CN113224304B - Copper-nickel co-doped silicon carbide lithium ion battery negative electrode material and preparation method thereof - Google Patents
Copper-nickel co-doped silicon carbide lithium ion battery negative electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN113224304B CN113224304B CN202110503644.2A CN202110503644A CN113224304B CN 113224304 B CN113224304 B CN 113224304B CN 202110503644 A CN202110503644 A CN 202110503644A CN 113224304 B CN113224304 B CN 113224304B
- Authority
- CN
- China
- Prior art keywords
- copper
- silicon carbide
- nickel
- lithium ion
- doped silicon
- 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
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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a copper-nickel co-doped silicon carbide lithium ion battery cathode material and a preparation method thereof, and the method realizes in-situ doping of copper and nickel in the synthesis process of silicon carbide through a gel-sol technology and a calcination heat treatment technology, and the prepared Cu, Ni-SiC electrode material shows high lithium storage capacity and electrochemical cycling stability, which shows important application value in lithium ion batteries.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries and silicon carbide, in particular to a copper-nickel co-doped silicon carbide lithium ion battery cathode material and a preparation method thereof.
Background
In recent years, with the rapid development of social economy and scientific technology, the demand of people for high-energy portable power supplies is greatly increased with the pace of market advance. Especially in the application of high-capacity power batteries, the demand of people on battery materials, especially on the negative electrode materials of high-energy density lithium ion batteries is stimulated. Silicon carbide (SiC) is theoretically favorable for realizing lithium ion intercalation-deintercalation electrochemical reaction due to its wide band gap, high electron mobility, high chemical stability, high energy density and large specific surface area, and is considered as a lithium ion battery negative electrode material with great prospect, but it still has the problems of difficult control of material structure, low lithium storage capacity, poor electrochemical cycle performance and the like in practical application. CN111668463A discloses a lithium ion battery cathode material and a preparation method thereof, the invention constructs a silicon-carbon electrode material with a three-dimensional tree structure by mixing a pyrolytic carbon-carbon fiber complex, a silicon-silicon carbide composite nanowire, silicon powder and carbon microspheres, so as to improve the combination degree of the components, and further improve the specific capacity and stability of the lithium ion battery cathode material; however, the invention only provides a synthetic method of the material, does not introduce the application effect of the material in the lithium ion battery cathode material, and has no practical significance for the exploration and development of the material. CN108400311B discloses a nitrogen-doped flocculent carbon-silicon composite electrode material and an in-situ preparation method thereof, the invention utilizes an irradiation technology to prepare the nitrogen-doped flocculent carbon-silicon composite electrode material in situ, and the material has a simple synthesis technology, but the electrochemical lithium storage capacity of the material is lower and needs to be further improved. Therefore, the development of a silicon carbide cathode material with high capacity and reliable cycling stability has caused the research heat of people.
Disclosure of Invention
In order to solve the problems, the invention provides a copper-nickel co-doped silicon carbide lithium ion battery negative electrode material and a preparation method thereof, wherein the technical scheme is as follows:
step 1: under magnetic stirring, tetraethyl silicate and absolute ethyl alcohol are mixed, then a carbon source is added for mixing and stirring for 5-20min, and then 0.5mol/L hydrochloric acid is added in a water bath environment until a test solution is hydrolyzed into a uniform sol solution; then adding nickel nitrate hexahydrate and copper acetate, uniformly dispersing by ultrasonic waves, continuously stirring for 3-5h, and transferring the mixture into an oven for low-temperature drying to obtain gel;
step 2: grinding the gel obtained in the step 1 into fine powder, then placing the fine powder into an alumina crucible, placing the alumina crucible at the central position of a tubular furnace, and carrying out high-temperature calcination under the protection of hydrogen-argon mixed gas; grinding the product, placing the product in a plastic beaker, cleaning the product by adopting a mixed solution of hydrofluoric acid and nitric acid, and filtering to remove silicon dioxide and other metal impurities; and finally, washing with deionized water, filtering and drying to obtain the copper-nickel co-doped silicon carbide material (Cu, Ni-SiC).
Preferably, the technical solution further comprises part or all of the following technical features:
preferably, the carbon source in step 1 is one of glucose, sucrose and sodium acetate.
Preferably, the volume ratio of the tetraethyl silicate to the carbon source in the step 1 is (2-4): (1-5), wherein the concentration of the carbon source solution is 0.6 g/mL.
Preferably, the water bath environment in step 1 is heated at 60-85 ℃.
