CN110707319A - Three-dimensional structured graphene-based iron oxide composite material and preparation and application thereof - Google Patents

Three-dimensional structured graphene-based iron oxide composite material and preparation and application thereof Download PDF

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CN110707319A
CN110707319A CN201910927035.2A CN201910927035A CN110707319A CN 110707319 A CN110707319 A CN 110707319A CN 201910927035 A CN201910927035 A CN 201910927035A CN 110707319 A CN110707319 A CN 110707319A
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graphene
composite material
iron oxide
solution
based iron
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CN110707319B (en
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韩生
马健
黄燕山
常宾
高丽
李原婷
胡晓敏
王露露
刘顺昌
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Shanghai Institute of Technology
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a graphene-based iron oxide composite material with a three-dimensional structure and preparation and application thereof, wherein the preparation method of the composite material comprises the following steps: 1) mixing a potassium ferrocyanide solution with a graphene oxide solution, and then adding water to obtain a mixed solution; 2) adding ferric chloride into the mixed solution, and then carrying out hydrothermal reaction to obtain aerogel; 3) washing and drying the aerogel, and then carbonizing at high temperature; the composite material is used for a lithium ion battery cathode material. Compared with the prior art, the raw materials have designability and low cost, the graphene-based iron oxide composite material is prepared by a high-temperature calcination and carbonization method, the assembly of the three-dimensional structure of graphene and iron oxide can be perfectly fused in a graphene framework in the calcination process, and the method is simple and convenient; the prepared graphene-based iron oxide composite material has high reversible capacity, very good cycle stability and rate capability, and has wide application prospect in the field of rechargeable batteries.

Description

Three-dimensional structured graphene-based iron oxide composite material and preparation and application thereof
Technical Field
The invention belongs to the technical field of material science and electrochemistry, and relates to a graphene-based iron oxide composite material with a three-dimensional structure, and preparation and application thereof.
Background
High performance Lithium Ion Batteries (LIBs) have the characteristics of high power density, high energy density, long cycle life and the like, and are key to the development of large-scale applications such as rapid upgrade of portable electronic equipment, electric vehicles, power grid energy storage and the like. However, the current commercial lithium battery mainly adopts graphite as a negative electrode, has low capacity (372mAh/g) and poor rate performance, and cannot meet the requirement. Therefore, the development of high capacity negative electrode materials such as metal oxides and metal sulfides has been receiving great attention.
The development of negative electrode materials with high capacity, long life and excellent rate performance is a current urgent task in the research of lithium ion batteries. Wherein, Fe is used2O3The metal oxides represented by these have been receiving wide attention because of their large theoretical capacity, large natural abundance, and good environmental friendliness. However, metal oxides as negative electrode materials for lithium ion batteries have some general problems and greatly affect the electrochemical performance of lithium ion batteries. For example, it is poor in conductivity, and is not favorable for sufficient and rapid electrochemistry of Li + insertion/de-insertion reactions in metal oxides. The too large volume expansion and contraction in the electrochemical reaction process leads to the pulverization and aggregation of the metal oxide, the short cycle life, the low utilization rate of the active metal oxide and the like.
Therefore, in order to obtain the desired electrochemical performance, the metal oxide and the entire electrode need to be optimally designed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a graphene-based iron oxide composite material with a three-dimensional structure, and a preparation method and an application thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a graphene-based iron oxide composite material with a three-dimensional structure comprises the following steps:
1) mixing a potassium ferrocyanide solution with a graphene oxide solution, and then adding water to obtain a mixed solution;
2) adding ferric chloride into the mixed solution, and then carrying out hydrothermal reaction to obtain aerogel;
3) and washing and drying the aerogel, and then carbonizing at high temperature to obtain the composite material.
Further, in the step 1), the concentration of the potassium ferrocyanide solution is 0.4-0.6mol/L, and the concentration of the graphene oxide solution is 1.5-2.5 mg/mL. The potassium ferrocyanide solution and the graphene oxide solution are mixed and then added with water, so that the mixed solution can reach a proper concentration ratio and can be well and uniformly dispersed.
