CN103400975A

CN103400975A - Preparation method of Cu2O secondary battery anode material

Info

Publication number: CN103400975A
Application number: CN2013103513334A
Authority: CN
Inventors: 李长明; 孙柏
Original assignee: Southwest University
Current assignee: Southwest University
Priority date: 2013-08-13
Filing date: 2013-08-13
Publication date: 2013-11-20
Anticipated expiration: 2033-08-13
Also published as: CN103400975B

Abstract

The invention discloses a preparation method of a Cu2O secondary battery anode material. The preparation method comprises the following steps: (1) dissolving copper acetate and polyvinylpyrrolidone in deionized water, and stirring so as to form a mixed solution; (2) inserting an electric conduction substrate into the mixed solution obtained in the step (1), and carrying out a hydrothermal reaction for 10 to 60 hours at 150 to 350 DEG C to obtain the electric conduction substrate on which Cu2O particles grow; and (3) washing and drying the electric conduction substrate on which the Cu2O particles grow, which is obtained in the step (2), thus obtaining the Cu2O secondary battery anode material. According to the preparation method, the hydrothermal reaction is used for directly growing the Cu2O particles on the electric conduction substrate. The Cu2O secondary battery anode material has relatively high insertion capacity of sodium ions and lithium ions and very good de-intercalation reversibility, is used as the anode material of a sodium-ion battery and a lithium-ion battery and can be used for increasing the practical capacity of the battery and prolonging the recycling service life of the battery.

Description

Cu 2The preparation method of O secondary cell anode material

Technical field

The present invention relates to a kind of preparation method of secondary cell anode material, particularly a kind of Cu ₂The preparation method of O secondary cell anode material.

Background technology

Since Gaston Plante in 1859 proposed lead-sour battery concept, chemical power source circle was being explored new high-energy-density, the secondary cell that has extended cycle life always.Japan Sony Corporation took the lead in succeeding in developing and realized commercial lithium ion battery nineteen ninety, in many-sides such as portable electric appts, electric automobile, space technology, national defense industry, show wide application prospect and potential great economic benefit, become rapidly the study hotspot of widely paying close attention in recent years.

At present, the large-scale development of lithium ion battery is subject to the restriction of lithium resource, and the lithium battery safety issue is also not basic solution technically.In the process of storage battery maximization from now on, the material cost proportion increases, and more is subject to the restriction of resource.Tokyo Electric Power and NGK company develop sodium-sulphur battery cooperatively as energy-storage battery, and, the implementation phase starting to enter commercialization in 2002, end in October, 2005 statistics, produce the sodium-sulphur battery amount per year and have surpassed 100MW, start simultaneously to overseas output.

Sodium-ion battery not only is beneficial to environmental protection, has more economy.The sodium ion radius is larger, and to compare Coulomb attraction little with lithium ion, and ligand solvent easily breaks away from, and diffusion velocity is fast, and sode cell high speed charge-discharge performance can be better.

One of key of exploitation sodium-ion battery is to find suitable anode material, makes battery have sufficiently high sodium embedded quantity and takes off the embedding invertibity with good sodium, with the high voltage that guarantees battery, large capacity and long circulation life.

Summary of the invention

In view of this, the invention provides a kind of Cu ₂The preparation method of O secondary cell anode material, the Cu of preparation ₂O secondary cell anode material can be used as the anode material of sodium-ion battery and lithium ion battery, can realize that the high power capacity of battery discharges and recharges, and have extended cycle life.

Cu of the present invention ₂The preparation method of O secondary cell anode material comprises the following steps:

1) Schweinfurt green and polyvinylpyrrolidone are dissolved in deionized water, stir and be made into mixed solution;

2) conductive substrate is inserted in the mixed solution that step 1) obtains, 150～350 ℃ of lower hydro-thermal reactions 10～60 hours, obtaining growth had Cu ₂The conductive substrate of O particle;

3) growth that flushing drying steps 2) obtains has Cu ₂The conductive substrate of O particle, obtain Cu ₂O secondary cell anode material.

Further, in described step 1), in mixed solution, the molar concentration of Schweinfurt green is 0.25mol/L, and the molar concentration of polyvinylpyrrolidone is 2 * 10 ^-5Mol/L.

