CN112701289A - Titanium niobate-containing negative electrode material for lithium ion battery and preparation method thereof - Google Patents

Titanium niobate-containing negative electrode material for lithium ion battery and preparation method thereof Download PDF

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CN112701289A
CN112701289A CN202011605699.6A CN202011605699A CN112701289A CN 112701289 A CN112701289 A CN 112701289A CN 202011605699 A CN202011605699 A CN 202011605699A CN 112701289 A CN112701289 A CN 112701289A
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negative electrode
titanium niobate
electrode material
titanium
lithium ion
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杨清华
张少波
王浩
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Shenzhen Borui Energy Technology Co ltd
Anhui Keda Borui Energy Technology Co ltd
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Shenzhen Borui Energy Technology Co ltd
Anhui Keda Borui Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/626—Metals
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 invention belongs to the technical field of lithium ion batteries, and particularly relates to a titanium niobate-containing negative electrode material for a lithium ion battery and a preparation method thereof, wherein the negative electrode material comprises titanium niobate particles and coated carbon; the titanium niobate particles can be Ti1‑xNb2+xO7Wherein 0 < x < 0.1; the primary particle size of the titanium niobate particles is less than 300 nm; the negative electrode material contains 90 wt% -99 wt% of titanium niobate particles and 1 wt% -10 wt% of coating carbon; the surface layer part of the negative electrode material is covered by a carbon layer, and the average thickness of the coated carbon layer is 10-300 nm; compared with the prior art, the titanium niobate-containing negative electrode material for the lithium ion battery has excellent electrochemical performance.

Description

Titanium niobate-containing negative electrode material for lithium ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of batteries, in particular to a titanium niobate-containing negative electrode material for a lithium ion battery and a preparation method thereof.
Background
Lithium ion batteries are considered to be the most potential energy storage technology at present, and are widely applied to various portable electronic products such as mobile phones, computers, watches, unmanned aerial vehicles and the like. In recent years, due to the rapid development of new energy electric vehicles, the demand of the market for lithium batteries is further increased. Lithium ion batteries have a huge market space, but still face many challenges, such as how to further improve the energy density, cycle performance, charging efficiency, service life, safety, and other performances of the batteries.
The lithium titanate negative electrode material is called a zero-strain material because the lattice parameter of lithium ions is hardly changed in the process of intercalation and deintercalation. The lithium ion is reversible in deintercalation, so that the lithium ion battery has quite excellent cycle performance, and the cycle life can reach about thirty thousand times. Meanwhile, the lithium ion de-intercalation potential is about 1.5V, the voltage platform is flat, a solid-electrolyte passive film (SEI film) cannot be formed in the charging and discharging process, and the potential safety hazard of internal short circuit caused by lithium dendrite formed on the surface of the anode is reduced. However, since lithium titanate materials have a relatively low theoretical capacity, attention is being paid to the development of power-type negative electrode materials having high safety, high specific capacity, and long cycle life.
Compared with lithium titanate, the titanium niobate has higher theoretical specific capacity, and the change of lattice parameters and unit cell volume is smaller in the lithium ion de-intercalation process, so that the reversibility is higher; and the charge-discharge potential is about 1.6V, and an SEI film and lithium dendrite are not easy to generate in the circulation process, so the lithium titanate composite material is a lithium titanate substitute material with a promising application prospect. However, titanium niobium oxides suffer from low ionic and electronic conductivity, which limits their electrochemical performance enhancement. In order to improve the electrochemical performance of titanium niobate, a high-conductivity carbon-coated material is urgently needed, and the carbon-coated material is mixed with the titanium niobate to be used as a negative electrode material of a lithium battery.
Disclosure of Invention
In order to solve the problems of the titanium niobate negative electrode material, the invention provides a titanium niobate-containing negative electrode material for a lithium battery and a preparation method thereof.
More specifically, the invention provides a titanium niobate-containing negative electrode material for a lithium ion battery, which is characterized in that: the negative electrode material comprises titanium niobate particles and coated carbon; the negative electrode material contains 90 wt% -99 wt% of titanium niobate, preferably 95 wt% -99 wt%; contains 1 wt% to 10 wt% of coated carbon, preferably 1 wt% to 5 wt%.
