CN106531966A - Preparation method for nanometer Cu@CuO material and application of nanometer Cu@CuO material to lithium ion battery - Google Patents
Preparation method for nanometer Cu@CuO material and application of nanometer Cu@CuO material to lithium ion battery Download PDFInfo
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- CN106531966A CN106531966A CN201611141213.1A CN201611141213A CN106531966A CN 106531966 A CN106531966 A CN 106531966A CN 201611141213 A CN201611141213 A CN 201611141213A CN 106531966 A CN106531966 A CN 106531966A
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- nanometer
- cuo
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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 discloses a preparation method for a nanometer Cu@CuO material and a lithium ion battery using the nanometer Cu@CuO material as a negative electrode material, belonging to the field of energy materials. According to the invention, a hydro-thermal reaction process is employed; sodium hydroxide provides an alkaline environment; hydrogen peroxide is used as an oxygen source; and the nanometer Cu@CuO negative electrode material is prepared through slow etching of a two-dimensional copper nanosheet. The preparation method is simple in process and equipment, controllable in technological parameters, mild in conditions and high in repeatability; raw materials used in the preparation method are widely available and low cost, so the preparation method can easily realize large-scale production; and the prepared nanometer Cu@CuO negative electrode material has high specific capacity and good cycle stability, is an ideal lithium ion battery negative electrode material and be extensively applied to fields like portable electronic equipment, electric tools, space technology and national defense industries.
Description
Technical field
The invention belongs to energy and material and electrochemical field, and in particular to a kind of system of novel cathode material for lithium ion battery
It is standby and its in the storage and conversion of electrochemical energy.
Background technology
As people are growing to the demand of the energy, the aggravation of fossil fuel reserves reductions and environmental pollution, open
The novel energy for sending out clean and effective becomes focus of concern.Lithium ion battery as a kind of energy storing device, due to having
The advantages of environmentally friendly, light, high power capacity, long-life, more and more applied.Can be applied not only to various portable electrics
Sub- equipment, has very big application in terms of the energy storage device as the new forms of energy such as electric powered motor power supply and solar energy, wind energy
Prospect.In recent years, the development of electrical equipment is put forward higher requirement to the power density and energy density of lithium ion battery, and
Electrode material is the deciding factor that performance of lithium ion battery is improved.In terms of negative material, current business-like lithium-ion electric
Pond negative material graphite theoretical capacity (372 mAh/g) is low, can not meet demand of the people to battery performance.Therefore study
Become an important topic with exploitation novel ion cell negative electrode material.Oxide cathode material has theoretical capacity height, circulation
Its theoretical specific capacity is 673 mAh/g as lithium ion battery negative material for the advantages of performance is good, security performance is high, wherein CuO,
It is 2-3 times of common carbon negative pole material battery capacity, is the lithium ion battery of new generation of a kind of great development and application potential
Negative material.However, CuO electrode materials cause significantly knot due to producing larger bulk effect in charge and discharge process
Structure breakage efflorescence, causes circulation volume rapid decrease then.In addition, the electric conductivity of CuO electrode materials is poor, this strong influence
Electric charge transmission in the electrodes, and then affect the electrochemical lithium storage performance of electrode material.For the disadvantage mentioned above of CuO materials,
Researchers conduct extensive research.Electrode material size is reduced to nanosized, is conducive to improving CuO in cyclic process
The release of the stress produced due to removal lithium embedded, is alleviated the volumetric expansion of CuO, can effectively improve the cyclical stability of CuO.Separately
Outward, CuO good with electric conductivity nano material is combined, the electrical conductivity of CuO electrode materials can be improved, electric charge is improved in electrode material
Migration rate in material further obtains the electrode material of preferable high rate performance.In current research, CuO and the good carbon of electric conductivity
The compound report of sill is more, but forms but being rarely reported for combination electrode material with nano-metallic copper, especially with
Hydrothermal method, using copper nanometer sheet as reaction template, obtains nanometer research of Cu@CuO electrode materials and has not been reported.
The content of the invention
Based on the problems referred to above, the present invention provides the preparation method of a kind of nanometer of Cu@CuO material and by this kind of method preparation
Application of the negative material as lithium ion battery and the lithium ion battery of the Cu@CuO negative materials using above-mentioned preparation.This
It is bright using copper nanometer sheet as conductive substrates, nanometer Cu@CuO negative materials are prepared by hydro-thermal reaction method.The preparation of the present invention
The method and apparatus of Cu@CuO materials is simple, and technological parameter is controllable and mild condition, repeatable high.Prepare needed raw material rich
Richness, low cost are easy to scale.
