CN110980699A - Preparation method of lithium ion battery negative electrode material - Google Patents
Preparation method of lithium ion battery negative electrode material Download PDFInfo
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- CN110980699A CN110980699A CN201911194004.7A CN201911194004A CN110980699A CN 110980699 A CN110980699 A CN 110980699A CN 201911194004 A CN201911194004 A CN 201911194004A CN 110980699 A CN110980699 A CN 110980699A
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- lithium ion
- graphene oxide
- ion battery
- deionized water
- negative electrode
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007773 negative electrode material Substances 0.000 title claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 88
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 36
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 34
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 18
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 18
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 18
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000010406 cathode material Substances 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000008367 deionised water Substances 0.000 claims description 48
- 229910021641 deionized water Inorganic materials 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 35
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 24
- 238000003760 magnetic stirring Methods 0.000 claims description 20
- 239000010941 cobalt Substances 0.000 claims description 19
- 229910017052 cobalt Inorganic materials 0.000 claims description 18
- 238000002386 leaching Methods 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 238000005119 centrifugation Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 3
- 239000010405 anode material Substances 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 230000010355 oscillation Effects 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 55
- 239000003755 preservative agent Substances 0.000 description 5
- 230000002335 preservative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
- H01M4/362—Composites
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium ion battery cathode material and a preparation method thereof, concentrated sulfuric acid, sodium nitrate and potassium permanganate are added into natural graphite to carry out strong oxidation reaction, graphene oxide is subjected to proper ultrasonic oscillation treatment, a graphene oxide solution and a cobalt nitrate solution subjected to ultrasonic oscillation treatment are mixed according to a certain proportion and subjected to ultrasonic oscillation treatment, so that metal cobalt atoms are doped and substituted into the graphene, and the cobalt-doped graphene composite material is prepared by heating, centrifuging and drying.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a lithium ion battery cathode material and a preparation method thereof.
Background
Since the commercialization of lithium ion batteries has been completed in the end of the 20 th century, lithium ion batteries have been widely used in the field of power batteries such as electric bicycles, electric tools, power-assisted vehicles, golf carts, model airplanes and mining lamps, portable electronic devices such as mobile phones, notebook computers and cameras, and electric vehicles, because of their advantages such as high energy density, light weight, long service life and no memory.
Although lithium ion batteries have been developed in recent years, they still have a large capacity to improve performance, and how to improve the performance of negative electrode materials is one of the key points, wherein graphene is an ideal negative electrode material for lithium ion batteries because of its special structure, high conductivity and good cycling stability, but because the charge-discharge specific capacity of carbon materials is low, it is unable to meet the requirements of high-capacity lithium batteries, and it is necessary to develop a novel negative electrode material to meet the requirements of high capacity and large-scale commercialization.
Disclosure of Invention
In view of this, the invention aims to design a lithium ion battery negative electrode material and a preparation method thereof, and the lithium ion battery negative electrode material is prepared by using a composite material of metal cobalt and graphene as the lithium ion battery negative electrode material, so that the lithium ion battery negative electrode material has the effects of higher charge and discharge capacity and good cycle stability.
The invention discloses a preparation method of a lithium ion battery cathode material based on the aim, which comprises the following steps:
a. placing natural graphite in a containing bottle, adding concentrated sulfuric acid into the containing bottle under an ice bath condition, simultaneously carrying out magnetic stirring, and carrying out normal-pressure acid leaching reaction after adding the concentrated sulfuric acid;
b. b, adding the reaction product obtained in the step a into deionized water, carrying out magnetic stirring, repeatedly carrying out centrifugal separation and deionized water washing so that the pH value of the supernatant obtained by centrifugation is neutral, collecting the product obtained by centrifugation, and drying at the temperature of 120 ℃ to obtain graphene oxide;
c. b, adding the graphene oxide obtained in the step b into deionized water, and performing ultrasonic dispersion for 30min to obtain a graphene oxide solution;
d. adding cobalt nitrate into deionized water, and performing ultrasonic dispersion for 1h to obtain a cobalt nitrate solution;
e. and d, mixing the graphene oxide solution obtained in the step c with the cobalt nitrate solution obtained in the step d, performing ultrasonic dispersion for 40min to obtain a cobalt acid/graphene oxide solution, heating to 140 ℃, keeping for 10h, centrifuging, and drying to obtain the cobalt-doped graphene composite material for the lithium battery cathode material.
Preferably, in the step a, the reaction time of the atmospheric pressure acid leaching reaction is 4 h.