Preferably, the specific surface area of the titanium niobate-containing negative electrode material is 2-20m2A/g, preferably of 5 to 15m2(ii)/g; the titanium niobate-containing material has a secondary particle median diameter D50 of 5 to 20 μm, preferably 10 to 15 μm.
Preferably, the titanium niobate particles can be Ti1-xNb2+xO7Wherein 0 < x < 0.1.
Preferably, the surface of the negative electrode material is covered with a carbon layer, and the average thickness of the coated carbon layer is 10 to 300nm, preferably 50 to 250 nm.
Preferably, the titanium niobate primary particles have a median particle diameter D50 of 300nm or less.
Preferably, the titanium niobate particles are prepared by the following method: introducing a titanium source, a niobium source and water with the median particle size of 1-200 mu m and the purity of more than 99% into a grinding tank of a sand mill, controlling the solid content of the mixed solution to be 10% -30%, the linear speed of the sand mill to be more than 14m/s, and grinding for 1-6h, preferably 2-4h to obtain first slurry; after spray drying, calcining the slurry at high temperature in the air, wherein the calcining temperature is 800-1300 ℃, preferably 950-1200 ℃, and the calcining time is 8-15h, preferably 10-12h, then naturally cooling to room temperature to obtain a titanium niobate material, and crushing the material by using a hammer mill to obtain titanium niobate powder;
the titanium source is titanium dioxide;
the niobium source is niobium pentoxide or niobium hydroxide.
Preferably, the wet grinding equipment is a sand mill, and the structural shape of a stirring shaft of the sand mill is a disc type, a rod type or a rod-disc type.
Preferably, the coated carbon comprises carbon formed by pyrolysis of a gas-phase carbon source or residual carbon obtained by high-temperature calcination of a solid-phase carbon source, and the high-temperature reaction is carried out in an inert atmosphere;
the gas phase carbon source comprises methane, ethane, ethylene, acetylene, propane, propylene, acetone, butane, butene, pentane, hexane, benzene, toluene, xylene, styrene, naphthalene, phenol, furan, pyridine, anthracene, or liquefied gas;
the solid-phase carbon source is not particularly limited, and includes, but is not limited to, small-molecule sugars such as glucose, maltose, sucrose, etc., starch, or polyethylene glycol;
the high temperature is 600-1000 ℃, preferably 700-800 ℃.
Preferably, the titanium niobate-containing negative electrode material has excellent chemical properties, and the first reversible capacity is more than 255 mAh/g; the cycle capacity retention rate is more than 98% in 50 times of charge and discharge of the cycle performance 1C, and the rate performance 10C reversible capacity is more than 189 mAh/g; the 10C/1C capacity retention rate is more than 78%.
The invention also relates to a lithium ion battery, which is characterized in that the lithium ion battery cathode material is any one of the titanium niobate-containing cathode materials for the lithium ion battery.
The invention is controlled by the titanium niobate TiNb2O7Compared with the composition with excessive niobium, the niobium doping is carried out, the energy band gap is reduced, the electronic conductivity is improved, and the cycle and rate performance are improved. By reducing the particle size of the primary particles of the titanium niobate, the interface charge transmission efficiency is improved, the lithium ion transmission path is shortened, the ionic conductivity is obviously improved, and the rate capability is further optimized. The coated carbon can obviously improve the conductivity of the surface of the material, isolate the electrolyte from corroding the cathode material and improve the cycle life and rate capability of the titanium niobate-containing cathode material.
Compared with the prior art, the invention has the advantages that:
(1) in the titanium niobate-containing cathode material prepared by the invention, TiNb is controlled to react with titanium niobate2O7Composition in excess of niobium (Ti)1-xNb2+xO7Expressed, x is more than 0 and less than 0.1) niobium doping is carried out, the energy band gap is reduced, the electronic conductivity is improved, and the cycle and rate performance are improved;
(2) in the titanium niobate-containing negative electrode material prepared by the invention, the particle size of the primary particles of titanium niobate is below 300nm, and the interface charge transmission efficiency is improved, the lithium ion transmission path is shortened, the ionic conductivity is obviously improved and the rate capability is further optimized by reducing the particle size of the primary particles of titanium niobate;
(3) in the titanium niobate-containing negative electrode material prepared by the invention, the carbon is coated, so that the conductivity of the surface of the material can be obviously improved, the corrosion of electrolyte on the negative electrode material is isolated, and the cycle life and the rate capability of the titanium niobate-containing negative electrode material are improved;
(4) the titanium niobate-containing negative electrode material prepared by the invention has excellent chemical properties, high first reversible capacity (>255mAh/g), excellent cycle performance (the cycle capacity retention ratio is > 98% after 50 times of 1C charge and discharge), and good rate performance (the reversible capacity of 10C is >189 mAh/g; and the capacity retention ratio of 10C/1C is > 78%).
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is an X-ray diffraction pattern of the carbon-coated titanium niobate material prepared in example 1;
FIG. 2 is a SEM image of the carbon-coated titanium niobate material prepared in example 1;
FIG. 3 is a TEM image of the carbon-coated titanium niobate material prepared in example 1;
FIG. 4 is a cycle performance diagram of the carbon-coated titanium niobate material prepared in example 1 at a magnification of 1C;
fig. 5 is a graph of rate capability of the carbon-coated titanium niobate material prepared in example 1 at different rates.
Detailed Description
The present invention will be further described with reference to the following examples. The described embodiments and their results are only intended to illustrate the invention and should not be taken as limiting the invention described in detail in the claims.
Example 1
A preparation method of a titanium niobate-containing negative electrode material for a lithium ion battery comprises the following steps:
(1) preparing titanium niobate: dispersing 81g of titanium dioxide with the median particle size of 1um and the purity of 99 percent and 283.1g of niobium pentoxide powder with the purity of 99.95 percent by using deionized water, controlling the solid content of the mixed solution to be 10 percent, and then introducing the mixed solution into a sand mill, wherein the linear speed of the sand mill is 16m/s, and the grinding time is 2 hours to obtain slurry; spray drying and granulating the slurry, putting the spray-dried powder into a muffle furnace, calcining at 950 ℃ for 12h at high temperature in an oxidizing atmosphere, naturally cooling to room temperature to obtain a titanium niobate material, and crushing the material by using a hammer mill to obtain titanium niobate powder;
(2) preparing a titanium niobate-containing negative electrode material: weighing 20g of glucose and 200g of titanium niobate powder and dispersing in deionized water; introducing the slurry into a sand mill, wherein the linear speed of the sand mill is 14m/s, the ball milling time is 2h, and the median particle size of the titanium niobate particles is detected to be 230nm by a Mastersizer 3000 particle size analyzer; spray-granulating the obtained slurry by using a spray dryer, and controlling the collected powder D50 to be about 10 um; putting the obtained powder into a tubular furnace, calcining for 3.5 hours at the high temperature of 700 ℃ in the nitrogen atmosphere, and naturally cooling to room temperature to obtain a carbon-coated titanium niobate material; the specific surface area of the negative electrode material was measured by using a American Mediascope and pore Analyzer (TriStar II 3020) to measure 9.6m2/g。
The general formula of the titanium niobate in the negative electrode material is Ti1-xNb2+xO7Expressed, the value of x is 0.04; the negative electrode material contained 97.1% of titanium niobate particles and 2.9% of coated carbon.
Example 2
(1) Preparing titanium niobate: dispersing 81g of titanium dioxide with the median particle size of 10 mu m and the purity of 99.5 percent and 271.3g of niobium pentoxide powder with the purity of 99.9 percent by using deionized water, controlling the solid content of the mixed solution to be 20 percent, and then introducing the mixed solution into a sand mill, wherein the linear speed of the sand mill is 14m/s, and the grinding time is 4 hours to obtain slurry; spray drying and granulating the slurry, putting the spray-dried powder into a muffle furnace, calcining at 1200 ℃ for 10h at high temperature in an oxidizing atmosphere, naturally cooling to room temperature to obtain a titanium niobate material, and crushing the material by using a hammer mill to obtain titanium niobate powder;
(2) preparing a titanium niobate-containing negative electrode material: 34g of maltose and 200g of titanium niobate powder are weighed and dispersed in deionized water; introducing the slurry into a sand mill, wherein the linear speed of the sand mill is 16m/s, the ball milling time is 3h, and detecting by a Mastersizer 3000 particle size analyzer to obtain the titanium niobate particles with the median particle size of 180 nm; the obtained slurry was spray-granulated with a spray dryer to control the collected powder D50 to be about 20um(ii) a Putting the obtained powder into a tubular furnace, calcining for 3h at the high temperature of 800 ℃ in the nitrogen atmosphere, and naturally cooling to room temperature to obtain a carbon-coated titanium niobate material; the specific surface area of the negative electrode material was measured by using a American Mediascope and pore Analyzer (TriStar II 3020) to be 15.8m2/g。
The general formula of the titanium niobate in the negative electrode material is Ti1-xNb2+xO7Expressed, its x value is 0.02; the negative electrode material contains 95% of titanium niobate particles and 5% of coated carbon.
