CN106129392B - A kind of room temperature liquid phase paddling process prepares flower-shaped Cu3V2O8The method of material and the Cu of preparation3V2O8Material - Google Patents
A kind of room temperature liquid phase paddling process prepares flower-shaped Cu3V2O8The method of material and the Cu of preparation3V2O8Material Download PDFInfo
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- CN106129392B CN106129392B CN201610513266.5A CN201610513266A CN106129392B CN 106129392 B CN106129392 B CN 106129392B CN 201610513266 A CN201610513266 A CN 201610513266A CN 106129392 B CN106129392 B CN 106129392B
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
A kind of room temperature liquid phase paddling process prepares flower-shaped Cu3V2O8The method of material and the Cu of preparation3V2O8Cuprous oxide is scattered in deionized water by material, forms uniform suspending liquid A, and ammonium metavanadate powder is then added and is added, stirs evenly, obtains suspension B；The pH value for adjusting suspension B is 5.0~10, then stirs evenly to form reaction precursor liquid；10~60h of reaction is carried out under reaction precursor liquid is stirred at room temperature；After reaction, precipitation filtered, washing, dried, gained powder is flower-shaped Cu3V2O8Material.Due to the present invention can be reacted at room temperature, avoid high temperature solid-state method using height temperate zone come energy consumption issues and pattern be unable to control the problem of.This method raw material is easy to get, and process equipment is very simple, is not necessarily to complex device, can prepare material requested at normal temperatures and pressures, and safety is good, and feasibility is strong, thus it is very economical, practical, there is good industrial prospect.
Description
Technical field
The invention belongs to the electrode material technical fields of battery, are related to a kind of Cu3V2O8The preparation method of material, especially relates to
And a kind of room temperature liquid phase paddling process prepares flower-shaped Cu3V2O8The method of material and the Cu of preparation3V2O8Material.
Background technology
Vanadic acid copper product with layer structure can carry out multistep reduction (Cu during insertion/deintercalate lithium ions2+/
Cu+And Cu+/Cu0), it is considered to be lithium ion battery negative material [Cheng F, Chen with potential using value
J.Transition metal vanadium oxides and vanadate materials for lithium
batteries[J].Journal of Materials Chemistry,2011,21(27):9841-9848.].Cu3V2O8Make
Have many advantages, such as that at low cost, specific capacity is high, energy density is high for lithium ion battery negative material, is expected to greatly improve lithium ion
The electrical property of cell negative electrode material
Cu3V2O8Synthetic method be mainly high temperature solid-state method.Hillel etc. using copper oxide and vanadic anhydride as raw material,
72h is kept the temperature at 700 DEG C, and Cu is made3V2O8Material [Hillel T, Ein-Eli Y.Copper vanadate as
promising high voltage cathodes for Li thermal batteries[J].Journal of Power
Sources,2013,229:112-116].Pure phase Cu is equally made in Yuan Chaojun etc. in this way3V2O8[Yuan is few towards army poplar for material
China, Cao Xiaohui wait .LiSi/LiNO3-KNO3/Cu3V2O8Research [J] power technologies of thermal cell discharge performance, 2015,39
(7):1479-1481.].There it can be seen that although high temperature solid-state method synthetic operation is simple, long-time high-temperature process is needed,
This can undoubtedly increase energy consumption, in actual production, can cost be sharply increased, and product morphology is unable to control, can be to product
Chemical property have an impact.It is difficult to realize large-scale industrial production in this way.
Invention content
The purpose of the present invention is to provide a kind of room temperature liquid phase paddling process to prepare flower-shaped Cu3V2O8The method of material and preparation
Cu3V2O8Material, this method use hard template-room temperature liquid phase paddling process, etch growing technology by situ, preparing has
The flower-shaped Cu of good chemical property3V2O8Material, this method is easy to operate, and repeatability is high, and production cost is low, is suitble to industry
Metaplasia is produced.
In order to achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of room temperature liquid phase paddling process prepares flower-shaped Cu3V2O8The method of material, includes the following steps：
1) cuprous oxide is scattered in deionized water, forms uniform suspending liquid A, ammonium metavanadate powder is then added and adds
Enter, stir evenly, obtains suspension B；Wherein, the mass ratio of cuprous oxide and ammonium metavanadate is 0.125g：0.102g；
2) pH value for adjusting suspension B is 5.0~10, then stirs evenly to form reaction precursor liquid；
3) 10~60h of reaction is carried out under reaction precursor liquid being stirred at room temperature；
4) after reaction, precipitation is filtered, washing, is dried, gained powder is flower-shaped Cu3V2O8Material.
