CN115676904A - Preparation method of manganese-cobalt-oxygen/carbon negative electrode material with high specific surface area, product and application thereof - Google Patents
Preparation method of manganese-cobalt-oxygen/carbon negative electrode material with high specific surface area, product and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- WSHADMOVDWUXEY-UHFFFAOYSA-N manganese oxocobalt Chemical compound [Co]=O.[Mn] WSHADMOVDWUXEY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000000047 product Substances 0.000 claims abstract description 24
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 239000011541 reaction mixture Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- 239000010406 cathode material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 85
- 239000011259 mixed solution Substances 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- BHVPEUGTPDJECS-UHFFFAOYSA-L manganese(2+);diformate Chemical compound [Mn+2].[O-]C=O.[O-]C=O BHVPEUGTPDJECS-UHFFFAOYSA-L 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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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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Abstract
A preparation method of a manganese cobalt oxygen/carbon negative electrode material with a high specific surface area comprises the steps of dissolving soluble manganese salt in an oleylamine solution, stirring, introducing argon, heating and dissolving to obtain A; injecting organic alcohol into the A, stirring and heating; the reaction mixture is kept at the temperature and naturally cooled to room temperature; dripping the obtained solution into liquid alkane, and centrifugally drying to obtain manganese dioxide/carbon; dissolving cobalt salt, manganese dioxide/carbon and nitric acid in deionized water, and stirring to obtain a uniform and clear precursor solution; adding the precursor solution into a sodium hydroxide alkali solution, and moving to a hydrothermal kettle for hydrothermal reaction; and centrifuging the product after reaction, and washing the precipitate obtained after centrifugation for multiple times to obtain the manganese-cobalt-oxygen/carbon cathode material. The invention provides a preparation method of a manganese-cobalt-oxygen/carbon negative electrode material with a high specific surface area, wherein the high specific surface area can be more contacted with an electrolyte, and the electrochemical performance of the material is improved. The preparation process is relatively simple and easy to operate.
Description
Technical Field
The invention relates to a preparation method of a lithium battery negative electrode material, in particular to a preparation method of a manganese-cobalt-oxygen/carbon negative electrode material with a high specific surface area, and a product and application thereof.
Background
With the progress of technology, lithium ion batteries are widely applied to the fields of electric automobiles, aerospace, biomedicine and the like, so that the research and development of lithium ion batteries for power and related materials have great significance. For power lithium ion batteries, the key is to increase the power density and energy density, and the improvement of the power density and energy density is fundamentally the improvement of electrode materials, particularly negative electrode materials. .
Since the early 90 s of the last century, the japanese scientists developed carbon materials with layered structures, which were the first materials studied by people and applied to the commercialization of lithium ion batteries, and still remain one of the major points of attention and research, but carbon negative electrode materials have some defects: when the battery is formed, the electrolyte solution reacts with the electrolyte solution to form an SEI film, so that the electrolyte solution is consumed and the first coulombic efficiency is low; when the battery is overcharged, metal lithium may be precipitated on the surface of the carbon electrode to form lithium dendrite to cause short circuit, so that the temperature is increased and the battery explodes; in addition, the diffusion coefficient of lithium ions in the carbon material is small, so that the battery cannot realize large-current charging and discharging, and the application range of the lithium ion battery is limited.
Mn 2 CoO 4 The lithium ion battery cathode material is a spinel-structured composite oxide, is a widely applied magnetic material, is commonly used as a fuel battery material, can be used as a lithium ion battery cathode material at present, and has higher Li & lt + & gt storage capacity through conversion and alloying reactions. The material is considered to be a promising lithium ion negative electrode material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a manganese-cobalt-oxygen/carbon negative electrode material with a high specific surface area.
Still another object of the present invention is to: there is provided a product obtained by the above process.
Yet another object of the present invention is to: provides an application of the product.
The invention provides a preparation method of a manganese-cobalt-oxygen/carbon negative electrode material with a high specific surface area, wherein the high specific surface area can be more in contact with an electrolyte, and the electrochemical performance of the material is improved.
