CN109360959B - Carbon selenium material, preparation method thereof and application thereof in energy storage device - Google Patents

Carbon selenium material, preparation method thereof and application thereof in energy storage device Download PDF

Info

Publication number
CN109360959B
CN109360959B CN201811188854.1A CN201811188854A CN109360959B CN 109360959 B CN109360959 B CN 109360959B CN 201811188854 A CN201811188854 A CN 201811188854A CN 109360959 B CN109360959 B CN 109360959B
Authority
CN
China
Prior art keywords
selenium
carbon
sodium
battery
containing organic
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
Application number
CN201811188854.1A
Other languages
Chinese (zh)
Other versions
CN109360959A (en
Inventor
纪效波
吴天景
侯红帅
邹国强
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201811188854.1A priority Critical patent/CN109360959B/en
Publication of CN109360959A publication Critical patent/CN109360959A/en
Application granted granted Critical
Publication of CN109360959B publication Critical patent/CN109360959B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/028—Positive 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)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a carbon selenium material, a preparation method thereof and application thereof in an energy storage device. The selenium in the carbon selenium material mainly exists in the forms of carbon selenium bond and selenium bond, the stability is good, and the carbon selenium material is used as an electrode material of a sodium ion battery and a sodium selenium battery and shows excellent electrochemical performance. The carbon selenium material is efficiently synthesized by one-step high-temperature heat treatment under simple conditions, has low cost and low requirement on equipment, and is beneficial to industrial production.

