CN108376767B - Red phosphorus/nitrogen doped graphene composite negative electrode material and preparation method and application thereof - Google Patents
Red phosphorus/nitrogen doped graphene composite negative electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN108376767B CN108376767B CN201810069146.XA CN201810069146A CN108376767B CN 108376767 B CN108376767 B CN 108376767B CN 201810069146 A CN201810069146 A CN 201810069146A CN 108376767 B CN108376767 B CN 108376767B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped graphene
- red phosphorus
- negative electrode
- electrode material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- 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
-
- 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
-
- 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 relates to a red phosphorus/nitrogen-doped graphene composite negative electrode material and a preparation method and application thereof, wherein nitrogen-doped graphene and red phosphorus are mixed according to the mass ratio of (2-4): (8-6) uniformly mixing to obtain a mixture; and carrying out ball milling on the obtained mixture under a protective atmosphere to obtain the red phosphorus/nitrogen doped graphene composite negative electrode material. According to the invention, the nitrogen-doped graphene material with good electronic conductivity is used as a base material, and is ball-milled with red phosphorus, so that insulating red phosphorus particles can be well dispersed in the conductive nitrogen-doped graphene material in the ball-milling process, the specific surface area of the compound is very large, the overall conductivity is improved, the contact area with an electrolyte is increased, the structural collapse and pulverization caused by volume expansion of the phosphorus-based material in the process of de-intercalation of potassium ions are relieved, and the diffusion rate of potassium ions is increased; as a negative electrode material of the potassium ion battery, the lithium ion battery has high reversible capacity, excellent rate capability and cycling stability.
Description
Technical Field
The invention relates to the field of batteries, in particular to a red phosphorus/nitrogen doped graphene composite negative electrode material and a preparation method and application thereof.
Background
The most serious problems have been energy and environment for the 21 st century. Non-renewable energy sources can cause large-area environmental pollution, and the condition is illustrated in haze weather in many areas nowadays. It is particularly necessary to develop new renewable energy sources. In recent years, most lithium ion batteries are used in industrial production, but with the deep development of lithium ion batteries, the problem of lithium resource shortage is more and more serious, and lithium element only accounts for 0.007% in the earth crust and is a rare metal, so that the cost of the lithium ion batteries is high, and the development and application of the lithium ion batteries are limited in a long-term consideration.
The sodium element, the potassium element and the lithium element are in the first main group of the periodic table of the elements, the electrochemical properties are similar, the reversible charge and discharge process can be realized, and the reserves of the sodium element and the potassium element in the earth crust are very abundant, which respectively account for 2.09 percent and 2.36 percent. However, the energy density of the sodium ion battery is relatively low due to the hydrogen potential (-2.71V vs E °) of the sodium ion battery compared to that of the lithium ion battery (-3.04V vs E °), which hinders practical application. The hydrogen potential (-2.93V vs E DEG) of the potassium ion battery is very close to that of the lithium ion battery, and the potassium ion battery has good prospect in practical application due to high energy density and low cost.
The red phosphorus has the advantages of rich resources, low price, higher theoretical specific capacity (2596mAh/g) and the like. However, red phosphorus has large volume change during cycling and low electron conductivity (10)-14S/cm) leads to lower actual specific capacity, indicating that the electrochemical performance of the red phosphorus negative electrode still needs to be further improved.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a red phosphorus/nitrogen-doped graphene composite negative electrode material, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method comprises the following steps:
(1) the method comprises the following steps of (2-4) mixing nitrogen-doped graphene and red phosphorus in a mass ratio: (8-6) uniformly mixing to obtain a mixture;
(2) and (3) carrying out ball milling on the mixture obtained in the step (1) under a protective atmosphere to obtain the red phosphorus/nitrogen doped graphene composite negative electrode material.
Further, the preparation method of the nitrogen-doped graphene comprises the following steps: mixing a GO solution with a cyanamide solution, heating for 1-4 hours at 60-80 ℃ under stirring, evaporating water to obtain dark gray GO-cyanamide powder, putting the GO-cyanamide powder into a tubular furnace, introducing nitrogen gas, and then heating for reaction to obtain nitrogen-doped graphene, wherein the mass ratio of GO to cyanamide is (1-2): (1-50).
