting the amount of the carbon element coating and the amount of the silicon element doped in the first calcination process to the preferred ranges in the present application is advantageous to further improve the electrical properties of the carbon-coated silicon-based titanium niobium composite material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

1. A preparation method of a carbon-coated silicon-based titanium-niobium composite material is characterized by comprising the following steps:
carrying out a first calcination process by taking a titanium source and a niobium source as raw materials to obtain a first calcination product, wherein the temperature of the first calcination process is 800-1200 ℃;
performing a second calcination process on a silicon source, the first calcination product and a carbon source to obtain the carbon-coated silicon-based titanium-niobium composite material, wherein the temperature of the second calcination process is 500-1000 ℃;
the titanium source is selected from one or more of anatase titanium dioxide, anatase titanium dioxide hydrate silicon powder and silicon oxide, the niobium source is niobium pentoxide, the silicon source is silicon powder or silicon oxide, and the carbon source is a hydrocarbon.
2. The production method according to claim 1, wherein the molar ratio of the titanium element in the titanium source to the niobium element in the niobium source in the first calcination process is 1 (0.5 to 6), preferably 1 (1 to 5).
3. The method of claim 1, wherein prior to performing the first calcination process, the method further comprises:
mixing the raw materials with a first solvent in an inert atmosphere, and then carrying out first wet grinding to obtain first slurry;
after the first slurry is subjected to first drying, the first calcining process is carried out again to obtain a first calcined product;
preferably, in the first wet grinding process, the solid content of the first slurry is 10-30%, the particle size D50 of solid particles in the first slurry is not more than 0.8 μm, and the grinding electric quantity is 5-15 kwh/kg.
4. The preparation method according to claim 3, wherein a drying device adopted in the first drying process is selected from oven drying or spray drying, preferably, the drying process is carried out in a spray drying device, the inlet temperature of the spray drying device is 200-300 ℃, the outlet temperature of the spray drying device is 60-150 ℃, and the air flow rate is 4.8-8.8 mL/min.
5. The preparation method according to claim 1, wherein the temperature of the first calcination process is 900 to 1100 ℃ and the calcination time is 4 to 16 hours.
6. The method according to claim 1, wherein the carbon source is one or more selected from glucose, sucrose, citric acid, and phenol resin.
7. The method of manufacturing according to claim 1, further comprising:
carrying out second wet grinding on the silicon source and a second solvent to obtain second slurry;
performing ball milling and second drying processes on the mixture of the second slurry, the first calcined product and the carbon source in sequence, and then performing a second calcining process to obtain the carbon-coated silicon-based titanium-niobium composite material;
preferably, the second solvent is selected from one or more of ethanol, ethylene glycol, isopropanol, and methanol;
preferably, in the second wet grinding process, the solid content of the second slurry is 10-30%, the particle size D50 of solid particles in the second slurry is not more than 0.5 μm, and the grinding electric quantity is 5-15 kwh/kg;
preferably, in the ball milling process, the carbon element coating amount is 3-10% and the silicon element doping amount is 30-80% in terms of weight percentage of the first calcined product.
8. The preparation method according to claim 1, wherein the temperature of the second calcination process is 600 to 800 ℃, and the calcination time is 2 to 10 hours.
9. The method of manufacturing according to claim 1, further comprising: screening the product of the second calcining process to obtain the carbon-coated silicon-based titanium-niobium composite material; preferably, a screen mesh of 200-300 meshes is adopted in the screening treatment process.
10. A carbon-coated silicon-based titanium-niobium composite material, which is prepared by the preparation method of any one of claims 1 to 9.
11. A lithium ion battery comprising a negative electrode sheet coated with a negative electrode material, wherein the negative electrode material comprises the carbon-coated silicon-based titanium niobium composite material of claim 10.
CN201911405060.0A 2019-12-30 2019-12-30 Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery Pending CN111170364A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911405060.0A CN111170364A (en) 2019-12-30 2019-12-30 Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911405060.0A CN111170364A (en) 2019-12-30 2019-12-30 Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery

Publications (1)

Publication Number Publication Date
CN111170364A true CN111170364A (en) 2020-05-19

Family

ID=70649072

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911405060.0A Pending CN111170364A (en) 2019-12-30 2019-12-30 Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery

Country Status (1)

Country Link
CN (1) CN111170364A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111668446A (en) * 2020-06-12 2020-09-15 江苏大学 Preparation method of silicon-niobium porous composite anode material of lithium ion battery
CN114388772A (en) * 2021-12-09 2022-04-22 格力钛新能源股份有限公司 Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10211600A1 (en) * 2002-03-15 2003-09-25 Hte Ag The High Throughput Exp Monolithic ceramic material used as, e.g. all-active catalysts and catalyst supports, comprises micropores, mesopores and/or macropores and is at least partially decomposable under physiological conditions
CN102790204A (en) * 2011-05-19 2012-11-21 中国科学院宁波材料技术与工程研究所 Preparation method of silicon carbon lithium ion battery cathode material
CN104852020A (en) * 2014-02-14 2015-08-19 北京有色金属研究总院 Lithium ion battery silicon oxide composite negative electrode material and preparation method thereof
CN105591080A (en) * 2016-01-18 2016-05-18 北京科技大学 Preparation method of lithium ion battery cathode material SiOX-TiO2/C
CN105958036A (en) * 2016-07-07 2016-09-21 天津普兰能源科技有限公司 Preparation method for carbon-coated silicon negative electrode material for lithium ion battery
CN107579227A (en) * 2017-08-31 2018-01-12 北方奥钛纳米技术有限公司 Preparation method, silicon-carbon cathode piece and the lithium ion battery of silicon-carbon cathode piece
CN108987717A (en) * 2018-07-18 2018-12-11 开封大学 A kind of lithium ion battery silicon based composite material and preparation method thereof
WO2019100233A1 (en) * 2017-11-22 2019-05-31 Bayerische Motoren Werke Aktiengesellschaft High voltage positive electrode material and cathode as well as lithium ion cell and battery including the same
CN110289399A (en) * 2019-05-22 2019-09-27 北方奥钛纳米技术有限公司 Negative electrode material and preparation method thereof, lithium ion battery
CN110336005A (en) * 2019-06-30 2019-10-15 东莞理工学院 A kind of titanium-based oxide lithium ion battery negative material and its performance test methods