Further, in the step 1), the volume ratio of the potassium ferrocyanide solution to the graphene oxide solution is 1 (5-8), and the volume ratio of the water to the graphene oxide solution is (0.8-1.2) to 1.
Further, in step 2), 5 to 10g of ferric chloride is added per 100mL of the mixed solution.
Further, in the step 2), the temperature is 180-220 ℃ and the time is 12-24h in the hydrothermal reaction process.
Further, in step 3), the washing process is as follows: soaking and washing the aerogel in water; the drying is freeze-drying.
Further, in the step 3), the temperature is 250-300 ℃ and the time is 3-4h in the high-temperature carbonization process.
Further, in step 3), the high-temperature carbonization process is performed in an air atmosphere.
The graphene-based iron oxide composite material with the three-dimensional structure is prepared by the method.
The application of the graphene-based iron oxide composite material with the three-dimensional structure is used for the negative electrode material of the lithium ion battery.
Graphene is an excellent two-dimensional conductive material, can be used as a substrate to load metal oxide to improve electron transfer and prevent polymerization, and can be further transformed into an independent three-dimensional (3D) porous structure to promote diffusion of electrons and ions in the whole electrode. Due to the characteristics, the graphene can be used as a main negative electrode material with excellent performance, can also be compounded with an active negative electrode material, can effectively improve the electrochemical performance of the electrode material through a synergistic effect, and has a very wide application prospect in lithium battery electrode materials. On the other hand, the composite material is obtained after three-dimensional assembly is carried out by utilizing the two-dimensional graphene, so that the contact between the composite material and the electrolyte can be greatly improved, and the electrochemical performance of the material can be further improved.
The invention provides graphene-based iron oxide (3 DG/Fe) with a three-dimensional structure2O3) The preparation method of the composite material is characterized in that 3 DG/Prussian Blue (PB) is converted into 3DG/Fe2O3Aerogel, but porous Fe2O3Can be well encapsulated in the graphene skeleton. The layered structure provides a highly interpenetrating porous conductive network of graphene and porous Fe2O3The three-dimensional graphene iron oxide cathode material obtained by the method has the advantages of simple process, mild conditions, low cost and the like. The graphene-based iron oxide composite material with the three-dimensional structure prepared by the invention has excellent electrochemical performance as a lithium ion battery cathode and has the electrochemical performance of 100 mA.g-1The capacity of the battery can reach 800 mAh.g under the charge-discharge current-1At 5A · g-1The lower capacity is 121mAh g-1Excellent rate capability. The method provides good experimental data and theoretical support for the research and application of the graphene-metal oxide material in the electrochemical field, and the establishment of the method for three-dimensional assembly by using the graphene also opens up a new design idea for constructing other novel composite materials based on the high-performance three-dimensional graphene, and has profound significance for the development and practical application expansion of the high-performance lithium ion battery electrode.
According to the invention, when the graphene-based Prussian blue composite material is prepared, a hydrothermal reaction mode is adopted, so that the hydrothermal method is simple to operate, the graphene is reduced more thoroughly by the hydrothermal method, and the effect is better compared with the mode of reducing the graphene by adding a reducing agent. The hydrothermal reaction adopts a one-pot method, the graphene can be condensed into blocks, the centrifugation step can be omitted, and the operation is quick and simple.
Compared with the prior art, the invention has the following characteristics:
1) according to the preparation method, graphene is used as a carbon source, metal oxide of iron is used as an active component to prepare the composite material, the raw materials are designable, the cost is low, the graphene-based iron oxide composite material is prepared by a high-temperature calcination carbonization method, the assembly of a three-dimensional structure of the graphene and the iron oxide can be perfectly fused in a graphene framework in the calcination process, and the method is simple and convenient;
2) the graphene-based iron oxide composite material prepared by the invention has high reversible capacity, very good cycle stability and rate capability, and has wide application prospect in the field of rechargeable batteries.
Drawings
Fig. 1 is an XRD pattern of the three-dimensional graphene-based iron oxide composite prepared in example 1;
fig. 2 is an SEM image of the three-dimensional graphene-based iron oxide composite prepared in example 1;
fig. 3 is a graph showing the cycle performance of the three-dimensional graphene-based iron oxide composite material prepared in example 1 and the iron oxide material prepared in comparative example 1, respectively, as a negative electrode material of a lithium ion battery;
fig. 4 is a graph of rate performance of the three-dimensional graphene-based iron oxide composite material prepared in example 1 and the iron oxide material prepared in comparative example 1, respectively, as a negative electrode material of a lithium ion battery.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
the preparation process of the three-dimensional graphene-based iron oxide composite material comprises the following steps:
firstly, preparing a graphene-based Prussian blue composite material:
(1) dissolving 2.25mL of 0.5M potassium ferrocyanide into 15mL of 2mg/mL graphene oxide solution;
(2) adding 15mL of deionized water into the solution, then adding 2.7g of ferric chloride into the solution, and uniformly stirring the mixture;
(3) pouring the solution into a glass lining of a reaction kettle, carrying out hydrothermal reaction for 12-24 hours at the temperature of 180-220 ℃, and soaking and washing the obtained aerogel in deionized water.
Step two, preparing the three-dimensional graphene-based iron oxide composite material:
(1) and putting the obtained aerogel material into a tubular furnace, carrying out high-temperature carbonization in the air atmosphere, and keeping the temperature at 250-300 ℃ for 3-4 hours to finally obtain the three-dimensional graphene-based iron oxide composite material, wherein XRD (X-ray diffraction) diagrams and SEM (scanning Electron microscope) diagrams of the three-dimensional graphene-based iron oxide composite material are respectively shown in figures 1 and 2. In fig. 2, (a) clearly shows the three-dimensional structure of the composite material due to the addition of graphene, and (b) clearly shows Fe in the three-dimensional structure at high magnification2O3An active factor. As can be seen from the figures 1 and 2, the composite material has stable structure, obvious activity factor and higher mechanical property.
(2) The prepared three-dimensional graphene-based iron oxide composite material is used as a lithium ion battery negative electrode material to assemble a lithium ion button type half battery (the counter electrode is made of metal)Lithium), the obtained aerogel pressed sheet is directly used as a negative electrode material, and a pure lithium sheet is used as a counter electrode. Mixing 1M NaPF6The electrolyte is prepared by dissolving the electrolyte in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio is 1:1), and electrochemical tests are carried out by using a button type half cell, and the cycle performance diagram and the rate performance diagram are respectively shown in fig. 3 and fig. 4. As can be seen from FIGS. 3 and 4, at 100mA g-1Under the current density of the graphene, the cycling performance is obviously improved after the graphene is added, the efficiency is also maintained to be more than 90%, the multiplying power performance is also improved, and the current density is 5000mA g-1The current density of the current can still keep high-efficiency electrochemical performance.
Comparative example 1:
the preparation process of the iron oxide material is as follows:
(1) dissolving 2.25mL of 0.5M potassium ferrocyanide into 15mL of deionized water;
(2) adding 2.7g of ferric chloride into the solution, and then centrifuging to remove supernatant;
(3) finally, the remaining solution was washed with deionized water and finally dried in an oven, and the resulting solid was ground to a powder.
The obtained powder material is used as a lithium ion battery negative electrode material to assemble a lithium ion button type half battery (a counter electrode is metal lithium), the powder material, carbon black (Super-P) and polyvinylidene fluoride (PVDF) are mixed according to the weight ratio of 8:1:1, then the mixture is uniformly coated on pure copper foil (99.6%) by a coating method to prepare a negative electrode, and a pure lithium sheet is used as the counter electrode. Mixing 1M NaPF6The electrolyte is prepared by dissolving the electrolyte in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio is 1:1), and electrochemical tests are carried out by using a button type half cell, and the cycle performance diagram and the rate performance diagram are respectively shown in fig. 3 and fig. 4. As can be seen from fig. 3 and 4, the performance of the composite material is obviously improved after the graphene is added, the stability of the composite material is also improved, and the mechanical properties of the composite material are also improved.
Example 2:
a graphene-based iron oxide composite material with a three-dimensional structure for a lithium ion battery negative electrode material is prepared by the following steps:
1) mixing a potassium ferrocyanide solution with the concentration of 0.4mol/L with a graphene oxide solution with the concentration of 2.5mg/mL, and then adding water to obtain a mixed solution; wherein the volume ratio of the potassium ferrocyanide solution to the graphene oxide solution is 1:5, and the volume ratio of the water to the graphene oxide solution is 1.2: 1.
2) Adding ferric chloride into the mixed solution, adding 5g of ferric chloride into every 100mL of the mixed solution, and then carrying out hydrothermal reaction at 220 ℃ for 12h to obtain aerogel;
3) soaking and washing the aerogel in water, freeze-drying, and carbonizing at 300 ℃ for 3h in the air atmosphere to obtain the composite material.
Example 3:
a graphene-based iron oxide composite material with a three-dimensional structure for a lithium ion battery negative electrode material is prepared by the following steps:
1) mixing a potassium ferrocyanide solution with the concentration of 0.6mol/L with a graphene oxide solution with the concentration of 1.5mg/mL, and then adding water to obtain a mixed solution; wherein the volume ratio of the potassium ferrocyanide solution to the graphene oxide solution is 1:8, and the volume ratio of the water to the graphene oxide solution is 0.8: 1.
2) Adding ferric chloride into the mixed solution, adding 10g of ferric chloride into every 100mL of the mixed solution, and then carrying out hydrothermal reaction at 180 ℃ for 24h to obtain aerogel;
3) soaking and washing the aerogel in water, freeze-drying, and carbonizing at high temperature of 250 ℃ for 4 hours in an air atmosphere to obtain the composite material.
Example 4:
a graphene-based iron oxide composite material with a three-dimensional structure for a lithium ion battery negative electrode material is prepared by the following steps:
1) mixing a potassium ferrocyanide solution with the concentration of 0.5mol/L with a graphene oxide solution with the concentration of 2mg/mL, and then adding water to obtain a mixed solution; wherein the volume ratio of the potassium ferrocyanide solution to the graphene oxide solution is 1:6, and the volume ratio of the water to the graphene oxide solution is 1: 1.
2) Adding ferric chloride into the mixed solution, adding 7g of ferric chloride into every 100mL of the mixed solution, and then carrying out hydrothermal reaction at the temperature of 200 ℃ for 18h to obtain aerogel;
3) soaking and washing the aerogel in water, freeze-drying, and carbonizing at high temperature of 270 ℃ for 3.5 hours in an air atmosphere to obtain the composite material.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A preparation method of a graphene-based iron oxide composite material with a three-dimensional structure is characterized by comprising the following steps:
1) mixing a potassium ferrocyanide solution with a graphene oxide solution, and then adding water to obtain a mixed solution;
2) adding ferric chloride into the mixed solution, and then carrying out hydrothermal reaction to obtain aerogel;
3) and washing and drying the aerogel, and then carbonizing at high temperature to obtain the composite material.
2. The method according to claim 1, wherein in step 1), the concentration of the potassium ferrocyanide solution is 0.4-0.6mol/L, and the concentration of the graphene oxide solution is 1.5-2.5 mg/mL.
3. The method for preparing the graphene-based iron oxide composite material with the three-dimensional structure according to claim 1, wherein in the step 1), the volume ratio of the potassium ferrocyanide solution to the graphene oxide solution is 1 (5-8), and the volume ratio of the water to the graphene oxide solution is (0.8-1.2) to 1.
4. The method for preparing the graphene-based iron oxide composite material with the three-dimensional structure according to claim 1, wherein 5-10g of ferric chloride is added to each 100mL of the mixed solution in the step 2).
