CN108011089B - Hexahydric cyclic cobalt oxyhydroxide/graphene nanocomposite and preparation method thereof - Google Patents
Hexahydric cyclic cobalt oxyhydroxide/graphene nanocomposite and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- -1 cobalt oxyhydroxide Chemical compound 0.000 title claims abstract description 38
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 27
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 53
- 230000032683 aging Effects 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 16
- 229910000428 cobalt oxide Inorganic materials 0.000 description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 7
- 238000005086 pumping Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 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 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910018916 CoOOH Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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Abstract
The invention relates to a preparation method of a hexabasic cyclic cobalt oxyhydroxide/graphene nanocomposite, belonging to the field of inorganic materials. The preparation method comprises the following specific processes: (1) mixing a cobalt salt aqueous solution and a graphene aqueous solution according to a certain proportion, and stirring for a certain time under the conditions of inert gas and room temperature; (2) adding strong alkali aqueous solution, and reacting for a certain time; (3) removing the inert gas, adding a strong oxidant, and aging for a certain time; (4) and filtering, washing and drying the turbid liquid obtained after the ageing to obtain the hexabasic cyclic cobalt oxyhydroxide/graphene nano composite material. The method has the advantages of simple process flow, mild reaction conditions, easiness in large-scale preparation and the like, the obtained product is controllable in shape, and the cobalt oxyhydroxide is uniformly dispersed on the surface of the graphene, so that the method is expected to be applied to the fields of supercapacitors, lithium ion batteries, catalysis and the like.
Description
Technical Field
The invention belongs to the field of inorganic materials, and particularly relates to a hexabasic cyclic cobalt oxyhydroxide/graphene nanocomposite and a preparation method thereof.
Technical Field
With the rapid development of economic society, the requirements of the world on energy storage equipment are higher and higher nowadays, so that the preparation of high-performance lithium ion batteries and electrochemical capacitors and the improvement of the effective utilization rate and the storage efficiency of energy become problems which need to be solved urgently. Wherein the electrode material is the key to the performance of the energy storage device. Lithium cobaltate is the most commonly used electrode material for lithium ion batteries at present because of its advantages of high discharge voltage, stable charge and discharge voltage, high specific energy, etc. Cobalt oxide (cobalt oxide, cobaltosic oxide, cobalt oxyhydroxide and cobaltous hydroxide) is used as one of common cobalt sources for producing lithium cobaltate, and the structure and the property of the cobalt oxide have obvious influence on the electrochemical performance of the lithium cobaltate. Therefore, the development of the high-performance cobalt oxide nano material and the preparation process have wide application prospects.
The theoretical capacity of cobalt oxide is very high, but the defects of poor conductivity, large volume change in the charging and discharging process and the like limit the application of the cobalt oxide to a certain extent. In order to improve the electrochemical performance of cobalt oxide, the hexabasic cyclic cobalt oxyhydroxide/graphene nanocomposite is prepared. Graphene is used as a novel carbon material, has a two-dimensional plane monoatomic layer structure, can enable metal oxide nanoparticles to be nucleated or inlaid on the surface or the side surface of the graphene, has unique properties such as ultrahigh specific surface area and good electron transmission property, and becomes an excellent composite material additive. The graphene serving as a carrier or a coating material can effectively improve the conductivity and the circulation stability of the cobalt oxyhydroxide, the cobalt oxyhydroxide can also prevent the folding and agglomeration of the graphene to a certain extent, and the nano composite material has the advantages of the graphene and the cobalt oxyhydroxide and improves the electrochemical performance of the nano composite material in the energy storage of the super capacitor and the lithium ion battery.
Researches find that the particle size, the particle size distribution and the morphology of the nano material have obvious influence on the performance and the application of the nano material. Controllable preparation of nanomaterials, i.e., size and morphology, is a goal sought by researchers in the relevant field. From the published papers and patents, there is less research on cobalt oxyhydroxide relative to cobaltous hydroxide and cobaltosic oxide, and the preparation process thereof is still in the preliminary stage. Patent CN201310375503.2 discloses a synthesis process of nano-grade cobalt oxyhydroxide, but the obtained cobalt oxyhydroxide has a random shape and a wide particle size distribution. In patent CN201210016504.3, after CoOOH is prepared, granulation needs to be carried out in a spray dryer, equipment is added, and the process is complicated. At present, no report is provided about a hexabasic cyclic cobalt oxyhydroxide/graphene nanocomposite material and a preparation method thereof. The invention provides a hexabasic annular cobalt oxyhydroxide/graphene nanocomposite and a preparation method thereof for the first time. The method has the advantages of simple process flow, low process energy consumption, controllable product appearance and particle size, good batch-to-batch repeatability, easiness in large-scale production and the like, and the obtained hexatomic cyclic cobalt oxyhydroxide/graphene nanocomposite is expected to be applied to the fields of lithium ion batteries, supercapacitors, catalysis and the like.
Disclosure of Invention
The invention aims to provide a hexabasic cyclic cobalt oxyhydroxide/graphene nanocomposite and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a hexabasic cyclic cobalt oxyhydroxide/graphene nanocomposite material comprises the following specific steps:
(1) respectively preparing cobalt salt and graphene aqueous solution, wherein cobalt ions (Co) in the cobalt salt aqueous solution2+) The molar concentration is 0.001-0.1 mol/L, and the mass concentration of graphene in the graphene aqueous solution is 0.1-2mg/m L;
(2) uniformly mixing a cobalt salt aqueous solution and a graphene aqueous solution, and stirring for 0.5-5 hours at room temperature in nitrogen or inert gas;
(3) adding strong alkaline aqueous solution, and reacting at 30-80 deg.C for 0.5-5 hr to obtain hydroxide ions (OH)-) The molar concentration is 0.01-1.0 mol/L;
(4) removing nitrogen or inert gas, adding strong oxidant, and continuing aging for 0.5-5 h; the mass fraction of the strong oxidant in the final reaction liquid is 2-10%;
(5) and after the aging is finished, filtering, washing and drying the obtained turbid liquid to obtain the hexabasic annular cobalt oxyhydroxide/graphene nano composite material.
The cobalt salt is one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate.
Cobalt ion (Co) in the cobalt salt aqueous solution2+) The mass ratio of the graphene to the graphene in the graphene aqueous solution is 1:5-5: 1.
The strong base in the strong base aqueous solution is one or more than two of lithium hydroxide, sodium hydroxide and potassium hydroxide.
And (3) adding the strong alkali aqueous solution at the flow rate of 2.5-20m L/min.
Cobalt ion (Co) in the cobalt salt aqueous solution2+) With hydroxide ions (OH) in an aqueous alkali solution-) In a molar ratio of 1:5 to 1: 40.
The strong oxidant is one or two of hydrogen peroxide (25-28 mass percent) and sodium hypochlorite.
Compared with the prior art, the invention has the following advantages:
(1) the nanoscale hexabasic annular cobalt oxyhydroxide/graphene composite material is synthesized for the first time, and the unique material is expected to be applied to the fields of lithium ion batteries, supercapacitors, catalysis and the like;
(2) the product has controllable morphology and granularity, and the preparation method has the advantages of low process energy consumption, simple process flow, easy large-scale production and the like.
Drawings
FIG. 1 is an SEM image of a product of example 1 of the present invention.
FIG. 2 is an SEM image of a product of example 2 of the present invention.
Figure 3 is an XRD pattern of the product of example 2 of the invention.
FIG. 4 is an SEM image of a product of example 3 of the invention.
Detailed Description
The following examples serve to illustrate the invention.
Example 1
(1) Preparing a cobalt chloride aqueous solution with the concentration of 0.025 mol/L and a graphene aqueous solution with the concentration of 2mg/m L, wherein each of the cobalt chloride aqueous solution and the graphene aqueous solution is 25m L, uniformly mixing, transferring the mixture into a three-neck flask, introducing nitrogen into the three-neck flask in advance, and mechanically stirring the mixture at room temperature for 4 hours, (2) preparing a sodium hydroxide aqueous solution with the concentration of 0.25 mol/L, wherein the sodium hydroxide aqueous solution is 50m L, pumping the sodium hydroxide aqueous solution into the three-neck flask at the flow rate of 5m L/min, reacting the mixture for 1 hour at the temperature of 50 ℃ under the stirring2Adding 10ml of 28% hydrogen peroxide, and aging for 2 h; (4) and after aging, filtering, washing and drying the obtained suspension, wherein an SEM picture of the suspension is shown in figure 1, and the hexatomic cyclic cobalt oxyhydroxide/graphene nanocomposite is prepared.
Example 2
(1) Preparing a cobalt chloride aqueous solution with the concentration of 0.025 mol/L and a graphene aqueous solution with the concentration of 2mg/m L, wherein each of the cobalt chloride aqueous solution and the graphene aqueous solution is 25m L, uniformly mixing, transferring the mixture into a three-neck flask, introducing nitrogen into the three-neck flask in advance, and mechanically stirring the mixture at room temperature for 4 hours, (2) preparing a hydroxide aqueous solution with the concentration of 0.25 mol/LAdding 50m of sodium water solution L into a three-neck flask at the flow rate of 5m L/min, reacting for 2h at 50 ℃ under stirring, and (3) removing N2Adding 10ml of 28 percent hydrogen peroxide, and aging for 3.5 hours; (4) and after aging, filtering, washing and drying the obtained suspension, wherein the SEM picture is shown in figure 2, and the XRD picture is shown in figure 3, so that the hexabasic cyclic cobalt oxyhydroxide/graphene nanocomposite is prepared.
Example 3
(1) Preparing 25ml of each of a cobalt chloride aqueous solution with the concentration of 0.05 mol/L and a graphene aqueous solution with the concentration of 2mg/m L, uniformly mixing, transferring the mixture into a three-neck flask, introducing nitrogen into the three-neck flask in advance, mechanically stirring the mixture at room temperature for 4 hours, (2) preparing a sodium hydroxide aqueous solution with the concentration of 0.25 mol/L with the concentration of 50m L, pumping the mixture into the three-neck flask at the flow rate of 5m L/min, reacting the mixture for 1 hour at the temperature of 50 ℃ under the stirring condition, and (3) removing N2Adding 10ml of 28% hydrogen peroxide, and aging for 2 h; (4) and after aging, filtering, washing and drying the obtained suspension, wherein an SEM picture of the suspension is shown in figure 4, and the hexatomic cyclic cobalt oxyhydroxide/graphene nanocomposite is prepared.
Example 4
(1) Preparing an aqueous solution of cobalt chloride with the concentration of 0.0125 mol/L and an aqueous solution of graphene with the concentration of 1mg/m L, 100m L respectively, uniformly mixing, transferring the mixture into a three-neck flask, introducing nitrogen into the three-neck flask in advance, and mechanically stirring the mixture at room temperature for 4 hours, (2) preparing an aqueous solution of sodium hydroxide with the concentration of 0.25 mol/L of 200m L, pumping the aqueous solution of sodium hydroxide into the three-neck flask at the flow rate of 10m L/min, reacting the aqueous solution for 2 hours at the temperature of 50 ℃ under the stirring condition, and (3) removing N2Adding 40ml of 28% hydrogen peroxide, and aging for 2 h; (4) and after the aging is finished, filtering, washing and drying the obtained turbid liquid to prepare the hexabasic cyclic cobalt oxyhydroxide/graphene nanocomposite.
Example 5
(1) Preparing an aqueous solution of cobalt chloride with a concentration of 0.025 mol/L and an aqueous solution of graphene with a concentration of 2mg/m L, each 100m L, uniformly mixing, transferring the mixture into a three-neck flask, introducing nitrogen into the three-neck flask in advance, and mechanically stirring the mixture at room temperature for 4 hours, (2) preparing an aqueous solution of sodium hydroxide with a concentration of 0.5 mol/L, 200m L, pumping the aqueous solution into the three-neck flask at a flow rate of 5m L/min, and reacting the mixture at 50 ℃ under stirring conditions for 2h; (3) remove N2Adding 40ml of 28% hydrogen peroxide, and aging for 2 h; (4) and after the aging is finished, filtering, washing and drying the obtained turbid liquid to prepare the hexabasic cyclic cobalt oxyhydroxide/graphene nanocomposite.
Example 6
(1) Preparing an aqueous solution of cobalt chloride with a concentration of 0.025 mol/L and an aqueous solution of graphene with a concentration of 2mg/m L, each 100m L, uniformly mixing, transferring the mixture into a three-neck flask, introducing nitrogen into the three-neck flask in advance, and mechanically stirring the mixture at room temperature for 4 hours, (2) preparing an aqueous solution of sodium hydroxide with a concentration of 0.25 mol/L of 200m L, pumping the aqueous solution into the three-neck flask at a flow rate of 5m L/min, reacting the aqueous solution for 2 hours at a temperature of 50 ℃ under stirring conditions, and (3) removing N2Adding 20ml of 28% hydrogen peroxide, and aging for 2 h; (4) and after the aging is finished, filtering, washing and drying the obtained turbid liquid to prepare the hexabasic cyclic cobalt oxyhydroxide/graphene nanocomposite.
Claims (6)
1. A preparation method of a hexabasic cyclic cobalt oxyhydroxide/graphene nanocomposite is characterized by comprising the following steps: the method comprises the following specific steps:
(1) respectively preparing cobalt salt and graphene aqueous solution, wherein cobalt ions Co in the cobalt salt aqueous solution2+The molar concentration is 0.001-0.1 mol/L, and the mass concentration of graphene in the graphene aqueous solution is 0.1-2mg/m L;
(2) uniformly mixing a cobalt salt aqueous solution and a graphene aqueous solution, and stirring for 0.5-5 hours at room temperature in nitrogen or inert gas;
(3) adding strong alkaline aqueous solution, and reacting at 30-80 deg.C for 0.5-5 hr to obtain hydroxide ions (OH)-) The molar concentration is 0.01-1.0 mol/L, and the cobalt ion Co in the cobalt salt water solution2+With hydroxide ions (OH) in an aqueous alkali solution-) In a molar ratio of 1:5 to 1: 40;
(4) removing nitrogen or inert gas, adding strong oxidant, and continuing aging for 0.5-5 h; the mass fraction of the strong oxidant in the final reaction liquid is 2-10%;
(5) and after the aging is finished, filtering, washing and drying the obtained turbid liquid to obtain the hexabasic annular cobalt oxyhydroxide/graphene nano composite material.
2. The method for preparing the six-membered cyclic cobalt oxyhydroxide/graphene nanocomposite material according to claim 1, wherein: the cobalt salt is one or more of cobalt sulfate, cobalt chloride, cobalt nitrate or cobalt acetate.
3. The method for preparing the six-membered cyclic cobalt oxyhydroxide/graphene nanocomposite material according to claim 1, wherein: cobalt ion Co in the cobalt salt aqueous solution2+The mass ratio of the graphene to the graphene in the graphene aqueous solution is 1:5-5: 1.
4. The method for preparing the six-membered cyclic cobalt oxyhydroxide/graphene nanocomposite material according to claim 1, wherein: the strong base in the strong base aqueous solution is one or more than two of lithium hydroxide, sodium hydroxide or potassium hydroxide.
5. The method for preparing the six-membered cyclic cobalt oxyhydroxide/graphene nanocomposite material according to claim 1, wherein the aqueous solution of the strong base is added at a flow rate of 2.5-20m L/min.
6. The method for preparing the six-membered cyclic cobalt oxyhydroxide/graphene nanocomposite material according to claim 1, wherein: the strong oxidant is one or two of sodium hypochlorite or hydrogen peroxide with the mass fraction of 25% -28%.
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| CN105633382A (en) * | 2016-03-16 | 2016-06-01 | 扬州大学 | Preparation method for cobalt oxide/graphene composite negative electrode material of lithium ion battery |
| CN106549153A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of hollow hexagonal shape hydroxy cobalt oxide nano material and preparation method thereof |
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| CN106549153A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of hollow hexagonal shape hydroxy cobalt oxide nano material and preparation method thereof |
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