CN109671925B - GaV2O5/Ga2O3Preparation method of composite lithium ion battery cathode material - Google Patents

GaV2O5/Ga2O3Preparation method of composite lithium ion battery cathode material Download PDF

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CN109671925B
CN109671925B CN201811466822.3A CN201811466822A CN109671925B CN 109671925 B CN109671925 B CN 109671925B CN 201811466822 A CN201811466822 A CN 201811466822A CN 109671925 B CN109671925 B CN 109671925B
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lithium ion
gav
ion battery
temperature
cathode material
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CN109671925A (en
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倪世兵
杨淑越
陈启长
杨学林
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China Three Gorges University CTGU
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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
    • H01M4/362—Composites
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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

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Abstract

The invention provides GaV2O5/Ga2O3A preparation method of a composite lithium ion battery cathode material. The specific operation is as follows: weighing Ga (NO)3)3、V2O5And C6H12N4Adding deionized water and stirring until the deionized water is completely dissolved; transferring the solution into the inner liner of a hydrothermal reaction kettle, reacting for 12-48 h at 120-180 ℃ in a blast oven, and naturally cooling to room temperature; transferring the obtained light yellow precipitate into a culture dish, and drying for 10-20 h in a forced air oven at the temperature of 60-80 ℃; calcining the light yellow precipitate in nitrogen atmosphere at the temperature of 2-5 ℃ for min‑1The temperature rise rate is increased, the heat preservation temperature is 800-2O5/Ga2O3And (3) powder. GaV for the first time2O5/Ga2O3The material is used as a negative electrode material of a lithium ion battery and shows good electrochemical performance.

