CN107732206A - A kind of preparation method of the bimetallic oxide composite negative pole material of multilevel hierarchy - Google Patents
A kind of preparation method of the bimetallic oxide composite negative pole material of multilevel hierarchy Download PDFInfo
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- CN107732206A CN107732206A CN201710968480.4A CN201710968480A CN107732206A CN 107732206 A CN107732206 A CN 107732206A CN 201710968480 A CN201710968480 A CN 201710968480A CN 107732206 A CN107732206 A CN 107732206A
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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
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- 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
- H01M4/36—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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
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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 discloses a kind of preparation method of the bimetallic oxide composite negative pole material of multilevel hierarchy, belong to technical field of lithium ion.This method comprises the concrete steps that：Nickel nitrate, cobalt nitrate, ammonium salt and acid amides are dissolved in water, stirred, moves into ptfe autoclave and adds appropriate foam metal, react 10 15h.Cooling drying, is then transferred into tube furnace in N21 5h is heat-treated under atmosphere, obtains the NiCoO grown on foam metal2‑Co3O4；It is then placed in small beaker, adds the aqueous solution of surfactant, ultrasound, stirring, sequentially add pyrroles, acid solution and oxidant, and washed after being stirred under ice-water bath, target product is obtained after drying.This method prepare Co, Ni bimetallic oxide composite negative pole material grain diameter is homogeneous, Stability Analysis of Structures, densification, there is considerable broad potential window reversible capacity, excellent high rate performance and stable cycle life.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of bimetallic oxide negative pole of lithium ion battery
Material, more particularly, to a kind of preparation method of the bimetallic oxide composite negative pole material of multilevel hierarchy.
Background technology
Traditional fossil energy is faced with shortage or even exhausted crisis, and brings immense pressure to environmental protection, recycling economy,
The new industrialization developing direction of low-carbon economy will promote the fast development of new-energy automobile industry.Lithium-ion-power cell conduct
Environmentally friendly, high-energy battery of new generation, it has also become new-energy automobile electrokinetic cell main product at present.However, since 20th century 90
Since age lithium ion battery is commercialized, positive electrode is weeded out the old and bring forth the new constantly, and negative material uses graphite-like material always
Material, compared to the continuous lifting of positive electrode capacity, the capacity of negative material has been limited to the relatively low theoretical capacity of graphite
(372mAh/g), this also counteracts that the further raising of lithium ion battery energy density so that current lithium ion battery can not
Fully meets the needs of user.As the alternative materials of graphite cathode, transition metal oxide is current high performance lithium-ion electric
One of focus of pond negative material research and development.Transition metal has a more valence state, and their oxide or
Compound is all relatively easy to be made, but different nanostructureds significantly affects to its chemical property.At the same time,
It is greatly emerging that the other unique performances of transition metal oxide make it that the researcher of more and more different fields generates to it
Interest.But the actual reversible lithium storage capacity of this kind of material is more much lower than theoretical capacity, such as Co3O4Negative material circulate 50 weeks it
Reversible specific discharge capacity afterwards only has 300-400mAh/g, thus transition metal oxide negative material can not meet society very well
To the demand of high power capacity, long-life negative material.
The content of the invention
For overcome the deficiencies in the prior art, the technical problem to be solved in the present invention is to provide a kind of bimetallic of multilevel hierarchy
The preparation method of oxide composite negative pole material, the synthetic method are intended by building a kind of CoNiO2、Co3O4With polypyrrole (PPy)
Composite, the high composite of a kind of Stability Analysis of Structures, electric conductivity is obtained, to the negative material of resulting multilevel hierarchy
Particle is homogeneous, particle diameter distribution is uniform, electronic conductivity is high, so as to can effectively improve Co, Ni bimetallic oxide negative material
Store up lithium performance.
Technical scheme is used by the present invention solves above-mentioned technical problem：A kind of bimetallic oxide of multilevel hierarchy is answered
The preparation method of negative material is closed, is comprised the following steps：
By 0.001mol Ni (NO3)2·6H2O、0.002mol Co(NO3)2·6H2O, 0.003mol ammonium salts and
0.005mol acid amides is dissolved in deionized water, stirs 1-3h, moves into 100mL ptfe autoclave and add appropriate foam
Metal, then in an oven 110-130 DEG C reaction 10-15h.After being cooled to room temperature, filtering, wash and dry, be then transferred into
In N in tube furnace21-5h is persistently heat-treated in 400-600 DEG C under atmosphere, obtains the NiCoO grown on foam metal2-Co3O4
A diameter of 14mm of bimetallic negative material, wherein foam metal, thickness 1mm.Then will grow on foam metal
NiCoO2-Co3O4Bimetallic negative material is placed in small beaker, then adds 50-70mL 0.1g/L surfactant water
Solution, and ultrasonic 3-9 minutes, then mechanical agitation 10-15h, then sequentially adds 0.03~0.15mL pyrroles, 1molL-1's
The volume ratio of the oxidant of acid solution and 0.1-0.2g, wherein pyrroles and acid is 0.07: 1, and stirs 1- under ice-water bath simultaneously
4h, stirring are washed with deionized 3-5 times after terminating, then washed 2-3 times with acetone, and multilevel hierarchy is obtained after drying
NiCoO2-Co3O4- PPy bimetallic oxide composite negative pole materials.
Described ammonium salt is NH4F, described acid amides are urea.
Described foam metal is nickel foam, and a diameter of 14mm, thickness 1mm, aperture 120PPI, wherein PPI refer to
The number of per inch endoporus.
The aqueous solution of described surfactant is the aqueous solution of dodecyl sodium sulfate.
Described acid solution is hydrochloric acid solution.
Described oxidant is (NH4)2S2O8。
The bimetallic oxide composite negative pole material that above-mentioned preparation method obtains can be answered as lithium ion battery negative pole
With.
Compared with prior art, the present invention has following technique effect：
1st, Co, Ni bimetallic oxide composite negative pole material prepared by this method grain diameter is homogeneous, Stability Analysis of Structures, cause
It is close.Wherein PPy plays skeletal support effect, NiCoO in the composite2And Co3O4It is filled in the Three Dimensional Cavities of PPy structures,
Perfect NiCoO2And Co3O4Space between particle, and then whole composite substance is uniformly dispersed, be fine and close, maintain
The stabilization and high conductivity of electrode structure.
2nd, the material granule uniformity of the invention synthesized, good dispersion, crystallinity are high, and obtained material is nanometer rods
Shape, be advantageous to improve the chemical property of material.
3rd, the material that the present invention obtains has considerable broad potential window reversible capacity, excellent high rate performance and stabilization
Cycle life so that there is the material very high actual use to be worth, and can effectively meet the various applications of lithium ion battery
Actual requirement.
4th, the lithium ion battery negative material that the present invention prepares has higher theoretical capacity and quick charge and discharge electrical
Energy, improve the energy density and power density of lithium ion battery.
Brief description of the drawings
Fig. 1 is gained NiCoO in the embodiment of the present invention 12-Co3O4The SEM figures of-PPy composite negative pole materials.
Fig. 2 is gained NiCoO in the embodiment of the present invention 12-Co3O4The cycle performance figure of-PPy composite negative pole materials.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments, but the present invention is not limited to following embodiments.
