CN109301198A - A kind of array-supported zinc oxide combination electrode of nickel nano film and preparation method - Google Patents

A kind of array-supported zinc oxide combination electrode of nickel nano film and preparation method Download PDF

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CN109301198A
CN109301198A CN201811087345.XA CN201811087345A CN109301198A CN 109301198 A CN109301198 A CN 109301198A CN 201811087345 A CN201811087345 A CN 201811087345A CN 109301198 A CN109301198 A CN 109301198A
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nickel
zinc oxide
array
combination electrode
nano film
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CN109301198B (en
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黄小华
吴建波
钟文武
申士杰
林燕
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Taizhou University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/626Metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The invention discloses array-supported zinc oxide combination electrode materials of a kind of nickel nano film and its preparation method and application.This method comprises: with chemical bath deposition on nickel foil substrate vertical-growth hydroxy nickel oxide (NiOOH) nano-chip arrays;With radio-frequency magnetron sputter method on hydroxy nickel oxide nano-chip arrays further depositing zinc oxide;It is reduced into metallic nickel with the hydrogen-argon-mixed hydroxy nickel oxide by gained composite material, finally the obtained array-supported zinc oxide combination electrode material of nickel nano film.When the material is used for negative electrode of lithium ion battery, there is excellent chemical property due to the complex effect between nickel nano film array and zinc oxide, it is compared with conventional zinc oxide negative electrode material, reversible capacity, initial coulomb efficiency, cyclical stability and high rate capability show to be substantially improved.