Further, the temperature rise reaction is carried out for 0.5-5 h when the temperature rises to 800-1000 ℃.
Further, ball milling is carried out for 2-40 h in the step (2).
Further, the protective atmosphere in the step (2) is argon.
The technical scheme of the cathode material is as follows: the method comprises the steps of uniformly ball-milling nitrogen-doped graphene and red phosphorus, wherein the mass ratio of the nitrogen-doped graphene to the red phosphorus is (2-4): (8-6).
Furthermore, the negative electrode material is composed of particles with the average particle size of 40-80 nm.
The application of the red phosphorus/nitrogen doped graphene composite negative electrode material in the preparation of lithium ion batteries, sodium ion batteries or potassium ion batteries.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the invention, a nitrogen-doped graphene material with good electronic conductivity is used as a substrate material, graphene in the nitrogen-doped graphene material has unique mechanical property and high specific surface area with excellent electronic transmission property, the electronic structure of the graphene can be modulated and the physical and chemical properties of the graphene can be improved by performing nitrogen-doping treatment on the graphene, and insulating red phosphorus (P) particles can be well dispersed in the conductive nitrogen-doped graphene material in the ball milling process by ball milling with red phosphorus, so that the specific surface area of the composite is very large, the overall conductivity is improved, the contact area with an electrolyte is increased, the collapse and pulverization of the structure caused by volume expansion of a phosphorus-based material in the de-intercalation process of potassium ions are relieved, and the diffusion rate of the potassium ions is increased. The material is used as a potassium ion battery cathode material, has a simple preparation method, has high reversible capacity, excellent rate capability and cycle stability, and is a lithium ion battery cathode material with application potential.
When the red phosphorus/nitrogen-doped graphene composite negative electrode material is used as a potassium ion battery negative electrode material, the prepared battery has the initial coulombic efficiency of 83.8% -84.2% and the initial discharge capacity of 1596 mAh/g-2450 mAh/g under the test condition that the current is 1300mA/g, the capacity is hardly attenuated after 100 weeks of circulation, and the circulation stability is high; the red phosphorus/carbon nanotube composite material in the reference sample has the initial coulombic efficiency of 77 percent, although the initial discharge capacity can reach 1700mAh/g, the capacity is obviously attenuated after circulation for about 20 weeks, and the capacity is attenuated to be below 500mAh/g after 100 weeks, which shows that the red phosphorus/nitrogen-doped graphene composite negative electrode material can generate specific coordination.
Drawings
Fig. 1 is a scanning electron microscope image of nitrogen-doped graphene prepared in example 1;
fig. 2 is an XRD pattern of the red phosphorus/nitrogen-doped graphene composite material prepared in example 1;
fig. 3 is a scanning electron microscope image of the red phosphorus/nitrogen-doped graphene composite material prepared in example 1;
fig. 4 is a graph of the specific capacity of cyclic discharge of the red phosphorus/nitrogen-doped graphene composite material prepared in example 1 and the red phosphorus/nanotube composite material prepared in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The preparation method comprises the following steps:
(1) mixing a GO (graphene oxide) solution with a cyanamide solution, heating for 1-4 hours at 60-80 ℃ under stirring, evaporating water to obtain dark gray GO-cyanamide powder, putting the GO-cyanamide powder into a tubular furnace, introducing nitrogen, heating to 800-1000 ℃ for 0.5-5 hours, and preparing nitrogen-doped graphene, wherein the mass ratio of GO to cyanamide is (1-2): (1-50) and preparing the nitrogen-doped graphene.
(2) Uniformly mixing a certain amount of nitrogen-doped graphene and red phosphorus, putting the mixture into a ball milling tank, introducing argon protective gas, and then carrying out ball milling for 2-40 h to obtain the red phosphorus/nitrogen-doped graphene composite negative electrode material. The mass ratio of the nitrogen-doped graphene to the red phosphorus is (2-4): (8-6).
The invention also provides a potassium ion battery which comprises a negative electrode, a positive electrode, electrolyte and a diaphragm, wherein the negative electrode material is the red phosphorus/nitrogen doped graphene composite material.
The present invention is further illustrated by the following specific examples.
Example 1:
mixing the GO solution with a cyanamide solution, heating for 2 hours at 70 ℃ under stirring, then evaporating water to obtain dark gray GO-cyanamide powder, putting the GO-cyanamide powder into a tubular furnace, introducing nitrogen, heating to 900 ℃ for 2 hours to obtain nitrogen-doped graphene, wherein the mass ratio of graphene oxide to cyanamide is 1: 1; and uniformly mixing the prepared nitrogen-doped graphene and red phosphorus in a mass ratio of 3:7, putting the mixture into a ball milling tank, and carrying out ball milling for 40 hours to obtain the red phosphorus/nitrogen-doped graphene composite negative electrode material.
Fig. 1 is a scanning electron microscope image of the nitrogen-doped graphene prepared in this example, and it can be seen from fig. 1 that the nitrogen-doped graphene is in a gauze shape, sheets are folded with each other, and curling occurs at edges.
Fig. 2 is an XRD chart of the red phosphorus/nitrogen-doped graphene composite material prepared in this embodiment, and it can be seen from fig. 2 that the prepared red phosphorus/nitrogen-doped graphene composite material is in an amorphous state.
Fig. 3 is a scanning electron microscope image of the red phosphorus/nitrogen-doped graphene composite material prepared in this example, and it can be seen from fig. 3 that the nitrogen-doped graphene is tightly combined with red phosphorus to form nanoparticles having an average particle size of about 40 nm.
The prepared red phosphorus and nitrogen doped graphene is mixed with a conductive agent and an adhesive to prepare slurry, then the slurry is coated on copper foil, vacuum drying and cutting are carried out to prepare a phosphorus-carbon electrode, the phosphorus-carbon electrode and a potassium sheet are assembled into a button 2016 cell in a vacuum glove box, the electrochemical performance of the red phosphorus/nitrogen doped graphene composite material is tested in a voltage range of 0.01-2V, under the test condition that the current is 1300mA/g, the result is shown in figure 4, the first coulombic efficiency is 84%, the first discharge capacity is 2450mAh/g, and the capacity is hardly attenuated after circulation for 100 weeks.
Example 2:
mixing the GO solution with a cyanamide solution, heating for 1 hour at 60 ℃ under stirring, then evaporating water to obtain dark gray GO-cyanamide powder, putting the GO-cyanamide powder into a tubular furnace, introducing nitrogen, heating to 800 ℃ for 5 hours to obtain nitrogen-doped graphene, wherein the mass ratio of graphene oxide to cyanamide is 1: 50; and uniformly mixing the prepared nitrogen-doped graphene and red phosphorus in a mass ratio of 4:6, putting the mixture into a ball milling tank, and carrying out ball milling for 20 hours to prepare the red phosphorus/nitrogen-doped graphene composite negative electrode material with the average particle size of about 60 nanometers.
Mixing the prepared red phosphorus and nitrogen doped graphene with a conductive agent and an adhesive to prepare slurry, coating the slurry on a copper foil, performing vacuum drying and cutting to prepare a phosphorus-carbon electrode, assembling the phosphorus-carbon electrode and a potassium sheet into a button 2016 cell in a vacuum glove box, testing the electrochemical performance of the red phosphorus/nitrogen doped graphene composite material in a voltage range of 0.01-2V, and under the test condition that the current is 1300mA/g, the first coulomb efficiency is 83.8 percent and the first-week discharge capacity is 1596 mAh/g.