5. The method as claimed in claim 1, wherein the hydrothermal reaction is carried out at 220 ℃ for 12-24h in step 2).
6. The method for preparing the graphene-based iron oxide composite material with the three-dimensional structure according to claim 1, wherein in the step 3), the washing process is as follows: soaking and washing the aerogel in water; the drying is freeze-drying.
7. The method as claimed in claim 1, wherein the temperature of the step 3) is 250-300 ℃ and the time is 3-4 h.
8. The method for preparing the graphene-based iron oxide composite material with the three-dimensional structure according to claim 1, wherein the high-temperature carbonization process is performed in an air atmosphere in the step 3).
9. A graphene-based iron oxide composite material having a three-dimensional structure, wherein the composite material is prepared by the method according to any one of claims 1 to 8.
10. Use of the three-dimensionally structured graphene-based iron oxide composite according to any one of claims 1 to 8 for a negative electrode material of a lithium ion battery.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103924261A (en) * 2014-04-18 2014-07-16 西南大学 Preparation method for oxygen evolution electrode based on graphene oxide reduction
CN104992852A (en) * 2015-07-21 2015-10-21 湖北吉隆危废处理技术有限公司 A method for preparing an electrode material with graphene coated with manganese dioxide
CN105219345A (en) * 2015-10-16 2016-01-06 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of Z 250 iron nucleocapsid structure-Graphene composite wave-suction material
CN106683740A (en) * 2017-03-16 2017-05-17 西北大学 Hydrothermal method based graphene coated sliver powder preparation and graphene coated silver powder modified lead-free paste preparation method
CN107026026A (en) * 2017-03-17 2017-08-08 东南大学 A kind of method of controllable preparation redox graphene nano bar-shape β manganese dioxide aeroges
CN107473261A (en) * 2017-09-01 2017-12-15 北京化工大学 A kind of preparation method of zinc oxide/redox graphene composite
CN109346686A (en) * 2018-09-12 2019-02-15 天津大学 Three-dimensional grapheme network structure loads the preparation method of Prussian blue similar object
CN109742350A (en) * 2018-12-28 2019-05-10 上海应用技术大学 A kind of ferroso-ferric oxide/graphene composite material preparation method of nitridation
CN109920979A (en) * 2017-12-12 2019-06-21 宁德时代新能源科技股份有限公司 Positive plate and electrochemical cell

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103924261A (en) * 2014-04-18 2014-07-16 西南大学 Preparation method for oxygen evolution electrode based on graphene oxide reduction
CN104992852A (en) * 2015-07-21 2015-10-21 湖北吉隆危废处理技术有限公司 A method for preparing an electrode material with graphene coated with manganese dioxide
CN105219345A (en) * 2015-10-16 2016-01-06 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of Z 250 iron nucleocapsid structure-Graphene composite wave-suction material
CN106683740A (en) * 2017-03-16 2017-05-17 西北大学 Hydrothermal method based graphene coated sliver powder preparation and graphene coated silver powder modified lead-free paste preparation method
CN107026026A (en) * 2017-03-17 2017-08-08 东南大学 A kind of method of controllable preparation redox graphene nano bar-shape β manganese dioxide aeroges
CN107473261A (en) * 2017-09-01 2017-12-15 北京化工大学 A kind of preparation method of zinc oxide/redox graphene composite
CN109920979A (en) * 2017-12-12 2019-06-21 宁德时代新能源科技股份有限公司 Positive plate and electrochemical cell
CN109346686A (en) * 2018-09-12 2019-02-15 天津大学 Three-dimensional grapheme network structure loads the preparation method of Prussian blue similar object
CN109742350A (en) * 2018-12-28 2019-05-10 上海应用技术大学 A kind of ferroso-ferric oxide/graphene composite material preparation method of nitridation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TIANCAI JIANG ETAL.: ""Porous Fe2O3 Nanoframeworks Encapsulated within Three-Dimensional Graphene as High Performance Flexible Anode for Lithium-Ion Battery"", 《ACS NANO》 *

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