Embodiment 1
By 1mmol Ni (NO3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol urea is dissolved in
70mL deionized waters, stir 1h, move into 100mL ptfe autoclave and add appropriate nickel foam (a diameter of 14mm,
Thickness is 1mm, aperture 120PPI), then in an oven 120 DEG C reaction 12h.After being cooled to room temperature, filtering, wash and dry,
It is then transferred into tube furnace in N22h is persistently heat-treated in 600 DEG C under atmosphere, obtains the NiCoO grown in nickel foam2-
Co3O4Bimetallic negative material.Then the NiCoO that will be grown in nickel foam2-Co3O4Bimetallic negative material is placed on small burning
In cup, the concentration for then adding 50mL is 0.1g/L sodium dodecyl sulfate aqueous solutions, and ultrasonic 9 minutes, then mechanical agitation
10h, then sequentially add 0.035mL pyrroles, 0.5mL 1molL-1Hydrochloric acid solution and 0.114g oxidant (NH4)2S2O8, and 2h is stirred under ice-water bath simultaneously, stirring is washed with deionized 4 times after terminating, and is then washed 3 times with acetone, does
The NiCoO of multilevel hierarchy is obtained after dry2-Co3O4- PPy bimetallic oxide composite negative pole materials.Resulting materials are in nano bar-shape
(Fig. 1).It is used as the product of gained as Electrode, metal lithium sheet to electrode, is assembled into the glove box full of argon gas
CR2016 type fastening lithium ionic cells, charge and discharge cycles are carried out in 0.0-3.0V potential regions with different current densities.
During 2000mA/g discharge and recharges, it is 1647.6mAh/g (Fig. 2) to take off lithium capacity first, and reversible de- lithium capacity is after 100 circulations
1203mAh/g (Fig. 2), it is shown that excellent high rate capability and cyclical stability.
Embodiment 2
By 1mmol Ni (NO3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol urea is dissolved in
70mL deionized waters, 1h is stirred, moves into 100mL ptfe autoclave and adds appropriate nickel foam (120PPI), so
Afterwards in an oven 110 DEG C reaction 10h.After being cooled to room temperature, filtering, wash and dry, be then transferred into tube furnace in N2Gas
5h is persistently heat-treated in 400 DEG C under atmosphere, obtains what is grown in nickel foam (a diameter of 14mm, thickness 1mm, aperture 120PPI)
NiCoO2-Co3O4Bimetallic negative material.Then the NiCoO that will be grown in nickel foam2-Co3O4Bimetallic negative material is placed
In small beaker, the concentration for then adding 70mL is 0.1g/L sodium dodecyl sulfate aqueous solutions, and ultrasonic 3 minutes, Ran Houji
Tool stirs 15h, then sequentially adds 0.03mL pyrroles, 0.43mL 1molL-1Hydrochloric acid solution and 0.1g oxidant
(NH4)2S2O8, and 1h is stirred under ice-water bath simultaneously, stirring is washed with deionized 3 times after terminating, and then washs 2 with acetone
It is secondary, obtain the NiCoO of multilevel hierarchy after drying2-Co3O4- PPy bimetallic oxide composite negative pole materials.Resulting materials are in nanometer
It is bar-shaped.It is used as the product of gained as Electrode, metal lithium sheet to electrode, is assembled into the glove box full of argon gas
CR2016 type fastening lithium ionic cells, charge and discharge cycles are carried out in 0.0-3.0V potential regions with different current densities.
During 2000mA/g discharge and recharges, it is 1620.1mAh/g to take off lithium capacity first, and reversible de- lithium capacity is after 100 circulations
1168.3mAh/g, it is shown that excellent high rate capability and cyclical stability.
Embodiment 3
By 1mmol Ni (NO3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol urea is dissolved in
70mL deionized waters, 3h is stirred, moves into 100mL ptfe autoclave and adds appropriate nickel foam (120PPI), so
Afterwards in an oven 130 DEG C reaction 10h.After being cooled to room temperature, filtering, wash and dry, be then transferred into tube furnace in N2Gas
1h is persistently heat-treated in 600 DEG C under atmosphere, obtains in nickel foam (a diameter of 14mm, thickness 1mm, aperture 120PPI) growth
NiCoO2-Co3O4Bimetallic negative material.Then the NiCoO that will be grown in nickel foam2-Co3O4Bimetallic negative material is placed
In small beaker, the concentration for then adding 60mL is 0.1g/L sodium dodecyl sulfate aqueous solutions, and ultrasonic 9 minutes, Ran Houji
Tool stirs 10h, then sequentially adds 0.15mL pyrroles, 2.1mL 1molL-1Hydrochloric acid solution and 0.2g oxidant (NH4)2S2O8.And 4h is stirred under ice-water bath simultaneously, stirring is washed with deionized 5 times after terminating, and is then washed 3 times with acetone, does
The NiCoO of multilevel hierarchy is obtained after dry2-Co3O4- PPy bimetallic oxide composite negative pole materials.Resulting materials are in nano bar-shape.
It is used as the product of gained as Electrode, metal lithium sheet to electrode, CR2016 is assembled into the glove box full of argon gas
Type fastening lithium ionic cell, charge and discharge cycles are carried out in 0.0-3.0V potential regions with different current densities.2000mA/g fills
During electric discharge, it is 1601.2mAh/g to take off lithium capacity first, and reversible de- lithium capacity is 1192.5mAh/g after 100 circulations, it is shown that
Excellent high rate capability and cyclical stability.
Embodiment 4
By 1mmol Ni (NO3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol urea is dissolved in
70mL deionized waters, 2h is stirred, moves into 100mL ptfe autoclave and adds appropriate nickel foam (120PPI), so
Afterwards in an oven 115 DEG C reaction 14h.After being cooled to room temperature, filtering, wash and dry, be then transferred into tube furnace in N2Gas
4h is persistently heat-treated in 500 DEG C under atmosphere, obtains what is grown in nickel foam (a diameter of 14mm, thickness 1mm, aperture 120PPI)
NiCoO2-Co3O4Bimetallic negative material.Then the NiCoO that will be grown in nickel foam2-Co3O4Bimetallic negative material is placed
In small beaker, the concentration for then adding 55mL is 0.1g/L sodium dodecyl sulfate aqueous solutions, and ultrasonic 8 minutes, Ran Houji
Tool stirs 13h, then sequentially adds 0.01mL pyrroles, 1.4mL 1molL-1Hydrochloric acid solution and 0.18g oxidant
(NH4)2S2O8.And 3h is stirred under ice-water bath simultaneously, stirring is washed with deionized 4 times after terminating, and then washs 3 with acetone
It is secondary, obtain the NiCoO of multilevel hierarchy after drying2-Co3O4- PPy bimetallic oxide composite negative pole materials.Resulting materials are in nanometer
It is bar-shaped.It is used as the product of gained as Electrode, metal lithium sheet to electrode, is assembled into the glove box full of argon gas
CR2016 type fastening lithium ionic cells, charge and discharge cycles are carried out in 0.0-3.0V potential regions with different current densities.
During 2000mA/g discharge and recharges, it is 1630.7mAh/g to take off lithium capacity first, and reversible de- lithium capacity is after 100 circulations
1168.9mAh/g, it is shown that excellent high rate capability and cyclical stability.
Embodiment 5
By 1mmol Ni (NO3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol urea is dissolved in
70mL deionized water, 1.5h is stirred, moves into 100mL ptfe autoclave and adds appropriate nickel foam (120PPI),
Then in an oven 125 DEG C reaction 13h.After being cooled to room temperature, filtering, wash and dry, be then transferred into tube furnace in N2
3h is persistently heat-treated in 550 DEG C under atmosphere, obtains growing in nickel foam (a diameter of 14mm, thickness 1mm, aperture 120PPI)
NiCoO2-Co3O4Bimetallic negative material.Then the NiCoO that will be grown in nickel foam2-Co3O4Bimetallic negative material is put
Put in small beaker, then add the aqueous solution for the dodecyl sodium sulfate that concentration is 0.1g/L, and ultrasonic 7 minutes, Ran Houji
Tool stirs 13h, then sequentially adds the hydrochloric acid solution of pyrroles.Wherein, the concentration of hydrochloric acid is 1molL-1, the body of pyrroles and hydrochloric acid
Product is than being 0.12: 1.Then the concentration for adding 65mL is 0.1g/L sodium dodecyl sulfate aqueous solutions, and ultrasonic 7 minutes, then
Mechanical agitation 14h, then sequentially add 0.14mL pyrroles, 2mL 1molL-1Hydrochloric acid solution and 0.19g oxidant
(NH4)2S2O8.And 3h is stirred under ice-water bath simultaneously, stirring is washed with deionized 3 times after terminating, and then washs 3 with acetone
It is secondary, obtain the NiCoO of multilevel hierarchy after drying2-Co3O4- PPy bimetallic oxide composite negative pole materials.Resulting materials are in nanometer
It is bar-shaped.It is used as the product of gained as Electrode, metal lithium sheet to electrode, is assembled into the glove box full of argon gas
CR2016 type fastening lithium ionic cells, charge and discharge cycles are carried out in 0.0-3.0V potential regions with different current densities.
During 2000mA/g discharge and recharges, it is 1608.9mAh/g to take off lithium capacity first, and reversible de- lithium capacity is after 100 circulations
1155.2mAh/g, it is shown that excellent high rate capability and cyclical stability.
Embodiment 6
By 1mmol Ni (NO3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol urea is dissolved in
70mL deionized waters, 2.5h is stirred, move into 100mL ptfe autoclave and to add appropriate nickel foam (a diameter of
14mm, thickness 1mm, aperture 120PPI), then in an oven 115 DEG C reaction 11h.After being cooled to room temperature, filtering, washing and
Drying, is then transferred into tube furnace in N23h is persistently heat-treated in 550 DEG C under atmosphere, obtains what is grown in nickel foam
NiCoO2-Co3O4Bimetallic negative material.Then the NiCoO that will be grown in nickel foam2-Co3O4Bimetallic negative material is placed
In small beaker, the aqueous solution for the dodecyl sodium sulfate that concentration is 0.1g/L is then added, and it is ultrasonic 4 minutes, it is then mechanical
14h is stirred, then sequentially adds the hydrochloric acid solution of pyrroles.Wherein, the concentration of hydrochloric acid is 1molL-1, the volume of pyrroles and hydrochloric acid
Than for 0.09: 1.Then the concentration for adding 52mL is 0.1g/L sodium dodecyl sulfate aqueous solutions, and ultrasonic 4 minutes, Ran Houji
Tool stirs 13h, then sequentially adds 0.03mL pyrroles, 0.43mL1molL-1Acid solution and 0.1g oxidant (NH4)2S2O8.And 3h is stirred under ice-water bath simultaneously, stirring is washed with deionized 3 times after terminating, and is then washed 3 times with acetone, does
The NiCoO of multilevel hierarchy is obtained after dry2-Co3O4- PPy bimetallic oxide composite negative pole materials.Resulting materials are in nano bar-shape.
It is used as the product of gained as Electrode, metal lithium sheet to electrode, CR2016 is assembled into the glove box full of argon gas
Type fastening lithium ionic cell, charge and discharge cycles are carried out in 0.0-3.0V potential regions with different current densities.2000mA/g fills
During electric discharge, it is 1599.8mAh/g to take off lithium capacity first, and reversible de- lithium capacity is 1156.8mAh/g after 100 circulations, it is shown that
Excellent high rate capability and cyclical stability.
Embodiment 7
By 1mmol Ni (NO3)2·6H2O、2mmol Co(NO3)2·6H2O、3mmol NH4F and 5mmol urea is dissolved in
70mL deionized waters, stir 2h, move into 100mL ptfe autoclave and add appropriate nickel foam (a diameter of 14mm,
Thickness is 1mm, aperture 120PPI), then in an oven 120 DEG C reaction 12h.After being cooled to room temperature, filtering, wash and dry,
It is then transferred into tube furnace in N22h is persistently heat-treated in 500 DEG C under atmosphere, obtains the NiCoO grown in nickel foam2-
Co3O4Bimetallic negative material.Then the NiCoO that will be grown in nickel foam2-Co3O4Bimetallic negative material is placed on small burning
In cup, the aqueous solution for the dodecyl sodium sulfate that concentration is 0.1g/L is then added, and ultrasound 7 minutes, then mechanical agitation
12h, then add the hydrochloric acid solution of pyrroles.Wherein, the concentration of hydrochloric acid is 1molL-1, the volume ratio of pyrroles and hydrochloric acid is 0.12
∶1.Then the concentration for adding 54mL is 0.1g/L sodium dodecyl sulfate aqueous solutions, and ultrasonic 7 minutes, then mechanical agitation
12h, then sequentially add 0.05mL pyrroles, 0.7mL1molL-1Hydrochloric acid solution and 0.15g oxidant (NH4)2S2O8.And
2h is stirred under ice-water bath simultaneously, stirring is washed with deionized 4 times after terminating, then washed 3 times with acetone, is obtained after drying
The NiCoO of multilevel hierarchy2-Co3O4- PPy bimetallic oxide composite negative pole materials.Resulting materials are in nano bar-shape.By gained
Product is used as to electrode as Electrode, metal lithium sheet, and CR2016 type button lithiums are assembled into the glove box full of argon gas
Ion battery, charge and discharge cycles are carried out in 0.0-3.0V potential regions with different current densities.It is first during 2000mA/g discharge and recharges
Secondary de- lithium capacity is 1604.1mAh/g, and reversible de- lithium capacity is 1175.8mAh/g after 100 circulations, it is shown that excellent high power
Rate performance and cyclical stability.
