CN111584863B - Preparation method and application of electrode material of secondary lithium ion battery - Google Patents

Preparation method and application of electrode material of secondary lithium ion battery Download PDF

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CN111584863B
CN111584863B CN202010401184.8A CN202010401184A CN111584863B CN 111584863 B CN111584863 B CN 111584863B CN 202010401184 A CN202010401184 A CN 202010401184A CN 111584863 B CN111584863 B CN 111584863B
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lithium ion
niobium
ion battery
electrode material
sodium
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CN111584863A (en
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林春富
黄慈辉
赵修松
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Qingdao University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
    • B60L50/64—Constructional details of batteries specially adapted for electric vehicles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

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Abstract

The invention belongs to the technical field of electrochemistry, material chemistry and chemical power supply products, and particularly relates to a preparation method and application of an electrode material of a secondary lithium ion battery. The chemical formula of the electrode material provided by the invention is NaNb13O 33. The electrode material provided by the invention is used for the cathode of a lithium ion battery, and has the advantages of high theoretical specific capacity, high safety performance, high reversible specific capacity, high coulombic efficiency, extremely excellent cycle performance and the like. The preparation method related to the electrode material provided by the invention is simple, is suitable for charging and discharging high-energy and high-power devices such as electric automobiles and the like, and has wide application prospect in the field of lithium ion batteries. The invention provides more choices for the materials for the lithium ion battery cathode, and greatly promotes the development of the lithium ion battery so as to accelerate the popularization of the electric automobile.

Description

Preparation method and application of electrode material of secondary lithium ion battery
Technical Field
The invention belongs to the technical field of electrochemistry, material chemistry and chemical power supply products, and particularly relates to a preparation method and application of an electrode material of a secondary lithium ion battery.
Background
Lithium ion batteries have been widely used in various fields of human life due to their advantages of high energy output, high conversion efficiency, and long service life. The lithium ion battery cathode materials which are commercialized at present mainly comprise graphite and lithium titanate (Li)4Ti5O12). Graphite has high reversible specific capacity (about 330 mAh/g), low cost and long cycle life, and is widely applied to small electronic equipment. However, graphite presents considerable safety concerns. Graphite has a low operating potential and tends to produce lithium dendrites during charging and discharging at a high rate. The generation of lithium dendrites greatly increases the probability of battery short circuits, thereby bringing about serious potential safety hazards. In addition, graphite has a low lithium ion diffusion rate, resulting in poor rate performance. These problems severely limit their application in high performance lithium ion batteries, especially in the field of electric vehicles. Li4Ti5O12Has a very safe and stable working platform and excellent cycle performance. Modified Li4Ti5O12And rapid charge and discharge can be realized. However, Li4Ti5O12The small reversible specific capacity (only about 170 mAh/g) makes it difficult to use in high energy density lithium ion batteries. Therefore, it is necessary to develop a lithium ion battery negative electrode material with high safety, reversible specific capacity, rate capability and cycle performance.
Disclosure of Invention
Aiming at the problem of poor comprehensive performance of the conventional commercialized cathode material of the lithium ion battery, the invention aims to provide a preparation method of an electrode material-niobium-based cathode material of a secondary lithium ion battery with good comprehensive performance, which has high safety performance, specific capacity, first-cycle coulombic efficiency, rate capability and cycle performance.
The invention also provides application of the prepared electrode material of the secondary lithium ion battery.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the invention relates to a NaNb13O33The application of the negative electrode material in a secondary lithium ion battery.
Further, the cathode material is applied to power lithium ion batteries of electric vehicles.
The preparation method of the negative electrode material NaNb13O33 used in the invention is as follows:
1) mixing a sodium source and a niobium source in a stoichiometric ratio by ball milling and then presintering to obtain NaNbO 3;
2) mixing NaNbO3 and a niobium source in a stoichiometric ratio by ball milling and then sintering to obtain NaNb13O33。
Further, the sodium source is sodium hydroxide or sodium salt; the niobium source is niobium pentoxide or a niobium salt; the sodium salt is sodium carbonate or sodium nitrate or sodium acetate or sodium chloride or sodium bicarbonate; the niobium salt is niobium pentachloride or niobium oxalate or niobium ethoxide.
Further, the sintering temperature is 950-1300 ℃, and the sintering time is 1-24 h.
The starting materials used in the above-mentioned production methods are all commercially available unless otherwise specified.
The NaNb13O33 prepared by the two-step solid-phase reaction method has the Nb source5+/Nb4+And Nb4+/Nb3+The safe working potential of the redox couple can reduce the decomposition of the electrolyte and avoid the generation of lithium dendrites. In the process of charging and discharging, Nb5+And Nb3+Can be converted into each other to bring higher specific capacity. In addition, the crystal structure of the NaNb13O33 is stable and spacious, has a large number of vacancies, and can ensure good cycle stability and improve the capability of fast charge and discharge. Therefore, the NaNb13O33 is very suitable for being used as a negative electrode material of a high-performance lithium ion battery.
The theoretical specific capacity of the secondary lithium ion battery electrode material NaNb13O33 prepared by the invention is up to 396 mAh/g. The average working potential is about 1.6V, so the safety performance is good. The NaNb13O33 micron particles prepared by the two-step solid phase reaction method have the first cycle coulombic efficiency of 91.7% under the multiplying power of 0.1C, and the reversible specific capacity is as high as 330 mAh/g; the reversible specific capacity can still reach 110 mAh/g under the multiplying power of 10C, and 99.5 percent of specific capacity is remained after 1000 cycles.
The invention has the beneficial effects that:
(1) the electrode material provided by the invention is applied to the negative electrode of the lithium ion battery, and has the advantages of high specific capacity, high safety performance, high first-cycle coulombic efficiency, good rate performance, extremely excellent cycle performance and the like.
(2) The preparation method provided by the invention is simple, is suitable for charging and discharging high-energy high-power devices such as electric automobiles and the like, and has wide application prospects in the field of lithium ion batteries (particularly in the field of power lithium ion batteries of electric automobiles).
Drawings
FIG. 1 is a flow chart of a two-step solid-phase reaction method employed in the preparation of an electrode material for a secondary lithium ion battery in example 1;
FIG. 2 is an X-ray diffraction (XRD) pattern of NaNb13O33 micron particles obtained in example 1;
FIG. 3 is an electron micrograph of NaNb13O33 micron particles obtained in example 1;
FIG. 4 is the charge and discharge curves of NaNb13O33 micron particles obtained in example 1 under different multiplying power;
FIG. 5 shows the cycling performance of NaNb13O33 microparticles obtained in example 1 at a rate of 10C.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The flow chart of the two-step solid phase reaction method adopted by the invention is shown in figure 1.
Example 1
Sodium carbonate and niobium pentoxide were ball-milled in a ball mill at a molar ratio of 1:1 for 1 h. Pre-burning the ball-milled mixture at 900 ℃ for 4h to obtain NaNbO3 micron particles.
The NaNbO3 micron particles and niobium pentoxide were ball milled in a ball mill at a molar ratio of 1:6 for 1 h. And sintering the ball-milled mixture at 1100 ℃ for 4h to obtain NaNb13O33 micron particles.
Electrode materials were prepared by a two-step solid phase reaction method, examples 2-17 are shown in table 1.
TABLE 1
Figure DEST_PATH_IMAGE001
Figure 23937DEST_PATH_IMAGE002
Fig. 2 is an XRD pattern of NaNb13O33 microparticles obtained in example 1, and analysis showed that NaNb13O33 microparticles prepared by the two-step solid phase reaction method were pure. FIG. 3 is an electron micrograph of NaNb13O33 microparticles obtained in example 1, and it can be seen that the NaNb13O33 microparticles are random particles having a particle size of 1.5-15 μm. Fig. 4 is a charge-discharge curve of NaNb13O33 microparticles obtained in example 1 at different rates. The average working potential of the NaNb13O33 micron particles is about 1.6V under the multiplying power of 0.1C, the first-cycle coulombic efficiency is 91.6 percent, the reversible specific capacity is up to 330 mAh/g, and the reversible specific capacity can still be up to 110 mAh/g under the multiplying power of 10C. FIG. 5 is a graph of the cycling performance of the NaNb13O33 microparticles obtained in example 1 at a rate of 10C. The NaNb13O33 micron particles have a specific capacity retention rate of 99.5 percent (reference circle) after 1000 cycles at a rate of 10C. The advantages of high safety performance, first cycle coulombic efficiency, specific capacity, rate capability and cycle performance fully indicate that the NaNb13O33 is a very promising lithium ion battery cathode material.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (3)