Preferably, the volume ratio of the tetraethyl silicate to the hydrochloric acid in the step 1 is 4 (1-3).
Preferably, the mole ratio of the tetraethyl silicate, the nickel nitrate hexahydrate and the copper acetate in the step 1 is 1 (0.003-0.03) to (0.003-0.03).
Preferably, the low-temperature drying in the step 1 is drying in an oven at 50-70 ℃ for 24 h.
Preferably, the aeration flow rate of the hydrogen-argon mixed gas in the step 2 is 30-50 mL/min; wherein the volume of the hydrogen accounts for 10 percent, and the volume of the argon accounts for 90 percent.
Preferably, the high-temperature calcination in step 2 is performed by raising the temperature to 1300 ℃ and 1500 ℃ at a rate of 5 ℃/min and continuing the calcination for 3-5 h.
Preferably, the volume ratio of the hydrofluoric acid to the nitric acid in the step 2 is 3 (7-10).
The synthesis mechanism of the invention is as follows:
the method takes tetraethyl silicate as a silicon source and hydrochloric acid solution as a hydrolysis-assisting agent, and carries out hydrolysis and polycondensation reaction in the environment of blending organic solvent anhydrous ethanol and a carbon source to carry out sol-gelation on the material; and nickel ions and copper ions are introduced after the hydrolysis precursor is generated, the nucleation and growth of the material are promoted in the solvothermal reaction process, and the material is reduced in the calcination of hydrogen-argon mixed gas, so that the copper-nickel co-doped silicon carbide material is prepared.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) because the silicon carbide has larger specific surface area and more exposed atoms on the surface, the in-situ doping of copper and nickel is realized in the sol-gel thermal synthesis process, and the copper-nickel co-doped silicon carbide lithium ion battery cathode material (Cu, Ni-SiC) is finally prepared, so that the unit cell structure of SiC is changed. Electrochemical experiment tests show that the electrode material has ultrahigh lithium storage capacity, excellent rate capability and very stable cycle performance.
(2) The reason why the Cu, Ni-SiC electrode material prepared by the invention has excellent electrochemical performance can be attributed to the double doping of copper and nickel, a stable heterostructure is formed between the copper, the nickel and the silicon carbide semiconductor, more transmission channels are provided for the insertion-extraction of lithium ions, and the introduction of the copper and the nickel also improves the conductivity of the silicon carbide semiconductor material and is beneficial to the rapid migration of electrons.
Detailed Description
To further clarify the disclosure, features and advantages of the present invention, reference will now be made to the following examples and to the accompanying drawings.
Example 1
The Cu, Ni-SiC lithium ion battery cathode material prepared in the embodiment 1 of the invention comprises the following steps:
step 1: under magnetic stirring, 5mL of tetraethyl silicate and 30mL of absolute ethyl alcohol are mixed, then 3mL of glucose solution is added, mixed and stirred for 10min, and then 2mL of 0.5mol/L hydrochloric acid is added in a water bath environment at 75 ℃ until a test solution is hydrolyzed into a uniform sol solution; then adding 28mg of nickel nitrate hexahydrate and 20mg of copper acetate, ultrasonically dispersing uniformly, continuously stirring for 4 hours, transferring the mixture into a 60 ℃ oven, heating and drying for 24 hours to gelatinize the sol;
and 2, step: grinding the gel obtained in the step 1, finely crushing, placing the gel into an alumina crucible, placing the alumina crucible at the central position of a tubular furnace, introducing a hydrogen-argon mixed gas at the speed of 40mL/min, heating to 1300 ℃ at the speed of 5 ℃/min, and continuously calcining for 3 h; grinding the product, placing the product in a plastic beaker, cleaning the product by adopting a mixed solution of hydrofluoric acid and nitric acid, and filtering to remove silicon dioxide and other metal impurities; and finally, washing with deionized water, filtering and drying to obtain the copper-nickel co-doped silicon carbide material (Cu, Ni-SiC).
