CN107732224A - The method for improving negative material CuO cyclical stabilities - Google Patents
The method for improving negative material CuO cyclical stabilities Download PDFInfo
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- CN107732224A CN107732224A CN201710835056.2A CN201710835056A CN107732224A CN 107732224 A CN107732224 A CN 107732224A CN 201710835056 A CN201710835056 A CN 201710835056A CN 107732224 A CN107732224 A CN 107732224A
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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 present invention discloses a kind of method for improving negative material CuO cyclical stabilities, includes following steps：（One）The preparation of graphene oxide；（Two）The preparation of nanometer CuO：1）Copper acetate is weighed, programming rate is 5 DEG C/min；2）The 10h of constant temperature 2 after to 800 DEG C of predetermined temperature 500 DEG C；3）Take out after the insulation scheduled time, cool down at room temperature.（Three）Graphene oxide is added in nanometer CuO, graphene oxide accounts for 2%-the 10% of CuO and the quality summation of graphene oxide.The present invention using fused salt combustion synthesis method by first preparing nanometer CuO, 2% -10% graphene oxide is added again, its charge specific capacity is 370.5 mAh/g after modified CuO is circulated 250 times as negative material, laid a good foundation for volume production and application, molten-salt growth method has the reaction time short, technique is simple, easily realize that industrialization large-scale production and the quick major advantage of combustion synthesis reaction, and can obtain the small product of crystal perfection, particle diameter and coated graphene Posterior circle performance in the short period of time.
Description
Technical field
The present invention relates to battery material production field technology, refers in particular to a kind of raising negative material CuO cyclical stabilities
Method.
Background technology
With the fast development of emerging economies, global energy consumption sharp increase.Lithium ion battery is with its high voltage, height
Energy density, have extended cycle life, have a safety feature, the advantages that cost is cheap is in portable electrics such as computer, camera and mobile phones
Have been obtained for being widely applied in sub- equipment.In recent years, countries in the world all apply to mix actively developing lithium ion battery
Power electric automobile（HEV）, pure electric automobile（PEV）Deng research, but lithium ion battery is as the main of vehicle mounted dynamic battery
Bottleneck is the performance of lithium ion battery negative material.
Graphite is current most widely used lithium ion battery negative material, however, the theoretical capacity of graphite only has 372
MAh/g, the demand of the height ratio capacity of power source can not be met.Compared to graphite, CuO has higher theoretical capacity（718
mAh/g）, and inexpensively, easily produce, property stabilization, it is considered to be a promising ion cathode material lithium.But CuO makees
For semi-conducting material, the shortcomings that first effect is low be present.For this shortcoming, there has been proposed different solutions, such as：Addition
High conductivity material.In the additive of all high conductivity, graphene due to high electrical conductivity, high specific surface area,
The advantages that excellent structural stability and attract attention, can also greatly improve electrode even if adding a small amount of graphene in the electrodes
Chemical property.
It is compound that Chinese invention patent application publication No. CN 102637860A disclose a kind of CuO/Cu of lithium ion battery
The preparation method of negative material and application, its method are：It for 50nm-10 μm of cupric oxide powder is raw material to use particle size,
In raw material atmosphere furnace, under 80-120 DEG C of atmosphere, reduced in mixed-gas atmosphere containing hydrogen reduction（Wherein mix
The content of hydrogen is 5% -50% in gas）, the recovery time is 10-120min.The content of copper is composite weight in composite
Measure 0.5-40wt.% of percentage.Be present consersion unit requirement height needed for technique in the above method, and needed not in heating process
It is open close enter reducing gas.
The content of the invention
In view of this, in view of the existing deficiencies of the prior art, its main purpose is to provide a kind of raising negative pole material to the present invention
Expect the method for CuO cyclical stabilities, it can improve production efficiency, reduce manufacturing cost, fast and effective prepares product and raising
Circulating battery stability.
To achieve the above object, the present invention is using following technical scheme：
A kind of method for improving negative material CuO cyclical stabilities, includes following steps：
（One）The preparation of graphene oxide；
（Two）The preparation of nanometer CuO：
1）Copper acetate is weighed, programming rate is 5 DEG C/min；
2）Constant temperature 2-10h after to 500 DEG C -800 DEG C of predetermined temperature；
3）Taken out after the insulation scheduled time, cool down at room temperature, that is, obtain nanometer CuO；
（Three）Graphene oxide is added in nanometer CuO, graphene oxide accounts for CuO and the quality summation of graphene oxide
2%—10%。
As a kind of preferred scheme, the step（One）The preparation of graphene oxide includes following steps：
1）In 250ml conical flasks, the 120ml concentrated sulfuric acids, 2.5g potassium peroxydisulfates, 2.5g phosphorus pentoxides are sequentially added, stirring is extremely
Potassium peroxydisulfate and phosphorus pentoxide all dissolve, and are slowly added to 3g graphite powders, react 4h in 80 DEG C of water-baths；
2）Conical flask is cooled to room temperature, adds 500ml deionized waters, overnight, filters, and deionized water is washed to neutrality, 50 DEG C of bakings
Dried in case；
3）250ml conical flasks are put into 0 DEG C of water-bath, are put into graphite powder after the 120ml concentrated sulfuric acids, drying, 15g potassium permanganate；
4）Potassium permanganate is added completely into rear conical flask and moved in 35 DEG C of water-baths, constant temperature stirring 2h；
5）20ml 30% H2O2 is added dropwise into solution, 55ml distilled water, stands 12h；
6) 3% dilute HCl is used, distilled water is rinsed to product, is centrifuged 3 times, freeze drier freeze-drying, is obtained final
Product.
