CN109534401B - Preparation method of copper vanadate, copper vanadate prepared by method and application of copper vanadate in lithium ion battery - Google Patents

Preparation method of copper vanadate, copper vanadate prepared by method and application of copper vanadate in lithium ion battery Download PDF

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CN109534401B
CN109534401B CN201811343067.XA CN201811343067A CN109534401B CN 109534401 B CN109534401 B CN 109534401B CN 201811343067 A CN201811343067 A CN 201811343067A CN 109534401 B CN109534401 B CN 109534401B
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copper vanadate
copper
vanadate
lithium ion
preparation
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CN109534401A (en
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韩吉姝
王磊
孙静
刘艳茹
赵瑞阳
陈瑞欣
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Sciengreen Shandong Environment Technology Co ltd
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Qingdao University of Science and Technology
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    • 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
    • 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
    • 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
    • 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 provides a preparation method of copper vanadate, which comprises the following steps: (1) mixing ammonium metavanadate and CuCl2·2H2Mixing O and phenanthroline, and carrying out hydrothermal reaction at 180-200 ℃ for 90-100 hours to obtain a vanadium-copper precursor; (2) and calcining the copper vanadate precursor at 500-600 ℃ for 2-3 hours to obtain the copper vanadate. The invention also provides the copper vanadate prepared by the method, and the battery capacity can be obviously improved by taking the copper vanadate as a negative electrode material of a lithium ion battery. At 50mA g‑1The first discharge capacity is up to 1197mAh g‑1Obviously higher than the theoretical capacity of commercial graphite, 340mAh g‑1。