Example 2
The Cu, Ni-SiC lithium ion battery cathode material prepared in the embodiment 2 of the invention comprises the following steps:
step 1: under magnetic stirring, mixing 4mL of tetraethyl silicate and 30mL of absolute ethyl alcohol, then adding 2mL of glucose solution, mixing and stirring for 10min, and then adding 2mL of 0.5mol/L hydrochloric acid in a water bath environment at 75 ℃ until the test solution is hydrolyzed into a uniform sol solution; then adding 20mg of nickel nitrate hexahydrate and 10mg of copper acetate, ultrasonically dispersing uniformly, continuously stirring for 4 hours, transferring the mixture to a 60 ℃ oven, heating and drying for 24 hours to gelatinize the sol;
step 2: grinding the gel obtained in the step 1, finely crushing, placing the gel into an alumina crucible, placing the alumina crucible at the central position of a tubular furnace, introducing a hydrogen-argon mixed gas at the speed of 40mL/min, heating to 1300 ℃ at the speed of 5 ℃/min, and continuously calcining for 3 h; grinding and finely crushing the product, placing the product in a plastic beaker, cleaning the product by adopting a mixed solution of hydrofluoric acid and nitric acid, and filtering to remove silicon dioxide and other metal impurities; and finally, washing with deionized water, filtering and drying to obtain the copper-nickel co-doped silicon carbide material (Cu, Ni-SiC).
Comparative example 1
Comparative example 1 of the present invention is different from example 1 in that a nickel-doped silicon carbide material was prepared without adding copper acetate.
Comparative example 2
Comparative example 2 of the present invention is different from example 1 in that a copper-doped silicon carbide material was prepared without adding nickel nitrate hexahydrate.
Comparative example 3
Comparative example 3 of the present invention is different from example 1 in that a silicon carbide material was prepared without adding nickel nitrate hexahydrate and copper acetate.
And (3) test characterization:
1. preparation of electrodes and assembly of batteries
Weighing the electrode material prepared by the embodiment, the super conductive carbon and the polyvinylidene fluoride according to the mass ratio of 8:1:1, dissolving the electrode material in N-methyl pyrrolidone, grinding the mixture into uniform slurry, coating the slurry on copper foil, drying the slurry at low temperature, putting the slurry in a vacuum drying oven for drying overnight, and finally cutting the slurry into wafers with uniform size by using a slicing machine; and then assembling the positive electrode shell, the gasket, the lithium sheet, the electrolyte, the diaphragm, the electrolyte, the prepared electrode wafer, the gasket and the negative electrode shell of the battery in an argon glove box, and finally sealing the battery by using a battery pressing machine.
2. Electrochemical performance test
(1) Charge and discharge cycle test
Placing the prepared battery in a battery clamp of a battery tester, setting the theoretical specific capacity of the material to be 2680mAh/g, and setting the voltage test interval to be 0-2V; the charge-discharge cycle program was then set to charge and discharge 100 cycles at 0.1C rate, followed by 500 cycles at 1C rate for a total of 600 cycles of charge-discharge cycle testing. After the test is finished, the data information of the cycle number and the specific capacity of the battery can be obtained from the battery system, and the specific data is shown in table 1.
Table 1: cycling Performance tables for materials prepared in inventive examples 1-2 and comparative examples 1-3
As can be seen from the data in table 1, the first-turn specific discharge capacities of the batteries prepared in the examples 1 and 2, the comparative examples 1 and 2 and the comparative example 3 of the present invention are 755.4mAh/g, 726.2mAh/g, 541.4mAh/g, 519.1mAh/g and 453.4mAh/g, respectively, wherein the copper-nickel doped silicon carbide batteries prepared in the examples 1 to 2 have excellent specific capacities; after 100 cycles, the capacity retention rates are respectively 95.4%, 95.1%, 92.7%, 90.3% and 86.1%, and it can be seen that the battery prepared in example 1-2 has not only higher lithium storage capacity but also good cycle performance.
When the batteries prepared in the examples 1, 2, 1, 2 and 3 are charged and discharged at the rate of 1C, the specific discharge capacity of the first circle of the batteries is 709.4mAh/g, 676.2mAh/g, 495.3mAh/g, 452.2mAh/g and 363.3 mAh/g; after 500 cycles, the discharge specific capacities are 644.3mAh/g, 610.4mAh/g, 419.7mAh/g, 355.4mAh/g and 246.2mAh/g respectively, and the cycle capacity retention rates are 90.8%, 90.3%, 84.7%, 78.6% and 65% respectively. From the above data, it can be seen that the copper-nickel co-doped silicon carbide cells prepared in examples 1-2 have excellent electrochemical cycling performance, and even after 500 cycles, the cells still have capacity retention rate of 90% or more, compared with the cells made of single-metal doped silicon carbide or silicon carbide without metal doping, the cells show poor electrochemical performance.