Example 3
(1) Preparing titanium niobate: dispersing 81g of titanium dioxide with the median particle size of 100 microns and the purity of 99.5 percent and 271.3g of niobium pentoxide powder with the purity of 99.9 percent by using deionized water, controlling the solid content of the mixed solution to be 30 percent, and then introducing the mixed solution into a sand mill, wherein the linear speed of the sand mill is 14m/s, and the grinding time is 5 hours to obtain slurry; spray drying and granulating the slurry, putting the spray-dried powder into a muffle furnace, calcining at 1050 ℃ for 11h at high temperature in an oxidizing atmosphere, naturally cooling to room temperature to obtain a titanium niobate material, and crushing the material by using a hammer mill to obtain titanium niobate powder;
(2) preparing a titanium niobate-containing negative electrode material: weighing 15g of sucrose and 200g of titanium niobate powder and dispersing in deionized water; introducing the slurry into a sand mill, wherein the linear speed of the sand mill is 15m/s, the ball milling time is 4h, and the median particle size of the titanium niobate particles is 170nm through detection of a Mastersizer 3000 particle size analyzer; spray-granulating the obtained slurry by using a spray dryer, and controlling the collected powder D50 to be about 15 um; putting the obtained powder into a tubular furnace, calcining for 3.5 hours at the high temperature of 750 ℃ in the nitrogen atmosphere, and naturally cooling to room temperature to obtain a carbon-coated titanium niobate material; the specific surface area of the negative electrode material was measured by using a American Mediascope and pore Analyzer (TriStar II 3020) to be 11.4m2/g。
The general formula of the titanium niobate in the negative electrode material is Ti1-xNb2+xO7Expressed, its x value is 0.02; the negative electrode material contained 98.2% of titanium niobate particles and 1.8% of coated carbon.
Example 4
(1) Preparing titanium niobate: dispersing 81g of titanium dioxide with the median particle size of 100 microns and the purity of 98.5 percent and 293.9g of niobium pentoxide powder with the purity of 99.5 percent by using deionized water, controlling the solid content of the mixed solution to be 25 percent, and then introducing the mixed solution into a sand mill, wherein the linear speed of the sand mill is 18m/s, and the grinding time is 4 hours to obtain slurry; spray drying and granulating the slurry, putting the spray-dried powder into a muffle furnace, calcining at 1000 ℃ for 11h at high temperature in an oxidizing atmosphere, naturally cooling to room temperature to obtain a titanium niobate material, and crushing the material by using a hammer mill to obtain titanium niobate powder;
(2) preparing a titanium niobate-containing negative electrode material: 200g of titanium niobate powder is placed in a vapor deposition furnace, nitrogen is introduced for protection, and then the temperature is raised to 700 ℃ at the temperature rise speed of 5 ℃/min; then introducing acetylene for vapor deposition, wherein the flow is 2L/min and the time is 1 h; and then switching to nitrogen protection and cooling to room temperature to obtain the titanium niobate-containing negative electrode material. The specific surface area of the negative electrode material was measured by using a U.S. Mega chart and pore Analyzer (TriStar II 3020) to determine 4.3m2/g。
The general formula of the titanium niobate in the negative electrode material is Ti1-xNb2+xO7Expressed, the value of x is 0.1; the negative electrode material contained 96.2% of titanium niobate particles and 3.8% of coated carbon.