Description

GaV2O5/Ga2O3Preparation method of composite lithium ion battery cathode material
Technical Field
The invention relates to a novel lithium ion battery cathode material, in particular to a novel GaV2O5/Ga2O3A composite cathode material and a preparation method thereof belong to the field of electrochemical power sources.
Background
As a typical secondary battery, a lithium ion battery has been widely used for small portable electronic devices because of its advantages of high capacity and high cycle, and is also considered as an ideal power source for future electric vehicles and large energy storage devices. However, the energy density and cycle life of lithium ion batteries still have difficulty meeting the ever-increasing energy storage requirements. The development of new and high-performance lithium ion batteries has been a focus of research, and depends on the research and development of high-capacity lithium ion battery electrode materials. At present, the theoretical capacity of commercial graphite carbon materials is low (372 mAh g)-1) Therefore, the overall energy density of the lithium ion battery is remarkably inhibited, and the research and development of novel alternative negative electrode materials are particularly urgent for the development of high-performance lithium ion batteries.
The complex vanadium-based compounds and metal oxide composites exhibit high theoretical capacities based on a particular conversion mechanism. And the lithium-containing vanadium oxide formed in the lithium inserting and removing processes has high conductivity, so that the compound has better cycle performance. The gallium vanadate and gallium oxide compound is used as a lithium ion battery cathode material, and Ga and Li are expected to form an alloy for deeply storing lithium, so that the material capacity is further improved. However, no relevant report is found at present. Based on the background, the patent provides a novel GaV2O5/Ga2O3The preparation method of the composite material shows good electrochemical performance when being used as the negative electrode of the lithium ion battery for the first time.
Disclosure of Invention
The invention aims to develop a novel GaV2O5/Ga2O3The composite lithium ion battery cathode material.
The preparation method of the invention specifically comprises the following steps:
(1) ga (NO)3)3、V2O5And C6H12N4After mixing, deionized water is added and stirred until the mixture is completely dissolved, and a proper amount of ammonia water is dripped to promote Ga (NO)3)3Hydrolysis of (2);
(2) transferring the mixed solution obtained in the step (1) into a lining of a hydrothermal reaction kettle, carrying out hydrothermal reaction in a blast oven, and naturally cooling to room temperature to obtain a precipitate;
(3) transferring the precipitate obtained in the step (2) into a culture dish, drying the precipitate in a forced air oven at the temperature of 60-80 ℃, calcining the dried precipitate in an inert atmosphere, and grinding the calcined product to obtain GaV2O5/Ga2O3And (3) powder.
Ga (NO) as described3)3、V2O5、C6H12N4And ammonia water in a molar ratio of 2: 0.8-1.2: 2-3: 0.01 to 0.05.
Further preferred is Ga (NO)3)3、V2O5、C6H12N4And ammonia waterIn a molar ratio of 2: 1: 2.5: 0.02.
the hydrothermal reaction temperature in the step (2) is 120-180 ℃, and the reaction time is 12-48 h.
The sintering step in the step (3) is carried out at 2-5 ℃ for min under nitrogen or argon-1The temperature rise rate is increased to 800-1200 ℃, and sintering is carried out for 5-10 h.
The technical scheme of the invention promotes V by adding ammonia water2O5Dissolving and hydrolyzing gallium nitrate to obtain intermediate phase product. The intermediate phase product is beneficial to in-situ adsorption of vanadium ions in hydrothermal reaction and formation of precursor compounds with controllable stoichiometric ratio of gallium and vanadium elements, and two uniformly compounded GaV are finally obtained in the subsequent sintering process2O5/Ga2O3A composite material. GaV for the first time2O5/Ga2O3The composite is used as a lithium ion battery cathode material.
The invention relates to a novel GaV2O5/Ga2O3The preparation method of the composite lithium ion battery cathode material has the following remarkable characteristics:
(1) the synthesis process is simple and has strong repeatability;
(2) prepared GaV2O5/Ga2O3The composite can be used as a lithium ion battery cathode material;
(3) prepared GaV2O5/Ga2O3The composite lithium ion battery has obvious charging and discharging platforms and has potential application value in the lithium ion battery.
Drawings
Figure 1 XRD pattern of the sample prepared in example 1.
FIG. 2 graph of (a) the first three charge and discharge curves and (b) the cycle performance of the sample prepared in example 1.
FIG. 3 is a graph of (a) the first three charge and discharge curves and (b) the cycle performance of the sample prepared in example 2.
FIG. 4 graph of (a) the first three charge and discharge curves and (b) the cycle performance of the sample prepared in example 3.
Detailed Description
Example 1
Weighing 2 mmol Ga (NO) according to the proportion3)3、1 mmol V2O5、2.5 mmol C6H12N4Adding deionized water into a 50 ml beaker, stirring for 30 min until the deionized water is completely dissolved, and dropwise adding 1.5 ml of 25% ammonia water during the stirring; transferring the solution into the inner liner of a hydrothermal reaction kettle, adding deionized water to 80% of the volume of the inner liner, reacting in a blast oven at 120 ℃ for 24h, and naturally cooling to room temperature; transferring the obtained light yellow precipitate into a culture dish, and drying in a forced air oven at 70 ℃ for 10 h; calcining the light yellow precipitate in nitrogen atmosphere at 3 deg.C for min-1The temperature is increased at the temperature rising rate, the heat preservation temperature is 900 ℃, the time is 5 hours, and black GaV is obtained after grinding2O5/Ga2O3And (3) powder. The prepared sample is analyzed by XRD spectrum as shown in figure 1, and the obtained diffraction peak and Ga2O3(PDF # 01-087) -2O5(PDF #01-073-0841) showed successful preparation of GaV2O5/Ga2O3A composite material.
The battery is prepared by the following method: mixing the prepared sample with acetylene black and polyvinylidene fluoride (PVDF) according to the ratio of 8:1:1 to prepare slurry, coating the slurry on a copper foil with the thickness of 10 mu m, drying the copper foil for 10 hours at a 60 ℃ baking lamp, cutting the copper foil into a wafer with the diameter of 14 mm, and drying the wafer for 12 hours at a temperature of 120 ℃ in vacuum. Using a metal lithium sheet as a counter electrode, a Celgard2400 membrane as a diaphragm and 1M LiPF6the/DMC EC =1: 1 solution was used as electrolyte and assembled into a CR2025 type cell in an argon-protected glove box. Standing for 8 hours after the battery is assembled, and then performing constant-current charge and discharge test by using a CT2001 battery test system, wherein the test voltage is 0.02-3V, and the current density is 100 mA g-1Prepared GaV as shown in FIG. 22O5/Ga2O3The first charge and discharge curve and the cycle performance chart of the anode of the lithium ion battery. As shown in the figure: (a) the first charge-discharge capacity is 590 mAh g-1And 795 mAh g-1The second charge-discharge capacity was 564 mAh g-1And 601 mAh g-1The third charge-discharge capacity is 540 mAh g-1And 574 mAh g-1. (b) The capacity decreases with the increase of the number of cycles, and after 20 th cycle, only 349 mAh g remains-1Discharge capacity of 335 mAh g-1The charging capacity of (1).
Example 2
Weighing 2 mmol Ga (NO) according to the proportion3)3、1 mmol V2O5、2.5 mmol C6H12N4Adding deionized water into a 50 ml beaker, stirring for 30 min until the deionized water is completely dissolved, and dropwise adding 1.5 ml of 25% ammonia water during the stirring; transferring the solution into the inner liner of a hydrothermal reaction kettle, adding deionized water to 80% of the volume of the inner liner, reacting in a blast oven at 120 ℃ for 24h, and naturally cooling to room temperature; transferring the obtained light yellow precipitate into a culture dish, and drying in a forced air oven at 70 ℃ for 10 h; calcining the light yellow precipitate in nitrogen atmosphere at 3 deg.C for min-1The temperature is raised at the temperature raising rate, the heat preservation temperature is 800 ℃, the time is 5 hours, and black GaV is obtained after grinding2O5/Ga2O3And (3) powder.
The material obtained in example 2 was used to prepare a battery by the method of example 1. As shown in fig. 3: its first charge-discharge capacity is 696 mAh g-1And 853 mAh g-1The second charge-discharge capacity is 575mAh g-1And 645 mAh g-1The third charge-discharge capacity is 507 mAh g-1And 554 mAh g-1. The capacity decreases with increasing cycle number, and only 202 mAh g remains after 20 th cycle-1Charge capacity of 212 mAh g-1The discharge capacity of (2).
Example 3
Weighing 2 mmol Ga (NO) according to the proportion3)3、1 mmol V2O5、2.5 mmol C6H12N4Adding deionized water into a 50 ml beaker, stirring for 30 min until the deionized water is completely dissolved, and dropwise adding 1.5 ml of 25% ammonia water during the stirring; transferring the solution into the inner liner of a hydrothermal reaction kettle, adding deionized water to 80% of the volume of the inner liner, reacting in a blast oven at 120 ℃ for 24h, and naturally cooling to room temperature; the resulting light yellow precipitate was transferred to a petri dish,drying in a blast oven at 70 ℃ for 10 h; calcining the light yellow precipitate in nitrogen atmosphere at 3 deg.C for min-1The temperature is raised at the temperature raising rate, the heat preservation temperature is 1000 ℃, the time is 5 hours, and black GaV is obtained after grinding2O5/Ga2O3And (3) powder.
The material obtained in example 3 was used to prepare a battery in accordance with example 1. As shown in FIG. 4, the first charge/discharge capacity was 367 mAh g-1And 438 mAh g-1The second charge-discharge capacity is 375 mAh g-1And 390 mAh g-1The third charge-discharge capacity is 378 mAh g-1And 391 mAh g-1. The capacity decreases with increasing cycle number, and only 240 mAh g remains after 20 th cycle-1Charge capacity of 245 mAh g-1The discharge capacity of (2).

