CN104993147B - A kind of preparation method of multilevel hierarchy copper nitrate negative material - Google Patents
A kind of preparation method of multilevel hierarchy copper nitrate negative material Download PDFInfo
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- CN104993147B CN104993147B CN201510307888.8A CN201510307888A CN104993147B CN 104993147 B CN104993147 B CN 104993147B CN 201510307888 A CN201510307888 A CN 201510307888A CN 104993147 B CN104993147 B CN 104993147B
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- copper nitrate
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/62—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
A kind of preparation method of multilevel hierarchy copper nitrate negative material of the present invention, comprises the following steps：Take 100 200g nitric acid copper powders, it is dissolved in 500ml distilled water, until completely dissolved, add 1 5g carbon fibers, high-speed stirred is warmed up to 60 80 DEG C after 30 minutes, be subsequently added into the acetic acid solution of 50 100ml ethanol and 5ml, 1mol/L, after stirring 3 minutes, 1 2g carbon blacks are added, continues to stir until solution evaporation is complete；Next, the head product of gained is put into baking oven being dried 24 hours at 60 DEG C, take out product and pulverize, products therefrom is the copper nitrate negative material of multilevel hierarchy.The advantage of the method is the multistage composite structure that the copper nitrate negative material for obtaining has stabilization, and this multistage composite structure causes that copper nitrate negative material has high power capacity and long-life characteristic.
Description
Technical field
The present invention relates to a kind of copper nitrate negative material of lithium ion battery, more particularly, to a kind of with multilevel hierarchy
The preparation method of copper nitrate negative material.
Background technology
Used as a kind of high performance energy storage device, lithium ion battery is in mobile phone, notebook computer, digital camera, electronic vapour
The fields such as car are widely used.In all parts of composition lithium ion battery, positive and negative pole material is to determine lithium ion
The key substance of the factors such as battery capacity size, service life, production prices.However, since the lithium-ion electric nineties in 20th century
Since pond is commercialized, positive electrode is weeded out the old and bring forth the new constantly, and negative material has been used up graphite type material, compared to positive pole
The continuous lifting of material capacity, the capacity of negative material has been limited to the relatively low theoretical capacity of graphite（372 mAh/g）, this
Hinder the further raising of lithium ion battery energy density so that current lithium ion battery can not fully meet the need of user
Ask.
Used as the alternative materials of graphite cathode, transition metal oxide is that current high performance lithium ion battery negative material grinds
Study carefully one of focus of exploitation.Because the characteristics of transition metal oxide negative material has Theoretical Mass specific capacity high
（800-1000 mAh/g）, but the actual reversible lithium storage capacity of this kind of material is more much lower than theoretical capacity, such as Co3O4Negative pole
Reversible specific discharge capacity of the material circulation after 50 weeks only has 300-400 mAh/g, thus transition metal oxide negative material
Society can not very well be met to high power capacity, the demand of long-life negative material.
By contrast, nitrate materials are a kind of negative materials of Theoretical Mass specific capacity superelevation, and it uses nitrate anion
Reversible reaction process carrys out storage energy, and after reaching the embedding lithium of saturation, up to 3000 mAh/g, this causes nitre to its Theoretical Mass specific capacity
Silicate material has potential reversible capacity higher, excellent chemistry and electrochemical stability, therefore, nitrate-based negative material
It is a kind of lithium ion battery negative material for having very much a DEVELOPMENT PROSPECT.
The preparation method of existing commercialization negative material, mainly uses carbon source（Such as pitch）Under 2000 DEG C of high temperature above
Under carry out for a long time carbonization obtain electrographite（Carbonaceous mesophase spherules）, thus, such synthesis technique has lacking for high energy consumption
Fall into, this is to result in the rising of synthesis process cost while pursuit raw material is cheap, so that one kind can not be obtained can be full
Sufficient the with low cost of current social demand, the negative material that capacity is high and security is good.
The content of the invention
The technical problems to be solved by the invention are to provide and a kind of prepare the side with multilevel hierarchy copper nitrate negative material
Method, the synthetic method passes through first to build the composite of a kind of copper nitrate and carbon fiber, is then combined again with carbon black, from
And a kind of Stability Analysis of Structures, fine and close composite are obtained, the particle of resulting copper nitrate negative material is homogeneous, particle diameter distribution is equal
Even, electronic conductivity is high, so as to be effectively improved the storage lithium performance of copper nitrate negative material.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：A kind of lithium ion battery multilevel hierarchy nitric acid
The preparation method of copper negative material, comprises the following steps：100-200g nitric acid copper powders are taken, is dissolved in 500ml distilled water, treated
After being completely dissolved, 1-5g carbon fibers are added, high-speed stirred is warmed up to 60-80 DEG C, is subsequently added into 50-100ml ethanol after 30 minutes
With the acetic acid solution of 5ml, 1mol/L, after stirring 3 minutes, 1-2g carbon blacks are added, continue to stir until solution evaporation is complete；Connect down
Come, the head product of gained is put into baking oven and is dried 24 hours at 60 DEG C, take out product and pulverize, products therefrom is multistage knot
The copper nitrate negative material of structure.
Compared with prior art, the advantage of the invention is that.
（1）Multilevel hierarchy copper nitrate negative material prepared by the method grain diameter is homogeneous, Stability Analysis of Structures, densification.Its
Middle carbon fiber plays skeletal support effect in the composite, and copper nitrate is filled in the Three Dimensional Cavities of carbon fiber structure, nanometer
Space between the perfect copper nitrate particle of level carbon black, so whole composite substance is uniformly dispersed, it is fine and close, maintain
The stabilization of electrode structure.
（2）Meanwhile, the method is also by the use of commodity copper nitrate as electrode material, and synthesis technique only relates to copper nitrate
Dissolving and recrystallization so that its with low cost, lithium storage content of this composite is higher, cycle life is good, can meet high power capacity
The need for lithium ion battery practical application.
Brief description of the drawings
Fig. 1 is charging and discharging curve figure of the gained with multilevel hierarchy copper nitrate negative material in the embodiment of the present invention.
Specific embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
Embodiment 1.
100g nitric acid copper powders are taken, is dissolved in 500ml distilled water, until completely dissolved, add 1g carbon fibers, high-speed stirring
60 DEG C are warmed up to after mixing 30 minutes, the acetic acid solution of 50ml ethanol and 5ml, 1mol/L is subsequently added into, after stirring 3 minutes, added
1g carbon blacks, continue to stir until solution evaporation is complete；Next, the head product of gained is put into baking oven, that 24 are dried at 60 DEG C is small
When, taking out product and pulverize, products therefrom is the copper nitrate negative material of multilevel hierarchy.Using the product of gained as research
Electrode, metal lithium sheet is assembled into fastening lithium ionic cell as to electrode in the glove box full of argon gas, with the multiplying power of 0.1C
Charge and discharge cycles are carried out in 0.0-3.4V potential regions, it is 2452mAh/g that can obtain discharge capacity first, and charging capacity is
1698mAh/g, its reversible capacity after circulating 100 weeks is 1501mAh/g, it is shown that excellent chemical property.
Embodiment 2.
200g nitric acid copper powders are taken, is dissolved in 500ml distilled water, until completely dissolved, add 5g carbon fibers, high-speed stirring
80 DEG C are warmed up to after mixing 30 minutes, the acetic acid solution of 100ml ethanol and 5ml, 1mol/L is subsequently added into, after stirring 3 minutes, added
2g carbon blacks, continue to stir until solution evaporation is complete；Next, the head product of gained is put into baking oven, that 24 are dried at 60 DEG C is small
When, taking out product and pulverize, products therefrom is the copper nitrate negative material of multilevel hierarchy.Using the product of gained as research
Electrode, metal lithium sheet is assembled into fastening lithium ionic cell as to electrode in the glove box full of argon gas, with the multiplying power of 0.1C
Charge and discharge cycles are carried out in 0.0-3.4V potential regions, it is 2389mAh/g that can obtain discharge capacity first, and charging capacity is
1780mAh/g, its reversible capacity after circulating 100 weeks is 1671mAh/g, it is shown that excellent chemical property.
