CN108172782A - A kind of preparation method and application with shell-core structure carbon package porous oxidation Asia cobalt nano material - Google Patents
A kind of preparation method and application with shell-core structure carbon package porous oxidation Asia cobalt nano material Download PDFInfo
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- CN108172782A CN108172782A CN201711329542.3A CN201711329542A CN108172782A CN 108172782 A CN108172782 A CN 108172782A CN 201711329542 A CN201711329542 A CN 201711329542A CN 108172782 A CN108172782 A CN 108172782A
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- 239000010941 cobalt Substances 0.000 title claims abstract description 66
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 66
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 60
- 230000003647 oxidation Effects 0.000 title claims abstract description 51
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 51
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007853 buffer solution Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000011258 core-shell material Substances 0.000 abstract 2
- 239000010405 anode material Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 229920001690 polydopamine Polymers 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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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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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Chemical property the present invention provides a kind of simple and easy method of carbon package porous oxidation Asia cobalt nano material prepared with core-shell structure and its as anode of lithium ion battery, specific preparation process include：Solid cobaltosic oxide nano cube is prepared using hydro-thermal method；After the nano cubic surface package PDA of preparation, calcine to obtain the porous oxidation Asia crust of cobalt core nano material of carbon package by high temperature, the porous oxidation Asia cobalt nano material of core-shell structure carbon package is formed finally by salt acid etch.The method of the present invention does not add the participation of any directed agents and surfactant, entire building-up process mild condition, environmentally protective, raw material is cheap, and the requirement to equipment is low, convenient for industrialization production, have great application prospect in terms of the preparation of the anode material of lithium ion battery.
Description
Technical field
The present invention relates to a kind of synthetic method prepared with shell-core structure carbon package porous oxidation Asia cobalt nano material and
Its application in power lithium-ion battery anode.
Background technology
With the continuous development of technology, people life style gradually changes, and status of the lithium ion battery in life is got over
It more protrudes, people are also more and more urgent for the demand of electrode material with high rate capability.It is born as lithium ion battery
Pole material, the theoretical specific capacity of cobalt protoxide are up to 715mAh g-1, it is 2 times of graphitized carbon or so.But the head of cobalt protoxide
Secondary coulombic efficiency and cycle performance are poor.In order to overcome these shortcomings, the structure design of cobalt protoxide is particularly important, and such as China is special
Sharp 103950994 B of document CN, by solvent thermal reaction, have finally synthesized bilayer using organic metal cobalt salt and two kinds of protective agents
Cobalt protoxide hollow Nano particle；K.J.An and N.Y.Lee et al. use cobalt chloride hexahydrate as Material synthesis oleic acid Asia cobalt, so
Afterwards by high temperature thermal decomposition oleic acid Asia cobalt, finally prepare CoO nanometer rods (J.Am.Chem.Soc.2006,128,9753-
9760)；101800302 A of Chinese patent literature CN have invented the graphene nanometer sheet-cobalt protoxide synthesized by hydro-thermal reaction
Composite negative pole material.At present, it is rare for the carbon package porous oxidation Asia cobalt nanocube three-dimensional material with shell-core structure
Report, therefore have practical meaning and application value for the research and development of the material.
Invention content
The object of the present invention is to provide a kind of carbon package porous oxidation Asia cobalt nano materials synthesized with shell-core structure
Synthetic method and the application on lithium ion battery.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method with shell-core structure carbon package porous oxidation Asia cobalt nano material, includes the following steps：
The first step prepares Co3O4 nanometer material using hydro-thermal method
By cabaltous nitrate hexahydrate dispersion in deionized water, magnetic agitation is added in sodium hydroxide, continues to stir thereto to transparent
It is extremely transparent, the solution of acquisition is transferred in reaction kettle, reacts at 180 DEG C for 24 hours, is cooled to room temperature after reaction, is centrifuged, institute
Solid with ethanol water centrifuge washing for several times, up to Co3O4 nanometer material after the drying of solid after centrifugation；
Second step wraps up PDA on Co3O4 nanometer material surface prepared by the first step
Co3O4 nanometer material prepared by the first step and Dopamine hydrochloride are dissolved in three（Methylol）Aminomethane buffer solution
In, after 3h is stirred at room temperature, centrifugation, obtained solid with ethanol water centrifuge washing for several times, after the drying of solid after centrifugation
Up to the Co3O4 nanometer material of surface package PDA；
Third walks, and the calcined material that second step obtains is obtained with shell-core structure carbon package porous oxidation Asia cobalt nano material
Calcination condition is heating speed of the Co3O4 nanometer material in 5 DEG C/min that PDA is wrapped up on the surface for obtaining second step
Rate, 2 ~ 4h of constant temperature at 450 DEG C ~ 500 DEG C.
Preferably, the 4th step salt acid etch is further included, the carbon package porous oxidation Asia cobalt nano material that third step is obtained
It is impregnated in hydrochloric acid solution and is less than or equal to 12min, then washed for several times with ethanol water, after centrifugation, solid is dried in vacuo, is obtained
The porous oxidation Asia cobalt nano material wrapped up to shell-core structure carbon.
Preferably, the amount ratio of the substance of cabaltous nitrate hexahydrate and sodium hydroxide is 4: 1 in the first step.
Preferably, three in the second step（Methylol）A concentration of 10mM of aminomethane buffer solution.
Preferably, in the second step cobaltosic oxide a concentration of 0.9g/ml, a concentration of 0.4g/ of Dopamine hydrochloride
ml。
Preferably, in the 4th step hydrochloric acid solution a concentration of 0.1mol/L.
Prepared by a kind of preparation method with shell-core structure carbon package porous oxidation Asia cobalt nano material described above
Application of the carbon package porous oxidation Asia cobalt nano material as negative material in lithium ion battery.
Compared with prior art, beneficial effects of the present invention are：
1st, the carbon package porous oxidation Asia cobalt nanocube three-dimensional material that prepared by preparation method of the invention has shell-core knot
Structure, the structure have many mesoporous, the delivering path of lithium ion and electronics can be effectively improved, so as to improve its high rate performance；
Secondly, the carbon of outside package can effectively prevent the attenuation for being in direct contact caused capacity of electrolyte and active material.
2nd, whole process of the invention all carries out in aqueous systems, does not add any directed agents and surface-active
Agent, and preparation process is simple, green, cheap, safety, it is easier to realize industrialized production.
Description of the drawings
Fig. 1 is the X-ray diffraction obtained that porous oxidation Asia cobalt nano material is wrapped up with shell-core structure carbon of embodiment 1
Figure；
Fig. 2 is the stereoscan photograph obtained that porous oxidation Asia cobalt nano material is wrapped up with shell-core structure carbon of embodiment 1；
Fig. 3 is the transmission electron microscope photo obtained that porous oxidation Asia cobalt nano material is wrapped up with shell-core structure carbon of embodiment 1；
Fig. 4 is etched for embodiment 2 made from 3 minutes, and there is shell-core structure carbon to wrap up porous oxidation Asia cobalt nano material transmission electricity
Mirror photo；
Fig. 5 is etched for embodiment 3 made from 6 minutes, and there is shell-core structure carbon to wrap up porous oxidation Asia cobalt nano material transmission electricity
Mirror photo；
Fig. 6 is etched for embodiment 4 made from 12 minutes, and there is shell-core structure carbon to wrap up porous oxidation Asia cobalt nano material transmission electricity
Mirror photo；
Fig. 7 is the cyclic voltammogram obtained that porous oxidation Asia cobalt nano material is wrapped up with shell-core structure carbon of embodiment 1；
There is Fig. 8 shell-core structure carbon to wrap up porous oxidation Asia cobalt nano material as electrode material not made from embodiment 1
With the cycle figure under current density.
Specific embodiment
With reference to embodiment, the present invention is described in further detail.
Embodiment 1
There is the present embodiment the preparation process of shell-core structure carbon package porous oxidation Asia cobalt nano material to be：
The first step, the cubical preparation of cobaltosic oxide nano
Using hydrothermal method（Also referred to as hydro-thermal method）Cobaltosic oxide is prepared, 0.04 mol cabaltous nitrate hexahydrates is taken to be scattered in 40 mL
In deionized water, stirred under magnetic stirring to transparent；0.01 mol sodium hydroxides is taken to be added in above-mentioned solution again to continue to stir
It mixes to obtaining clear solution；Above-mentioned solution is transferred in the ptfe autoclave of 50 mL, and place in an oven in
24 h are reacted at 180 DEG C；After reaction, reaction kettle cooled to room temperature, gained sample are centrifuged, and with water/second
Mixed alkoxide solution centrifuge washing three times, dries 12 h at 65 DEG C；
Second step, PDA（Poly-dopamine）The cubical preparation of cobaltosic oxide nano of package
The Dopamine hydrochloride of cobaltosic oxide prepared by the first step of 90 mg and 40 mg is taken to be placed in 100 mL, a concentration of 10 mM
Tris-buffer solution in, stir 3 h at room temperature；Deposit is centrifuged later, and molten with water/ethyl alcohol mixing
Liquid centrifuge washing three times, dries 12 h at 65 DEG C；
Third walks, and temperature control converts the preparation of porous carbon package cobalt protoxide
Product prepared by second step is placed in tube furnace, heated up with 5 DEG C/min and at 500 DEG C 3 h of constant temperature be made with shell-
The carbon package porous oxidation Asia cobalt nanocube three-dimensional material of nuclear structure.
Carbon manufactured in the present embodiment wraps up the XRD diagram of cobalt protoxide material as shown in Figure 1, comparing with standard card, says
Bright material carbon package cobalt protoxide material manufactured in the present embodiment.Its scanning electron microscope (SEM) photograph and transmission electron microscope picture are as shown in Figures 2 and 3.
Embodiment 2
It is same as Example 1, unlike,
4th step, the preparation of the porous carbon package cobalt protoxide of salt acid etch
Product prepared by third step is dispersed in a concentration of 0.1 mol/L hydrochloric acid solutions and etches 3 min, then through deionized water/
Ethyl alcohol embathes to remove soluble impurity, obtained material be centrifuged after through being dried in vacuo at 65 DEG C, being made has shell-core structure
Carbon package porous oxidation Asia cobalt nanocube three-dimensional material.
The transmission electron microscope of carbon package porous oxidation Asia cobalt nanocube three-dimensional material of the present embodiment after salt acid etch
Figure is as shown in Figure 4.
Embodiment 3
It is same as Example 1, unlike,
4th step, the preparation of the porous carbon package cobalt protoxide of salt acid etch
Product prepared by third step is dispersed in a concentration of 0.1 mol/L hydrochloric acid solutions and etches 6 min, then through deionized water/
Ethyl alcohol embathes to remove soluble impurity, obtained material be centrifuged after through being dried in vacuo at 65 DEG C, being made has shell-core structure
Carbon package porous oxidation Asia cobalt nanocube three-dimensional material.
The transmission electron microscope of carbon package porous oxidation Asia cobalt nanocube three-dimensional material of the present embodiment after salt acid etch
Figure is as shown in Figure 5.
Embodiment 4
It is same as Example 1, unlike,
4th step, the preparation of the porous carbon package cobalt protoxide of salt acid etch
Product prepared by third step is dispersed in a concentration of 0.1 mol/L hydrochloric acid solutions and etches 12 min, then through deionized water/
Ethyl alcohol embathes to remove soluble impurity, obtained material be centrifuged after through being dried in vacuo at 65 DEG C, being made has shell-core structure
Carbon package porous oxidation Asia cobalt nanocube three-dimensional material.
The transmission electron microscope of carbon package porous oxidation Asia cobalt nanocube three-dimensional material of the present embodiment after salt acid etch
Figure is as shown in Figure 6.
The above-mentioned process for preparing carbon package porous oxidation Asia cobalt nanocube three-dimensional material will for entire reaction condition
Ask succinct, it is at low cost and environmentally protective, it is more suitable for industrialization production.The obtained carbon package porous oxidation with shell-core structure
The X-ray diffractogram of sub- cobalt nanocube three-dimensional material from figure as shown in Figure 1, understand the cobalt protoxide that sample is single-phase
(JCPDS:48-1719).Fig. 2 represents that the carbon package porous oxidation Asia cobalt nanocube with shell-core structure is made in embodiment 1
The SEM figures of three-dimensional material, cobalt protoxide uniformly wraps up one layer of carbon-coating, and has apparent hole；Fig. 3 represents embodiment 1
The TEM figures of the carbon package porous oxidation Asia cobalt nanocube three-dimensional material with shell-core structure are made；Fig. 4 represents to pass through
The TEM figures of the carbon package porous oxidation Asia cobalt nanocube three-dimensional material with shell-core structure are made in 3min etchings；Fig. 5 tables
Show that the TEM that the carbon package porous oxidation Asia cobalt nanocube three-dimensional material with shell-core structure is made by 6min etchings schemes；
Fig. 6 represents that the carbon package porous oxidation Asia cobalt nanocube three-dimensional material with shell-core structure is made by 12 min etchings
TEM figures, internal cobalt protoxide etched completely, leaves behind carbon shell；Fig. 7 represents that embodiment 1 is made with shell-core structure
The cyclic voltammogram of carbon package porous oxidation Asia cobalt nanocube three-dimensional material；Fig. 8 shows for embodiment 1 be made have shell-
Electrochemistry cycle of the carbon package porous oxidation Asia cobalt nanocube three-dimensional material of nuclear structure in the case where current density is 0.2 A/g
Figure.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding without departing from the principles and spirit of the present invention can carry out these embodiments a variety of variations, modification, replace
And modification, the scope of the present invention is defined by the appended.
Claims (7)
1. a kind of preparation method with shell-core structure carbon package porous oxidation Asia cobalt nano material, which is characterized in that including with
Lower step：
The first step prepares Co3O4 nanometer material using hydro-thermal method
By cabaltous nitrate hexahydrate dispersion in deionized water, magnetic agitation is added in sodium hydroxide, continues to stir thereto to transparent
It is extremely transparent, the solution of acquisition is transferred in reaction kettle, reacts at 180 DEG C for 24 hours, is cooled to room temperature after reaction, is centrifuged, institute
Solid with ethanol water centrifuge washing for several times, up to Co3O4 nanometer material after the drying of solid after centrifugation；
Second step wraps up PDA on Co3O4 nanometer material surface prepared by the first step
Co3O4 nanometer material prepared by the first step and Dopamine hydrochloride are dissolved in three（Methylol）Aminomethane buffer solution
In, after 3h is stirred at room temperature, centrifugation, obtained solid with ethanol water centrifuge washing for several times, after the drying of solid after centrifugation
Up to the Co3O4 nanometer material of surface package PDA；
Third walks, and the calcined material that second step obtains is obtained with shell-core structure carbon package porous oxidation Asia cobalt nano material
Calcination condition is heating speed of the Co3O4 nanometer material in 5 DEG C/min that PDA is wrapped up on the surface for obtaining second step
Rate, 2 ~ 4h of constant temperature at 450 DEG C ~ 500 DEG C.
2. a kind of preparation side with shell-core structure carbon package porous oxidation Asia cobalt nano material according to claim 1
Method, which is characterized in that further include the 4th step salt acid etch, the carbon package porous oxidation Asia cobalt nano material that third step obtains is existed
It is impregnated in hydrochloric acid solution and is less than or equal to 12min, then washed for several times with ethanol water, after centrifugation, solid is dried in vacuo, is obtained
The porous oxidation Asia cobalt nano material of shell-core structure carbon package.
3. a kind of preparation with shell-core structure carbon package porous oxidation Asia cobalt nano material according to claim 1 or 2
Method, which is characterized in that the amount ratio of the substance of cabaltous nitrate hexahydrate and sodium hydroxide is 4: 1 in the first step.
4. a kind of preparation with shell-core structure carbon package porous oxidation Asia cobalt nano material according to claim 1 or 2
Method, which is characterized in that three in the second step（Methylol）A concentration of 10mM of aminomethane buffer solution.
5. a kind of preparation with shell-core structure carbon package porous oxidation Asia cobalt nano material according to claim 1 or 2
Method, which is characterized in that a concentration of 0.9g/ml of cobaltosic oxide, a concentration of 0.4g/ of Dopamine hydrochloride in the second step
ml。
6. a kind of preparation side with shell-core structure carbon package porous oxidation Asia cobalt nano material according to claim 2
Method, which is characterized in that a concentration of 0.1mol/L of hydrochloric acid solution in the 4th step.
7. a kind of preparation method with shell-core structure carbon package porous oxidation Asia cobalt nano material described in claims 1 or 2
Application of the carbon package porous oxidation Asia cobalt nano material of preparation as negative material in lithium ion battery.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711329542.3A CN108172782B (en) | 2017-12-13 | 2017-12-13 | Preparation method and application of carbon-coated porous cobaltous oxide nano material with shell-core structure |
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| CN114551882A (en) * | 2022-01-12 | 2022-05-27 | 华南师范大学 | Ferric fluoride cathode material and preparation method and application thereof |
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