(2) Electrochemical impedance testing
Placing the cell in a cell holder of an electrochemical workstation, setting a voltage test interval of 0-2V, and then using a 5mV sine wave at 10-2Hz to 10-5The ac impedance test was performed on the batteries at Hz frequency, and the specific resistance data are shown in table 3.
Table 2: electrochemical impedance table of examples 1-2 of the present invention and comparative examples 1-3
| Item | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Resistance (RC) | 103Ω | 119Ω | 148Ω | 155Ω | 251Ω |
As can be seen from table 2, the batteries prepared in examples 1-2 have smaller impedance values, because doping copper and nickel improves the conductivity of the material, accelerates the electron transport, and thus has excellent electrochemical properties.
The raw materials listed in the invention, the values of the upper and lower intervals of the raw materials of the invention and the values of the upper and lower intervals of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed here. While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. Such modifications and variations are considered to be within the scope of the invention.
Claims (1)
1. A preparation method of a copper-nickel co-doped silicon carbide lithium ion battery negative electrode material is characterized by comprising the following steps:
step 1: under magnetic stirring, tetraethyl silicate and absolute ethyl alcohol are mixed, then a carbon source is added for mixing and stirring for 5-20min, and then 0.5mol/L hydrochloric acid is added in a water bath environment until a test solution is hydrolyzed into a uniform sol solution; then adding nickel nitrate hexahydrate and copper acetate, uniformly dispersing by ultrasonic waves, continuously stirring for 3-5h, and transferring the mixture into an oven for low-temperature drying to obtain gel;
step 2: grinding the gel obtained in the step 1 into fine powder, then placing the fine powder into an alumina crucible, placing the alumina crucible at the central position of a tubular furnace, and carrying out high-temperature calcination under the protection of hydrogen-argon mixed gas; grinding the product, placing the product in a plastic beaker, cleaning the product by adopting a mixed solution of hydrofluoric acid and nitric acid, and filtering to remove silicon dioxide and other metal impurities; finally, washing, filtering and drying the silicon carbide material by using deionized water to obtain a copper-nickel co-doped silicon carbide material (Cu, Ni-SiC);
wherein, the volume ratio of the tetraethyl silicate to the carbon source in the step 1 is (2-4) to (1-5), and the concentration of the carbon source solution is 0.6 g/mL; the water bath environment in the step 1 is heating at 60-85 ℃; the volume ratio of the tetraethyl silicate to the hydrochloric acid in the step 1 is 4 (1-3); the mole ratio of the tetraethyl silicate, the nickel nitrate hexahydrate and the copper acetate in the step 1 is 1 (0.003-0.03) to 0.003-0.03; the low-temperature drying in the step 1 is drying in an oven at 50-70 ℃ for 24 hours; the ventilation flow of the hydrogen-argon mixed gas in the step 2 is 30-50 mL/min; wherein the volume of the hydrogen accounts for 10 percent, and the volume of the argon accounts for 90 percent; the high-temperature calcination in the step 2 is to heat up to 1300 ℃ and 1500 ℃ at the speed of 5 ℃/min and continuously calcine for 3-5 h; the volume ratio of the hydrofluoric acid to the nitric acid in the step 2 is 3 (7-10); the carbon source in the step 1 is one of glucose, sucrose and sodium acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110503644.2A CN113224304B (en) | 2021-05-10 | 2021-05-10 | Copper-nickel co-doped silicon carbide lithium ion battery negative electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110503644.2A CN113224304B (en) | 2021-05-10 | 2021-05-10 | Copper-nickel co-doped silicon carbide lithium ion battery negative electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113224304A CN113224304A (en) | 2021-08-06 |
| CN113224304B true CN113224304B (en) | 2022-07-05 |
Family
ID=77093965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110503644.2A Active CN113224304B (en) | 2021-05-10 | 2021-05-10 | Copper-nickel co-doped silicon carbide lithium ion battery negative electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113224304B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177269A (en) * | 2007-12-13 | 2008-05-14 | 复旦大学 | Meso-porous structural high specific surface carborundum material and preparation method thereof |
| CN102674354A (en) * | 2012-05-11 | 2012-09-19 | 南京工业大学 | Preparation method for mesoporous silicon carbide material |
| CN103137973A (en) * | 2013-03-08 | 2013-06-05 | 张泽森 | Carbonization base electrode material |