As a kind of preferred scheme, the preparation process 2 of the nanometer CuO）In, preferably 600 DEG C of calcining heat, soaking time
It is preferred that 6h.
As a kind of preferred scheme, the copper acetate is low melting point copper acetate, and its fusing point is 115 DEG C.
The present invention has clear advantage and beneficial effect compared with prior art, specifically, by above-mentioned technical proposal
Understand：
The present invention overcomes the shortcomings that CuO is as negative material, by first preparing nanometer CuO using fused salt combustion synthesis method, then
The graphene oxide of addition 2% -10%, its charge specific capacity is 370.5 after modified CuO is circulated 250 times as negative material
MAh/g, laid a good foundation for volume production and application, the present invention is synthetically prepared using molten-salt growth method, and molten-salt growth method has that the reaction time is short, work
Skill is simple, easily realizes industrialization large-scale production and the quick major advantage of combustion synthesis reaction, and can is in the short period of time
The small product of crystal perfection, particle diameter and coated graphene Posterior circle performance can be obtained.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum of CuO in the preferred embodiments of the invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of CuO in the preferred embodiments of the invention；
Fig. 3 is CuO cycle performance figures in the preferred embodiments of the invention；
Fig. 4 is CuO@Graphene cycle performance figures in the preferred embodiments of the invention.
Embodiment
Present invention is disclosed a kind of method for improving negative material CuO cyclical stabilities, include following steps：
（One）The preparation of graphene oxide；
1）In 250ml conical flasks, the 120ml concentrated sulfuric acids, 2.5g potassium peroxydisulfates, 2.5g phosphorus pentoxides are sequentially added, stirring is extremely
Potassium peroxydisulfate and phosphorus pentoxide all dissolve, and are slowly added to 3g graphite powders, react 4h in 80 DEG C of water-baths.
2）Conical flask is cooled to room temperature, adds 500ml deionized waters, overnight, filters, and deionized water is washed to neutrality, and 50
Dried in DEG C baking oven.
3）250ml conical flasks are put into 0 DEG C of water-bath, are put into graphite powder after the 120ml concentrated sulfuric acids, drying, 15g potassium permanganate.
4）Potassium permanganate is added completely into rear conical flask and moved in 35 DEG C of water-baths, constant temperature stirring 2h.
5）20ml 30% H2O2 is added dropwise into solution, 55ml distilled water, stands 12h.
6) 3% dilute HCl is used, distilled water is rinsed to product, is centrifuged 3 times, freeze drier freeze-drying, is obtained
Final product.
（Two）The preparation of nanometer CuO；
1）Copper acetate is weighed, programming rate is 5 DEG C/min.The copper acetate is low melting point copper acetate, and its fusing point is 115 DEG C.
2）Constant temperature 2-10h after to 500 DEG C -800 DEG C of predetermined temperature；Preferably 600 DEG C of calcining heat, the preferred 6h of soaking time.
3）Taken out after the insulation scheduled time, cool down at room temperature, that is, obtain nanometer CuO.
（Three）Graphene oxide is added in nanometer CuO, graphene oxide accounts for CuO and graphene oxide quality summation
2% -10%.
With specific embodiment, the present invention will be further described below：
Weigh the g of a water acetic acid copper 7.5297 to be positioned in 300 ml crucibles, then, be put into pre- with 5 DEG C/min in room temperature Muffle furnace
Heat, which to 600 DEG C, after Heat preservation reaction 6h directly from Muffle furnace is taken out crucible and is positioned in air, is cooled to room temperature, obtains nanometer
CuO。
As shown in figure 1, it is the CuO obtained in this specific embodiment X ray diffracting spectrum, as shown in Figure 1, CuO products
CuO (JCPDS, No. 48-1548) structure is presented, it is CuO to show made sample.
As shown in Fig. 2 it is the CuO obtained in this specific embodiment scanning electron microscope (SEM) photograph.Made sample is microcosmic as shown in Figure 2
Pattern is about 150 Nanoparticulates, illustrates that the CuO prepared is nanometer CuO.
| Material | Multiplying power (mA/g) | First discharge specific capacity (mAh/g) | Initial charge specific capacity (mAh/g) | Efficiency (%) first | 250th charge specific capacity |
| CuO | 0.5 C | 1058.1 | 654.5 | 61.9 | 342.4 |
| CuO@Graphene | 0.5 C | 1077.9 | 712.6 | 66.1 | 370.5 |
The charge-discharge performance at different conditions of battery is tested by Land cell testers, such as Fig. 3, Fig. 4 and upper table
Shown, voltage is 0.01-2.5 V, 0.5C to the present invention in a particular embodiment（1C=718 mA/g）Under the conditions of cyclicity first
Can figure.The first discharge specific capacity of nanometer CuO is 1058.1mAh/g, and initial charge specific capacity is 654.5mAh/g, first efficiency
For 61.9%；The discharge capacity first added after graphene oxide is 1077.9mAh/g, and initial charge capacity is 712.6mAh/g,
Efficiency is 66.1% first.After circulation 250 times, adding the CuO negative materials of graphene oxide its charge specific capacities is
370.5mAh/g, hence it is evident that higher than be not added with graphene oxide CuO negative materials circulate 250 times after charge specific capacity.