Further, described conductive substrate is copper sheet.

Further, described step 2) in, first with watery hydrochloric acid, clean the oxide layer of removing the copper sheet surface, then copper sheet is inserted in the mixed solution that step 1) obtains.

Further, described step 2) in, hydrothermal temperature is 180 ℃, the reaction time is 48 hours.

Beneficial effect of the present invention is: the present invention utilizes the method for the hydro-thermal reaction Cu that directly grows on conductive substrate ₂The O particle, Cu ₂O and conductive substrate tack are good, do not need to add binding agent again, and the Cu of growth ₂The amount of O and the size of particle diameter can regulate and control by the length in reaction time, simultaneously, between particle, have larger space, thereby more be conducive to the embedded quantity of lithium ion and sodium ion and well take off the embedding invertibity, therefore can be using it as sodium-ion battery and the anode material of lithium ion battery, not only the actual capacity of battery can be improved, and charge and discharge cycles useful life can be extended widely; Cu prepared by the present invention ₂O secondary cell anode material can be realized longer life, the higher capacity of battery, can be used in the secondary cell of various electronic devices.

The accompanying drawing explanation

In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is described in further detail below in conjunction with accompanying drawing, wherein:

Fig. 1 is the Cu that embodiment prepares ₂XRD figure and the EDX elementary analysis figure of O secondary cell anode material;

Fig. 2 is the Cu that embodiment prepares ₂The SEM plane graph of O secondary cell anode material and sectional view thereof, TEM High-Resolution Map;

Fig. 3 is the button sodium-ion battery for preparing of embodiment and the CV curve of button lithium ion battery;

Fig. 4 is first three time charge and discharge cycles curve of the button sodium-ion battery for preparing of embodiment and button lithium ion battery;

Fig. 5 is button sodium-ion battery and the capacity of button lithium ion battery under different discharge-rates---cycle-index curve prepared by embodiment;

Fig. 6 is button sodium-ion battery and the capacity of button lithium ion battery under same discharge-rate---cycle-index curve prepared by embodiment;

Fig. 7 is the button sodium-ion battery for preparing of embodiment and the impedance curve of button lithium ion battery.

Embodiment

Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.

The Cu of the present embodiment ₂The preparation method of O secondary cell anode material comprises the following steps:

1) take 2.02g Schweinfurt green and 1.0g polyvinylpyrrolidone (Polyvinyl pyrrolidone, PVP) and be dissolved in the 40ml deionized water, stir and be made into mixed solution; The mixed solution that is made into, is inserted in 50ml pyroreaction still after 2 hours with magnetic stirrer;

2) first with watery hydrochloric acid, clean to remove the oxide layer on copper sheet surface, then copper sheet is inserted in the mixed solution that step 1) obtains, 180 ℃ of lower hydro-thermal reactions 48 hours, obtaining growth had Cu ₂The copper sheet of O particle;

3) growth that flushing drying steps 2) obtains has Cu ₂The copper sheet of O particle, obtain Cu ₂O secondary cell anode material, its quality is approximately 2mg.

The Cu that Fig. 1 (a) prepares for embodiment ₂The XRD figure of O secondary cell anode material, as shown in the figure, can find out prepared Cu from XRD figure ₂The O particle crystallization is good, and without any dephasign.

The Cu that Fig. 1 (b) prepares for embodiment ₂The EDX elementary analysis figure of O secondary cell anode material, as shown in the figure, can find out prepared Cu from EDX figure ₂In the O particle without any impurity element.

Fig. 2 (a) and the Cu that (b) prepares for embodiment ₂The SEM plane graph of O secondary cell anode material, the Cu of preparation as shown in the figure ₂The O particle becomes octahedral structure, and the size of particle is approximately 1 μ m between 10 μ m, and Fig. 2 (c) is the prepared Cu of embodiment ₂The sectional view of O particle, as can be seen from Figure, Cu ₂The thickness of O layer is approximately 2 μ m, and Fig. 2 (d) is the prepared Cu of embodiment ₂The TEM High-Resolution Map of O particle, illustration are the prepared Cu of embodiment ₂The diffraction pattern of O particle, as can be seen from the figure, Cu ₂The O particle crystallization is good, (111), (100) and (200) crystal face preferred growth.