Embodiment 3.
150g nitric acid copper powders are taken, is dissolved in 500ml distilled water, until completely dissolved, add 3g carbon fibers, high-speed stirring
70 DEG C are warmed up to after mixing 30 minutes, the acetic acid solution of 80ml ethanol and 5ml, 1mol/L is subsequently added into, after stirring 3 minutes, added
1g carbon blacks, continue to stir until solution evaporation is complete；Next, the head product of gained is put into baking oven, that 24 are dried at 60 DEG C is small
When, taking out product and pulverize, products therefrom is the copper nitrate negative material of multilevel hierarchy.Using the product of gained as research
Electrode, metal lithium sheet is assembled into fastening lithium ionic cell as to electrode in the glove box full of argon gas, with the multiplying power of 0.1C
Charge and discharge cycles are carried out in 0.0-3.4 V potential regions, it is 2783mAh/g that can obtain discharge capacity first, and charging capacity is
2109mAh/g, its reversible capacity after circulating 100 weeks is 1842mAh/g, it is shown that excellent chemical property.
Embodiment 4.
100g nitric acid copper powders are taken, is dissolved in 500ml distilled water, until completely dissolved, add 5g carbon fibers, high-speed stirring
60 DEG C are warmed up to after mixing 30 minutes, the acetic acid solution of 100ml ethanol and 5ml, 1mol/L is subsequently added into, after stirring 3 minutes, added
2g carbon blacks, continue to stir until solution evaporation is complete；Next, the head product of gained is put into baking oven, that 24 are dried at 60 DEG C is small
When, taking out product and pulverize, products therefrom is the copper nitrate negative material of multilevel hierarchy.Using the product of gained as research
Electrode, metal lithium sheet is assembled into fastening lithium ionic cell as to electrode in the glove box full of argon gas, with the multiplying power of 0.1C
Charge and discharge cycles are carried out in 0.0-3.4 V potential regions, it is 2555mAh/g that can obtain discharge capacity first, and charging capacity is
2067mAh/g, its reversible capacity after circulating 100 weeks is 1897mAh/g, it is shown that excellent chemical property.
Embodiment 5.
200g nitric acid copper powders are taken, is dissolved in 500ml distilled water, until completely dissolved, add 2g carbon fibers, high-speed stirring
80 DEG C are warmed up to after mixing 30 minutes, the acetic acid solution of 50ml ethanol and 5ml, 1mol/L is subsequently added into, after stirring 3 minutes, added
1g carbon blacks, continue to stir until solution evaporation is complete；Next, the head product of gained is put into baking oven, that 24 are dried at 60 DEG C is small
When, taking out product and pulverize, products therefrom is the copper nitrate negative material of multilevel hierarchy.Using the product of gained as research
Electrode, metal lithium sheet is assembled into fastening lithium ionic cell as to electrode in the glove box full of argon gas, with the multiplying power of 0.1C
Charge and discharge cycles are carried out in 0.0-3.4 V potential regions, it is 2249mAh/g that can obtain discharge capacity first, and charging capacity is
1948mAh/g, its reversible capacity after circulating 100 weeks is 1768mAh/g, it is shown that excellent chemical property.
Claims (3)
1. a kind of preparation method of multilevel hierarchy copper nitrate negative material, it is characterised in that comprise the following steps：Take 100-200g
Nitric acid copper powders, are dissolved in 500ml distilled water, until completely dissolved, add 1-5g carbon fibers, and high-speed stirred rises after 30 minutes
Temperature is subsequently added into the acetic acid solution of 50-100ml ethanol and 5ml, 1mol/L to 60-80 DEG C, after stirring 3 minutes, adds 1-2g carbon
It is black, continue to stir until solution evaporation is complete；Next, the head product of gained is put into baking oven being dried 24 hours at 60 DEG C, take
Go out product and pulverize, products therefrom is the copper nitrate negative material of multilevel hierarchy.
2. the preparation method of a kind of multilevel hierarchy copper nitrate negative material according to claim 1, it is characterised in that：It is described
Multilevel hierarchy copper nitrate negative material composition be copper nitrate, carbon fiber and carbon black.
3. the preparation method of a kind of multilevel hierarchy copper nitrate negative material according to claim 1, it is characterised in that：It is described
Nitric acid copper raw material be the Cu (NO containing the crystallization water3)2·3H2O。
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Families Citing this family (11)
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| CN106784733A (en) * | 2017-01-17 | 2017-05-31 | 宁波大学 | A kind of ZnO coats Ni2+、Co2+Doping amorphous copper nitrate lithium cell negative pole material and preparation method thereof |
| CN106803583A (en) * | 2017-01-17 | 2017-06-06 | 宁波大学 | A kind of double-component coats Cr3+、Cu2+Doping amorphous nickel nitrate lithium cell negative pole material and preparation method thereof |
| CN106602040A (en) * | 2017-01-17 | 2017-04-26 | 宁波大学 | SiO<2> coated Co<2+>-Cu<2+> doped amorphous nickel nitrate lithium battery negative electrode material and preparation method thereof |
| CN106684366A (en) * | 2017-01-17 | 2017-05-17 | 宁波大学 | Two-component coated Co<2+> and Cu<2+> doped amorphous nickel nitrate negative electrode material and preparation method thereof |
| CN106602041A (en) * | 2017-01-17 | 2017-04-26 | 宁波大学 | Liquid-phase SiO<2> coated Fe<3+>-Cr<3+> doped amorphous cobalt nitrate lithium battery anode material and preparation method thereof |
| CN107046123A (en) * | 2017-01-17 | 2017-08-15 | 宁波大学 | A kind of ZnO coats Ni2+、Cu2+Adulterate amorphous cobalt nitrate lithium cell negative pole material and preparation method thereof |
| CN106848304A (en) * | 2017-01-17 | 2017-06-13 | 宁波大学 | A kind of double-component coats Ni2+、Cu2+Doping amorphous cobalt nitrate lithium cell negative pole material and preparation method thereof |
| CN106602042A (en) * | 2017-01-17 | 2017-04-26 | 宁波大学 | Liquid-phase ZnO coated Ni<2+>-Cr<3+> doped amorphous cobalt nitrate lithium battery anode material and preparation method thereof |
| CN106803584A (en) * | 2017-01-17 | 2017-06-06 | 宁波大学 | A kind of liquid phase double-component coats Cu2+、Cr3+Doping amorphous nickel nitrate lithium cell negative pole material and preparation method thereof |
| CN106803585A (en) * | 2017-01-17 | 2017-06-06 | 宁波大学 | A kind of liquid phase double-component coats Co2+、Cr3+Doping amorphous copper nitrate lithium cell negative pole material and preparation method thereof |
| CN116487595B (en) * | 2023-06-16 | 2023-09-08 | 国网浙江省电力有限公司宁波供电公司 | Preparation method of high-capacity composite electrode material for sodium ion energy storage battery |
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| US9136526B2 (en) * | 2012-04-20 | 2015-09-15 | Korea Institute Of Energy Research | Method of manufacturing anode active material, and anode and lithium battery using the anode active material |
| CN103521225A (en) * | 2013-10-31 | 2014-01-22 | 内蒙古工业大学 | Method for preparing carbon fiber copper-carried catalyst for reaction of preparing ethanediol through oxalic ester |
| CN103831108A (en) * | 2014-03-18 | 2014-06-04 | 南京大学 | Copper ferrite-loaded activated carbon fiber, preparation method and application of fiber, and method for degrading activated azo dye wastewater |
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