Example 3:
mixing the GO solution with a cyanamide solution, heating for 4 hours at 80 ℃ under stirring, then evaporating water to obtain dark gray GO-cyanamide powder, putting the GO-cyanamide powder into a tubular furnace, introducing nitrogen, heating to 1000 ℃ for 0.5 hours to obtain nitrogen-doped graphene, wherein the mass ratio of graphene oxide to cyanamide is 2: 1, preparing nitrogen-doped graphene to obtain the nitrogen-doped graphene; and uniformly mixing the prepared nitrogen-doped graphene and red phosphorus in a mass ratio of 2:8, putting the mixture into a ball milling tank, and carrying out ball milling for 2 hours to prepare the red phosphorus/nitrogen-doped graphene composite negative electrode material with the average particle size of about 80 nanometers.
Mixing the prepared red phosphorus and nitrogen doped graphene with a conductive agent and an adhesive to prepare slurry, then coating the slurry on a copper foil, performing vacuum drying and cutting to prepare a phosphorus-carbon electrode, assembling the phosphorus-carbon electrode and a potassium sheet into a button 2016 cell in a vacuum glove box, testing the electrochemical performance of the red phosphorus/nitrogen doped graphene composite material in a voltage range of 0.01-2V, and under the test condition that the current is 1300mA/g, the first coulomb efficiency is 84.2 percent and the first-week discharge capacity is 1665 mAh/g.
Comparative example 1:
according to the embodiments, the mass ratio of the nitrogen-doped graphene to the red phosphorus is 3:7, and the red phosphorus/nitrogen-doped graphene composite negative electrode material prepared by ball milling is good in electrochemical performance. Therefore, under the condition, the red phosphorus/carbon nano tube composite negative electrode material is prepared under the same preparation condition, namely the carbon nano tube and the red phosphorus are put into a ball milling tank with the mass ratio of 3:7, argon protective gas is introduced, and ball milling is carried out for 40 hours.
Fig. 4 is a graph of the specific capacity of cyclic discharge of the red phosphorus/nitrogen-doped graphene composite material prepared in example 1 and the red phosphorus/nanotube composite material prepared in comparative example 1. The result shows that the first coulombic efficiency of the red phosphorus/carbon nanotube composite material is 77 percent, the first discharge capacity is 1700mAh/g, the capacity is obviously attenuated in about 20 weeks, the capacity is attenuated to be below 500mAh/g after 100 weeks, the red phosphorus/nitrogen-doped graphene composite material has higher first coulombic efficiency of 84 percent, the first discharge capacity is 2450mAh/g, and the capacity is hardly attenuated after 100 weeks of circulation, so that the material has higher circulation stability and is a potassium ion battery cathode material with very application potential.
The red phosphorus/nitrogen-doped graphene composite material is an amorphous nano granular P-NG composite obtained by ball milling of red phosphorus and nitrogen-doped graphene (NG), and has the advantages of good potassium ion de-intercalation capability, abundant raw materials, low cost and simple preparation through electrochemical test representation, and is very expected to become a used potassium ion battery cathode material.
The invention provides a red phosphorus/nitrogen doped graphene composite material which has high electronic conductivity and relieves volume expansion and is used as a potassium ion battery cathode material, wherein the nitrogen doped graphene is a high-conductivity material, and the red phosphorus is uniformly dispersed in nitrogen doped graphene material particles through ball milling, so that the conductivity and the discharge cycle stability of phosphorus are effectively improved.
Claims (2)
1. A preparation method of a red phosphorus/nitrogen doped graphene composite negative electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) the method comprises the following steps of (2-4) mixing nitrogen-doped graphene and red phosphorus in a mass ratio: (8-6) uniformly mixing to obtain a mixture;
(2) ball-milling the mixture obtained in the step (1) in a protective atmosphere to obtain a red phosphorus/nitrogen doped graphene composite negative electrode material;
the preparation method of the nitrogen-doped graphene comprises the following steps: mixing a GO solution with a cyanamide solution, heating for 1-4 hours at 60-80 ℃ under stirring, evaporating water to obtain dark gray GO-cyanamide powder, putting the GO-cyanamide powder into a tubular furnace, introducing nitrogen gas, and then heating for reaction to obtain nitrogen-doped graphene, wherein the mass ratio of GO to cyanamide is (1-2): (1-50);
the nitrogen-doped graphene is in a gauze shape, and the sheets are mutually folded and curled at the edge;
the temperature rise reaction is carried out for 0.5-5 h when the temperature rises to 800-1000 ℃;
and (3) ball-milling for 2-40 h in the step (2).