Present invention employs following technical scheme：
The preparation method of a kind of nanometer of Cu@CuO material, first prepares thickness about 600-700 nm by self-assembly method, and diameter is big
The about copper nanometer sheet of 20-200 um, then by the copper nanometer sheet of gained through hydrothermal treatment process, prepare nanometer Cu@CuO and bear
Pole material；
Concrete technology step is：
(1) water, glucose, polyvinylpyrrolidone are pressed into certain mass than mixing, is stirred more than 3 hours, obtain clarification mixed
Liquid；
(2) under conditions of stirring, copper sulfate solution is added dropwise in the mixed liquid of clarification in step (1), is stirred at room temperature
After 30-60min, in being transferred to hydrothermal reaction kettle, 2.5-4h is reacted at 160-200 DEG C；
(3) after the product obtained by step (2) being centrifuged, using deionized water and absolute ethanol washing, vacuum drying successively
Obtain copper nanometer sheet；
(4) a certain amount of water, NaOH are added in copper nanometer sheet obtained by step (3), that hydrogenperoxide steam generator is put into hydro-thermal is anti-
In answering kettle, stirring 1-5min insulation reactions 6-14h in 100-150 DEG C of baking oven；
(5) after room temperature cooling, by the centrifugation of step (4) products therefrom, deionized water and absolute ethanol washing, vacuum are used successively
Nanometer Cu@CuO negative electrode material powders are obtained after drying.
Further, solution in step (1), water, glucose, the mass ratio of polyvinylpyrrolidone are controlled 25:0.5-
1:0.2-1。
Further, in step (2), copper sulphate and the amount ratio of the material of glucose in step (1) are 1: 2.5-5.
Further, in step (4), the mass ratio of water, NaOH and hydrogen peroxide is：50-150:1.6-8:4.5-
27.8。
Further, in step (4), copper nanometer sheet with the mol ratio of NaOH is：0.03-0.78:4-20.
Further, the drying described in step (5) is vacuum drying, and it is 40 ~ 80 DEG C that baking oven arranges temperature.
Further, the present invention provides a kind of lithium ion battery, and the negative material of lithium ion battery adopts above-mentioned nanometer
Cu@CuO negative materials.The present invention first obtains copper nanometer sheet material using the method for self assembly, is combining hydrothermal reaction process, profit
With the corrasion of NaOH and hydrogen peroxide to copper nanometer sheet, nanometer Cu@CuO materials are prepared.The material is by electrochemistry
Activity core material and conductive nano matrix are constituted, and electro-chemical activity core material CuO homoepitaxials are in conducting base copper nanometer
On piece.The copper nanometer sheet substrate of nanoscale can alleviate the stress that CuO is produced during removal lithium embedded, while nanometer CuO banding
Space between pattern is arranged can also reduce the electrode efflorescence effect that volumetric expansion during removal lithium embedded brings.Particularly copper nanometer sheet
Substrate has excellent electric conductivity, can improve conduction of the electronics in electrode material, improves the utilization rate and material of active material
Electrical conductivity, obtain then the lithium ion battery with higher specific discharge capacity and high rate performance.With the nanometer Cu@of the present invention
CuO materials are lithium ion battery negative material, are that 2025 button batteries are prepared into electrode with lithium piece, are shown good comprehensive
Close chemical property.
The invention has the beneficial effects as follows：The preparation method and equipment of the present invention is simple, and technological parameter is controllable and mild condition,
It is repeatable high.Prepare needed raw material to enrich, low cost is easy to scale.The nanometer Cu@CuO negative materials of preparation have
Higher specific discharge capacity and stable high rate performance, can meet growing Portable power source to height ratio capacity lithium
The demand of ion battery.
Description of the drawings
Fig. 1 is the SEM pictures of nanometer Cu@CuO materials of the present invention；
Fig. 2 is the XRD piece of nanometer Cu@CuO materials of the present invention；
Fig. 3 is the TEM pictures of nanometer Cu@CuO materials of the present invention；
Fig. 4 is the SEM pictures of Cu nanometer sheets material of the present invention；
Fig. 5 is 200 charging and discharging curves of the nanometer Cu@CuO materials obtained in embodiment 1；
Fig. 6 is the voltage-specific capacity relation curve of the nanometer Cu@CuO materials obtained in embodiment 2；
Fig. 7 is the high rate performance curve of the nanometer Cu@CuO materials obtained in embodiment 3.