Example 5
(1) Preparing titanium niobate: dispersing 81g of titanium dioxide with the median particle size of 200 mu m and the purity of 98.5 percent and 289.4g of niobium pentoxide powder with the purity of 98.5 percent by using deionized water, controlling the solid content of the mixed solution to be 25 percent, and then introducing the mixed solution into a sand mill, wherein the linear speed of the sand mill is 18m/s, and the grinding time is 4 hours, so as to obtain slurry; spray drying and granulating the slurry, putting the spray-dried powder into a muffle furnace, calcining at 1000 ℃ for 11h at high temperature in an oxidizing atmosphere, naturally cooling to room temperature to obtain a titanium niobate material, and crushing the material by using a hammer mill to obtain titanium niobate powder;
(2) preparing a titanium niobate-containing negative electrode material: 200g of titanium niobate powder is placed in a vapor deposition furnace, nitrogen is introduced for protection, and then the temperature is raised to 800 ℃ at the temperature rise speed of 5 ℃/min; then methane is introducedCarrying out vapor deposition with the flow rate of 2L/min and the time of 0.5 h; and then switching to nitrogen protection and cooling to room temperature to obtain the titanium niobate-containing negative electrode material. The specific surface area of the negative electrode material was measured by using a U.S. Mega chart and pore Analyzer (TriStar II 3020) to be 7.2m2/g。
The general formula of the titanium niobate in the negative electrode material is Ti1-xNb2+xO7Expressed, the value of x is 0.07; the negative electrode material contains 99% of titanium niobate particles and 1% of coated carbon.
Example 6
(1) Preparing titanium niobate: dispersing 81g of titanium dioxide with the median particle size of 150 mu m and the purity of 98.5 percent and 293.9g of niobium pentoxide powder with the purity of 99.5 percent by using deionized water, controlling the solid content of the mixed solution to be 20 percent, and then introducing the mixed solution into a sand mill, wherein the linear speed of the sand mill is 16m/s, and the grinding time is 3 hours to obtain slurry; spray drying and granulating the slurry, putting the spray-dried powder into a muffle furnace, calcining at 1000 ℃ for 12h at high temperature in an oxidizing atmosphere, naturally cooling to room temperature to obtain a titanium niobate material, and crushing the material by using a hammer mill to obtain titanium niobate powder;
(2) preparing a titanium niobate-containing negative electrode material: 200g of titanium niobate powder is placed in a vapor deposition furnace, nitrogen is introduced for protection, and then the temperature is raised to 750 ℃ at the temperature raising speed of 5 ℃/min; then introducing ethylene for vapor deposition, wherein the flow rate is 2L/min, and the time is 1.5 h; and then switching to nitrogen protection and cooling to room temperature to obtain the titanium niobate-containing negative electrode material. The specific surface area of the negative electrode material was measured by using a American Mediascope and pore Analyzer (TriStar II 3020) to be 5.2m2/g。
The general formula of the titanium niobate in the negative electrode material is Ti1-xNb2+xO7Expressed, the value of x is 0.1; the negative electrode material contained 95.2% of titanium niobate particles and 4.8% of coated carbon.
Comparative example 1
The difference from example 1 is that no carbon coating, i.e., step (2), is performed, and the description is omitted for the rest of example (1).
Comparative example 2
And implementation ofExample 1 differs in that niobium doping is not carried out, i.e. 265.9g of niobium pentoxide powder 81g (titanium niobate in the negative electrode material if used in the general formula Ti)1-xNb2+xO7Represents that x has a value of 0); the rest of the process is the same as example (1), and the description thereof is omitted.
Comparative example 3
The difference from example 1 is that the primary particles of the titanium niobate powder are not subjected to nanocrystallization, that is, in step (2), the slurry is introduced into a sand mill, the linear speed of the sand mill is 8m/s, the sand milling time is 0.5h, and the median particle size of the titanium niobate particles detected by a Mastersizer 3000 particle size analyzer is 850 nm. The rest of the process is the same as example (1), and the description thereof is omitted.
Comparative example 4
The difference from example 1 is that the calcination temperature of glucose in a nitrogen atmosphere is raised to 1000 ℃ and the rest is the same as example (1), and the description is omitted. The negative electrode material contained 99.7% of titanium niobate particles and 0.3% of coated carbon.
Comparative example 5
The difference from example 4 is that the flow rate of acetylene vapor deposition is increased to 7L/min in step (2) so that the average thickness of the coated carbon layer is 600-800nm, which is the same as example (1) and will not be described herein. The negative electrode material contained 86% of titanium niobate particles and 14% of coated carbon.
