CN107910515B - Fe capable of being used for lithium ion battery cathode3O4Preparation method of/nitrogen-doped graphene material - Google Patents
Fe capable of being used for lithium ion battery cathode3O4Preparation method of/nitrogen-doped graphene material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 34
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 150000002505 iron Chemical class 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 230000007935 neutral effect Effects 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 16
- 229920001690 polydopamine Polymers 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052744 lithium Inorganic materials 0.000 abstract description 14
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- 239000007773 negative electrode material Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- -1 graphene compound Chemical class 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 14
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 9
- 239000007983 Tris buffer Substances 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 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
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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Abstract
The invention belongs to the technical field of material preparation, and discloses Fe capable of being used for a lithium ion battery cathode3O4A preparation method of a nitrogen-doped graphene material. Two-dimensional graphene oxide is used as a raw material, and dopamine hydrochloride is polymerized in situ under an alkaline condition to compound graphene oxide, so that the graphene compound substrate rich in electronegative groups is obtained. Then dispersing the graphene-based compound into deionized water, adding an iron salt precursor, dropwise adding alkali liquor to adjust the pH, and controlling the alkali liquor dropwise adding rate and the subsequent high-temperature treatment process conditions to realize Fe3O4The nanoparticles are uniformly loaded on the surface of the nitrogen-doped graphene. The raw materials used in the invention are rich, and the preparation method has strong controllability. The preparation method can better control Fe3O4Growing the nano particles; obtained Fe3O4Uniformly dispersing the nano particles on the surface of the graphene; with the Fe thus prepared3O4The/nitrogen-doped graphene material is used as a lithium battery negative electrode material and has excellent lithium battery performance.
Description
Technical Field
The invention belongs to the technical field of material preparation, and relates to Fe capable of being used for a lithium ion battery cathode3O4A nitrogen-doped graphene material and a preparation method thereof.
Background
The cathode material is used as an important component of the lithium ion battery, and directly influences the energy density, the cycle life and the safety performance of the battery. At present, the cathode of the lithium ion battery is mature carbon-based material, but the carbon-based material has low theoretical capacity and poor rate performance, and the requirement of the high-performance lithium ion battery is difficult to meet. Thus Fe with very high theoretical specific capacity3O4While inorganic materials have received much attention from researchers, Fe3O4The material has poor conductivity, and meanwhile, the volume effect is obvious during charging and discharging, so that the active substances are easy to fall off, and further, the electrode is damaged. Thus Fe can be transformed3O4The material is compounded with the carbon-based material to achieve the purpose of improving the lithium battery performance. The graphene has super-strong conductivity and a unique structure, can promote rapid mass transfer when applied to a lithium battery, shortens a lithium ion diffusion path, and can improve the electrochemical performance of the lithium ion battery. Shenyang metals Li Feng researchers et al (Li F, et al, Chemsisty of Materials,2010, 22: 5306) successfully prepared graphene composite Fe with graphene as a carrier3O4The cycle period and the first coulombic efficiency of the material are obviously improved by introducing the graphene. Generally, the graphene-based iron-based oxide composite material is prepared by mixing graphene and an iron-based precursor, and then carrying out hydrothermal and high-temperature treatment, but the controllability of the method is poor, the general size uniformity of the formed particles is poor, the interaction between the particles and a graphene carrier is weak, and the particles are easy to fall off in the charging and discharging process, so that the improvement on the lithium battery performance is limited.
Disclosure of Invention
The invention provides Fe for a lithium ion battery cathode3O4The preparation method of the nitrogen-doped graphene material improves the controllability of preparation operation, so that the nano particles are uniformly dispersed on the surface of the graphene, and excellent lithium battery performance is obtained.
The invention is realized by the following technical scheme. Two-dimensional graphene oxide graphene is used as a substrate, in an alkaline environment, dopamine is polymerized on the surface of the substrate to form a graphene compound substrate rich in electronegative groups, and the material is easy to combine with positively charged metal ions. Then dispersing the graphene-based compound into a certain amount of deionized water, adding a certain amount of ferric salt precursor, dropwise adding alkali liquor at a certain speed to adjust the pH of the solution, and controlling the dropwise adding speed of the alkali liquor and the conditions of a high-temperature treatment process to obtain Fe3O4Fe with uniformly dispersed nanoparticles3O4The nitrogen-doped graphene composite material.
The technical scheme of the invention is as follows:
fe capable of being used for lithium ion battery cathode3O4The preparation method of the nitrogen-doped graphene material comprises the following steps:
(a) preparing 0.5-2 mg/mL graphene oxide solution, and adding dopamine hydrochloride, wherein the mass ratio of the graphene oxide to the dopamine hydrochloride is 1: 0.5-1: 5; then adding Tris (hydroxymethyl) aminomethane (Tris) to adjust the pH value of the solution to 8.5, reacting at room temperature for 12-24 hours, carrying out suction filtration, washing with deionized water to be neutral, and drying at 80 ℃ for 12 hours to obtain polydopamine/graphene;
(b) uniformly dispersing polydopamine/graphene prepared in the step (a) in an aqueous solution, adding iron salt according to the mass ratio of graphene oxide to a used iron salt precursor of 1: 3-1: 10, dropwise adding 1mol/L NaOH solution into the solution at the speed of 250-1000 mu L/min through an injection pump to adjust the pH value of the whole solution to 9, reacting at room temperature-50 ℃ for 12-24 h, performing suction filtration, washing with deionized water to be neutral, and drying at 80 ℃ for 12h to obtain an iron hydroxide/polydopamine/graphene composite material;
(c) taking the ferric hydroxide/polydopamine/graphene composite material prepared in the step (b) as a raw material, heating to 400-500 ℃ at a heating rate of 1-5 ℃ under the protection of inert gas, and reacting for 1-3 h to obtain Fe3O4A/nitrogen-doped graphene material.
The inert gas is nitrogen, argon or helium.
The ferric salt is ferric nitrate, ferric chloride or ferric sulfate.
The invention has the beneficial effects that: 1) the raw materials are rich, and the preparation method has strong controllability. The preparation method can better control Fe3O4Growing the nano particles; 2) obtained Fe3O4Uniformly dispersing the nano particles on the surface of the graphene; 3) with the Fe thus prepared3O4The/nitrogen-doped graphene material is used as a lithium battery negative electrode material and has excellent lithium battery performance.
Drawings
Fig. 1 is a transmission photograph of example 1.
FIG. 2 is a transmission photograph of example 3.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
Dispersing 50mg of graphene oxide in 50ml of deionized water, adding 50mg of dopamine hydrochloride, stirring for 30min, adding a certain amount of Tris to adjust the pH value of the solution to 8.5, then reacting for 24 hours at room temperature, after the reaction is finished, performing suction filtration on the product to be neutral by using deionized water, and drying for 12 hours at 80 ℃. The polydopamine/graphene complex obtained was redispersed in 50mL of deionized water. Then 400mg of ferric nitrate is added into the solution, after stirring for 30min, 1mol/L NaOH solution is added into the solution at the rate of 250 mu L/min by using a syringe pump to adjust the pH value to 9, the solution is reacted for 24h under the condition of room temperature and is washed to be neutral by deionized water, and the solution is dried for 12h at the temperature of 80 ℃.
Grinding the obtained material, putting the ground material into a tube furnace, heating the ground material to 500 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, and then keeping the temperature for 2 hours to obtain Fe3O4The nitrogen-doped graphene composite material. The obtained nano particles are uniformly distributed on the surface of the nitrogen-doped graphene, and the particle size is about 10 nm. The specific capacity of the lithium battery performance measured as the lithium battery negative electrode material at the charge-discharge rate of 100mA/g is 891.2 mAh/g; the specific discharge capacities of the materials are respectively 200mA/g, 500mA/g, 1A/g, 2A/g and 5A/g under the charge-discharge rates: 798.7, 720.0, 621.3, 511.8 and 450.7 mAh/g. In 2Ag-1The specific charge-discharge capacity of 492.1mAh/g is still remained after repeated charge-discharge for 200 weeks.
Example 2
Dispersing 100mg of graphene oxide in 50ml of deionized water, adding 100mg of dopamine hydrochloride, stirring for 30min, adding a certain amount of Tris to adjust the pH value of the solution to 8.5, then reacting for 12 hours at room temperature, after the reaction is finished, performing suction filtration on the product to be neutral by using deionized water, and drying for 12 hours at 80 ℃. Re-dispersing the polydopamine/graphene composite into 50mL of deionized water, then adding 1000mg of ferric nitrate into the solution, stirring for 30min, adding 1mol/L of NaOH solution at the speed of 500 mu L/min by using a syringe pump to adjust the pH value to 9, reacting for 12h at the temperature of 50 ℃, washing to be neutral by using deionized water, and drying for 12h at the temperature of 80 ℃.
Grinding the obtained material, putting the ground material into a tube furnace, heating the ground material to 500 ℃ at the speed of 2 ℃/min under the argon atmosphere, and then keeping the temperature for 2 hours to obtain Fe3O4The nitrogen-doped graphene composite material.