| CN107001052A (en) * | 2014-11-18 | 2017-08-01 | 帕德博恩大学 | Method for producing the electrode material for battery electrode |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8753545B2 (en) * | 2010-03-03 | 2014-06-17 | 3M Innovative Properties Company | Composite negative electrode materials |
-
2021
- 2021-05-10 CN CN202110503644.2A patent/CN113224304B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177269A (en) * | 2007-12-13 | 2008-05-14 | 复旦大学 | Meso-porous structural high specific surface carborundum material and preparation method thereof |
| CN102674354A (en) * | 2012-05-11 | 2012-09-19 | 南京工业大学 | Preparation method for mesoporous silicon carbide material |
| CN103137973A (en) * | 2013-03-08 | 2013-06-05 | 张泽森 | Carbonization base electrode material |
| CN107001052A (en) * | 2014-11-18 | 2017-08-01 | 帕德博恩大学 | Method for producing the electrode material for battery electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113224304A (en) | 2021-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109399601B (en) | Preparation method and application of nitrogen-phosphorus co-doped biochar material | |
| CN104103821B (en) | The preparation method of silicon-carbon cathode material | |
| CN113725432B (en) | ZIF-67 and preparation method of cobalt selenide/carbon electrode material derived from ZIF-67 | |
| CN110518213A (en) | A kind of porous silicon-carbon nano tube compound material and its preparation method and application | |
| LU500866B1 (en) | CATHODE MATERIAL Mo-VS4/N-GNTS OF MAGNESIUM-ION BATTERY AND USE THEREOF | |
| CN108011105A (en) | Carbon nanosheet material, preparation thereof and application thereof in sodium-ion battery | |
| CN107195893A (en) | A kind of lithium ion battery boron-doping silicon base negative material | |
| CN110660987B (en) | Boron-doped hollow silicon spherical particle/graphitized carbon composite material and preparation method thereof | |
| CN109860526B (en) | Preparation method of graphite material doped with metal oxalate lithium battery composite negative electrode material | |
| CN109671935B (en) | Preparation method and application of silicon dioxide/biochar composite material | |
| CN112038614B (en) | Negative electrode material for sodium ion battery and preparation method thereof | |
| CN112850708A (en) | Preparation method and application of nitrogen-doped porous carbon material with high specific surface area | |
| CN109346685B (en) | SiO (silicon dioxide)xPreparation method and application of/C spherical powder | |
| CN114890403A (en) | Nitrogen-doped polymer derived carbon material and application thereof in sodium ion battery | |
| CN113644269B (en) | Preparation method of nitrogen-doped hard carbon material, product and application thereof | |
| CN113036097B (en) | Sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material and preparation method thereof | |
| CN113782724A (en) | Ferro-nickel phosphide-carbon composite material and preparation method and application thereof | |
| CN107316974B (en) | Preparation method of nano-silver composite lithium iron phosphate cathode material | |
| CN113224304B (en) | Copper-nickel co-doped silicon carbide lithium ion battery negative electrode material and preparation method thereof | |
| CN112299389A (en) | Method for preparing sodium ion carbon negative electrode material by using nitrogen-doped porous biomass carbon | |
| CN112018383A (en) | Boron-phosphorus co-doped MXene material and preparation method thereof | |
| CN114105149B (en) | Carbon-coated nitrogen-phosphorus double-doped silicon oxide composite material, preparation method thereof and application thereof in lithium ion battery | |
| CN106684383B (en) | Mesoporous molybdenum nitride nanowire and preparation method and application thereof | |
| CN113299892B (en) | Preparation method of iron-doped titanium dioxide/tungsten carbide lithium ion battery cathode material | |
| CN114899382A (en) | N-doped porous carbon double-shell microsphere structure coated Co 3 O 4 Material, 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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220615 Address after: 044000 north of Zhenxing East Road, new material industrial park, Fenglingdu Development Zone, Ruicheng County, Yuncheng City, Shanxi Province Applicant after: Shanxi lvpu photoelectric New Material Technology Co.,Ltd. Address before: 311100 Room 102, building 6, shangfengxuan, happy city, Nanyuan street, Yuhang District, Hangzhou City, Zhejiang Province Applicant before: Zhejiang liaojiang New Material Co.,Ltd. Effective date of registration: 20220615 Address after: 335000 south of Weiyi road and west of Shenghua Avenue, Guixi sulfur and phosphorus chemical base, Yingtan City, Jiangxi Province Applicant after: Jiangxi PRINSEN New Energy Technology Co.,Ltd. Address before: 044000 north of Zhenxing East Road, new material industrial park, Fenglingdu Development Zone, Ruicheng County, Yuncheng City, Shanxi Province Applicant before: Shanxi lvpu photoelectric New Material Technology Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |