CN108199014A - A kind of porous nitrogen-doped carbon/Fe2O3/ grapheme foam flexible composite, preparation method and applications - Google Patents
A kind of porous nitrogen-doped carbon/Fe2O3/ grapheme foam flexible composite, preparation method and applications Download PDFInfo
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- CN108199014A CN108199014A CN201711312326.8A CN201711312326A CN108199014A CN 108199014 A CN108199014 A CN 108199014A CN 201711312326 A CN201711312326 A CN 201711312326A CN 108199014 A CN108199014 A CN 108199014A
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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
- 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
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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
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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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- H—ELECTRICITY
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 present invention provides a kind of porous nitrogen-doped carbon/Fe2O3/ graphene flexible composite, preparation method and applications.In the flexible composite, graphene coated Fe2O3Nano particle, nitrogen-doped carbon have porous foaming structure.This method includes：Pure melamine foamed plastic is prepared, nitrogen-doped carbon foam base plate is obtained after being calcined in nitrogen, by nanometer Fe2O3, graphene oxide solution and polyvinylpyrrolidone mixing after spinning solution is prepared, by nitrogen-doped carbon foam base plate be reception device, spinning solution is directly spinned in carbon foam using high-voltage electrostatic spinning technology, obtains porous nitrogen-doped carbon/Fe2O3/ graphene oxide/PVP composite materials, then obtains the flexible composite after high temperature cabonization cools down.The material is used for the negative material of lithium ion battery, has the characteristics that good flexible, high conductivity and height ratio capacity.
Description
Technical field
The present invention relates to new energy materials field more particularly to a kind of porous nitrogen-doped carbon/Fe2O3/ grapheme foam is flexible
Composite material and its preparation method and application.
Background technology
In recent years, the flexible electronic device demand of flexible folding increases year by year, and flexible lithium ion battery is flexible
The core component of electronic device.Active material, conductive agent, binding agent are mainly mixed and are coated in gold by traditional lithium ion battery
Belong on collector, formed by drying roll-in, electrode material does not have a flexibility, and to substantially reduce material whole for the presence of collector
The energy density of body.Therefore, it is necessary to develop the self-supporting flexible electrode material of binder free, conductive agent and collector, to meet
The demand of flexible electronic device.
At present, commercialized ion cathode material lithium is mainly carbon material, with many limitations：Theoretical capacity
Low, with lithium metal close to that may generate dendrite etc. on surface, security performance cannot be guaranteed current potential.In recent years, Fe2O3Because of it
Theoretical specific capacity is high, resourceful, it is of low cost and safe and non-toxic the advantages that, it is considered to be have the lithium of potential application foreground from
One of sub- cell negative electrode material, but in cyclic process material enormousness itself variation caused by capacity attenuation and its compared with
The adjoint poor high rate performance of low electronic conductivity, seriously hinders its practical application.In order to improve Fe2O3Material follows
Ring stability, the modified method used at present mainly have carbon coating, adulterate and prepare the Fe of nano-porous structure2O3Material.
Carbon coating can improve Fe2O3The compatibility of based composites and electrolyte can also improve the conductivity of composite material.It is porous
Structure can be Fe2O3The volume expansion of material provides reserved space, alleviates volumetric stress caused by volume expansion.Graphene is made
For a kind of two-dimentional carbon material, there is excellent mechanical property and good conductivity, by with Fe2O3Material cladding can improve
The conductivity and chemical property of composite material.
It to sum up analyzes, with reference to the characteristics of self-supporting flexible electrode and Fe2O3Advantage and disadvantage, by melamine foamed plastic,
Fe2O3Carry out tri compound with graphene, using the synergistic effect of composite material, the flexible compound electrode of self-supporting as lithium from
Sub- cell negative electrode material is hopeful to be obviously improved its chemical property.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of porous nitrogen-doped carbon/Fe2O3/ graphene flexible composite
And its preparation method and application.The composite material has the characteristics that good flexible, high conductivity and height ratio capacity, soap-free emulsion polymeization
The self-supporting flexible electrode material of agent, conductive agent and collector can be significantly improved under energy density and the bending condition of material
Chemical property.
The present invention adopts the following technical scheme that：A kind of porous nitrogen-doped carbon/Fe2O3/ graphene flexible composite, wherein：
Graphene coated Fe2O3Nano particle, nitrogen-doped carbon have three-dimensional porous foaming structure.