Description

A kind of array-supported zinc oxide combination electrode of nickel nano film and preparation method
Technical field
The present invention relates to lithium ion battery electrode materials, and in particular to a kind of array-supported zinc oxide compound electric of nickel nano film Pole material and its preparation method and application.
Background technique
With the continuous exhaustion of fossil energy and getting worse for problem of environmental pollution, active development new energy, construction are low Carbon society has become the strategic issue that countries in the world are all paid close attention to.Lithium ion battery as a kind of high energy green secondary cell, With high voltage, high capacity, high power, the notable feature of long-life, large-scale commercial applications have been obtained.In recent years Come, with the development of technology, the energy density of lithium ion battery is put forward new requirements, and existing commercialization graphite cathode Material is highly developed, and capacity has almost been exhibited to the limit, it is difficult to meet this requirement.Therefore, it is badly in need of exploitation Novel cheap cathode material for high capacity lithium ion battery.
In lithium ion battery negative material, zinc oxide is a kind of high-capacity material, and theoretical capacity is 988 mAh/g, Much higher than graphite material.It has many advantages, such as that chemical property is stable, is easy preparation, is low in cost.But its lower library for the first time Logical sequence efficiency, poor cyclical stability and conductive capability but limit its practical application.Therefore, how to overcome these disadvantages, It is its key scientific problems as lithium ion battery negative material application urgent need to resolve.
Summary of the invention
The purpose of the present invention is to provide a kind of array-supported zinc oxide combination electrode material of nickel nano film and its preparation sides Method, when which is applied to negative electrode of lithium ion battery, reversible capacity, initial coulomb efficiency, cyclical stability and high power Rate performance can be substantially improved.
A kind of array-supported zinc oxide combination electrode material of nickel nano film and preparation method thereof, comprising the following steps:
(1) chemical bath deposition vertical-growth hydroxy nickel oxide nano-chip arrays on nickel foil substrate are used;
(2) video magnetron sputtering method further depositing zinc oxide on the resulting hydroxy nickel oxide array of step (1) is used, is obtained Zinc oxide composite is loaded to hydroxy nickel oxide nano-chip arrays;
(3) reduction method is used, is reduced into metal with the hydrogen-argon-mixed hydroxy nickel oxide by composite material obtained by step (2) Nickel finally obtains the array-supported zinc oxide combination electrode material of nickel nano film.
In step (1), using chemical bath deposition on nickel foil substrate vertical-growth hydroxy nickel oxide nano-chip arrays, Actual conditions are as follows: reaction solution is the mixed solution of nickel sulfate and potassium peroxydisulfate, and concentration of nickel sulfate is 0.2 ~ 0.6 mol/L, mistake Sulfuric acid potassium concn is 0.05 ~ 0.1 mol/L, and the size of nickel foil substrate used is ~ (5 cm × 5 (cm of 1 cm × 1) Cm), 5 ~ 15 mL concentrated ammonia liquors are added and trigger deposition reaction, control reaction temperature is 10 ~ 40oC, reaction time are 0.5 ~ 3 h.
In step (2), using radio-frequency magnetron sputter method on the resulting upright hydroxy nickel oxide nano-chip arrays of step (1) Depositing zinc oxide, actual conditions are as follows: target is zinc oxide ceramics, and sample stage and target spacing are 15 ~ 25 cm, and work gas is height Pure argon, pressure are 5 ~ 10 mTorr, and sputtering power is 50 ~ 100 W, and sputtering time is 2 ~ 12 h.
In step (3), using reduction method, reducing atmosphere be it is hydrogen-argon-mixed, will be in step (2) resulting composite material Hydroxy nickel oxide is reduced into metallic nickel, finally the obtained array-supported zinc oxide combination electrode material of nickel nano film, actual conditions are as follows: Hydrogeneous volume fraction is 5% ~ 10% in hydrogen-argon-mixed, and reduction temperature is 300 ~ 500oC, reduction reaction time are 1 ~ 3 h.
In the array-supported zinc oxide combination electrode material of nickel nano film, array heights are 0.5 ~ 3 μm, wherein nickel Surface density is 0.05 ~ 0.4 mg/cm2, the surface density of zinc oxide is 0.2 ~ 1.2 mg/cm2
Exist in combination electrode material of the invention, between nickel nano film array and zinc oxide active material apparent compound Effect can significantly increase its chemical property.Compared with prior art, have the advantages that in following performance:
One, reversible electrochemistry turn occurs for the lithia that the nano nickel component energy in electrode and zinc oxide generate after discharging for the first time Change reaction (Ni+Li2O NiO+2Li), the utilization rate of electrode material is substantially increased, to improve the head of electrode Secondary coulombic efficiency and reversible capacity.Initial coulomb efficiency of the combination electrode material under 0.1 C multiplying power is 75% ~ 85%, for the first time may be used Inverse capacity is 850 ~ 950 mAh/g.
Two, the zinc oxide component with electro-chemical activity is uniformly filled in the hole in nickel nano film array, they Between it is uniform compound, nickel nano film array acts as three-dimensional buffer network and conductive network inside zinc oxide film, enhances Electrode structure stability simultaneously improves its electric conductivity, so as to improve the cycle performance and high rate capability of zinc oxide.Compound electric Reversible capacity conservation rate after pole material recycles 100 times under 0.1 C multiplying power is 80 ~ 95%;Under 0.5,1 and 2 C multiplying powers Capacity is respectively 750 ~ 850,650 ~ 750,500 ~ 600 mAh/g for the first time.
Figure of description
In order to illustrate more clearly of the technical solution that the present invention is implemented, letter will be made to attached drawing needed in the embodiment below Singly introduce.
Fig. 1 is the preparation process schematic diagram of the array-supported zinc oxide combination electrode material of nickel nano film in embodiment.
Fig. 2 is the scanning electron micrograph of the array-supported zinc oxide combination electrode material of nickel nano film in embodiment.
Specific embodiment
The present invention is made below by specific embodiment and further being illustrated, but the invention is not limited to following Example.
Embodiment:
(1) nickel foil is placed in the mixed solution being made of nickel sulfate and potassium peroxydisulfate, wherein the concentration of nickel sulfate is 0.4 The concentration of mol/L, potassium peroxydisulfate are 0.075 mol/L, persistently stir and are heated to 25oC is put into having a size of 1 cm × 1 The nickel foil substrate of cm is added 10 mL concentrated ammonia liquors and triggers deposition reaction, takes out after 60 min, washed and dried with deionized water, made Obtain hydroxy nickel oxide array.
(2) radiofrequency magnetron sputtering technology is used, using zinc oxide ceramics as target, target is mounted on 20 cm above sample stage Place, sputtering sedimentation aoxidizes zinc coating on the resulting upright hydroxy nickel oxide array of step (1).Sputtering atmosphere is high-purity argon gas (99.999%), operating air pressure is 8 mTorr, and sputtering power is 60 W, and sputtering time is 8 h.
(3) reduction method is used, with hydrogen-argon-mixed for reducing gas containing 5% hydrogen, to step (2) resulting composite wood Hydroxy nickel oxide in material is reduced into metallic nickel, reduction temperature 400oC, recovery time are 2 h, and nickel nano film is finally made Array-supported zinc oxide combination electrode material, with a thickness of 2 μm, the surface density of nickel is 0.25 mg/cm2, the face of zinc oxide is close Degree is 0.75 mg/cm2
Electrochemical property test is carried out to material using CR2025 button cell, it is multiple with the array-supported zinc oxide of nickel nano film Composite electrode is used as working electrode, lithium piece to electrode, 1 mol/L LiPF6DEC+EC (volume ratio DEC:EC=1: 1) solution is electrolyte, using Celgard2400 polypropylene screen as diaphragm.Battery assembling process is below 1 ppm in water, oxygen concentration Glove box in complete.Battery stands 12 h after installing, using galvanostatic charge/discharge, in the voltage range of 0.02 ~ 3.0 V, Constant current charge-discharge is carried out to it using different multiplying, test reversible capacity, initial coulomb efficiency, cycle performance and high power are forthright Energy.
The array-supported zinc oxide combination electrode material of nickel nano film of the invention, nickel nano film array and zinc oxide activity material There are apparent complex effect between material, its chemical property is significantly enhanced.This material magnetron sputtering technique identical as use The conventional pure zinc oxide negative electrode material that preparation is deposited on smooth nickel foil is compared, and is had the advantage that
1, initial coulomb efficiency and reversible capacity are improved significantly.In combination electrode, nano nickel can be put for the first time with zinc oxide Reversible conversion reaction (Ni+Li occurs for the lithia generated after electricity2O NiO+2Li), join more electrode materials With electrochemical reaction, to improve initial coulomb efficiency and reversible capacity.The nickel nano film of the embodiment of the present invention is array-supported The initial coulomb efficiency and reversible capacity comparison for the first time of zinc oxide combination electrode and conventional pure zinc oxide electrode under 0.1 C multiplying power It is shown in Table 1.
Table 1
2, cycle performance be improved significantly.Nickel nano film array and the compound of zinc oxide improve electrode structure intensity, it A three-dimensional buffer network is formd inside zinc oxide, ensure that stability of electrode during iterative cycles, so as to improve The cycle performance of electrode.The array-supported zinc oxide combination electrode material of the nickel nano film of the embodiment of the present invention and conventional pure oxygen Change the reversible capacity conservation rate after the recycle 100 times at 0.1 C of zinc electrode and compare and is also shown in Table 1.
3, high rate capability is remarkably reinforced.Nickel nano film array forms a three-dimensional conduction inside zinc oxide Network improves the electric conductivity of electrode entirety, reduces electrode polarization, to improve the high rate capability of electrode.Table 2 compares The nickel nano film array-supported zinc oxide combination electrode of the embodiment of the present invention and conventional pure zinc oxide electrode are 0.5,1 and 2 Reversible capacity for the first time under C multiplying power.
Table 2