Preferably, in step a, sodium nitrate and potassium permanganate are added while magnetically stirring.
Preferably, in the step a, the mass ratio of the added natural graphite to the added sodium nitrate to the added potassium permanganate is 1: 0.8: 4.5.
preferably, in the step b, while magnetically stirring, hydrogen peroxide with the concentration of 30% is added.
Preferably, in the step c, the mass ratio of the graphene oxide to the deionized water is 2-8: 50-150.
Preferably, in the step d, the mass ratio of the cobalt nitrate to the deionized water is 2-8: 50-150.
Preferably, the mass ratio of the graphene oxide solution to the cobaltic acid solution is 120-150: 60-90.
The lithium ion battery cathode material is prepared by the preparation method.
Optionally, in the lithium ion battery negative electrode material, the mass ratio of the graphene oxide solution to the cobaltic acid solution is 150: 60-90.
From the above, according to the lithium ion battery negative electrode material and the preparation method thereof designed by the invention, concentrated sulfuric acid, sodium nitrate and potassium permanganate are added into natural graphite to carry out a strong oxidation reaction, oxidized graphene has a large amount of active groups such as carboxyl, hydroxyl and epoxy groups and is good in hydrophilicity, the oxidized graphene is easily dispersed into a uniform single-layer oxidized graphene turbid liquid in an aqueous solution or an organic solution through proper ultrasonic oscillation treatment, the oxidized graphene turbid liquid and the cobalt nitrate solution subjected to the ultrasonic oscillation treatment are mixed according to a certain ratio and subjected to ultrasonic oscillation treatment to enable metal cobalt atoms to be doped and substituted into the graphene, and the cobalt-doped graphene composite material is prepared through heating, centrifuging and drying, and due to the fact that the metal cobalt and lithium ions can carry out a good reversible reaction, the specific volume of the oxide of the metal cobalt as the lithium ion battery negative electrode material can reach 700-1200mAh The specific capacity of the composite material is far higher than that of a graphene negative electrode material, but the defect that the cycle stability is poor when the oxide of the metal cobalt is used as the negative electrode material of the lithium ion battery is that the cobalt-doped graphene composite material is prepared by using the metal cobalt as the doping, so that the problem that the specific capacity of the negative electrode material of the graphene lithium ion battery is not high is solved while the cycle stability is maintained.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to specific embodiments below.
It should be noted that all expressions using "first" and "second" in the embodiments of the present invention are used for distinguishing two entities with the same name but different names or different parameters, and it should be noted that "first" and "second" are merely for convenience of description and should not be construed as limitations of the embodiments of the present invention, which are not described in any more detail in the following embodiments.
A lithium ion battery cathode material and a preparation method thereof are disclosed, natural graphite is placed in a containing bottle, concentrated sulfuric acid is added into the containing bottle under the condition of ice bath, magnetic stirring is carried out simultaneously, after the concentrated sulfuric acid is added, normal-pressure acid leaching reaction is carried out, then a reaction product obtained by the normal-pressure acid leaching is added into deionized water, magnetic stirring is carried out simultaneously, centrifugal separation and deionized water washing are carried out repeatedly so that the PH value of a supernatant obtained by centrifugation is neutral, a product obtained by centrifugation is collected and dried under the condition that the temperature is 120 ℃, graphene oxide is obtained, then the graphene oxide is added into the deionized water, ultrasonic dispersion is carried out for 30min so as to obtain a graphene oxide solution, cobalt nitrate is added into the deionized water, ultrasonic dispersion is carried out for 1h so as to obtain a cobalt nitrate solution, then the graphene oxide solution and the cobalt nitrate solution are mixed, the ultrasonic dispersion is carried out for 40min so as to obtain a cobalt acid/graphene, and (3) heating to 140 ℃, keeping for 10h, centrifuging, and drying to obtain the cobalt-doped graphene composite material for the lithium battery cathode material.
The reaction time for the atmospheric acid leaching reaction was 4 hours in order to make the reaction complete.
In order to further improve the strong oxidation effect of the graphene oxidation reaction, sodium nitrate and potassium permanganate are added while magnetic stirring is carried out.
In order to match each reactant in the graphene oxidation reaction to ensure that the reaction is sufficient and avoid excessive or small amount of the reactant, the mass ratio of the added natural graphite to the added sodium nitrate to the added potassium permanganate is 1: 0.8: 4.5.
in order to further improve the strong oxidation effect of the graphene oxidation reaction, hydrogen peroxide with the concentration of 30% is added while magnetic stirring is carried out.