The titanium niobate-containing negative electrode materials in examples 1 to 6 and comparative examples 1 to 5 were tested by the following methods:
the particle size range of the material was tested using a malvern laser particle sizer Mastersizer 3000.
The specific surface area of the negative electrode material was measured using a U.S. Mach Chart and pore Analyzer (TriStar II 3020).
The material was subjected to phase analysis using an XRD diffractometer (X' Pert3 Powder).
The morphology and the graphical processing of the material were analyzed using a field emission Scanning Electron Microscope (SEM) (JSM-7160).
The morphology of the material, the state of the amorphous carbon, and the thickness of the carbon coating were analyzed using a field emission Transmission Electron Microscope (TEM) (JEM-F200).
Detect the presence ofThe silicon-containing negative electrode materials described in examples 1 to 6 had specific surface areas of 2 to 20m2(ii)/g; the median particle diameter D50 of the primary particles of the titanium niobate-containing negative electrode material is below 300 nm.
Scanning the whole composite material by using a TEM (transmission electron microscope), and measuring that the surface layer part of the negative electrode material is uniformly covered by the carbon layer, wherein the thickness of the coated carbon layer is 10-300 nm.
And (3) testing the cycle performance and rate performance of the titanium niobate-containing negative electrode material: the carbon-coated titanium niobate of example 1 is used as a positive electrode material to prepare a CR2032 type button cell for electrochemical performance test, and the method comprises the following steps: the positive electrode active material comprises the following components in percentage by mass: PVDF: adding acetylene black (8: 1: 1) into a sealed weighing bottle, adding a proper amount of N-methyl pyrrolidone to enable the slurry to reach a viscous state, and stirring on a magnetic stirrer for 6 hours until the slurry is uniformly mixed; coating the slurry on a copper foil, drying the copper foil in a vacuum drying oven at 100 ℃ for 10 hours, and subsequently rolling to prepare a pole piece; the negative electrode material uses a lithium sheet; the solvents used were EC: DMC: 1mol of LiPF6 with EMC 1:1:1v/v as electrolyte; taking polypropylene fiber as a diaphragm; and assembling the button cell in the glove box.
Cycle performance test the charge-discharge voltage is limited to 1.0-2.5V, the nominal capacity of the material is 280mAh/g, the activation is carried out by cycling for 3 cycles at 0.2C, and then the 1C cycle is carried out for 50 cycles. The multiplying power performance test is performed for 3 cycles at 0.2C, then for 5 cycles at 1C, 2C, 5C and 10C respectively, and then the 1C cycle is recovered for 10 cycles.
The button cell testing equipment is a LAND cell testing system of Wuhanjinnuo electronic Co.
Table 1 performance test data of titanium niobate-containing negative electrode materials in examples 1 to 6 and comparative examples 1 to 5
Figure BDA0002873303700000081
As can be seen from table 1, the titanium niobate-containing negative electrode material prepared by the method of the present application combines titanium niobate particles with coated carbon, and has excellent electrochemical properties. In examples 1 to 6, the negative electrode material containing titanium niobate had a high first reversible capacity (>255mAh/g), and also had excellent cycle performance (1C 50 cycle capacity retention ratio > 98%) and rate performance (10C reversible capacity >186 mAh/g; 10C/1C capacity retention ratio > 75%).
In the comparative example 1, if the titanium niobate-containing negative electrode material is not coated by carbon, the surface conductivity of the material is poor, so that the first reversible capacity is reduced, and the cycle capacity retention rate and the rate capability are obviously poor; in the comparative example 2, niobium doping is not carried out on the titanium niobate, so that the conductivity of the material is reduced, and the corresponding cycle performance and the rate performance are reduced; in the comparative example 3, the primary particles of the titanium niobate powder are not nanocrystallized, and the increase of the primary particles leads to the increase of the diffusion distance of lithium ions, the ionic conductivity of the material is reduced, and the cycle performance and the rate performance of the material are further caused; in comparative example 4, the calcination temperature in the inert gas atmosphere in the carbon coating process is increased to 1000 ℃, so that the carbon coating amount of the material is reduced, only 0.3 wt% is left, the surface conductivity of the material cannot be effectively improved, and the cycle and rate performance of the obtained material are reduced; in comparative example 5, the flow rate of acetylene vapor deposition was increased to increase the average thickness of the coated carbon layer to 600-800nm, which is outside the scope of the present invention, and too thick coating layer would increase the impedance of the negative electrode material, and the first reversible capacity, cycle performance and rate capability of the obtained titanium niobate-containing negative electrode material were all reduced to some extent.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The titanium niobate-containing negative electrode material for the lithium ion battery is characterized in that: the negative electrode material comprises titanium niobate particles and coated carbon; the negative electrode material contains 90 wt% -99 wt% of titanium niobate, preferably 95 wt% -99 wt%; contains 1 wt% to 10 wt% of coated carbon, preferably 1 wt% to 5 wt%.