Description

Preparation method of copper vanadate, copper vanadate prepared by method and application of copper vanadate in lithium ion battery
Technical Field
The invention relates to the technical field of battery materials, in particular to a preparation method of copper vanadate, copper vanadate prepared by the method, and application of the copper vanadate in a lithium ion battery.
Background
The development of lithium ion batteries is accompanied by the discovery and discovery of new electrode materials. For example, the successful application of lithium cobaltate and lithium iron phosphate as positive electrode materials and lithium titanate as negative electrode materials have promoted the development of lithium ion batteries to a great extent. To date, lithium ion batteries have made significant progress, and the search for new materials is still ongoing.
Vanadium is a typical metal element with multiple valence states, and a series of metal vanadium oxides (M) can be formed by combining other metal elements and oxygen elementxVyOzAnd M ═ Fe, Cu, Z/, Ag, Co), it shows great potential for use in lithium ion batteries. Among them, copper vanadate has attracted great attention because of its high theoretical capacity, safety, easy preparation and low cost. CuV2O6Has been considered a positive electrode material due to its relatively high voltage plateau. For the positive electrode, CuV at low voltage2O6Excessive lithiation of (a) is not suitable. On the one hand, due to CuV2O6It may cause irreversible phase changes; on the other hand, when the lithium ion battery is matched with a negative electrode material, the low-voltage platform is not beneficial to improving the energy density of the lithium ion battery. In contrast, CuV at low voltage2O6Has attracted considerable interest as a potential application for the negative electrode of lithium ion batteries.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of copper vanadate.
The second purpose of the invention is to provide the copper vanadate prepared by the method.
The third purpose of the invention is to provide the application of the copper vanadate in the lithium ion battery.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention relates to a preparation method of copper vanadate, which comprises the following steps:
(1) mixing ammonium metavanadate and CuCl2·2H2Mixing O and phenanthroline, and carrying out hydrothermal reaction at 180-200 ℃ for 30-50 hours to obtain a vanadium-copper precursor;
(2) and calcining the copper vanadate precursor at 500-600 ℃ for 2-3 hours to obtain the copper vanadate.
Preferably, the ammonium metavanadate, CuCl2·2H2The molar ratio of O to phenanthroline is (1.5-3) to 1: 1.
Preferably, tetrabutylammonium hydroxide is also added before the hydrothermal reaction in step (1).
Preferably, in step (1), the tetrabutylammonium hydroxide is reacted with CuCl2·2H2The molar ratio of O is (1X 10)-4～3×10-4):1。
Preferably, in step (2), the calcination is performed in an air atmosphere.
Preferably, in the step (2), the temperature rise rate of the calcination is 1-5 ℃/m//.
Preferably, in step (1), the hydrothermal reaction is performed in a polytetrafluoroethylene reaction kettle, and the calcination is performed in a muffle furnace.
The invention also relates to the copper vanadate prepared by the method.
The invention also relates to application of the copper vanadate in a lithium ion battery.
Preferably, the copper vanadate is used as a lithium ion battery negative electrode material and is added at 50mA g-1The first discharge capacity is more than or equal to 1190mAhg at the current density of-1。
The invention provides a preparation method of copper vanadate, which comprises the steps of preparing a copper vanadate precursor with phenanthroline as an organic ligand under a hydrothermal condition, and then carrying out heat treatment at a high temperature to obtain granular CuV2O6. Compared with the prior art, the invention has the following main advantages and beneficial effects:
1) in the preparation method provided by the invention, the used raw materials are easy to purchase, the resources are rich, the price is lower, the preparation method is green and environment-friendly, and the large-scale preparation cost is low. And the preparation method is simple, easy to operate and convenient for large-scale production.
2) The copper vanadate prepared by the method is used as a lithium ion battery cathode material, so that the battery capacity is obviously improved, and good cycle stability can be kept in the lithium ion battery. At 50mA g-1Current density ofThe first discharge capacity is up to 1197mAhg-1Obviously higher than the theoretical capacity of commercial graphite, 340mAh g-1。
Drawings
FIG. 1 is a photomicrograph of the vanadium copper precursor prepared in example 1;
FIG. 2 is an XRD (X-ray diffraction) pattern of the vanadium copper precursor prepared in example 1;
FIG. 3a is a thermogravimetric plot of the copper vanadate prepared in example 1 and FIG. 3b is an XRD pattern of the copper vanadate prepared in example 1;
FIG. 4 is an SEM (scanning electron microscope) image of copper vanadate prepared in example 1;
FIG. 5 is a cyclic voltammogram of copper vanadate prepared in example 1 as an electrode material;
FIG. 6 is a constant current charge and discharge curve using the copper vanadate prepared in example 1 as an electrode material;
FIG. 7 is a long cycle test chart of copper vanadate prepared in example 1 as an electrode material;
fig. 8 is a graph showing rate capability of the copper vanadate prepared in example 1 as an electrode material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The embodiment of the invention relates to a preparation method of copper vanadate, which comprises the following steps:
(1) mixing ammonium metavanadate and CuCl2·2H2And (3) mixing O and phenanthroline, and carrying out hydrothermal reaction for 30-50 hours at 180-200 ℃ to obtain the vanadium-copper precursor.
In one embodiment of the invention, ammonium metavanadate, CuCl2·2H2The molar ratio of O to phenanthroline is (1.5-3) to 1: 1. PhenanthreneRooline, also known as 1, 10-phenanthroline, is primarily used as an organic ligand in the preparation of vanadium copper precursors.
Further, tetrabutylammonium hydroxide (TBAOH) is added in a trace amount before hydrothermal reaction, and tetrabutylammonium hydroxide and CuCl are added2·2H2The molar ratio of O may be (1X 10)-4～3×10-4):1. TBAOH is mainly used as a template agent to participate in the preparation of the vanadium copper precursor.
(2) And calcining the copper vanadate precursor at 500-600 ℃ for 2-3 hours to obtain the copper vanadate.
In one embodiment of the invention, the calcination is carried out in an air atmosphere. The temperature can be raised to the target temperature at a rate of 1 to 5 ℃/m// h.
The embodiment of the invention also relates to the copper vanadate prepared by the method. The material is used as a lithium ion battery cathode material and is added at 50mA g-1The first discharge capacity is more than or equal to 1190mAhg at the current density of-1Higher than the theoretical capacity of commercial graphite.