Claims (3)

1. GaV2O5/Ga2O3The preparation method of the lithium ion battery cathode material of the composite is characterized by comprising the following specific preparation processes of:
(1) ga (NO)3)3、V2O5And C6H12N4After mixing, deionized water was added and stirred until it was completely dissolved, while adding dropwise ammonia water to dissolve Ga (NO)3)3Hydrolysis, Ga (NO)3)3、V2O5、C6H12N4And ammonia water in a molar ratio of 2: 0.8-1.2: 2-3: 0.01 to 0.05;
(2) transferring the mixed solution obtained in the step (1) into a lining of a hydrothermal reaction kettle, carrying out hydrothermal reaction in a blast oven, and naturally cooling to room temperature to obtain a precipitate;
(3) transferring the precipitate obtained in the step (2) into a culture dish, drying the precipitate in a forced air oven at the temperature of 60-80 ℃, calcining the dried precipitate in an inert atmosphere, and grinding the calcined product to obtain GaV2O5/Ga2O3And (3) powder.
2. GaV according to claim 12O5/Ga2O3The preparation method of the lithium ion battery cathode material of the composite is characterized in that the hydrothermal reaction temperature in the step (2) is 120-180 ℃, and the reaction time is 12-48 h.
3. GaV according to claim 12O5/Ga2O3The preparation method of the lithium ion battery cathode material of the composite is characterized in that in the step (3), the sintering step is carried out at 2-5 ℃ for min under nitrogen or argon-1The temperature rise rate is increased to 800-1200 ℃, and sintering is carried out for 5-10 h.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015086461A1 (en) * 2013-12-13 2015-06-18 Basf Se Nitrogen-containing composite materials, production and use thereof
CN104900906A (en) * 2015-06-09 2015-09-09 三峡大学 Vanadium-based compound Zn3V3O8, as well as preparation method and application of vanadium-based compound Zn3V3O8
CN107732221A (en) * 2017-11-27 2018-02-23 三峡大学 A kind of stable compound lithium ion battery negative material α Ga2O3 and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015086461A1 (en) * 2013-12-13 2015-06-18 Basf Se Nitrogen-containing composite materials, production and use thereof
CN104900906A (en) * 2015-06-09 2015-09-09 三峡大学 Vanadium-based compound Zn3V3O8, as well as preparation method and application of vanadium-based compound Zn3V3O8
CN107732221A (en) * 2017-11-27 2018-02-23 三峡大学 A kind of stable compound lithium ion battery negative material α Ga2O3 and preparation method

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