2. The titanium niobate-containing negative electrode material for the lithium ion battery according to claim 1, wherein: the specific surface area of the titanium niobate-containing negative electrode material is 2-20m2A/g, preferably of 5 to 15m2(ii)/g; the titanium niobate-containing material has a secondary particle median diameter D50 of 5 to 20 μm, preferably 10 to 15 μm.
3. The titanium niobate-containing negative electrode material for the lithium ion battery according to claim 1, wherein: the titanium niobate particles can be Ti1-xNb2+xO7Wherein 0 < x < 0.1.
4. The titanium niobate-containing negative electrode material for the lithium ion battery according to claim 1, wherein: the surface of the negative electrode material is covered by a carbon layer, and the average thickness of the coating carbon layer is 10-300nm, preferably 50-250 nm.
5. The titanium niobate-containing negative electrode material for the lithium ion battery according to claim 1, wherein: the titanium niobate primary particles have a median diameter D50 of 300nm or less.
6. The titanium niobate-containing negative electrode material for the lithium ion battery according to claim 1, wherein: the titanium niobate particles are prepared by the following method: introducing a titanium source, a niobium source and water with the median particle size of 1-200 mu m and the purity of more than 99% into a grinding tank of a sand mill, controlling the solid content of the mixed solution to be 10% -30%, the linear speed of the sand mill to be more than 14m/s, and grinding for 1-6h, preferably 2-4h to obtain first slurry; after spray drying, calcining the slurry at high temperature in the air, wherein the calcining temperature is 800-1300 ℃, preferably 950-1200 ℃, and the calcining time is 8-15h, preferably 10-12h, then naturally cooling to room temperature to obtain a titanium niobate material, and crushing the material by using a hammer mill to obtain titanium niobate powder;
the titanium source is titanium dioxide;
the niobium source is niobium pentoxide or niobium hydroxide.
7. The titanium niobate-containing negative electrode material for the lithium ion battery according to claim 6, wherein: the wet grinding equipment is a sand mill, and the structural shape of a stirring shaft of the sand mill is a disc type, a rod type or a rod-disc type.
8. The titanium niobate-containing negative electrode material for the lithium ion battery according to claim 1, wherein: the coating carbon comprises carbon formed by high-temperature decomposition of a gas-phase carbon source or residual carbon formed by high-temperature calcination of a solid-phase carbon source, and high-temperature reaction is carried out in an inert atmosphere;
the gas phase carbon source comprises methane, ethane, ethylene, acetylene, propane, propylene, acetone, butane, butene, pentane, hexane, benzene, toluene, xylene, styrene, naphthalene, phenol, furan, pyridine, anthracene, or liquefied gas;
the solid-phase carbon source comprises micromolecular saccharides such as glucose, maltose, sucrose and the like, starch or polyethylene glycol;
the high temperature is 600-1000 ℃, preferably 700-800 ℃.
9. The titanium niobate-containing negative electrode material for the lithium ion battery according to claim 1, wherein: the titanium niobate-containing negative electrode material has excellent chemical properties, and the first reversible capacity is more than 255 mAh/g; the cycle capacity retention rate is more than 98% in 50 times of charge and discharge of the cycle performance 1C, and the rate performance 10C reversible capacity is more than 186 mAh/g; the 10C/1C capacity retention rate is greater than 75%.
10. A lithium ion battery, wherein the lithium ion battery negative electrode material is the titanium niobate-containing negative electrode material for a lithium ion battery according to any one of claims 1 to 9.
CN202011605699.6A 2020-12-30 2020-12-30 Titanium niobate-containing negative electrode material for lithium ion battery and preparation method thereof Pending CN112701289A (en)

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