Claims (4)

1. a kind of preparation method of the array-supported zinc oxide combination electrode material of nickel nano film, it is characterised in that including following step It is rapid:
(1) chemical bath deposition vertical-growth hydroxy nickel oxide nano-chip arrays on nickel foil substrate are used;
(2) radio-frequency magnetron sputter method further depositing zinc oxide on the resulting hydroxy nickel oxide array of step (1) is used, is obtained Zinc oxide composite is loaded to hydroxy nickel oxide nano-chip arrays;
(3) reduction method is used, is reduced into metal with the hydrogen-argon-mixed hydroxy nickel oxide by composite material obtained by step (2) Nickel finally obtains the array-supported zinc oxide combination electrode material of nickel nano film.
2. the preparation method of the array-supported zinc oxide combination electrode material of nickel nano film according to claim 1, feature It is, in step (1), reaction solution is the mixed solution of nickel sulfate and potassium peroxydisulfate composition, and the concentration of nickel sulfate is 0.2 ~ 0.6 Mol/L, potassium peroxydisulfate concentration are 0.05 ~ 0.1 mol/L, and 5 ~ 15 mL concentrated ammonia liquors are added and trigger deposition reaction, reaction temperature 10 ~40 oC, reaction time are 0.5 ~ 3 h;In step (2), target is zinc oxide ceramics, and radio-frequency power is 50 ~ 100 W, when sputtering Between be 2 ~ 12 h;In step (3), reducing atmosphere be it is hydrogen-argon-mixed, reduction temperature be 300 ~ 500 oC, reaction time are 1 ~ 3 h。
3. a kind of array-supported zinc oxide combination electrode material of nickel nano film, the combination electrode material is according to claim 2 institute The method stated is prepared, which is characterized in that the combination electrode material is due to answering between nickel nano film array and zinc oxide It closes effect and there is excellent chemical property, initial coulomb efficiency of the combination electrode material under 0.1 C multiplying power is 75% ~ 85%, reversible capacity is 850 ~ 950 mAh/g for the first time, and the reversible capacity conservation rate after circulation 100 times is 80 ~ 95%, 0.5, Capacity for the first time under 1 and 2 C multiplying powers is respectively 750 ~ 850,650 ~ 750,500 ~ 600 mAh/g.
4. the array-supported zinc oxide combination electrode material of nickel nano film according to claim 3 is as lithium ion cell electrode The application of material.
CN201811087345.XA 2018-09-18 2018-09-18 Nickel nanosheet array loaded zinc oxide composite electrode and preparation method thereof Expired - Fee Related CN109301198B (en)

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Cited By (1)

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CN109817879A (en) * 2019-03-19 2019-05-28 北京航空航天大学 A kind of zinc metal composite electrode of array structure and preparation method thereof

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