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10211600A1 (en) * 2002-03-15 2003-09-25 Hte Ag The High Throughput Exp Monolithic ceramic material used as, e.g. all-active catalysts and catalyst supports, comprises micropores, mesopores and/or macropores and is at least partially decomposable under physiological conditions
CN102790204A (en) * 2011-05-19 2012-11-21 中国科学院宁波材料技术与工程研究所 Preparation method of silicon carbon lithium ion battery cathode material
CN104852020A (en) * 2014-02-14 2015-08-19 北京有色金属研究总院 Lithium ion battery silicon oxide composite negative electrode material and preparation method thereof
CN105591080A (en) * 2016-01-18 2016-05-18 北京科技大学 Preparation method of lithium ion battery cathode material SiOX-TiO2/C
CN105958036A (en) * 2016-07-07 2016-09-21 天津普兰能源科技有限公司 Preparation method for carbon-coated silicon negative electrode material for lithium ion battery
CN107579227A (en) * 2017-08-31 2018-01-12 北方奥钛纳米技术有限公司 Preparation method, silicon-carbon cathode piece and the lithium ion battery of silicon-carbon cathode piece
WO2019100233A1 (en) * 2017-11-22 2019-05-31 Bayerische Motoren Werke Aktiengesellschaft High voltage positive electrode material and cathode as well as lithium ion cell and battery including the same
CN108987717A (en) * 2018-07-18 2018-12-11 开封大学 A kind of lithium ion battery silicon based composite material and preparation method thereof
CN110289399A (en) * 2019-05-22 2019-09-27 北方奥钛纳米技术有限公司 Negative electrode material and preparation method thereof, lithium ion battery
CN110336005A (en) * 2019-06-30 2019-10-15 东莞理工学院 A kind of titanium-based oxide lithium ion battery negative material and its performance test methods

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘方;李林林;杨化滨;: "Si/Li_2TiO_3复合材料的制备与电化学性能", 南开大学学报(自然科学版), no. 06, pages 94 - 99 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111668446A (en) * 2020-06-12 2020-09-15 江苏大学 Preparation method of silicon-niobium porous composite anode material of lithium ion battery
CN114388772A (en) * 2021-12-09 2022-04-22 格力钛新能源股份有限公司 Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery

Similar Documents

Publication Publication Date Title
CN108232145B (en) Silicon oxide composite material with space buffering and lithium doping functions, preparation method of silicon oxide composite material and lithium ion battery
CN111628155B (en) Molybdenum-tin bimetallic sulfide as negative electrode material of lithium ion/sodium ion battery and preparation method thereof
CN110752356B (en) Preparation method of sodium ion battery anode material of double-metal selenide
WO2016201979A1 (en) Preparation method for silicon-carbon composite anode material
WO2011009231A1 (en) Method for preparing carbon-coated positive material of lithium ion battery
CN103123967A (en) SiO/C composite cathode material of lithium ion battery and preparation method of SiO/C composite cathode material
CN110326136B (en) Novel high-potential multilayer carbon-coated polyanionic sodium-ion battery positive electrode material and preparation method thereof
CN102694152A (en) Cathode active material and preparation method and lithium ion battery thereof
CN105226267B (en) Three dimensional carbon nanotubes modification spinel nickel lithium manganate material and its preparation method and application
WO2020108132A1 (en) Nitrided lithium titanate-nitrided aluminum oxide composite material, preparation method therefor and application thereof
CN112928246B (en) Composite material, preparation method and application thereof
CN111170364A (en) Carbon-coated silicon-based titanium-niobium composite material, preparation method thereof and lithium ion battery
EP4203102A1 (en) Boron oxide-coated quaternary positive electrode material, and preparation method therefor and application thereof
CN112736233B (en) Lithium ion battery electrode active material, preparation method thereof, electrode and battery
TW201912585A (en) Preparation method and application of lithium-lithium nickel manganese oxide enriched cathode composite synthesizing the lithium-lithium nickel manganese oxide enriched cathode composite by using a solid phase method
CN108598458B (en) Nitrogen-doped lithium titanate composite material, preparation method thereof and lithium ion battery
CN107681131B (en) Preparation method of low-cost nano silicon powder and silicon carbon material
CN113066988A (en) Negative pole piece and preparation method and application thereof
CN107516734A (en) A kind of preparation method of carbon-coating nickel tin alloy nanosphere and its application in lithium battery
CN108183216B (en) Carbon-coated lithium-rich manganese-based positive electrode material, preparation method thereof and lithium ion battery
CN107845787B (en) Pomegranate-shaped Fe3O4Preparation method of @ N-C lithium battery negative electrode material
WO2023056636A1 (en) Lithium cobalt oxide layered positive electrode material, and preparation method therefor and use thereof
CN112018360B (en) Lithium ion battery cathode material, preparation method thereof and lithium ion battery
CN109037607B (en) Preparation method of coated lithium manganate composite material
CN112397701A (en) Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination