CN104925846A - Preparation method of nano copper oxide and application of nano copper oxide in lithium ion battery - Google Patents
Preparation method of nano copper oxide and application of nano copper oxide in lithium ion battery Download PDFInfo
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- CN104925846A CN104925846A CN201410099531.0A CN201410099531A CN104925846A CN 104925846 A CN104925846 A CN 104925846A CN 201410099531 A CN201410099531 A CN 201410099531A CN 104925846 A CN104925846 A CN 104925846A
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- 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 nano copper oxide and a lithium ion battery negative electrode material. The preparation method comprises the steps: firstly, treating a copper based powder in a complexing agent solution, to obtain copper hydroxide nanoribbons; and then, post-treating the copper hydroxide nanoribbons, to obtain nano copper oxide. The obtained nano copper oxide is used in the lithium ion battery negative electrode material, the electrode material has the reversible discharge specific capacity as high as 824 mAh/g at the current density of 50 mA/g; when the current density is increased from 50 mAh/g to 500 mA/g, the capacity retention ratio reaches 88.4%, and the discharge specific capacity is still kept at 430 mAh/g even if the electrode material is circulated for 50 times under large current. The electrode material shows higher discharge specific capacity, excellent cycle stability and rate performance.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, particularly a kind of preparation method of nano cupric oxide.
Background technology
Transition metal oxide CuO is a kind of p-type semiconductor, there is the feature of the low and easy acquisition of hypotoxicity, price, copper oxide nano material has significant quantum confined effect and most advanced and sophisticated nano effect, be applied to field-effect transistor at present, photovoltaic cell, Flied emission nano-device and sensor of chemical gas etc.It also demonstrates huge application prospect in field of lithium ion battery simultaneously.
Nano cupric oxide can reach 674mAh/g as its theoretical specific capacity during lithium ion battery negative, but because its electroconductibility is very poor and volume change can occur in charge and discharge cycles process, therefore can cause the decay of capacity.In order to address these problems, investigators adopt the means of nanometer and Material cladding to change the microtexture of CuO negative material, to improve its process capacity and cycle performance usually.Sun etc. obtain Copper oxide nano-belt negative pole by CuO nano belt being deposited directly on copper current collector, under the current density of 175mA/g, the specific discharge capacity of 608mAh/g is maintained after 275 circulations, carry out reacting [Ke F in the water-bath of 86 DEG C after its preparation process needs several raw material to mix according to a certain percentage, Huang L, Wei G, et al.One-step fabrication of CuO nanoribbons array electrode and its excellent lithium storage performance.Electrochimica Acta, 2009, 54:5825-5829].Gao etc. utilize Moist chemical synthesis polycrystalline and monocrystalline two kinds of cupric oxide nano lines, and use it for lithium ion battery negative.In second time circulation, specific discharge capacity multicrystal nano-wire is 766mAh/g, monocrystalline be 416mAh/g, after 100 circulations, its specific discharge capacity is respectively 550mAh/g and 470mAh/g, the capacity relative of multicrystal nano-wire is higher, and the cyclical stability of monocrystalline cupric oxide nano line is better than polycrystalline cupric oxide nano line [Gao X P, Bao J L, Pan G L, et al.Preparation and electrochemical performance of polycrystalline and single crystalline CuO nanorods as anode materials for Li ion battery [J] .The Journal of Physical Chemistry B, 2004, 108:5547-5551.].
Although nanostructure and the matrix material of current CuO improve its lithium storage content and cycle performance all to a certain extent, but the preparation process of these materials all relative complex, proportioning and the concentration of various raw material in solution is strictly controlled than the nano belt process need prepared by the people such as Sun as the aforementioned, and the reaction conditions parameter such as the temperature of reaction system; Or the prices of raw and semifnished materials are higher, these are all unfavorable for the application of nano oxidized copper product in lithium ion battery.
Summary of the invention
The technical problem that the present invention solves is the preparation method providing a kind of nano cupric oxide, comprising:
1, a preparation method for nano cupric oxide, comprises the steps:
Step one: Cu-base powder is dispersed in enveloping agent solution after reacting 12h ~ 72h and obtains copper hydroxide nano belt;
Step 2: step one gained copper hydroxide nano belt is carried out aftertreatment, obtains cupric oxide nano structure.