Claims (7)
1. the preparation method of the bimetallic oxide composite negative pole material of a kind of multilevel hierarchy, it is characterised in that including following step
Suddenly：
(1) by 0.001mol Ni (NO3)2·6H2O、0.002mol Co(NO3)2·6H2O, 0.003mol ammonium salts and 0.005mol
Acid amides is dissolved in deionized water, stirs 1~3h, moves into 100mL ptfe autoclave and add appropriate foam metal, so
Afterwards in an oven 110~130 DEG C reaction 10~15h；After being cooled to room temperature, filtering, wash and dry, be then transferred into tube furnace
In in N21~5h is persistently heat-treated in 400~600 DEG C under atmosphere, obtains the NiCoO grown on foam metal2-Co3O4Double gold
Belong to negative material；
(2) NiCoO for obtaining step (1)2-Co3O4Bimetallic negative material is placed in small beaker, then add 50~
70mL 0.1g/L aqueous surfactant solution, and it is ultrasonic 3~9 minutes, and then 10~15h of mechanical agitation, is then sequentially added
0.03~0.15mL pyrroles, 1molL-1Acid solution and 0.1~0.2g oxidant, wherein pyrroles and acid solution volume ratio
For 0.07:1, and 1~4h is stirred under ice-water bath simultaneously, stirring is washed with deionized 3~5 times after terminating, and then uses acetone
Washing 2~3 times, the NiCoO of multilevel hierarchy is obtained after drying2-Co3O4- PPy bimetallic oxide composite negative pole materials.
2. the preparation method of the bimetallic oxide composite negative pole material of multilevel hierarchy as claimed in claim 1, its feature exist
In：Ammonium salt described in step (1) is NH4F, described acid amides are urea.
3. the preparation method of the bimetallic oxide composite negative pole material of multilevel hierarchy as claimed in claim 1, its feature exist
In：Foam metal described in step (1) is nickel foam, a diameter of 14mm, thickness 1mm, aperture 120PPI.
4. the preparation method of the bimetallic oxide composite negative pole material of multilevel hierarchy as claimed in claim 1, its feature exist
In：Surfactant described in step (2) is dodecyl sodium sulfate.
5. the preparation method of the bimetallic oxide composite negative pole material of multilevel hierarchy as claimed in claim 1, its feature exist
In：Acid solution described in step (2) is hydrochloric acid solution.