2. The preparation method of the red phosphorus/nitrogen-doped graphene composite anode material according to claim 1, characterized by comprising the following steps: and (3) the protective atmosphere in the step (2) is argon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810069146.XA CN108376767B (en) | 2018-01-24 | 2018-01-24 | Red phosphorus/nitrogen doped graphene composite negative electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810069146.XA CN108376767B (en) | 2018-01-24 | 2018-01-24 | Red phosphorus/nitrogen doped graphene composite negative electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108376767A CN108376767A (en) | 2018-08-07 |
| CN108376767B true CN108376767B (en) | 2021-02-09 |
Family
ID=63016743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810069146.XA Active CN108376767B (en) | 2018-01-24 | 2018-01-24 | Red phosphorus/nitrogen doped graphene composite negative electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108376767B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301178A (en) * | 2018-08-17 | 2019-02-01 | 福建新峰二维材料科技有限公司 | A kind of sodium Dual-ion cell of the novel carbon negative pole material preparation of doping phosphorus |
| CN109390572B (en) * | 2018-10-12 | 2021-02-12 | 大连海事大学 | Phosphorus-sulfur/carbon composite material and preparation and application thereof |
| CN110190256A (en) * | 2019-05-23 | 2019-08-30 | 广东工业大学 | A kind of antimony oxide/nitrogen-doped graphene composite material and preparation method and application |
| CN110492105B (en) * | 2019-08-26 | 2022-11-25 | 东莞维科电池有限公司 | Positive electrode material, positive electrode plate prepared from positive electrode material and lithium ion battery obtained from positive electrode plate |
| CN111029549A (en) * | 2019-12-16 | 2020-04-17 | 成都爱敏特新能源技术有限公司 | High-performance lithium ion battery cathode structure and preparation method thereof |
| CN111082028A (en) * | 2019-12-31 | 2020-04-28 | 中南大学 | High-capacity negative electrode material, preparation method and lithium ion battery |
| CN112420999B (en) * | 2020-10-13 | 2023-07-11 | 天津大学 | Phosphorus-based negative electrode material with coating structure and preparation method and application thereof |
| CN113023697A (en) * | 2021-02-02 | 2021-06-25 | 厦门大学 | Red phosphorus/graphene composite roll |
| CN113023713A (en) * | 2021-02-02 | 2021-06-25 | 厦门大学 | Preparation method of red phosphorus/graphene composite roll |
| CN113437281A (en) * | 2021-05-31 | 2021-09-24 | 天津市天大赛达协同创新科技研究院有限公司 | Black phosphorus-based negative electrode material and preparation method thereof |
| CN113307247A (en) * | 2021-06-17 | 2021-08-27 | 西安交通大学 | Preparation method of porous hard carbon/red phosphorus composite material |
| CN114420936B (en) * | 2022-03-29 | 2022-05-27 | 太原科技大学 | Nitrogen-doped expanded-layer graphite/tin phosphide multilayer composite material and preparation method thereof |
| CN114975925A (en) * | 2022-05-24 | 2022-08-30 | 广东凯金新能源科技股份有限公司 | Phosphorus-graphene doped composite graphite negative electrode material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668552A (en) * | 2014-12-08 | 2016-06-15 | 中国科学院成都有机化学有限公司 | Preparation method of easy-to-disperse nitrogen-doped graphene powder |
| CN107293725A (en) * | 2017-07-18 | 2017-10-24 | 深圳市泽纬科技有限公司 | A kind of preparation method of nanometer of red phosphorus and graphene composite negative pole |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860312B (en) * | 2015-05-27 | 2017-01-11 | 上海理工大学 | Preparation method for corrugated nitrogen-doped graphene |
-
2018
- 2018-01-24 CN CN201810069146.XA patent/CN108376767B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668552A (en) * | 2014-12-08 | 2016-06-15 | 中国科学院成都有机化学有限公司 | Preparation method of easy-to-disperse nitrogen-doped graphene powder |
| CN107293725A (en) * | 2017-07-18 | 2017-10-24 | 深圳市泽纬科技有限公司 | A kind of preparation method of nanometer of red phosphorus and graphene composite negative pole |
Non-Patent Citations (1)
| Title |
|---|