The design focal point of the present invention is：The present invention overcomes the shortcomings that CuO is as negative material, by first using fused salt to fire
Burnt together prepares out nanometer CuO into method, then adds 2% -10% graphene oxide, and modified CuO circulates as negative material
Its charge specific capacity is 370.5 mAh/g after 250 times, is laid a good foundation for volume production and application, and the present invention is synthesized using molten-salt growth method
Prepare, molten-salt growth method has the reaction time short, and technique is simple, easily realizes that industrialization large-scale production and combustion synthesis reaction are quick
Major advantage, and can obtain the small product of crystal perfection, particle diameter and coated graphene Posterior circle in the short period of time
Energy.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore any subtle modifications, equivalent variations and modifications that every technical spirit according to the present invention is made to above example, still
Belong in the range of technical solution of the present invention.
Claims (4)
- A kind of 1. method for improving negative material CuO cyclical stabilities, it is characterised in that：Include following steps：（One）The preparation of graphene oxide；（Two）The preparation of nanometer CuO：1）Copper acetate is weighed, programming rate is 5 DEG C/min；2）Constant temperature 2-10h after to 500 DEG C -800 DEG C of predetermined temperature；3）Taken out after the insulation scheduled time, cool down at room temperature, that is, obtain nanometer CuO；（Three）Graphene oxide is added in nanometer CuO, graphene oxide accounts for CuO and the quality summation of graphene oxide 2%—10%。
- 2. the method according to claim 1 for improving negative material CuO cyclical stabilities, it is characterised in that：The step （One）The preparation of graphene oxide includes following steps：1）In 250ml conical flasks, the 120ml concentrated sulfuric acids, 2.5g potassium peroxydisulfates, 2.5g phosphorus pentoxides are sequentially added, stirring is extremely Potassium peroxydisulfate and phosphorus pentoxide all dissolve, and are slowly added to 3g graphite powders, react 4h in 80 DEG C of water-baths；2）Conical flask is cooled to room temperature, adds 500ml deionized waters, overnight, filters, and deionized water is washed to neutrality, 50 DEG C of bakings Dried in case；3）250ml conical flasks are put into 0 DEG C of water-bath, are put into graphite powder after the 120ml concentrated sulfuric acids, drying, 15g potassium permanganate；4）Potassium permanganate is added completely into rear conical flask and moved in 35 DEG C of water-baths, constant temperature stirring 2h；5）20ml 30% H2O2 is added dropwise into solution, 55ml distilled water, stands 12h；6) 3% dilute HCl is used, distilled water is rinsed to product, is centrifuged 3 times, freeze drier freeze-drying, is obtained final Product.
- 3. the method according to claim 2 for improving negative material CuO cyclical stabilities, it is characterised in that：The nanometer CuO preparation process 2）In, preferably 600 DEG C of calcining heat, the preferred 6h of soaking time.
- 4. the method according to claim 1 for improving negative material CuO cyclical stabilities, it is characterised in that：The acetic acid Copper is low melting point copper acetate, and its fusing point is 115 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113675393A (en) * | 2021-08-20 | 2021-11-19 | 西安热工研究院有限公司 | Morphology-controllable high-performance lithium ion battery negative electrode material and preparation method thereof |
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| CN106744907A (en) * | 2015-11-24 | 2017-05-31 | 青岛智信生物科技有限公司 | The preparation method of graphene oxide |
| CN106938852A (en) * | 2017-01-19 | 2017-07-11 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of lithium ion battery negative material nanometer CuO |
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2017
- 2017-09-15 CN CN201710835056.2A patent/CN107732224A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744907A (en) * | 2015-11-24 | 2017-05-31 | 青岛智信生物科技有限公司 | The preparation method of graphene oxide |
| CN106938852A (en) * | 2017-01-19 | 2017-07-11 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of lithium ion battery negative material nanometer CuO |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113675393A (en) * | 2021-08-20 | 2021-11-19 | 西安热工研究院有限公司 | Morphology-controllable high-performance lithium ion battery negative electrode material and preparation method thereof |
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Address after: No. 38 Shuidong Park, Gongchuan Town, Yongan City, Fujian Province Applicant after: FUJIAN XFH BATTERY MATERIAL CO., LTD. Address before: 9, J building, building 20, block C, 1 Science Park, Shenzhen Road, Longhua New District, Longhua, Guangdong, 518000, China Applicant before: FUJIAN XFH BATTERY MATERIAL CO., LTD. |
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