The purpose of the invention is realized by the following scheme: a preparation method of a manganese-cobalt-oxygen/carbon negative electrode material with a high specific surface area comprises the following specific steps:
(1) Putting soluble manganese salt into an oil amine solution, magnetically stirring for 1-2 hours until the solution is uniform, then introducing argon into the solution for 20-30 minutes, gradually heating the solution to 120-150 ℃, and completely dissolving the manganese salt to obtain a transparent solution; obtaining a solution A;
(2) Injecting 1-1.5 mL of organic alcohol into the solution A, magnetically stirring for 20-60 min under the temperature condition, then heating to 220-250 ℃, keeping the reaction mixture at the temperature for 20-30 min, and then naturally cooling to room temperature;
(3) Dropwise adding the solution obtained in the step (2) into liquid alkane, centrifugally separating precipitates, and drying the obtained product in a vacuum oven at 60-80 ℃ to obtain manganese dioxide/carbon;
(4) Dissolving cobalt salt, manganese dioxide/carbon and 1mL nitric acid in deionized water, and stirring to obtain a uniform and clear precursor solution; adding the mixed solution into 15 mL sodium hydroxide alkali solution, moving the mixed solution into a 25 mL hydrothermal kettle, and carrying out hydrothermal reaction in an oven at 180-200 ℃ for 1-3 h; and centrifuging the product after reaction, washing the precipitate obtained after centrifugation for many times by using deionized water and absolute ethyl alcohol, and grinding by using an agate mortar to obtain the manganese-cobalt-oxygen/carbon negative electrode material.
The manganese salt is one or the combination of manganese acetate, manganese nitrate or manganese formate.
The organic alcohol is one or the combination of n-butanol, n-heptanol or ethyl pentanol.
The liquid alkane is one or the combination of pentane, hexane and tert-butane.
The soluble cobalt salt is one or the combination of cobalt acetate, cobalt nitrate or cobalt formate.
A manganese-cobalt-oxygen/carbon negative electrode material with a high specific surface area is prepared by any one of the methods.
An application of a manganese cobalt oxygen/carbon negative electrode material with a high specific surface area in a negative electrode material of a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a preparation method of a manganese-cobalt-oxygen/carbon negative electrode material with a high specific surface area, wherein the high specific surface area can be more contacted with an electrolyte, and the electrochemical performance of the material is improved. The preparation process is relatively simple and easy to operate.
Drawings
Fig. 1 is a graph of rate capability of a manganese cobalt oxygen/carbon anode material of example 1.
Detailed Description
The present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to these examples.
Example 1
A manganese-cobalt-oxygen/carbon negative electrode material with a high specific surface area is prepared by the following steps:
(1) Dissolving soluble manganese acetate in oleylamine solution, magnetically stirring for 1h until the solution is uniform, introducing argon gas into the solution for 20min, gradually heating the solution to 120 ℃, and completely dissolving the manganese acetate to obtain a transparent solution; obtaining a solution A;
(2) Injecting 1mL of n-butanol into the solution A obtained in the step (1), magnetically stirring for 30min, heating to 220 ℃, keeping the temperature of the obtained reaction mixture for 30min, and naturally cooling to room temperature to obtain a mixed solution;
(3) Dripping the mixed solution obtained in the step (2) into liquid pentane, centrifugally separating precipitates, and drying the obtained product in a vacuum oven at 60 ℃ to obtain manganese dioxide/carbon;
(4) Dissolving cobalt acetate, manganese dioxide/carbon and 1mL nitric acid in deionized water, and stirring to obtain a uniform and clear precursor solution; adding the precursor solution into 15 mL sodium hydroxide alkali solution, moving the solution to a 25 mL hydrothermal kettle, and carrying out hydrothermal reaction in an oven at 200 ℃ for 1h; and centrifuging the product after reaction, washing the obtained precipitate with deionized water and absolute ethyl alcohol, and grinding with an agate mortar to obtain the manganese-cobalt-oxygen/carbon negative electrode material.
The specific surface area of the manganese-cobalt-oxygen/carbon anode material is 36.8 m 2 /g。
Fig. 1 is a graph of rate capability of a manganese cobalt oxygen/carbon anode material. When the current density is 100 mA/g, the 5-time average specific discharge capacity is 1665.6 mAh/g; when the current density is 400 mA/g, the 5-time average specific discharge capacity is 1482.2 mAh/g; when the current density is 800 mA/g, the 5-time average specific discharge capacity is 989.6 mAh/g; when the current density is 1000 mA/g, the 5-time average specific discharge capacity is 798.4 mAh/g; when the current density is returned to 100 mA/g, the 5-time average specific discharge capacity is 1561.4 mAh/g. When the capacity returns to 100 mA/g after different multiplying powers, the capacity retention rate is 93.7 percent.
Example 2
A manganese-cobalt-oxygen/carbon negative electrode material with a high specific surface area is prepared by the following steps:
(1) Dissolving soluble manganese nitrate in oleylamine solution, magnetically stirring for 2h until the solution is uniform, introducing argon into the solution for 20min, gradually heating the solution to 150 ℃, and completely dissolving the manganese nitrate to obtain a transparent solution; obtaining a solution A;
(2) Injecting 1.5 mL isoamyl alcohol into the solution A obtained in the step (1), magnetically stirring for 20min, heating to 250 ℃, keeping the obtained reaction mixture at the temperature for 20min, and naturally cooling to room temperature to obtain a mixed solution;
(3) Dripping the mixed solution obtained in the step (2) into liquid hexane, centrifugally separating precipitates, and drying the obtained product in a vacuum oven at the temperature of 80 ℃ to obtain manganese dioxide/carbon;
(4) Dissolving cobalt nitrate, manganese dioxide/carbon and 1mL nitric acid in deionized water, and stirring to obtain a uniform and clear precursor solution; adding the precursor solution into 15 mL sodium hydroxide alkali solution, moving the solution to a 25 mL hydrothermal kettle, and carrying out hydrothermal reaction in an oven at 180 ℃ for 3 hours; and centrifuging the product after reaction, washing the obtained precipitate for multiple times by using deionized water and absolute ethyl alcohol, and grinding by using an agate mortar to obtain the manganese-cobalt-oxygen/carbon negative electrode material.
The specific surface area of the manganese-cobalt-oxygen/carbon anode material is 38.5 m 2 /g。
Example 3
A manganese-cobalt-oxygen/carbon negative electrode material with a high specific surface area is prepared by the following steps:
(1) Dissolving soluble manganese formate in oleylamine solution, magnetically stirring for 2h to be uniform, introducing argon into the solution for 20min, gradually heating the solution to 140 ℃, and completely dissolving the manganese formate to obtain transparent solution; obtaining a solution A;
(2) Injecting 1-1.5 mL of n-heptanol into the solution A obtained in the step (1), magnetically stirring for 20min, heating to 250 ℃, keeping the obtained reaction mixture at the temperature for 20min, and naturally cooling to room temperature to obtain a mixed solution;
(3) Dropwise adding the mixed solution obtained in the step (2) into liquid tert-butane, centrifugally separating the obtained precipitate, and drying the obtained product in a vacuum oven at 80 ℃ to obtain manganese dioxide/carbon;
(4) Dissolving cobalt formate, manganese dioxide/carbon and 1mL nitric acid in deionized water, and stirring to obtain a uniform and clear precursor solution; adding the precursor solution into 15 mL sodium hydroxide alkali solution, moving the solution to a 25 mL hydrothermal kettle, and carrying out hydrothermal reaction at 200 ℃ for 1h; and centrifuging the product after reaction, washing the obtained precipitate with deionized water and absolute ethyl alcohol for multiple times, and porphyrizing with an agate mortar to obtain the manganese-cobalt-oxygen/carbon negative electrode material.
The specific surface area of the manganese-cobalt-oxygen/carbon anode material is 35.6 m 2 /g。
Claims (10)
1. A preparation method of a manganese cobalt oxygen/carbon cathode material with high specific surface area is characterized by comprising the following steps,
(1) Dissolving soluble manganese salt in an oil amine solution, magnetically stirring for 1-2 hours until the solution is uniform, then introducing argon into the solution for 20-30 minutes, gradually heating the solution to 120-150 ℃, and completely dissolving the manganese salt to obtain a transparent solution; obtaining a solution A;
(2) Injecting 1-1.5 mL of organic alcohol into the solution A obtained in the step (1), magnetically stirring for 20-60 min, then heating to 220-250 ℃, keeping the temperature of the obtained reaction mixture for 20-30 min, and then naturally cooling to room temperature to obtain a mixed solution;
(3) Dripping the mixed solution obtained in the step (2) into liquid alkane, centrifugally separating precipitates, and drying the obtained product in a vacuum oven at the temperature of 60-80 ℃ to obtain manganese dioxide/carbon;
(4) Dissolving cobalt salt, manganese dioxide/carbon and 1mL nitric acid in deionized water, and stirring to obtain a uniform and clear precursor solution; adding the precursor solution into 15 mL sodium hydroxide alkali solution, moving the solution into a 25 mL hydrothermal kettle, and carrying out hydrothermal reaction for 1 to 3h at 180 to 200 ℃; and centrifuging the product after reaction, washing the obtained precipitate with deionized water and absolute ethyl alcohol, and grinding with an agate mortar to obtain the manganese-cobalt-oxygen/carbon negative electrode material.
2. The method for preparing a high specific surface area manganese cobalt oxygen/carbon negative electrode material according to claim 1, characterized in that the manganese salt is one or a combination of manganese acetate, manganese nitrate or manganese formate.
3. The method for preparing a manganese cobalt oxygen/carbon anode material with high specific surface area as claimed in claim 1, wherein the organic alcohol is one or a combination of n-butanol, n-heptanol or ethylpentanol.
4. The method for preparing the high specific surface area manganese cobalt oxygen/carbon negative electrode material as claimed in claim 1, wherein the liquid alkane is one of pentane, hexane, tert-butane or a combination thereof.
5. The method for preparing a manganese cobalt oxygen/carbon negative electrode material with high specific surface area according to claim 1, wherein the soluble cobalt salt is one or a combination of cobalt acetate, cobalt nitrate and cobalt formate.
6. The preparation method of the high-specific-surface-area manganese-cobalt-oxygen/carbon negative electrode material as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) Dissolving soluble manganese acetate in oleylamine solution, magnetically stirring for 1h until the solution is uniform, introducing argon gas into the solution for 20min, gradually heating the solution to 120 ℃, and completely dissolving the manganese acetate to obtain a transparent solution; obtaining a solution A;
(2) Injecting 1mL of n-butanol into the solution A obtained in the step (1), magnetically stirring for 30min, heating to 220 ℃, keeping the obtained reaction mixture at the temperature for 30min, and naturally cooling to room temperature to obtain a mixed solution;
(3) Dripping the mixed solution obtained in the step (2) into liquid pentane, centrifugally separating precipitates, and drying the obtained product in a vacuum oven at 60 ℃ to obtain manganese dioxide/carbon;
(4) Dissolving cobalt acetate, manganese dioxide/carbon and 1mL nitric acid in deionized water, and stirring to obtain a uniform and clear precursor solution; adding the precursor solution into 15 mL sodium hydroxide alkali solution, moving the solution to a 25 mL hydrothermal kettle, and carrying out hydrothermal reaction in an oven at 200 ℃ for 1h; centrifuging the product after reaction, washing the obtained precipitate with deionized water and absolute ethyl alcohol, and grinding the precipitate with an agate mortar to obtain the product with the specific surface area of 36.8 m 2 Manganese cobalt oxygen/carbon negative electrode material/g.
7. The preparation method of the high-specific-surface-area manganese-cobalt-oxygen/carbon negative electrode material as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) Dissolving soluble manganese nitrate in oleylamine solution, magnetically stirring for 2h until the solution is uniform, introducing argon into the solution for 20min, gradually heating the solution to 150 ℃, and completely dissolving the manganese nitrate to obtain a transparent solution; obtaining a solution A;
(2) Injecting 1.5 mL isoamyl alcohol into the solution A obtained in the step (1), magnetically stirring for 20min, heating to 250 ℃, keeping the obtained reaction mixture at the temperature for 20min, and naturally cooling to room temperature to obtain a mixed solution;
(3) Dripping the mixed solution obtained in the step (2) into liquid hexane, centrifugally separating precipitates, and drying the obtained product in a vacuum oven at the temperature of 80 ℃ to obtain manganese dioxide/carbon;
(4) Dissolving cobalt nitrate, manganese dioxide/carbon and 1mL nitric acid in deionized water, and stirring to obtain a uniform and clear precursor solution; adding the precursor solution into 15 mL sodium hydroxide alkali solution, moving the solution to a 25 mL hydrothermal kettle, and carrying out hydrothermal reaction in an oven at 180 ℃ for 3 hours; centrifuging the product after reaction, washing the obtained precipitate for many times by using deionized water and absolute ethyl alcohol, and grinding the precipitate by using an agate mortar to obtain the product with the specific surface area of 38.5 m 2 Manganese cobalt oxygen/carbon negative electrode material/g.
8. The preparation method of the high-specific-surface-area manganese-cobalt-oxygen/carbon negative electrode material as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
(1) Dissolving soluble manganese formate in oleylamine solution, magnetically stirring for 2h to be uniform, introducing argon into the solution for 20min, gradually heating the solution to 140 ℃, and completely dissolving the manganese formate to obtain transparent solution; obtaining a solution A;
(2) Injecting 1 to 1.5 mL of n-heptanol into the solution A obtained in the step (1), magnetically stirring for 20min, heating to 250 ℃, keeping the temperature of the obtained reaction mixture for 20min, and naturally cooling to room temperature to obtain a mixed solution;
(3) Dropwise adding the mixed solution obtained in the step (2) into liquid tert-butane, centrifugally separating the obtained precipitate, and drying the obtained product in a vacuum oven at 80 ℃ to obtain manganese dioxide/carbon;
(4) Dissolving cobalt formate, manganese dioxide/carbon and 1mL nitric acid in deionized water, and stirring to obtain a uniform and clear precursor solution; adding the precursor solution into 15 mL sodium hydroxide alkali solution, moving the solution to a 25 mL hydrothermal kettle, and carrying out hydrothermal reaction at 200 ℃ for 1h; centrifuging the product after reaction, washing the obtained precipitate for many times by using deionized water and absolute ethyl alcohol, and grinding the precipitate by using an agate mortar to obtain the product with the specific surface area of 35.6 m 2 Manganese cobalt oxygen/carbon negative electrode material/g.
9. A high specific surface area manganese cobalt oxygen/carbon negative electrode material prepared by the method of any one of claims 1 to 8.
10. Use of the high specific surface area manganese cobalt oxygen/carbon anode material of claim 9 in a lithium ion battery anode material.
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| CN109422294A (en) * | 2017-09-05 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of preparation method for the cobaltosic oxide nano particle that size is controllable |
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| CN103545122A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | Preparation method for manganese dioxide/carbon composite materials used for super capacitor |
| CN106925220A (en) * | 2017-04-22 | 2017-07-07 | 杨彦成 | A kind of preparation method of manganese dioxide/carbon composite nano tube |
| CN109422294A (en) * | 2017-09-05 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of preparation method for the cobaltosic oxide nano particle that size is controllable |
| CN108598426A (en) * | 2018-04-26 | 2018-09-28 | 吉林大学 | The method for improving its charge/discharge capacity by preparing cobalt acid manganese/N doping carbon/manganese dioxide nucleocapsid |
| CN110165184A (en) * | 2019-05-31 | 2019-08-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Manganese cobalt oxide/porous carbon microsphere negative electrode material preparation method and product and application |
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