The further preferred version of the present invention is: described Cu-base powder is selected from the one in micron cuprous oxide powder, Micron-Sized Copper Powders Coated and nano-scale copper powder.
The further preferred version of the present invention is: described complexing agent be selected from ammoniacal liquor, the sodium amide aqueous solution or aqueous solution of urea, tetramethylammonium hydroxide aqueous solution one or more.
The further preferred version of the present invention is: the concentration of described enveloping agent solution is 0.1mol/L ~ 10mol/L.
The further preferred version of the present invention is: also comprise hydrogen peroxide in described enveloping agent solution.
The further preferred version of the present invention is: the aftertreatment in described step 2 is selected from the one in following manner:
I () processes in potassium hydroxide aqueous solution;
(ii) hydro-thermal reaction;
(iii) the copper hydroxide nano belt of step one gained calcined at 200 DEG C, the product cupric oxide nano structure of gained is zonal structure.
Present invention also offers lithium ion battery negative material prepared by described nano cupric oxide
Compared with prior art, the invention provides a kind of preparation method of nano cupric oxide and the application in lithium ion battery negative material thereof.The present invention processes by being dispersed in enveloping agent solution by Cu-base powder, first monovalence cupric ammine complex is formed, monovalence cupric ammine complex is oxidized to rapidly cupric ammonia complex in atmosphere, then this complex compound is converted into copper hydroxide in alkali lye, process copper hydroxide further and obtain the cupric oxide of nanostructure, the diameter of products therefrom is 5nm ~ 20nm, and thickness distribution is between 10nm ~ 30nm.The micron cuprous oxide powder preferred size that the present invention uses is 1 μm ~ 1000 μm, and the preferred size of Micron-Sized Copper Powders Coated is 1 μm ~ 1000 μm, and nano-scale copper powder is preferably of a size of 10nm ~ 1000nm.
The nano cupric oxide of gained has very high slotting lithium activity, be applied to lithium ion battery negative material, not only be conducive to shortening the diffusion length of lithium ion between cupric oxide electrode and electrolytic solution, volume change phenomenon when can also effectively avoid metal oxide to do electrode materials.This electrode materials is under the current density of 50mA/g, and reversible discharge specific storage can up to 824mAh/g; When current density increases to 500mA/g from 50mA/g, capability retention reaches 88.4%, even if circulate under big current still maintain the specific discharge capacity of 430mAh/g after 50 times.Good high rate performance and cycle performance are showed.
The present invention has reaction conditions gentleness, simple to operate, preparation cost is low, excellent product performance and easily realize the advantage of scale operation, has very large practice significance.
Accompanying drawing explanation
Accompanying drawing 1 is the scanning electron microscope (SEM) photograph of copper hydroxide nano belt;
Accompanying drawing 2 is the scanning electron microscope (SEM) photograph of the cupric oxide nano structure through potassium hydroxide aqueous solution aftertreatment gained;
Accompanying drawing 3 is the scanning electron microscope (SEM) photograph of the cupric oxide nano structure through hydro-thermal aftertreatment gained;
Accompanying drawing 4 is the scanning electron microscope (SEM) photograph of the cupric oxide nano structure through calcining aftertreatment gained;
Accompanying drawing 5 is that the specific discharge capacity of three kinds of cupric oxide nano structures under current density is 50mA/g is with discharge and recharge number of times change curve.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
Embodiment 1
Take 2g cuprous oxide powder, be scattered in the ammoniacal liquor complexing agent of 10mol/L, then 15 DEG C of lower magnetic forces stir in atmosphere.Obtain copper hydroxide nano belt.
As shown in Figure 1, the mean thickness of copper hydroxide nano belt is between 10nm ~ 100nm.
Embodiment 2
Take 2g cuprous oxide powder, be scattered in 0.1mol/L sodium amide complexing agent, then stir lower than 20 DEG C of lower magnetic forces in atmosphere.Obtain copper hydroxide nano belt.
Embodiment 3
Take 2g cuprous oxide powder, be scattered in 3mol/L Tetramethylammonium hydroxide complexing agent, then magnetic agitation in atmosphere.Obtain copper hydroxide nano belt.
Embodiment 4
Take the copper hydroxide nano belt of gained in 2g embodiment 1, be scattered in potassium hydroxide aqueous solution, then at room temperature magnetic agitation.Obtain cupric oxide nano structure.
As shown in Figure 2, the cupric oxide nano structure through potassium hydroxide solution aftertreatment gained is cotton-shaped pelletizing, and these cotton-shaped pelletizings are made up of a large amount of nano wires, and the diameter of nano wire is between 5nm ~ 20nm.
As accompanying drawing 5 electrochemical property test result shows, the specific discharge capacity of this electrode materials under 50mA/g current density can reach 813mAh/g, and after 50 circulations, capability retention is 99%.
Embodiment 5
Take the copper hydroxide nano belt of gained in 2g embodiment 1, be scattered in ammoniacal liquor, then at room temperature magnetic agitation.Obtain cupric oxide nano structure.
As shown in Figure 3, the cupric oxide nano structure through ammoniacal liquor aftertreatment gained is flower-shaped pelletizing, and these pelletizings are made up of irregular nanometer sheet, and its thickness distribution is between 10nm ~ 30nm.
As accompanying drawing 5 electrochemical property test result shows, the specific discharge capacity of this electrode materials under 50mA/g current density can reach 662mAh/g, and after 50 circulations, capability retention is 105%.
Embodiment 6
Take the copper hydroxide nano belt of gained in 2g embodiment 1, to be placed in retort furnace in atmosphere, calcine at 200 DEG C.Obtain cupric oxide nano structure.
As shown in Figure 4, the cupric oxide nano structure through calcining aftertreatment gained is zonal structure, and it maintains the basic pattern of the copper hydroxide nano belt of gained in embodiment 1, but surface is comparatively coarse, and thickness increases.
As accompanying drawing 5 electrochemical property test result shows, the specific discharge capacity of this electrode materials under 50mA/g current density can reach 779mAh/g, and after 50 circulations, capability retention is 89%.
Embodiment 7
Take the copper hydroxide nano belt of gained in 2g embodiment 1, be scattered in potassium hydroxide aqueous solution, then react under 120 DEG C of hydrothermal conditions.Obtain cupric oxide nano structure.
Embodiment 8
Take the copper hydroxide nano belt of gained in 2g embodiment 1, be scattered in ammoniacal liquor, then react under 150 DEG C of hydrothermal conditions.Obtain cupric oxide nano structure.
Embodiment 9
Take the copper hydroxide nano belt of gained in 2g embodiment 1, be scattered in ammoniacal liquor, then react under 200 DEG C of hydrothermal conditions.Obtain cupric oxide nano structure.
Embodiment 10
Take 2g cuprous oxide powder, be scattered in the ammoniacal liquor complexing agent of 10mol/L, this enveloping agent solution contains the hydrogen peroxide of 0.2mol/L, then at room temperature magnetic agitation.Obtain cupric oxide nano structure.
Embodiment 11
Take 2g cuprous oxide powder, be scattered in the ammoniacal liquor complexing agent of 10mol/L, this enveloping agent solution contains the Peracetic Acid of 0.5mol/L, then at room temperature magnetic agitation.Obtain cupric oxide nano structure.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. a preparation method for nano cupric oxide, comprises the steps:
Step one: Cu-base powder is dispersed in enveloping agent solution after reacting 2h ~ 72h and obtains copper hydroxide nano belt;
Step 2: step one gained copper hydroxide nano belt is carried out aftertreatment, obtains cupric oxide nano structure.
2. the preparation method of a kind of nano cupric oxide according to claim 1, is characterized in that: described Cu-base powder is selected from the one in micron cuprous oxide powder, Micron-Sized Copper Powders Coated or nano-scale copper powder.
3. the preparation method of a kind of nano cupric oxide according to claim 1, is characterized in that: described complexing agent be selected from ammoniacal liquor, the sodium amide aqueous solution or aqueous solution of urea, tetramethylammonium hydroxide aqueous solution one or more.
4. the preparation method of a kind of nano cupric oxide according to claim 1, is characterized in that: the concentration of described enveloping agent solution is 0.1mol/L ~ 10mol/L.