A kind of porous nitrogen-doped carbon/Fe2O3The preparation method of/graphene flexible composite, includes the following steps：
(1) pure melamine foamed plastic is prepared；
(2) melamine foamed plastic made from step (1) is transferred in tube furnace, is calcined in nitrogen atmosphere, calcination temperature
It it is 300-1200 DEG C, calcination time is 1-10 hours, obtains nitrogen-doped carbon foam base plate；Preferably, melamine foamed plastic is forged
It is 800-1200 DEG C to burn temperature, and calcination time is 3-10 hours；
(3) by nanometer Fe2O3, graphene oxide solution mix according to a certain percentage, be stirred until homogeneous, add in quality be mixed
The polyvinylpyrrolidone of the 5-10%, preferably 8-10% of solution is closed, it is lasting to stir, obtain spinning solution after standing；
(4) the nitrogen-doped carbon foam base plate prepared using step (2) will be walked as reception device using high-voltage electrostatic spinning technology
Suddenly the spinning solution in (3) is directly spinned in carbon foam, obtains porous nitrogen-doped carbon/Fe2O3/ graphene oxide/PVP is compound
Material；
(5) the porous nitrogen-doped carbon/Fe that will be obtained in step (4)2O3/ graphene oxide/PVP composite materials are transferred to height
High temperature cabonization is carried out in warm tube type resistance furnace, porous nitrogen-doped carbon/Fe is obtained after cooling2O3/ graphene flexible composite.
Preferably, step (1) prepare pure melamine foamed plastic be specially：Melamine foamed plastic is taken to be put into 1mol/L
Dilute hydrochloric acid in impregnate 6 hours, then melamine foamed plastic is transferred in the mixed solution of absolute ethyl alcohol/acetone to impregnate 3 small
When, then obtained melamine foamed plastic absolute ethyl alcohol, deionized water are cleaned, drying in drying box is then placed in, obtains
Pure melamine foamed plastic；Further preferably, it is put into 60 DEG C of drying boxes 12 hours dry.
Preferably, in step (3), the nanometer Fe2O3Mass ratio with graphene oxide is 1:(1-5), more preferable 1:
(3-5)。
Preferably, in step (4), the spinning voltage of high-voltage electrostatic spinning technology is 10000-40000V, and spinneret speed is
The distance of 1-5mL/h, spinning head and nickel foam is 5-20cm, it is furthermore preferred that the distance of spinning head and nickel foam is 10-20cm.
Preferably, in step (5), under the protection of argon gas and hydrogen mixed gas atmosphere, with the heating of 3 DEG C/min-7 DEG C/min
Rate is warming up to 400~900 DEG C of 1~5h of carbonization, then naturally cools to room temperature；It is furthermore preferred that carburizing temperature is 550~900
DEG C, the time is 1~3h.
Preferably, in step (3), the Fe2O3Powder is Nano grade, and particle size is at 300-500 nanometers；With the concentrated sulfuric acid,
Potassium permanganate is oxidant, and graphite powder is oxidized to graphite oxide, then remove graphite oxide into oxidation stone using ultrasound stripping
Black alkene.
Porous nitrogen-doped carbon/Fe of the present invention2O3The cathode material of/graphene flexible composite as lithium ion battery
Material, after preparing lithium ion battery, with the current density charge and discharge of 0.1A/g, discharge capacity reaches 1195mAh/g for the first time, 60 times
Discharge capacity after cycle reaches more than 951mAh/g, has the characteristics that good flexible, high conductivity and height ratio capacity.
Compared with prior art, the present invention with advantageous effect following prominent：
(1) flexible composite electrode material prepared by does not need to the additives such as metal collector, binding agent and conductive carbon, directly
It connects as electrode material, is conducive to improve the energy density and power density of electrode.
(2) nitrogen-doped carbon has porous foaming structure, can effectively alleviate nanometer Fe2O3Bulk effect, and nitrogen
Doping can change the band structure of material, reduce lithium ion diffusion rate, while cause the fault of construction of material, improve material
Storage lithium performance, prepared porous nitrogen-doped carbon/Fe2O3/ graphene flexible composite prepares 2025 as battery cathode
Type button cell, with the current density charge and discharge of 0.1A/g, discharge capacity is up to 1195mAh/g for the first time, after 60 cycles
Discharge capacity reaches more than 951mAh/g, has the characteristics that high conductivity and height ratio capacity.
(3) porous nitrogen-doped carbon/Fe prepared by the present invention2O3In/graphene flexible composite, graphene coated
Fe2O3Nano particle effectively alleviates nanometer Fe2O3Bulk effect, improve Fe2O3Electric conductivity.
(4) in preparation process, porous nitrogen-doped carbon/Fe2O3/ graphene oxide/PVP composite materials as other product,
Middle polyvinylpyrrolidone (PVP) can increase graphene/nanometer Fe2O3With the binding force of carbon foam matrix, flexible material is kept
Structural stability.
Description of the drawings
Fig. 1 is the porous nitrogen-doped carbon/Fe of sample in the embodiment of the present invention 12O3The flexibility of/graphene flexible composite
Test.
Fig. 2 is the stereoscan photograph of sample nitrogen-doped carbon foam in the embodiment of the present invention 1.
Fig. 3 is the porous nitrogen-doped carbon/Fe of sample in the embodiment of the present invention 12O3/ graphene flexible composite cycle performance
Curve.
Specific embodiment
Embodiment 1
A kind of porous nitrogen-doped carbon/Fe2O3The preparation method of/graphene flexible composite, using following steps：
(1) melamine foamed plastic is taken to be put into the dilute hydrochloric acid of 1mol/L to impregnate 6 hours, then shifts melamine foamed plastic
To absolute ethyl alcohol/acetone (1:1) impregnate 3 hours in mixed solution, then by obtained melamine foamed plastic absolute ethyl alcohol,
Deionized water is cleaned 3-5 times, is then placed in drying 12 hours in 60 DEG C of drying boxes, is obtained pure melamine foamed plastic.
(2) melamine foamed plastic of step (1) is transferred in tube furnace, is calcined in nitrogen atmosphere, calcination temperature 800
DEG C, calcination time is 3 hours, obtains nitrogen-doped carbon foam base plate.
(3) by nanometer Fe2O3, graphene oxide solution mix according to a certain percentage, be stirred until homogeneous.It is mixed to add in quality
10% polyvinylpyrrolidone (PVP) of solution is closed, is persistently stirred 4 hours, 2 hours is stood and obtains spinning solution；Wherein receive
Rice Fe2O3Mass ratio with graphene oxide is 1:3；The Fe2O3Powder is Nano grade, and particle size is received in 300-500
Rice；Using the concentrated sulfuric acid, potassium permanganate as oxidant, graphite powder is oxidized to graphite oxide, then remove graphite oxide using ultrasound
Remove into graphene oxide.
(4) the nitrogen-doped carbon foam prepared using step (2) is reception device, using high-voltage electrostatic spinning technology by step
(3) spinning solution obtained in directly spinning in carbon foam, obtains porous nitrogen-doped carbon/Fe2O3/ graphene oxide/PVP is soft
Property composite material；Wherein the spinning voltage of high-voltage electrostatic spinning technology is 40000V, and spinneret speed is 1mL/h, spinning head and bubble
The distance of foam nickel is 10cm.
(5) the porous nitrogen-doped carbon/Fe that will be obtained in step (4)2O3/ graphene oxide/PVP flexible composites transfer
Into high temperature tubular resistor furnace, under the protection of argon hydrogen gas, 550 DEG C of carbonization 3h are warming up to the heating rate of 5 DEG C/min,
Then room temperature is naturally cooled in argon hydrogen gas, obtains porous nitrogen-doped carbon/Fe2O3/ graphene flexible composite.
Fig. 1 is the flexibility test for the composite material that the present embodiment obtains, and as can be seen from the figure composite material exhibits go out
Excellent mechanical flexibility.
Fig. 2 is the stereoscan photograph of nitrogen-doped carbon foam that the present embodiment obtains, it can be seen that nitrogen-doped carbon foam has
There is three-dimensional porous structure.
Further, the present embodiment is obtained into porous nitrogen-doped carbon/Fe2O3/ graphene flexible composite is as work electricity
Pole, lithium piece are auxiliary and reference electrode, and electrolyte is general lithium-ion battery electrolytes, prepares 2025 type button cells, with
The current density charge and discharge of 0.1A/g, the cycle performance curve of the electrode material are as shown in Figure 3, it can be seen that the composite material is first
For secondary discharge capacity up to 1195mAh/g, the discharge capacity after 60 cycles is 951.1mAh/g.
Embodiment 2
A kind of porous nitrogen-doped carbon/Fe2O3The preparation method of/graphene flexible composite, using following steps：
(1) melamine foamed plastic prepared by step (1) in embodiment 1 is transferred in tube furnace, is calcined in nitrogen atmosphere,
Calcination temperature is 300 DEG C, and calcination time is 10 hours, obtains nitrogen-doped carbon foam base plate.