The prepared solution is diluted, and the mass ratio of the graphene oxide to the deionized water is 2-8: 50-150.
The prepared solution is diluted, and the mass ratio of the cobalt nitrate to the deionized water is 2-8: 50-150.
In order to quantitatively dope to prepare the cobalt-doped graphene composite material, the mass ratio of the graphene oxide solution to the cobaltic acid solution is 120-150: 60-90.
Specifically, in the lithium ion battery negative electrode material and the preparation method thereof provided in embodiment 1 of the present invention, natural graphite is placed in a containing bottle, concentrated sulfuric acid is added into the containing bottle under an ice bath condition, magnetic stirring is performed, and sodium nitrate and potassium permanganate are added simultaneously, wherein a mass ratio of the natural graphite to the sodium nitrate to the potassium permanganate is 1: 0.8: 4.5, covering the bottle mouth of the containing bottle with a preservative film, carrying out normal-pressure acid leaching reaction for 4 hours, then adding a reaction product obtained by normal-pressure acid leaching into deionized water, adding hydrogen peroxide with the concentration of 30%, carrying out magnetic stirring, repeatedly carrying out centrifugal separation and deionized water washing so that the pH value of a supernatant obtained by centrifugation is neutral, collecting a product obtained by centrifugation, drying at the temperature of 120 ℃ to obtain graphene oxide, then adding the graphene oxide into the deionized water, wherein the mass ratio of the graphene oxide to the deionized water is 5:100, carrying out ultrasonic dispersion for 30 minutes to obtain a graphene oxide solution, adding cobalt nitrate into the deionized water, wherein the mass ratio of the cobalt nitrate to the deionized water is 5:100, carrying out ultrasonic dispersion for 1 hour to obtain a cobalt nitrate solution, then mixing the graphene oxide solution and the cobalt nitrate solution, and (3) carrying out ultrasonic dispersion on the graphene oxide solution and the cobalt acid solution at a mass ratio of 120:90 for 40min to obtain a cobalt acid/graphene oxide solution, heating to 140 ℃, keeping for 10h, centrifuging, and drying to obtain the cobalt-doped graphene composite material for the lithium battery cathode material.
Specifically, in the lithium ion battery negative electrode material and the preparation method thereof provided in embodiment 2 of the present invention, natural graphite is placed in a containing bottle, concentrated sulfuric acid is added into the containing bottle under an ice bath condition, magnetic stirring is performed, and sodium nitrate and potassium permanganate are added simultaneously, wherein a mass ratio of the natural graphite to the sodium nitrate to the potassium permanganate is 1: 0.8: 4.5, covering the bottle mouth of the containing bottle with a preservative film, carrying out normal-pressure acid leaching reaction for 4 hours, then adding a reaction product obtained by normal-pressure acid leaching into deionized water, adding hydrogen peroxide with the concentration of 30%, carrying out magnetic stirring, repeatedly carrying out centrifugal separation and deionized water washing so that the pH value of a supernatant obtained by centrifugation is neutral, collecting a product obtained by centrifugation, drying at the temperature of 120 ℃ to obtain graphene oxide, then adding the graphene oxide into the deionized water, wherein the mass ratio of the graphene oxide to the deionized water is 5:100, carrying out ultrasonic dispersion for 30 minutes to obtain a graphene oxide solution, adding cobalt nitrate into the deionized water, wherein the mass ratio of the cobalt nitrate to the deionized water is 5:100, carrying out ultrasonic dispersion for 1 hour to obtain a cobalt nitrate solution, then mixing the graphene oxide solution and the cobalt nitrate solution, and (2) carrying out ultrasonic dispersion on the graphene oxide solution and the cobalt acid solution at a mass ratio of 120:80 for 40min to obtain a cobalt acid/graphene oxide solution, heating to 140 ℃, keeping for 10h, centrifuging, and drying to obtain the cobalt-doped graphene composite material for the lithium battery cathode material.
Specifically, in the lithium ion battery negative electrode material and the preparation method thereof provided in embodiment 3 of the present invention, natural graphite is placed in a containing bottle, concentrated sulfuric acid is added into the containing bottle under an ice bath condition, magnetic stirring is performed, and sodium nitrate and potassium permanganate are added simultaneously, wherein a mass ratio of the natural graphite to the sodium nitrate to the potassium permanganate is 1: 0.8: 4.5, covering the bottle mouth of the containing bottle with a preservative film, carrying out normal-pressure acid leaching reaction for 4 hours, then adding a reaction product obtained by normal-pressure acid leaching into deionized water, adding hydrogen peroxide with the concentration of 30%, carrying out magnetic stirring, repeatedly carrying out centrifugal separation and deionized water washing so that the pH value of a supernatant obtained by centrifugation is neutral, collecting a product obtained by centrifugation, drying at the temperature of 120 ℃ to obtain graphene oxide, then adding the graphene oxide into the deionized water, wherein the mass ratio of the graphene oxide to the deionized water is 5:100, carrying out ultrasonic dispersion for 30 minutes to obtain a graphene oxide solution, adding cobalt nitrate into the deionized water, wherein the mass ratio of the cobalt nitrate to the deionized water is 5:100, carrying out ultrasonic dispersion for 1 hour to obtain a cobalt nitrate solution, then mixing the graphene oxide solution and the cobalt nitrate solution, and (2) carrying out ultrasonic dispersion on the graphene oxide solution and the cobalt acid solution at a mass ratio of 120:60 for 40min to obtain a cobalt acid/graphene oxide solution, heating to 140 ℃, keeping for 10h, centrifuging, and drying to obtain the cobalt-doped graphene composite material for the lithium battery cathode material.
Specifically, in the lithium ion battery negative electrode material and the preparation method thereof provided in embodiment 4 of the present invention, natural graphite is placed in a containing bottle, concentrated sulfuric acid is added into the containing bottle under an ice bath condition, magnetic stirring is performed, and sodium nitrate and potassium permanganate are added simultaneously, wherein a mass ratio of the natural graphite to the sodium nitrate to the potassium permanganate is 1: 0.8: 4.5, covering the bottle mouth of the containing bottle with a preservative film, carrying out normal-pressure acid leaching reaction for 4 hours, then adding a reaction product obtained by normal-pressure acid leaching into deionized water, adding hydrogen peroxide with the concentration of 30%, carrying out magnetic stirring, repeatedly carrying out centrifugal separation and deionized water washing so that the pH value of a supernatant obtained by centrifugation is neutral, collecting a product obtained by centrifugation, drying at the temperature of 120 ℃ to obtain graphene oxide, then adding the graphene oxide into the deionized water, wherein the mass ratio of the graphene oxide to the deionized water is 5:100, carrying out ultrasonic dispersion for 30 minutes to obtain a graphene oxide solution, adding cobalt nitrate into the deionized water, wherein the mass ratio of the cobalt nitrate to the deionized water is 5:100, carrying out ultrasonic dispersion for 1 hour to obtain a cobalt nitrate solution, then mixing the graphene oxide solution and the cobalt nitrate solution, and (3) carrying out ultrasonic dispersion on the graphene oxide solution and the cobalt acid solution at a mass ratio of 130:60 for 40min to obtain a cobalt acid/graphene oxide solution, heating to 140 ℃, keeping for 10h, centrifuging, and drying to obtain the cobalt-doped graphene composite material for the lithium battery cathode material.
Specifically, in the lithium ion battery negative electrode material and the preparation method thereof provided in embodiment 5 of the present invention, natural graphite is placed in a containing bottle, concentrated sulfuric acid is added into the containing bottle under an ice bath condition, magnetic stirring is performed, and sodium nitrate and potassium permanganate are added simultaneously, wherein a mass ratio of the natural graphite to the sodium nitrate to the potassium permanganate is 1: 0.8: 4.5, covering the bottle mouth of the containing bottle with a preservative film, carrying out normal-pressure acid leaching reaction for 4 hours, then adding a reaction product obtained by normal-pressure acid leaching into deionized water, adding hydrogen peroxide with the concentration of 30%, carrying out magnetic stirring, repeatedly carrying out centrifugal separation and deionized water washing so that the pH value of a supernatant obtained by centrifugation is neutral, collecting a product obtained by centrifugation, drying at the temperature of 120 ℃ to obtain graphene oxide, then adding the graphene oxide into the deionized water, wherein the mass ratio of the graphene oxide to the deionized water is 5:100, carrying out ultrasonic dispersion for 30 minutes to obtain a graphene oxide solution, adding cobalt nitrate into the deionized water, wherein the mass ratio of the cobalt nitrate to the deionized water is 5:100, carrying out ultrasonic dispersion for 1 hour to obtain a cobalt nitrate solution, then mixing the graphene oxide solution and the cobalt nitrate solution, and (2) carrying out ultrasonic dispersion on the graphene oxide solution and the cobalt acid solution at a mass ratio of 150:60 for 40min to obtain a cobalt acid/graphene oxide solution, heating to 140 ℃, keeping for 10h, centrifuging, and drying to obtain the cobalt-doped graphene composite material for the lithium battery cathode material.
The cobalt-doped graphene composite material prepared in the examples 1-5 is used as a lithium battery negative electrode material, the prepared lithium ion battery is subjected to charge and discharge tests, the first discharge capacity and the discharge capacity after 50 cycles are tested and evaluated, and the test results are shown in table 1.
TABLE 1 Charge and discharge test results for lithium batteries
From the data, it can be seen that, in the cobalt-doped graphene composite material according to the embodiment of the present invention, as the cobalt doping amount is gradually increased, the discharge capacity of the cobalt-doped graphene composite material as a negative electrode material of a lithium battery is facilitated.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the contemplation of the invention, also combinations between technical features in the above embodiments or in different embodiments are possible, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A preparation method of a lithium ion battery cathode material is characterized by comprising the following steps:
a. placing natural graphite in a containing bottle, adding concentrated sulfuric acid into the containing bottle under an ice bath condition, simultaneously carrying out magnetic stirring, and carrying out normal-pressure acid leaching reaction after adding the concentrated sulfuric acid;
b. b, adding the reaction product obtained in the step a into deionized water, carrying out magnetic stirring, repeatedly carrying out centrifugal separation and deionized water washing so that the pH value of the supernatant obtained by centrifugation is neutral, collecting the product obtained by centrifugation, and drying at the temperature of 120 ℃ to obtain graphene oxide;
c. b, adding the graphene oxide obtained in the step b into deionized water, and performing ultrasonic dispersion for 30min to obtain a graphene oxide solution;
d. adding cobalt nitrate into deionized water, and performing ultrasonic dispersion for 1h to obtain a cobalt nitrate solution;
e. and d, mixing the graphene oxide solution obtained in the step c and the cobalt nitrate solution obtained in the step d, performing ultrasonic dispersion for 40min to obtain a cobalt acid/graphene oxide solution, heating to 140 ℃, keeping for 10h, centrifuging, and drying to obtain the cobalt-doped graphene composite material for the lithium battery cathode material.
2. The method for preparing the negative electrode material of the lithium ion battery according to claim 1, wherein the reaction time of the atmospheric pressure acid leaching reaction in the step a is 4 h.
3. The method for preparing the negative electrode material of the lithium ion battery according to claim 1, wherein in the step a, sodium nitrate and potassium permanganate are added while magnetic stirring is carried out.
4. The preparation method of the negative electrode material of the lithium ion battery according to claim 3, wherein in the step a, the mass ratio of the added natural graphite to the added sodium nitrate to the added potassium permanganate is 1: 0.8: 4.5.
5. the preparation method of the lithium ion battery anode material according to claim 1, wherein in the step b, hydrogen peroxide with a concentration of 30% is added while magnetic stirring is carried out.
6. The preparation method of the negative electrode material of the lithium ion battery according to claim 1, wherein in the step c, the mass ratio of the graphene oxide to the deionized water is 2-8: 50-150.
7. The preparation method of the lithium ion battery anode material according to claim 1, wherein in the step d, the mass ratio of the cobalt nitrate to the deionized water is 2-8: 50-150.
8. The method for preparing the negative electrode material of the lithium ion battery as claimed in claim 1, wherein the mass ratio of the graphene oxide solution to the cobaltic acid solution is 120: 150-90.
9. A lithium ion battery negative electrode material is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The lithium ion battery negative electrode material as claimed in claim 9, wherein the mass ratio of the graphene oxide solution to the cobaltic acid solution is 120-150: 60-90.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112103499A (en) * | 2020-09-22 | 2020-12-18 | 黄秉润 | Graphene-based negative electrode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108615612A (en) * | 2018-05-04 | 2018-10-02 | 上海应用技术大学 | A kind of flower-shaped cobaltosic oxide-graphene composite material and preparation method thereof |
| CN110429255A (en) * | 2019-07-31 | 2019-11-08 | 蚌埠学院 | Cobalt oxide/phosphorus doping graphene composite material preparation method and application |
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| CN108615612A (en) * | 2018-05-04 | 2018-10-02 | 上海应用技术大学 | A kind of flower-shaped cobaltosic oxide-graphene composite material and preparation method thereof |
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| CN112103499A (en) * | 2020-09-22 | 2020-12-18 | 黄秉润 | Graphene-based negative electrode material and preparation method thereof |
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