Example 1
(1) Ammonium metavanadate with purity of more than 99.9% and copper chloride (CuCl)2·2H2O), 0.52mmol, 0.28mmol are weighed respectively for phenanthroline.
(2) 0.28mmol of cupric chloride was placed in a beaker and 12ml of deionized water was added and stirred for 10 minutes to form a homogeneous solution. Then 0.28mmol of phenanthroline and 0.52mmol of ammonium metavanadate were added to the solution, and the mixture was stirred for 30 m//.
(3) To the solution obtained in step (2) was added 0.2ml of a 10% by mass aqueous tetrabutylammonium hydroxide solution (TBAOH 7.7X 10)-5mmol), stirring uniformly, transferring the uniform solution into a polytetrafluoroethylene hydrothermal reaction kettle of 15ml, and reacting for 48h at 200 ℃. And after the natural cooling is finished, filtering, washing, drying and collecting the reaction liquid to obtain the vanadium-copper precursor.
(4) And (4) transferring the vanadium-copper precursor obtained in the step (3) into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃ at the speed of 2 ℃/m// in the air atmosphere, and calcining for 2h to obtain the copper vanadate.
And (4) placing the vanadium-copper precursor prepared in the step (3) under a microscope, and observing that black cuboid crystals are generated, as shown in figure 1.
XRD diffraction test was performed on the crystal, and the test result is shown in FIG. 2. When the X-ray diffraction line of the crystal is compared with the result obtained by fitting the crystal data by software, two curves are completely coincided, the peak positions are the same, no impurity peak exists, and the high purity of the crystal is shown.
The crystals were subjected to differential scanning calorimetry and the results of the TG curve are shown in FIG. 3 a. A weight loss of 9.3% at 210-360 ℃ corresponds to evaporation of the remaining water, and a weight loss of 32.7% at 360-530 ℃ corresponds to decomposition of the precursor. Calcination at 550 ℃ was therefore chosen.
FIG. 3b shows the XRD analysis of the copper vanadate obtained by calcination in example 1. It can be seen that diffraction peaks at 20.7 °, 26.7 °, 27.6 °, 28.9 °, 29.5 °, 31.6 °, 36.8 °, 38.6 °, 39.4 °, 39.5 °, 43.4 ° and 48.5 ° can be attributed to CuV2O6(JCPDS, No.30-0513) the following crystal planes (200), (1-10), (110), (-1-11), (-301), (1-11), (-1-12), (-311), (3-10), (-3-11), (-312) and (-1-13). Meanwhile, diffraction peaks are located at 15.4 °, 20.3 °, 21.7 °, 26.2 °, 31.0 °, 32.4 °, 34.3 °, 45.5 °, 47.3 ° and 61.2 ° corresponding to V2O5(JCPDS, No.09-0317) as follows, crystal planes (200), (001), (101), (110, (400), (011), (310), (411), (600) and (420), indicating that the resulting product is CuV2O6And V2O5A mixture of (a).
FIG. 4 is a scanning electron micrograph of calcined copper vanadate showing a large number of micron-sized particles with a particle size ranging from 500/m to 1 μm in length.
The copper vanadate obtained in example 1 was used to prepare a battery as follows: mixing the prepared copper vanadate, carbon black and polyvinylidene fluoride according to the mass ratio of 7:2:1, fully grinding by taking N-methyl pyrrolidone as a solvent, coating the ground slurry on a copper foil, and drying for 6 hours in vacuum at 120 ℃. Using metal lithium as counter electrode and Celgard membrane as diaphragm, dissolving L/PF6(1mol/L) EC + DMC + DEC (volume ratio is 1: 1: 1) is taken as electrolyte, and the electrolyte is assembled in a glove box in argon atmosphereCR2032 type battery. And standing for 6 hours, and then, selecting an LANHE CT2001A test system to perform constant-current charge and discharge test, wherein the test voltage is 3-0.01V.
FIG. 5 is a CV (cyclic voltammetry) curve of a cell, showing two peaks at 1.15V and 0.93V in the first cathodic scan, corresponding to CuV, respectively2O6Transition of → CuO → Cu and Solid Electrolyte Interface (SEI) formation, and concomitant L +xV2O5Is performed. An anodic peak of 0.76-1.45V reveals that the lithium ion is based on L-xV2O5Is de-intercalation and L-2And (4) decomposing the O.
At 50mA g-1Next, constant current charge and discharge test was performed, and the results are shown in FIG. 6. The first turn firstly appears as a potential platform at 2.1-1.6V and disappears in the later circulation. A stable discharge platform appears between 0.7V and 0.45V, and the first discharge capacity is up to 1197mAhg-1Charging capacity 833mAhg-1The coulombic efficiency was 69.6%. The discharge capacity is only 731mAhg after 3 circles of reduction in the subsequent cycle-1This is due to irreversible capacity loss, e.g. SEI formation and some undigested L-2O。
FIG. 7 shows the voltage at 50mA g-1Performance plots of the cell cycled 200 times at current density. The discharge capacity in the first 40 times is reduced all the time, short rise occurs in 40-50 times, then the stability is kept, the capacity slowly rises after 125 times, and 323mAhg is kept after 200 times of circulation-1The reason for this is some gel-like polymers formed by decomposition of the electrolyte.
In addition to good cycling performance, rate performance at different currents is also improved. As shown in fig. 8, 10 cycles were performed at each current density. When the current density increased to 100mA g-1、200mA g-1、400mA g-1、500mA g-1The discharge capacity is 440mAh g respectively-1、315mAh g-1、237mAh g-1，213mAh g-1Then, it is reduced to 100mA g again-1Then, the discharge capacity was maintained at 344mAh g-1，295mAh g-1，235mAh g-1Almost in agreement with the previous cycle. The better electrochemical performance can be attributed to lithium ionSynergistic effect of two metals in sub-insertion/de-intercalation, and good electronic conductivity thereof.
Example 2
TBAOH was not added during the preparation of copper vanadate, and the amounts of the remaining reagents and the procedure were the same as in example 1.
Example 3
The preparation process of copper vanadate does not add phenanthroline, and the amounts of other reagents and operation steps are the same as those in example 1.
XRD tests are carried out on the products obtained in the examples 2 and 3, and the results are the same as those in figure 2, which proves that the copper vanadate with higher purity is obtained and no impurity peak appears. The copper vanadate obtained in examples 2 and 3 was assembled into a battery at 50mA g in the same manner as in example 1-1Constant current charge and discharge tests are carried out, a stable discharge platform appears at 0.7V-0.45V, and the first discharge capacities are 1180mAhg respectively-1And 1169mAhg-1The discharge capacity decreased to 600mAhg after 3 cycles in the subsequent cycle-1The following. The addition of the complexing agent and the template agent is shown to improve the electrochemical performance of the copper vanadate.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (5)