(2) by nanometer Fe2O3, graphene oxide solution mix according to a certain percentage, be stirred until homogeneous, add in quality be mixed
5% polyvinylpyrrolidone (PVP) of solution is closed, is persistently stirred 4 hours, 2 hours is stood and obtains spinning solution.Wherein nanometer
Fe2O3Mass ratio with graphene oxide is 1:1；The Fe2O3Powder is Nano grade, and particle size is at 300-500 nanometers；
Using the concentrated sulfuric acid, potassium permanganate as oxidant, graphite powder is oxidized to graphite oxide, then graphite oxide is removed using ultrasound stripping
Into graphene oxide.
(3) the nitrogen-doped carbon foam prepared using step (1) is reception device, using high-voltage electrostatic spinning technology by step
(3) spinning solution obtained in directly spinning in carbon foam, obtains porous nitrogen-doped carbon/Fe2O3/ graphene oxide/PVP is soft
Property composite material；Wherein the spinning voltage of high-voltage electrostatic spinning technology is 30000V, and spinneret speed is 5mL/h, spinning head and bubble
The distance of foam nickel is 20cm；
(4) the porous nitrogen-doped carbon/Fe that will be obtained in step (3)2O3/ graphene oxide/PVP flexible composites transfer
Into high temperature tubular resistor furnace, under the protection of argon hydrogen gas, 900 DEG C of carbonization 1h are warming up to the heating rate of 7 DEG C/min,
Then room temperature is naturally cooled in argon hydrogen gas, obtains porous nitrogen-doped carbon/Fe2O3/ graphene flexible composite.
Electrochemical property test is carried out to the present embodiment material according to step as described in Example 1, test result is：
Under the current density of 0.1A/g, the discharge capacity after 60 cycles is 642.2mAh/g.
Embodiment 3
A kind of porous nitrogen-doped carbon/Fe2O3The preparation method of/graphene flexible composite, using following steps：
(1) melamine foamed plastic prepared by step (1) in embodiment 1 is transferred in tube furnace, is calcined in nitrogen atmosphere,
Calcination temperature is 1200 DEG C, and calcination time is 1 hour, obtains nitrogen-doped carbon foam base plate.
(2) by nanometer Fe2O3, graphene oxide solution mix according to a certain percentage, be stirred until homogeneous, add in quality be mixed
8% polyvinylpyrrolidone (PVP) of solution is closed, is persistently stirred 4 hours, 2 hours is stood and obtains spinning solution, wherein nanometer
Fe2O3Mass ratio with graphene oxide is 1:5；The Fe2O3Powder is Nano grade, and particle size is at 300-500 nanometers；
Using the concentrated sulfuric acid, potassium permanganate as oxidant, graphite powder is oxidized to graphite oxide, then graphite oxide is removed using ultrasound stripping
Into graphene oxide.
(3) the nitrogen-doped carbon foam prepared using step (1) is reception device, using high-voltage electrostatic spinning technology by step
(3) spinning solution obtained in directly spinning in carbon foam, obtains porous nitrogen-doped carbon/Fe2O3/ graphene oxide/PVP is soft
Property composite material；Wherein the spinning voltage of high-voltage electrostatic spinning technology is 10000V, and spinneret speed is 2mL/h, spinning head and bubble
The distance of foam nickel is 16cm；
(4) the porous nitrogen-doped carbon/Fe that will be obtained in step (3)2O3/ graphene oxide/PVP flexible composites transfer
Into high temperature tubular resistor furnace, under the protection of argon hydrogen gas, 400 DEG C of carbonization 5h are warming up to the heating rate of 3 DEG C/min,
Then room temperature is naturally cooled in argon hydrogen gas, obtains porous nitrogen-doped carbon/Fe2O3/ graphene flexible composite.
According to step as described in Example 1 to the present embodiment material carry out electrochemical property test, test result be
Under the current density of 0.1A/g, the discharge capacity after 60 cycles is 786.5mAh/g.
Invention described above specific embodiment, is not intended to limit the scope of the present invention..It is any this
Modifications, equivalent substitutions and improvements made within the spirit and principle of invention etc., should be included in the claim of the present invention
Within protection domain.
Claims (10)
1. a kind of porous nitrogen-doped carbon/Fe2O3/ graphene flexible composite, it is characterised in that：Graphene coated Fe2O3Nanometer
Particle, nitrogen-doped carbon are three-dimensional porous foaming structure.
2. a kind of prepare porous nitrogen-doped carbon/Fe described in claim 12O3The method of/graphene flexible composite, including
Following steps：
(1) pure melamine foamed plastic is prepared；
(2) melamine foamed plastic made from step (1) is transferred in tube furnace, is calcined in nitrogen atmosphere, calcination temperature is
300-1200 DEG C, calcination time is 1-10 hours, obtains nitrogen-doped carbon foam base plate；Preferably, the calcining of melamine foamed plastic
Temperature is 800-1200 DEG C, and calcination time is 3-10 hours；
(3) by nanometer Fe2O3, graphene oxide solution mix according to a certain percentage, be stirred until homogeneous, add in quality for mix it is molten
The polyvinylpyrrolidone (PVP) of the 5-10% of liquid, preferably 8-10%, it is lasting to stir, obtain spinning solution after standing；
(4) the nitrogen-doped carbon foam base plate prepared using step (2) is reception device, using high-voltage electrostatic spinning technology by step
(3) spinning solution in is directly spinned on carbon foam matrix, obtains porous nitrogen-doped carbon/Fe2O3/ graphene oxide/PVP is multiple
Condensation material；
(5) the porous nitrogen-doped carbon/Fe that will be obtained in step (4)2O3/ graphene oxide/PVP composite materials are transferred to high temperature pipe
High temperature cabonization is carried out in formula resistance furnace, porous nitrogen-doped carbon/Fe is obtained after cooling2O3/ graphene flexible composite.
3. according to the method described in claim 2, it is characterized in that：Step (1) prepares the specific of pure melamine foamed plastic
For：Melamine foamed plastic is taken to be put into the dilute hydrochloric acid of 1mol/L to impregnate 6 hours, melamine foamed plastic is then transferred to anhydrous second
It impregnates 3 hours in the mixed solution of alcohol/acetone, then cleans obtained melamine foamed plastic absolute ethyl alcohol, deionized water,
Drying in drying box is then placed in, obtains pure melamine foamed plastic.
4. according to the method described in claim 3, it is characterized in that：It is put into 60 DEG C of drying boxes 12 hours dry.
5. according to the method in claim 2 or 3, it is characterised in that：In step (3), the nanometer Fe2O3With graphite oxide
The mass ratio of alkene is 1:(1-5), preferably 1:(3-5).
6. according to the method in claim 2 or 3, it is characterised in that：In step (4), the spinning of high-voltage electrostatic spinning technology
Voltage is 10000-40000V, and spinneret speed is 1-5mL/h, and the distance of spinning head and nickel foam is 5-20cm, it is preferred that spinneret
The distance of head and nickel foam is 10-20cm.
7. according to the method in claim 2 or 3, it is characterised in that：In step (5), in argon gas and hydrogen mixed gas atmosphere
Under protection, 400~900 DEG C of 1~5h of carbonization are warming up to the heating rate of 3 DEG C/min~7 DEG C/min, then naturally cool to room
Temperature；Preferably, carburizing temperature is 550~900 DEG C, and the time is 1~3h.
8. according to the method described in claim 2, it is characterized in that：The Fe2O3Powder is Nano grade, and particle size is in 300-
500 nanometers；Using the concentrated sulfuric acid, potassium permanganate as oxidant, graphite powder is oxidized to graphite oxide, then will oxidation using ultrasound stripping
Graphite is removed into graphene oxide.
9. a kind of porous nitrogen-doped carbon/Fe described in claim 12O3The application of/graphene flexible composite, it is characterised in that：
For the negative material of lithium ion battery.
10. application according to claim 9, it is characterised in that：After the flexible composite prepares lithium ion battery, with
The current density charge and discharge of 0.1A/g, for the first time discharge capacity reach 1195mAh/g, the discharge capacity after 60 cycles reaches
More than 951mAh/g.
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| CN109616615A (en) * | 2018-12-10 | 2019-04-12 | 合肥国轩高科动力能源有限公司 | A kind of method that electrostatic spinning prepares graphene composite nano-fiber material |
| CN109698341A (en) * | 2018-12-27 | 2019-04-30 | 银隆新能源股份有限公司 | A kind of electrode preparation method, electrode and battery |
| CN110918007A (en) * | 2019-11-04 | 2020-03-27 | 江苏一夫新材料产业技术研究院有限公司 | PVP polymerized SnO2-graphene aerogels and method for the production thereof |
| CN111215111A (en) * | 2020-01-13 | 2020-06-02 | 山西大学 | Carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies and preparation method and application thereof |
| CN113871591A (en) * | 2021-09-24 | 2021-12-31 | 中国科学院过程工程研究所 | Iron-based electrode material and preparation method and application thereof |
| CN114094073A (en) * | 2021-11-12 | 2022-02-25 | 中博龙辉装备集团股份有限公司 | Tin dioxide @ carbon foam self-supporting composite material and preparation method and application thereof |
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