5. the preparation method of a kind of nano cupric oxide according to claim 1, is characterized in that: also comprise oxygenant in described enveloping agent solution.
6. the preparation method of a kind of nano cupric oxide according to claim 5, is characterized in that: described oxygenant be selected from hydrogen peroxide, Peracetic Acid one or both.
7. the preparation method of a kind of nano cupric oxide according to claim 1, is characterized in that: the aftertreatment in described step 2 is selected from the one in following manner:
I () processes in potassium hydroxide aqueous solution;
(ii) hydro-thermal reaction;
(iii) the copper hydroxide nano belt of step one gained is calcined in retort furnace.
8. the lithium ion battery negative material prepared by method gained nano cupric oxide described in claim 1 to 7.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105486649A (en) * | 2015-11-23 | 2016-04-13 | 衡水学院 | Method for determining influence on catalytic action of nanometer copper oxide on decomposition of hydrogen peroxide before and after modification |
| CN106410232A (en) * | 2016-08-31 | 2017-02-15 | 襄阳艾克特电池科技股份有限公司 | Manufacturing method for lithium-copper oxide cell |
| CN106450466A (en) * | 2016-08-31 | 2017-02-22 | 襄阳艾克特电池科技股份有限公司 | Preparation technology of lithium copper oxide battery |
| CN108987703A (en) * | 2018-07-17 | 2018-12-11 | 澳洋集团有限公司 | A kind of preparation method based on copper oxide composite lithium ion battery negative electrode material |
| CN110514700A (en) * | 2019-09-27 | 2019-11-29 | 西安电子科技大学 | A kind of copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material, ethylene glycol sensor and preparation method |
| CN112014452A (en) * | 2019-05-29 | 2020-12-01 | 天津理工大学 | Method for electrochemically detecting hydrogen peroxide based on nano-copper oxide modified printing electrode |
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| CN1870330A (en) * | 2005-05-27 | 2006-11-29 | 深圳市比克电池有限公司 | Multicomponent oxide containing cobalt nickel and preparation and application thereof |
| CN101289221A (en) * | 2008-06-12 | 2008-10-22 | 金川集团有限公司 | Method for preparing cupric oxide powder by oxygenizing raw copper powder |
| CN103101957A (en) * | 2012-12-21 | 2013-05-15 | 泰兴冶炼厂有限公司 | Method for preparing high-purity low-chlorine electroplating-grade cupric oxide |
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2014
- 2014-03-17 CN CN201410099531.0A patent/CN104925846A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1870330A (en) * | 2005-05-27 | 2006-11-29 | 深圳市比克电池有限公司 | Multicomponent oxide containing cobalt nickel and preparation and application thereof |
| CN101289221A (en) * | 2008-06-12 | 2008-10-22 | 金川集团有限公司 | Method for preparing cupric oxide powder by oxygenizing raw copper powder |
| CN103101957A (en) * | 2012-12-21 | 2013-05-15 | 泰兴冶炼厂有限公司 | Method for preparing high-purity low-chlorine electroplating-grade cupric oxide |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105486649A (en) * | 2015-11-23 | 2016-04-13 | 衡水学院 | Method for determining influence on catalytic action of nanometer copper oxide on decomposition of hydrogen peroxide before and after modification |
| CN106410232A (en) * | 2016-08-31 | 2017-02-15 | 襄阳艾克特电池科技股份有限公司 | Manufacturing method for lithium-copper oxide cell |
| CN106450466A (en) * | 2016-08-31 | 2017-02-22 | 襄阳艾克特电池科技股份有限公司 | Preparation technology of lithium copper oxide battery |
| CN108987703A (en) * | 2018-07-17 | 2018-12-11 | 澳洋集团有限公司 | A kind of preparation method based on copper oxide composite lithium ion battery negative electrode material |
| CN112014452A (en) * | 2019-05-29 | 2020-12-01 | 天津理工大学 | Method for electrochemically detecting hydrogen peroxide based on nano-copper oxide modified printing electrode |
| CN110514700A (en) * | 2019-09-27 | 2019-11-29 | 西安电子科技大学 | A kind of copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material, ethylene glycol sensor and preparation method |
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