1. The application of copper vanadate in a lithium ion battery is characterized in that the preparation method of the copper vanadate comprises the following steps:
(1) mixing ammonium metavanadate and CuCl2·2H2Mixing O and phenanthroline, performing hydrothermal reaction at 180-200 ℃ for 30-50 hours to obtain a vanadium-copper precursor, wherein ammonium metavanadate and CuCl are2·2H2The molar ratio of O to phenanthroline is (1.5-3): 1:1, and tetrabutylammonium hydroxide and CuCl are added before hydrothermal reaction2·2H2The molar ratio of O is (1X 10)-4～3×10-4):1；
(2) And calcining the copper vanadate precursor at 500-600 ℃ for 2-3 hours to obtain the copper vanadate.
2. Use according to claim 1, characterized in that in step (2), the calcination is carried out in an air atmosphere.
3. The use according to claim 1, wherein in the step (2), the temperature rise rate of the calcination is 1-5 ℃/min.
4. The use according to claim 1, wherein in step (1), the hydrothermal reaction is carried out in a polytetrafluoroethylene reaction vessel and the calcination is carried out in a muffle furnace.
5. The application of claim 1, wherein the copper vanadate is used as a lithium ion battery negative electrode material and is added at 50mA g-1The first discharge capacity is more than or equal to 1190mAhg at the current density of-1。
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Application publication date: 20190329

Assignee: Zibo High tech Zone Xingrui Qingke Environmental Technology Research Institute

Assignor: SCIENGREEN (SHANDONG) ENVIRONMENT TECHNOLOGY CO.,LTD.

Contract record no.: X2023980047555

Denomination of invention: A preparation method for copper vanadate, the prepared copper vanadate and its application in lithium-ion batteries

Granted publication date: 20210827

License type: Common License

Record date: 20231204