1. Negative electrode material NaNb in secondary lithium ion battery13O33The preparation method is characterized in that the cathode material is applied to a power lithium ion battery of an electric automobile; the negative electrode material NaNb13O33Is micron particle with particle size of 1.5-15 μm;
the method specifically comprises the following steps:
1) sodium source and niobium source with stoichiometric ratio are ball-milled, mixed and presintered to obtain NaNbO3；
The pre-sintering is performed for 4 hours at 900 ℃;
2) adding stoichiometric ratio of NaNbO3Mixing with niobium source by ball milling and sintering to obtain NaNb13O33。
2. The method of claim 1, wherein the sodium source is sodium hydroxide or sodium salt; the niobium source is niobium pentoxide or a niobium salt; the sodium salt is sodium carbonate or sodium nitrate or sodium acetate or sodium chloride or sodium bicarbonate; the niobium salt is niobium pentachloride or niobium oxalate or niobium ethoxide.
3. The method as claimed in claim 1 or 2, wherein the sintering temperature is 950 ℃ and 1300 ℃, and the sintering time is 1-24 h.
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CN105322143A (en) * 2014-07-04 2016-02-10 中信国安盟固利动力科技有限公司 Nano microsphere niobium-based composite oxide and preparation method thereof
CN107925075A (en) * 2015-08-20 2018-04-17 日本电气硝子株式会社 Negative electrode active material for electricity storage device
CN109360978A (en) * 2018-10-09 2019-02-19 瑞声科技（南京）有限公司 Lithium ion battery negative material and nonaqueous electrolyte battery
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

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CN102364729A (en) * 2011-11-10 2012-02-29 中南大学 High-power Li4Ti5O12/activated carbon composite electrode material and preparation method thereof
CN110380054A (en) * 2019-08-02 2019-10-25 北方奥钛纳米技术有限公司 A kind of titanium niobium oxide electrode material and preparation method thereof, lithium ion button shape cell

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105322143A (en) * 2014-07-04 2016-02-10 中信国安盟固利动力科技有限公司 Nano microsphere niobium-based composite oxide and preparation method thereof
CN107925075A (en) * 2015-08-20 2018-04-17 日本电气硝子株式会社 Negative electrode active material for electricity storage device
CN109360978A (en) * 2018-10-09 2019-02-19 瑞声科技（南京）有限公司 Lithium ion battery negative material and nonaqueous electrolyte battery
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

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