6. the preparation method of the bimetallic oxide composite negative pole material of multilevel hierarchy as claimed in claim 1, its feature exist
In：Oxidant described in step (2) is (NH4)2S2O8。
7. the bimetallic oxide composite negative pole material that preparation method as claimed in claim 1 obtains is as lithium ion battery negative pole
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| CN109755037A (en) * | 2018-12-28 | 2019-05-14 | 南昌大学 | Nickel cobalt oxide-stannic oxide hybrid supercapacitor electrode material preparation method |
| CN110387559A (en) * | 2018-04-16 | 2019-10-29 | 中国科学院福建物质结构研究所 | A kind of electro-catalysis produces the preparation method and its product and application of oxygen thin-film electrode material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103117389A (en) * | 2013-01-25 | 2013-05-22 | 浙江大学 | Nickel-cobalt oxide/graphene composite material as well as preparation method and application thereof |
| US20130171502A1 (en) * | 2011-12-29 | 2013-07-04 | Guorong Chen | Hybrid electrode and surface-mediated cell-based super-hybrid energy storage device containing same |
| US20130330611A1 (en) * | 2012-06-11 | 2013-12-12 | Gourong Chen | Rechargeable lithium cell having a meso-porous conductive material structure-supported phthalocyanine compound cathode |
| CN104319371A (en) * | 2014-11-06 | 2015-01-28 | 深圳职业技术学院 | Preparation method of lithium ion battery SnS2/CNTs/PPy composite anode material |
| CN105958059A (en) * | 2016-07-18 | 2016-09-21 | 合肥工业大学 | Three-dimensional Cu/Co3O4 multi-stage nanowire array and preparation method and application thereof |
| CN106129401A (en) * | 2016-06-29 | 2016-11-16 | 北京化工大学 | A kind of foamed nickel supported high surface roughness cobalt acid nickel nm wall and preparation method thereof |
| CN106525933A (en) * | 2016-11-03 | 2017-03-22 | 天津大学 | Method for producing polypyrrole-coated nickel cobaltate nano wire array graphene electrode and application of graphene electrode for detecting heavy metallic lead ion |
-
2017
- 2017-10-18 CN CN201710968480.4A patent/CN107732206B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130171502A1 (en) * | 2011-12-29 | 2013-07-04 | Guorong Chen | Hybrid electrode and surface-mediated cell-based super-hybrid energy storage device containing same |
| US20130330611A1 (en) * | 2012-06-11 | 2013-12-12 | Gourong Chen | Rechargeable lithium cell having a meso-porous conductive material structure-supported phthalocyanine compound cathode |
| CN103117389A (en) * | 2013-01-25 | 2013-05-22 | 浙江大学 | Nickel-cobalt oxide/graphene composite material as well as preparation method and application thereof |
| CN104319371A (en) * | 2014-11-06 | 2015-01-28 | 深圳职业技术学院 | Preparation method of lithium ion battery SnS2/CNTs/PPy composite anode material |
| CN106129401A (en) * | 2016-06-29 | 2016-11-16 | 北京化工大学 | A kind of foamed nickel supported high surface roughness cobalt acid nickel nm wall and preparation method thereof |
| CN105958059A (en) * | 2016-07-18 | 2016-09-21 | 合肥工业大学 | Three-dimensional Cu/Co3O4 multi-stage nanowire array and preparation method and application thereof |
| CN106525933A (en) * | 2016-11-03 | 2017-03-22 | 天津大学 | Method for producing polypyrrole-coated nickel cobaltate nano wire array graphene electrode and application of graphene electrode for detecting heavy metallic lead ion |
Non-Patent Citations (2)
| Title |
|---|
| XIN XU等: ""Rational Design of NiCoO2@SnO2 Heterostructure Attached on Amorphous Carbon Nanotubes with Improved Lithium Storage Properties"", 《ACS APPL. MATER. INTERFACES》 * |
| XING GAO 等: ""Facile synthesis of Co3O4@NiCo2O4 core–shell arrays on Ni foam for advanced binder-free supercapacitor electrodes"", 《CERAMICS INTERNATIONAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110387559A (en) * | 2018-04-16 | 2019-10-29 | 中国科学院福建物质结构研究所 | A kind of electro-catalysis produces the preparation method and its product and application of oxygen thin-film electrode material |
| CN110387559B (en) * | 2018-04-16 | 2021-06-18 | 中国科学院福建物质结构研究所 | Preparation method of electrocatalytic oxygen production film electrode material, product and application thereof |
| CN109755037A (en) * | 2018-12-28 | 2019-05-14 | 南昌大学 | Nickel cobalt oxide-stannic oxide hybrid supercapacitor electrode material preparation method |
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