Example 3
Dispersing 100mg of graphene oxide in 50ml of deionized water, adding 100mg of dopamine hydrochloride, stirring for 30min, adding a certain amount of Tris to adjust the pH value of the solution to 8.5, then reacting for 24 hours at room temperature, after the reaction is finished, performing suction filtration on the product to be neutral by using deionized water, and drying for 12 hours at 80 ℃. Re-dispersing the polydopamine/graphene composite into 50mL of deionized water, then adding 200mg of ferric chloride into the solution, stirring for 30min, adding 1mol/L of NaOH solution at the speed of 1000 mu L/min by using a syringe pump to adjust the pH value to 9, reacting at 40 ℃ for 12h, washing with deionized water to be neutral, and drying at 80 ℃ for 12 h.
Grinding the obtained material, putting the ground material into a tube furnace, heating the ground material to 400 ℃ at the speed of 5 ℃/min under argon atmosphere, and then keeping the temperature for 1h to obtain Fe3O4The nitrogen-doped graphene composite material. The obtained nano particles are uniformly distributed on the surface of the nitrogen-doped graphene, and the particle size is about 20 nm. The specific capacity of the lithium battery performance measured as the lithium battery negative electrode material at the charge-discharge rate of 100mA/g is 580.7 mAh/g; charging at 200mA/g, 500mA/g, 1A/g, 2A/g and 5A/gThe specific discharge capacities at the discharge rate were respectively: 512.5, 414.9, 348.9, 281.7 and 202.5 mAh/g.
Example 4
Dispersing 25mg of graphene oxide in 50ml of deionized water, adding 500mg of dopamine hydrochloride, stirring for 30min, adding a certain amount of Tris to adjust the pH value of the solution to 8.5, then reacting for 24 hours at room temperature, after the reaction is finished, performing suction filtration on the product to be neutral by using deionized water, and drying for 12 hours at 80 ℃. The polydopamine/graphene complexes were redispersed in 50mL of deionized water. Then 75mg of ferric chloride is added into the solution, after stirring for 30min, 1mol/L NaOH solution is added into the solution at the speed of 1000 mu L/min by using a syringe pump to adjust the pH value to 9, the solution is reacted for 24h at room temperature and is washed to be neutral by deionized water, and the solution is dried for 12h at the temperature of 80 ℃.
Grinding the obtained material, putting the ground material into a tube furnace, heating the ground material to 400 ℃ at the speed of 1 ℃/min under the argon atmosphere, and then keeping the temperature for 1h to obtain Fe3O4The nitrogen-doped graphene composite material.
Example 5
Dispersing 50mg of graphene oxide in 50ml of deionized water, adding 100mg of dopamine hydrochloride, stirring for 30min, adding a certain amount of Tris to adjust the pH value of the solution to 8.5, then reacting for 12 hours at room temperature, after the reaction is finished, performing suction filtration on the product to be neutral by using deionized water, and drying for 12 hours at 80 ℃. The polydopamine/graphene complexes were redispersed in 50mL of deionized water. Then, 500mg of ferric sulfate is added into the solution, after stirring for 30min, 1mol/L NaOH solution is added at the rate of 500 mu L/min by using a syringe pump to adjust the pH value to 9, the mixture is reacted for 24h at room temperature and is washed to be neutral by deionized water, and the mixture is dried for 12h at 80 ℃.
Grinding the obtained material, placing the ground material into a tube furnace, heating to 400 ℃ at the speed of 2 ℃/min in the atmosphere of helium, and then keeping the temperature for 3 hours to obtain Fe3O4The nitrogen-doped graphene composite material.
Example 6
Dispersing 50mg of graphene oxide in 50ml of deionized water, adding 50mg of dopamine hydrochloride, stirring for 30min, adding a certain amount of Tris to adjust the pH value of the solution to 8.5, then reacting for 24 hours at room temperature, after the reaction is finished, performing suction filtration on the product to be neutral by using deionized water, and drying for 12 hours at 80 ℃. The polydopamine/graphene complexes were redispersed in 50mL of deionized water. Then 150mg of ferric nitrate is added into the solution, after stirring for 30min, 1mol/L NaOH solution is added into the solution at the rate of 250 mu L/min by using a syringe pump to adjust the pH value to 9, the solution is reacted for 24h at room temperature and is washed to be neutral by deionized water, and the solution is dried for 12h at the temperature of 80 ℃.
Grinding the obtained material, putting the ground material into a tube furnace, heating the ground material to 500 ℃ at the speed of 3 ℃/min in the argon atmosphere, and then keeping the temperature for 2 hours to obtain Fe3O4The nitrogen-doped graphene composite material.
Example 7
Dispersing 50mg of graphene oxide in 50ml of deionized water, adding 150mg of dopamine hydrochloride, stirring for 30min, adding a certain amount of Tris to adjust the pH value of the solution to 8.5, then reacting for 24 hours at room temperature, after the reaction is finished, performing suction filtration on the product to be neutral by using deionized water, and drying for 12 hours at 80 ℃. The polydopamine/graphene complexes were redispersed in 50mL of deionized water. 300mg of ferric nitrate is added into the solution, after stirring for 30min, 1mol/L of NaOH solution is added into the solution at the speed of 500 mu L/min by using a syringe pump to adjust the pH value to 9, the solution is reacted for 24h at room temperature and is washed to be neutral by deionized water, and the solution is dried for 12h at the temperature of 80 ℃.
Grinding the obtained material, putting the ground material into a tube furnace, heating the ground material to 500 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, and then keeping the temperature for 2 hours to obtain Fe3O4The nitrogen-doped graphene composite material. The specific capacity of the lithium battery performance measured as the lithium battery negative electrode material at the charge-discharge rate of 100mA/g is 795.8 mAh/g; the specific discharge capacities at the charge and discharge rates of 200mA/g, 500mA/g, 1A/g, 2A/g and 5A/g are respectively as follows: 650.2, 578.5, 490.9, 422.3 and 345.4 mAh/g.
Claims (2)
1. Fe capable of being used for lithium ion battery cathode3O4The preparation method of the/nitrogen-doped graphene material is characterized by comprising the following steps:
(a) preparing 0.5-2 mg/mL graphene oxide solution, and adding dopamine hydrochloride, wherein the mass ratio of the graphene oxide to the dopamine hydrochloride is 1: 0.5-1: 5; adding trihydroxymethyl aminomethane to adjust the pH value of the solution to 8.5, reacting for 12-24 hours at room temperature, performing suction filtration, washing with deionized water to be neutral, and drying at 80 ℃ for 12 hours to obtain polydopamine/graphene;
(b) uniformly dispersing polydopamine/graphene prepared in the step (a) in an aqueous solution, adding iron salt according to the mass ratio of graphene oxide to a used iron salt precursor of 1: 3-1: 10, dropwise adding 1mol/L NaOH solution into the solution at the speed of 250-1000 mu L/min through an injection pump to adjust the pH value of the whole solution to 9, reacting at room temperature-50 ℃ for 12-24 h, performing suction filtration, washing with deionized water to be neutral, and drying at 80 ℃ for 12h to obtain an iron hydroxide/polydopamine/graphene composite material; the ferric salt is ferric nitrate, ferric chloride or ferric sulfate;
(c) taking the ferric hydroxide/polydopamine/graphene composite material prepared in the step (b) as a raw material, heating to 400-500 ℃ at a heating rate of 1-5 ℃/min under the protection of inert gas or nitrogen, and reacting for 1-3 h to obtain Fe3O4A/nitrogen-doped graphene material.
2. The method of claim 1, wherein the inert gas is argon or helium.
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| CN109461599B (en) * | 2018-09-29 | 2020-10-02 | 四川大学 | One-step high-temperature reaction preparation of N-graphene/Fe3O4Method for compounding electrode material |
| CN111252753A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Three-dimensional ordered porous nitrogen-doped graphene and preparation method and application thereof |
| CN109728290A (en) * | 2019-01-25 | 2019-05-07 | 安徽益佳通电池有限公司 | A kind of preparation method and applications of transition metal oxide/graphitized intermediate-phase carbosphere composite material |
| CN109741964A (en) * | 2019-02-18 | 2019-05-10 | 南阳理工学院 | Iron oxide-poly-dopamine-graphene composite material, preparation method and application |
| CN112768678B (en) * | 2019-11-05 | 2024-09-17 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
| CN111403701B (en) * | 2020-03-09 | 2022-07-26 | 南京邮电大学 | Preparation method of iron-based compound composite nitrogen-doped graphene sodium ion negative electrode battery material |
| CN111863462A (en) * | 2020-07-10 | 2020-10-30 | 大连理工大学 | Ferroferric oxide/nitrogen-doped hollow carbon sphere composite material for supercapacitor and preparation method thereof |
| CN113362985A (en) * | 2021-06-30 | 2021-09-07 | 深圳市正蓝实业有限公司 | Nano rare earth thick film electronic paste and preparation method thereof |
| CN113479871B (en) * | 2021-07-30 | 2023-03-28 | 绍兴文理学院 | Preparation method of in-situ self-growth-based ultra-small metal oxide nanoparticle modified graphene |
| CN114068896A (en) * | 2021-11-01 | 2022-02-18 | 广东佳纳能源科技有限公司 | Composite material and preparation method thereof |
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