Specific embodiment
With reference to specific embodiment, the present invention is further elucidated.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member is made various changes or modifications to the present invention, and these equivalent form of values equally fall within the model limited by the application appended claims
Enclose.
Embodiment 1
The deionized water of 0.4g glucose, 0.2g polyvinylpyrrolidones and 15mL is stirred into 4h at ambient temperature, obtains clear
Liquid mixed clearly.The copper-bath of 0.8mmoL is added thereto to, is reacted at 160 DEG C during hydrothermal reaction kettle is transferred to after stirring 1h
4h, product centrifugation, deionized water, absolute ethanol washing three times, products therefrom is dried to obtain in vacuum drying chamber successively
Copper nanometer sheet.0.025g copper nanometer sheets, 10g water, 0.16g NaOH, 30% hydrogen peroxide of 0.16g are placed in reactor and are stirred
1min is mixed, insulation reaction 6h in 110 DEG C of baking oven.By products therefrom centrifugation, use successively deionized water and absolute ethanol washing,
Nanometer Cu@CuO material powders are obtained after 50 DEG C of vacuum drying.
Will be the PVDF mixing of the nanometer Cu@CuO materials, the acetylene black of 15 wt.% and 10 wt.% of obtained 75 wt.% equal
It is even, slurry is made, is coated uniformly on Copper Foil, after vacuum drying, be stamped into circular electrode pole piece, be to electrode group with lithium metal
Into test cell.Constant current charge-discharge test is carried out to battery, charging/discharging voltage scope is 0.01 ~ 3 V, is as a result shown, which has
Preferable chemical property, Fig. 5 is which under 0.1C current densities, circulates the battery performance of material after 200 times, and its specific capacity is
620 mAh/g, material have good cyclical stability.
Embodiment 2
The deionized water of 1g glucose, 0.6g polyvinylpyrrolidones and 20mL is stirred into 4h at ambient temperature, is clarified
Mixed liquid.The copper-bath of 1mmoL is added thereto to, and reacts 3h, produce in hydrothermal reaction kettle being transferred to after stirring 1h at 170 DEG C
Thing is centrifuged, deionized water, absolute ethanol washing three times successively, and products therefrom is dried to obtain in vacuum drying chamber copper nanometer
Piece.0.03g copper nanometer sheets, 6g water, 0.2g NaOH, 30% hydrogen peroxide of 0.3g are placed in reactor and stir 1min, in
Insulation reaction 8h in 110 DEG C of baking oven.By products therefrom centrifugation, deionized water and absolute ethanol washing, true in 50 DEG C are used successively
Sky obtains nanometer Cu@CuO material powders after being dried.
Will be the PVDF mixing of the nanometer Cu@CuO materials, the acetylene black of 15 wt.% and 10 wt.% of obtained 75 wt.% equal
It is even, slurry is made, is coated uniformly on Copper Foil, after vacuum drying, be stamped into circular electrode pole piece, be to electrode group with lithium metal
Into test cell.Constant current charge-discharge test is carried out to battery, charging/discharging voltage scope is 0.01 ~ 3 V, is as a result shown, which has
Preferable chemical property, Fig. 6 is which under 0.2C current densities, and the voltage that charge and discharge cycles are 200 times-specific volume magnitude relation is bent
Line, its specific capacity are still maintained at 580 mAh/g or so, it is seen that this material has good cyclical stability.
Embodiment 3
The deionized water of 1.5g glucose, 1g polyvinylpyrrolidones and 45mL is stirred into 4h at ambient temperature, is clarified
Mixed liquid.The copper-bath of 1.8mmoL is added thereto to, is reacted at 180 DEG C during hydrothermal reaction kettle is transferred to after stirring 1h
4.5h, product centrifugation, successively deionized water, absolute ethanol washing three times are dry in vacuum drying chamber by products therefrom
To copper nanometer sheet.0.04g copper nanometer sheets, 10g water, 0.3g NaOH, 30% hydrogen peroxide of 0.5g are placed in reactor and are stirred
3min is mixed, insulation reaction 12h in 110 DEG C of baking oven.By products therefrom centrifugation, washed using deionized water and absolute ethyl alcohol successively
Wash, nanometer Cu@CuO material powders are obtained after 60 DEG C of vacuum drying.
Will be the PVDF mixing of the nanometer Cu@CuO materials, the acetylene black of 15 wt.% and 10 wt.% of obtained 75 wt.% equal
It is even, slurry is made, is coated uniformly on Copper Foil, after vacuum drying, be stamped into circular electric pole piece, be that electrode is constituted with lithium metal
Test cell.Fig. 7 carries out high rate performance test to battery for which, as a result shows, Cu@CuO materials through 0.1C, 0.2C,
After 0.3C, 0.5C, 1C, 2C circulation, return and remain to keep its capacity that big change does not occur when 0.2C is circulated, illustrate that material has
There is preferable high rate performance.
Claims (7)
1. the preparation method of a kind of nanometer of Cu@CuO material, it is characterised in that：Methods described prepares thickness by self-assembly method for first
For 600-700 nm, the copper nanometer sheet of a diameter of 20-200 um, then by the copper nanometer sheet of gained through hydrothermal treatment process, system
Standby nanometer Cu@CuO negative materials；Concrete grammar is comprised the following steps：
(1) water, glucose, polyvinylpyrrolidone are pressed into certain mass than mixing, is stirred more than 3 hours, obtain clarification mixed
Liquid；
(2) under conditions of stirring, copper sulfate solution is added dropwise in the mixed liquid of clarification in step (1), is stirred at room temperature
After 30-60min, in being transferred to hydrothermal reaction kettle, 2.5-4h is reacted at 160-200 DEG C；
(3) after the product obtained by step (2) being centrifuged, using deionized water and absolute ethanol washing, vacuum drying successively
Obtain copper nanometer sheet；
(4) a certain amount of water, NaOH, hydrogenperoxide steam generator are added in copper nanometer sheet obtained by step (3), is put into hydro-thermal
In reactor, insulation reaction 6-14h in 100-150 DEG C of baking oven；
(5) after room temperature cooling, by step（4）Products therefrom is centrifuged, uses deionized water and absolute ethanol washing, vacuum successively
Nanometer Cu@CuO material powders are obtained after drying.
2. the preparation method of according to claim 1 nanometer of Cu@CuO material, it is characterised in that：In step (1), gained is molten
Liquid, water, glucose, the mass ratio of polyvinylpyrrolidone are controlled 25:0.5-1:0.2-1.
3. the preparation method of according to claim 1 nanometer of Cu@CuO material, it is characterised in that：Copper sulphate in step (2)
Amount ratio with the material of glucose in step (1) is 1: 2.5-5.
4. the preparation method of according to claim 1 nanometer of Cu@CuO material, it is characterised in that：Water, hydrogen-oxygen in step (4)
The mass ratio for changing sodium and hydrogen peroxide is：50-150:1.6-8:4.5-27.8.
5. the preparation method of according to claim 1 nanometer of Cu@CuO material, it is characterised in that：In step (4), copper nanometer
Piece with the mol ratio of NaOH is：0.03-0.78:4-20.
6. the preparation method of according to claim 1 nanometer of Cu@CuO material, it is characterised in that：Described in step (5)
It is dried to be vacuum dried, it is 40 ~ 80 DEG C that baking oven arranges temperature.
7. lithium ion battery, it is characterised in that：The negative material of the battery is using the nanometer Cu@CuO materials described in right 1.
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Cited By (3)
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| CN108374167A (en) * | 2018-02-13 | 2018-08-07 | 桂林理工大学 | A kind of hydro-thermal method preparation Cu2The method of O nano thin-films |
| CN112941556A (en) * | 2021-01-27 | 2021-06-11 | 国家纳米科学中心 | Copper-based solid material and preparation method and application thereof |
| CN112974831A (en) * | 2021-03-05 | 2021-06-18 | 西北有色金属研究院 | Cu-Cu with nano array structure3Preparation method of P material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108374167A (en) * | 2018-02-13 | 2018-08-07 | 桂林理工大学 | A kind of hydro-thermal method preparation Cu2The method of O nano thin-films |
| CN108374167B (en) * | 2018-02-13 | 2020-06-05 | 桂林理工大学 | Hydrothermal method for preparing Cu2Method for preparing O nano film |
| CN112941556A (en) * | 2021-01-27 | 2021-06-11 | 国家纳米科学中心 | Copper-based solid material and preparation method and application thereof |
| CN112941556B (en) * | 2021-01-27 | 2023-09-15 | 国家纳米科学中心 | Copper-based solid material and preparation method and application thereof |
| CN112974831A (en) * | 2021-03-05 | 2021-06-18 | 西北有色金属研究院 | Cu-Cu with nano array structure3Preparation method of P material |
| CN112974831B (en) * | 2021-03-05 | 2022-04-19 | 西北有色金属研究院 | Cu-Cu with nano array structure3Preparation method of P material |
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