| Chemically Bonded Phosphorus/Graphene Hybrid as a High Performance Anode for Sodium-Ion Batteries;Jiangxuan Song等;《Nano letters》;20141029(第14期);第6329-6335页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108376767A (en) | 2018-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108376767B (en) | Red phosphorus/nitrogen doped graphene composite negative electrode material and preparation method and application thereof | |
| CN103779564B (en) | High-performance vanadium phosphate sodium symmetric form sodium-ion battery material and its preparation method and application | |
| CN105006551B (en) | A kind of sodium-ion battery phosphorization tin/Graphene anode material and preparation method thereof | |
| CN108172770B (en) | Carbon-coated NiP with monodisperse structural featuresxNano composite electrode material and preparation method thereof | |
| CN108598394B (en) | Carbon-coated titanium manganese phosphate sodium microspheres and preparation method and application thereof | |
| CN110247037B (en) | Preparation method and application of sodium vanadium oxygen fluorophosphate/graphene compound | |
| CN110808179B (en) | Nitrogen-oxygen co-doped biomass hard carbon material and preparation method and application thereof | |
| CN110957490A (en) | Preparation method of carbon-coated sodium iron phosphate electrode material with hollow structure | |
| CN105185963A (en) | High-performance nitrogen-rich carbon composite electrode material and preparation method thereof | |
| CN113517426B (en) | Sodium vanadium fluorophosphate/reduced graphene oxide composite material and preparation method and application thereof | |
| CN114520323A (en) | Double-strategy modified layered oxide sodium ion battery positive electrode material and preparation method and application thereof | |
| CN105591090A (en) | Preparation method of zinc oxide/nitrogen-doped carbon composite material capable of being used for lithium ion battery negative electrode | |
| CN113314700A (en) | Dual-action modified high-nickel positive electrode material of lithium ion battery and preparation method of dual-action modified high-nickel positive electrode material | |
| CN113479860A (en) | SbPO4Preparation method of/nitrogen-doped carbon composite material | |
| CN110649259A (en) | Positive electrode material K for potassium ion battery0.75MnO2And method for preparing the same | |
| CN109360961B (en) | Hollow composite microsphere for lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN112786853B (en) | High-rate composite negative electrode material of sodium ion battery and preparation method thereof | |
| CN103531813B (en) | A kind of preparation method of high-capacity nano-level lithium iron phosphate/carbon composite positive material | |
| CN110504450B (en) | Preparation method of heteroatom-doped hierarchical pore carbon material and application of heteroatom-doped hierarchical pore carbon material in lithium battery negative electrode slurry | |
| CN114944480B (en) | Preparation method of honeycomb porous tin-carbon composite material | |
| CN114843459B (en) | Antimony pentasulfide-based material and preparation method and application thereof | |
| CN109713263A (en) | A kind of anode material for lithium-ion batteries stratiform δ-MnO2The preparation method of/rGO | |
| CN110797535B (en) | Preparation method of nitrogen-cobalt-oxygen tri-doped network carbon material used as potassium ion battery cathode | |
| CN108987694B (en) | Reduced graphene oxide coated Na4MnV(PO4)3@ rGO microsphere nano material and preparation and application thereof | |
| CN113526486A (en) | Ultrahigh-sulfur-content hard carbon material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221212 Address after: 712046 Floor 2, Building 7, Incubation Park, Gaoke Second Road, Xianyang Hi tech Industrial Development Zone, Shaanxi Province Patentee after: Xianyang Gazelle Valley New Material Technology Co.,Ltd. Address before: Beilin District Xianning West Road 710049, Shaanxi city of Xi'an province No. 28 Patentee before: XI'AN JIAOTONG University |
|
| TR01 | Transfer of patent right |