The present invention, which further improves, to be, ammonium metavanadate is that analysis is pure in the step 1).
The present invention, which further improves, to be, uniform hang is formed by 0.2~5h of magnetic agitation in the step 1)
Supernatant liquid A.
The present invention, which further improves, to be, cuprous oxide and the ratio of deionized water are 0.125g in the step 1)：
80mL。
The present invention, which further improves, to be, mixing time is 0.5~2h in the step 2).
The present invention, which further improves, to be, pH value is adjusted using ammonium hydroxide in the step 2).
The present invention, which further improves, to be, the washing in the step 4) is specifically to use deionized water and absolute ethyl alcohol
It washs 4~6 times respectively.
The present invention further improve is, the drying in the step 4) is 50~100 DEG C, the time be 2~
12h。
A kind of flower-shaped Cu3V2O8Material, the Cu3V2O8Material be by the nanometer sheet of 20~30nm of thickness constitute 0.8~
The thin slice of 1.2um, the floriform appearance of 1.0~1.5um of diameter made of self assembly.
Compared with prior art, the present invention has technique effect beneficial below：
The method of the present invention uses liquid phase paddling process, and using cuprous oxide as copper source and template, ammonium hydroxide leads to as etching agent
Etching growth in situ is crossed, at room temperature, it is only necessary to simple stirring, you can prepare flower-shaped Cu3V2O8Material.This method uses
Hard template-room temperature liquid phase paddling process avoids high temperature solid-state method and uses high temperature since the present invention can be reacted at room temperature
The problem of energy consumption issues and pattern brought are unable to control.This method raw material is easy to get, and process equipment is very simple, without multiple
Miscellaneous equipment can prepare material requested at normal temperatures and pressures, and safety is good, and feasibility is strong, thus it is very economical, practical, have
Good industrial prospect.
Cu prepared by the present invention3V2O8Material is the thin of 0.8~1.2um being made of the nanometer sheet that thickness is 20~30nm
Piece, the floriform appearance of diameter about 1.0~1.5um made of self assembly.The Cu prepared due to the present invention3V2O8Material is nanoscale
Powder, floriform appearance make the material have larger specific surface area, contribute to the diffusion road for shortening lithium ion in charge and discharge process
Diameter improves its high rate performance and cycle performance.Its contact area with electrolyte can also effectively be increased simultaneously, to have
Excellent chemical property.
Description of the drawings
Fig. 1 is Cu prepared by the present invention3V2O8The X-ray diffractogram of material；
Fig. 2 is Cu prepared by the present invention3V2O8The 10.0K scanning electron microscope shape appearance figures of material；
Fig. 3 is Cu prepared by the present invention3V2O8The 50K scanning electron microscope shape appearance figures of material.
Specific implementation mode
Embodiment 1
1) the freshly prepd cuprous oxide (Cu of 0.125g are weighed2O it) is scattered in 80mL deionizations, magnetic agitation 0.5h is obtained
To suspending liquid A, the analytically pure ammonium metavanadate (NH of 0.102g are then added4VO3) powder, magnetic agitation 2h obtains suspension B；
2) it is 7.0 to adjust the pH value of suspension B with ammonium hydroxide, then proceedes to magnetic agitation 0.5h and forms reaction precursor liquid；
3) 30h is stirred at room temperature in reaction precursor liquid to react；
4) after reaction, precipitation is filtered, is washed respectively 4~6 times with deionized water and absolute ethyl alcohol, is dried at 60 DEG C
Dry 10h, gained powder is flower-shaped Cu3V2O8Material.
It will be seen from figure 1 that prepared copper vanadate is Cu3V2O8, diffraction maximum and standard card (JCPDS No.74-
1503) base peak matches, without apparent impurity.
From figures 2 and 3, it will be seen that the Cu3V2O8Material be by grain size be 20~30nm particle constitute 0.8~
The thin slice of 1.2um, the floriform appearance of diameter about 1.0~1.5um made of self assembly.Wherein the thickness of nanometer sheet be 20~
30nm。
Embodiment 2
1) freshly prepd cuprous oxide is scattered in deionized water, magnetic agitation 2h forms uniform suspending liquid A, so
After analytically pure ammonium metavanadate powder be added be added, stir 2h, obtain suspension B；Wherein, it cuprous oxide, ammonium metavanadate and goes
The ratio of ionized water is 0.125g：0.102g：80mL；
2) it is 5.0 to use ammonium hydroxide to adjust the pH value of suspension B, then stirs 1h, formation reaction precursor liquid；
3) reaction 10h is carried out under reaction precursor liquid being stirred at room temperature；
4) after reaction, precipitation suction filtration, deionized water and absolute ethyl alcohol are washed 4 times respectively, dried at 50 DEG C
12h, gained powder are flower-shaped Cu3V2O8Material.
Embodiment 3
1) freshly prepd cuprous oxide is scattered in deionized water, magnetic agitation 3h forms uniform suspending liquid A, so
After analytically pure ammonium metavanadate powder be added be added, stir 1h, obtain suspension B；Wherein, it cuprous oxide, ammonium metavanadate and goes
The ratio of ionized water is 0.125g：0.102g：80mL；
2) it is 10 to use ammonium hydroxide to adjust the pH value of suspension B, then stirs 1.5h, formation reaction precursor liquid；
3) reaction 60h is carried out under reaction precursor liquid being stirred at room temperature；
4) after reaction, precipitation suction filtration, deionized water and absolute ethyl alcohol are washed 5 times respectively, dried at 100 DEG C
2h, gained powder are flower-shaped Cu3V2O8Material.
Embodiment 4
1) freshly prepd cuprous oxide is scattered in deionized water, magnetic agitation 5h forms uniform suspending liquid A, so
After analytically pure ammonium metavanadate powder be added be added, stir 0.5h, obtain suspension B；Wherein, cuprous oxide, ammonium metavanadate with
The ratio of deionized water is 0.125g：0.102g：80mL；
2) it is 6 to use ammonium hydroxide to adjust the pH value of suspension B, then stirs 2h, formation reaction precursor liquid；
3) reaction 50h is carried out under reaction precursor liquid being stirred at room temperature；
4) after reaction, precipitation suction filtration, deionized water and absolute ethyl alcohol are washed 6 times respectively, 6h is dried at 80 DEG C,
Gained powder is flower-shaped Cu3V2O8Material.
Cu prepared by the present invention3V2O8Material is the thin slice for 0.8~1.2um being made of the nanometer sheet of 20~30nm of thickness,
The floriform appearance of 1.0~1.5um of diameter made of self assembly.
Claims (7)
1. a kind of room temperature liquid phase paddling process prepares flower-shaped Cu3V2O8The method of material, which is characterized in that include the following steps：
1) cuprous oxide is scattered in deionized water, forms uniform suspending liquid A, ammonium metavanadate powder is then added and is added,
It stirs evenly, obtains suspension B；Wherein, the mass ratio of cuprous oxide and ammonium metavanadate is 0.125g：0.102g；Cuprous oxide
And the ratio of deionized water is 0.125g：80mL；
2) it uses ammonium hydroxide to adjust the pH value of suspension B as 5.0~10, then stirs evenly to form reaction precursor liquid；
3) 10~60h of reaction is carried out under reaction precursor liquid being stirred at room temperature；
4) after reaction, precipitation is filtered, washing, is dried, gained powder is flower-shaped Cu3V2O8Material, the Cu3V2O8Material
It is the thin slice for 0.8~1.2um being made of the nanometer sheet of 20~30nm of thickness, the flower of 1.0~1.5um of diameter made of self assembly
Shape pattern.
2. a kind of room temperature liquid phase paddling process according to claim 1 prepares flower-shaped Cu3V2O8The method of material, feature exist
In ammonium metavanadate is that analysis is pure in the step 1).
3. a kind of room temperature liquid phase paddling process according to claim 1 prepares flower-shaped Cu3V2O8The method of material, feature exist
In forming uniform suspending liquid A by 0.2~5h of magnetic agitation in the step 1).
4. a kind of room temperature liquid phase paddling process according to claim 1 prepares flower-shaped Cu3V2O8The method of material, feature exist
In mixing time is 0.5~2h in the step 2).
5. a kind of room temperature liquid phase paddling process according to claim 1 prepares flower-shaped Cu3V2O8The method of material, feature exist
In the washing in the step 4) is specifically to be washed respectively 4~6 times with deionized water and absolute ethyl alcohol.
6. a kind of room temperature liquid phase paddling process according to claim 1 prepares flower-shaped Cu3V2O8The method of material, feature exist
In the temperature dried in the step 4) is 50~100 DEG C, and the time is 2~12h.
7. one kind is based on flower-shaped Cu made from claim 1 the method3V2O8Material, which is characterized in that the Cu3V2O8Material is
By the thin slice for 0.8~1.2um that the nanometer sheet of 20~30nm of thickness is constituted, 1.0~1.5um's of diameter is flower-shaped made of self assembly
Pattern.
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| CN201610513266.5A CN106129392B (en) | 2016-07-01 | 2016-07-01 | A kind of room temperature liquid phase paddling process prepares flower-shaped Cu3V2O8The method of material and the Cu of preparation3V2O8Material |
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| CN201610513266.5A CN106129392B (en) | 2016-07-01 | 2016-07-01 | A kind of room temperature liquid phase paddling process prepares flower-shaped Cu3V2O8The method of material and the Cu of preparation3V2O8Material |
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| CN108134058B (en) * | 2017-12-14 | 2020-08-04 | 陕西科技大学 | Cu5V2O10Preparation method of-CuO composite powder |
| CN110120520B (en) * | 2019-03-08 | 2020-09-22 | 北京化工大学 | Self-supporting flower-shaped Co of conductive carrier3V2O8Lithium ion battery cathode material and preparation |
| CN113353981B (en) * | 2021-07-01 | 2023-01-31 | 陕西理工大学 | Cu 3 (VO 4 ) 2 Preparation method of irregular nanorod |
| CN115064680A (en) * | 2022-06-29 | 2022-09-16 | 上海空间电源研究所 | Cu for thermal battery 2 V 2 O 7 Nano cage-shaped conductive substrate composite positive electrode material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101051685A (en) * | 2007-04-11 | 2007-10-10 | 南开大学 | Method for preparing transition metal vanadate one dimension electrode material and its use |
| CN101920993A (en) * | 2010-08-03 | 2010-12-22 | 复旦大学 | Preparation method and application of copper vanadate electrode material |
| CN103130278A (en) * | 2013-02-28 | 2013-06-05 | 安徽工业大学 | Copper vanadate nanoneedles and preparation method thereof |
| CN103928654A (en) * | 2014-04-29 | 2014-07-16 | 石家庄学院 | Copper vanadate nanoparticles and preparation method thereof |
| CN104638241A (en) * | 2015-02-06 | 2015-05-20 | 武汉理工大学 | Graphene-coated amorphous nano-flower copper vanadate, as well as preparation method and application of nano-flower copper vanadate |
| CN105895894A (en) * | 2016-04-20 | 2016-08-24 | 淮阴工学院 | Copper vanadate material as well as preparation method and electrochemical performance thereof |
-
2016
- 2016-07-01 CN CN201610513266.5A patent/CN106129392B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101051685A (en) * | 2007-04-11 | 2007-10-10 | 南开大学 | Method for preparing transition metal vanadate one dimension electrode material and its use |
| CN101920993A (en) * | 2010-08-03 | 2010-12-22 | 复旦大学 | Preparation method and application of copper vanadate electrode material |
| CN103130278A (en) * | 2013-02-28 | 2013-06-05 | 安徽工业大学 | Copper vanadate nanoneedles and preparation method thereof |
| CN103928654A (en) * | 2014-04-29 | 2014-07-16 | 石家庄学院 | Copper vanadate nanoparticles and preparation method thereof |
| CN104638241A (en) * | 2015-02-06 | 2015-05-20 | 武汉理工大学 | Graphene-coated amorphous nano-flower copper vanadate, as well as preparation method and application of nano-flower copper vanadate |
| CN105895894A (en) * | 2016-04-20 | 2016-08-24 | 淮阴工学院 | Copper vanadate material as well as preparation method and electrochemical performance thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Cu3V2O8 hollow spheres in photocatalysis and primary lithium batteries";Shaoyan Zhang等;《Solid State Sciences》;20130819;第25卷;第15-21页 * |
| "Cu3V2O8 Nanoparticles as Intercalation-Type Anode Material for Lithium-Ion Batteries";Malin Li等;《Chem. Eur. J.》;20160630;第22卷 * |
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