The Cu that embodiment is prepared ₂O secondary cell anode material is as work electrode, and the sodium metal sheet, as to electrode, is dissolved in EC/EMC(1:1, vol%) in concentration be the NaClO of 1M ₄As electrolyte, be prepared into CR2025 type button sodium-ion battery.

The Cu that embodiment is prepared ₂O secondary cell anode material is as work electrode, and metal lithium sheet, as to electrode, is dissolved in EC/DEC(1:1, vol%) in concentration be the LiPF6 of 1M as electrolyte, be prepared into CR2025 type button lithium ion battery.

Fig. 3 is the button sodium-ion battery for preparing of embodiment and the CV curve of button lithium ion battery, as shown in Figure 3, from the CV curve, can find out the Cu that embodiment is prepared ₂The O particle has good redox characteristic.

Fig. 4 is first three time charge and discharge cycles curve of the button sodium-ion battery for preparing of embodiment and button lithium ion battery, as shown in Figure 4, can obviously find out Cu ₂O secondary cell anode material as the discharge platform voltage of sodium-ion battery anode material in the 0.3V left and right, as the discharge platform voltage of lithium ion battery anode material in the 0.6V left and right.

Fig. 5 is button sodium-ion battery and the capacity of button lithium ion battery under different discharge-rates---cycle-index curve prepared by embodiment, as shown in Figure 5, can find out, the button sodium-ion battery is under different discharging currents, and its capacity is all little with respect to the capacity of button lithium ion battery under different discharging currents.This is because the radius of the radius ratio lithium ion of sodium ion wants large, causes it at Cu ₂The cause that embedded quantity in the O crystal is less.

Fig. 6 is button sodium-ion battery and the capacity of button lithium ion battery under same discharge-rate---cycle-index curve prepared by embodiment, as shown in Figure 6, can find out, the reversible capacity of button sodium-ion battery is approximately 250mAh g ^-1, it is basic not significantly decay after 200 circulations, and the reversible capacity of button lithium ion battery is approximately 580mAh g ^-1, it is basic not significantly decay after 300 circulations.

Fig. 7 is the button sodium-ion battery for preparing of embodiment and the impedance curve of button lithium ion battery, as shown in Figure 7, can find out, the impedance of lithium ion battery is less, and this may be because the radius of lithium ion is less, at Cu ₂The cause that more easily embeds and deviate from the O lattice.

By above-mentioned experiment, can prove, embodiment is by the method for the hydro-thermal reaction Cu that directly grows on copper sheet ₂The O particle, have the embedded quantity of higher sodium ion and lithium ion and well take off the embedding invertibity, using it as sodium-ion battery with the anode material of lithium ion battery, improved the actual capacity of battery, extended the service life cycle of battery.

In the present invention, hydrothermal temperature can be 150～350 ℃, and preferred 180 ℃, the reaction time can be 10～60 hours, preferred 48 hours, and the Cu of growth ₂What of the thickness of O particle layer and the amount of adhering to can be by changing reaction condition STOCHASTIC CONTROL; Conductive substrate is not limited to copper sheet, and other sheet metal or conductive film also can be used for the present invention.

Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can to it, make various changes in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.

Claims

1. Cu ₂The preparation method of O secondary cell anode material is characterized in that: comprise the following steps:

2. Cu according to claim 1 ₂The preparation method of O secondary cell anode material is characterized in that: in described step 1), in mixed solution, the molar concentration of Schweinfurt green is 0.25mol/L, and the molar concentration of polyvinylpyrrolidone is 2 * 10 ^-5Mol/L.

3. Cu according to claim 1 ₂The preparation method of O secondary cell anode material is characterized in that: described conductive substrate is copper sheet.

4. Cu according to claim 3 ₂The preparation method of O secondary cell anode material is characterized in that: described step 2), first with watery hydrochloric acid, clean to remove the oxide layer on copper sheet surface, then copper sheet is inserted in the mixed solution that step 1) obtains.

5. Cu according to claim 1 ₂The preparation method of O secondary cell anode material is characterized in that: described step 2), hydrothermal temperature is 180 ℃, and the reaction time is 48 hours.