Description

Carbon selenium material, preparation method thereof and application thereof in energy storage device
Technical Field
The invention relates to a carbon-selenium material and preparation and application thereof, in particular to a method for generating the carbon-selenium material by taking selenium-containing organic matters as a carbon source and a selenium source through one-step high-temperature reaction, and also relates to application of the carbon-selenium material as an electrode material of energy storage devices such as a sodium ion battery or a sodium-selenium battery, belonging to the technical field of battery materials.
Background
The selenium resource is widely distributed, the existing forms are diversified, in addition, the selenium-containing compound has the advantages of controllable shape and structure, high theoretical capacity and the like, and particularly, the selenium and cheap carbon composite material mainly comprises selenium-doped carbon and a selenium/carbon composite material. In recent years, these materials have wide application prospects in the fields of lithium ion batteries, sodium ion batteries, lithium selenium batteries, sodium selenium batteries, capacitors and the like. Although selenium has a lower theoretical specific mass capacity than sulfur, selenium has a higher density relative to sulfur, and therefore the theoretical volumetric energy density of selenium is comparable to that of sulfur. At the same time, selenium, which is semiconducting, exhibits better conductivity than nearly insulating sulfur, and thus exhibits higher activity and utilization even in a high loading and high areal density battery system. Of course, the single selenium-doped carbon or carbon-selenium composite has some defects in practical application: when the selenium content is low, the battery capacity is also low; when the selenium content is high, the selenium is easy to distribute unevenly to form clusters, so that the performance of the material is unstable; in addition, the elementary selenium mainly used in the process of introducing the selenium is easy to generate a shuttle flying effect, so that the capacity of the battery is rapidly attenuated, and the cycle performance is unstable. Therefore, the preparation method of the carbon selenium material needs to be improved, so that the carbon selenium material and the carbon selenium material are uniformly distributed, and a certain amount of chemical bonds are constructed between the carbon selenium and the carbon selenium, so that the shuttle effect of the material in the energy storage application is favorably relieved, and the performance of the material is greatly improved. Therefore, finding a suitable method for preparing the selenized carbon material becomes a hot point of research.
At present, the method for preparing the carbon-selenium material mainly uses different carbon materials as carbon sources, uses simple substance selenium (CN105070892A, CN104201349A, CN102078816A) as selenium sources, and prepares the carbon-selenium material through a series of reactions such as high temperature and the like. The method firstly prepares the carbon material, and then introduces the selenium under a series of conditions, the process is relatively complex, the conditions are harsh, and the energy consumption is high. When the elemental selenium is introduced into the material, the obtained product is easy to be uneven, the shuttle flying effect of the energy storage device in the use process is difficult to inhibit, and the energy storage performance of the material is not obviously improved.
Disclosure of Invention
The invention aims to solve the problems of high cost, low performance and the like caused by complicated steps, high condition requirements, non-uniform carbon and selenium distribution, unstable structure and the like in the preparation process of the conventional carbon and selenium material, and aims to provide a carbon and selenium material with uniform selenium distribution, stable structure and easily-controlled selenium content.
The second purpose of the invention is to provide a method for preparing the carbon selenium material, which has the advantages of mild conditions, simple operation, low cost and low equipment requirement, and is beneficial to industrial production.
The third purpose of the invention is to provide an application of the carbon selenium material, and the carbon selenium material as an electrode material can obtain a sodium ion battery or a sodium selenium battery with good cycle stability and high rate capability.
In order to realize the technical purpose, the invention provides a preparation method of a carbon selenium material, which comprises the step of carbonizing selenium-containing organic matters in a protective atmosphere to obtain the carbon selenium material.
The invention takes selenium-containing organic matters as a carbon source and a selenium source at the same time, a series of complex chemical reactions occur in the high-temperature reaction process, including carbonization reaction, generation of carbon-selenium bonds and the like, the selenium-containing organic matters are partially dehydrogenated and deoxidized in the protective gas atmosphere, carbonized to form an activation center, and the activation center is combined with the simultaneously fractured partial selenium to form a new carbon-selenium bond and a carbon-selenium long chain, so that the selenium is stably introduced into a carbon structure, and meanwhile, the selenium in the carbon-selenium material is generated in situ from the selenium-containing organic matters and is combined with carbon, and the uniform dispersion of the selenium in the carbon-selenium material is realized.
In a preferable scheme, the ratio of selenium atoms to carbon atoms in the selenium-containing organic compound is more than or equal to 1: 6. Preferred selenium-containing organic compounds include benzoselenophenol (C)10H6Se2) Polyselenophenol, polyselenophenol (C)8H4Se3) 2, 5-dicarboxylselenophenol, selenoether (C)8H6Se3) And at least one of tetramethyltetraselenfulvalene. According to different selected selenium-containing organic matters, carbon selenium materials with different selenium contents can be obtained under the same carbonization condition, and effective regulation and control of selenium in the carbon selenium materials can be realized; but preferably, the selenium-containing organic matter with the selenium-carbon atomic ratio higher than 1:6 is selected, and if the selenium-containing organic matter with the selenium-carbon atomic ratio lower than 1:6 is selected, after high-temperature carbonization, the selenium content is low or even carbon-selenium materials cannot be obtained, so that the application requirements of the sodium ion battery or the sodium-selenium battery are difficult to meet.
Preferably, the carbonization conditions are as follows: and preserving the heat for 1-8 h at the temperature of 400-800 ℃ in a protective atmosphere. The protective atmosphere is generally an inert atmosphere or nitrogen, or a mixed gas of an inert atmosphere and nitrogen. The carbonization treatment is carried out at too low or too high temperature, or the carbonization time is too long or too short, which is not beneficial to the generation of the carbon selenium material, the carbon selenium bond is easy to break and remove selenium due to too high temperature or too long time, the carbon selenium bond is not beneficial to the generation due to too low temperature or too short time, and the carbon selenium material cannot be obtained if the carbonization treatment is not carried out in the protective atmosphere. Under proper carbonization conditions, the carbon selenium material is generated. The preferable carbonization temperature is 500-650 ℃. The preferable carbonization time is 1-3 h.
The crude product of the carbon selenium material prepared by the invention is washed to be neutral, then is centrifugally separated and is dried in vacuum. The centrifugal rotating speed is 5000-10000 r/min. The temperature of vacuum drying is 50-100 ℃, and the drying time is 12 h.
The invention also provides a carbon selenium material which is obtained by the preparation method.
In the carbon selenium material, selenium is physically coated on the surface of the carbon material or is combined with carbon by a covalent bond; selenium is mainly present in the form of selenium bonds or selenium carbon bonds.
The selenium in the carbon selenium material mainly exists in a carbon selenium bonded selenium bond form, the selenium is bonded on the carbon material through the carbon selenium bond, the stability of the material is greatly improved, the selenium is generated in situ and is dispersed stably, and the problems of uneven dispersion and the like in the process of compounding elemental selenium and carbon are solved.
The invention also provides application of the carbon selenium material, and the carbon selenium material is used as an electrode material to be applied to a sodium ion battery or a sodium selenium battery.
The carbon selenium material is used for preparing a sodium ion battery: uniformly mixing the prepared carbon selenium material, sodium carboxymethylcellulose (CMC) and conductive carbon black according to a mass ratio of 80:10:10, adding a proper amount of deionized water to prepare slurry, coating the slurry on a copper foil, and drying the copper foil for 4-12 hours at 40-100 ℃ in a vacuum drying oven after a solvent is volatilized to obtain the electrode for the sodium battery.
The carbon selenium material is used for preparing the sodium selenium battery: 1M NaClO with carbon selenium material as anode, metal sodium as cathode, glass fiber as diaphragm4And the electrolyte is used for assembling the sodium-selenium battery.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the invention adopts selenium-containing organic matters as a carbon source and a selenium source at the same time, organic carbon generates a porous carbon material framework, selenium is generated in situ and is combined on the carbon framework to obtain the carbon-selenium material, the selenium-containing organic matters are common chemical raw materials, the raw material source is wide, and the use of elemental selenium is avoided.
In the preparation process of the carbon-selenium material, carbon and selenium are synchronously formed in real time, and selenium elements in the obtained material are uniformly distributed and form a bonding effect with a carbon framework.
The carbon selenium material has simple reaction conditions, good controllability and rich material sources in the preparation process, and is beneficial to industrial production;
in the preparation process of the carbon selenium material, the organic selenide is used as a direct raw material, so that the carbon selenium material has low requirement on production equipment, low preparation cost and higher economic value;
the invention can adjust and control the selenium content in the carbon selenium material by changing the conditions of the organic selenide, the polymer species, the reaction time, the heating temperature and the like, and is beneficial to obtaining the high-performance carbon selenium material.
The carbon selenium material structure of the invention has a large number of carbon selenium bonds, which is beneficial to the fixation of selenium element, and meanwhile, the carbon selenium material is a porous material, which improves the physical fixation effect on selenium, and the selenium can be stably fixed among the pores of the porous carbon material, therefore, the carbon selenium material is applied to a sodium ion battery or a sodium selenium battery, can well solve the shuttle effect generated in the use process of the electrode material, and thus shows excellent electrochemical performance.
Drawings
Fig. 1 is a scanning electron microscope image and a high-resolution projection electron microscope image of the carbon selenium material prepared in example 1; from fig. 1, it can be seen that the carbon selenium material is partially graphitized and the carbon selenium element is uniformly distributed.
Fig. 2 is an XPS analysis chart of the carbon selenium material prepared in example 1; from fig. 2, it can be illustrated that stable carbon selenium bonds are generated in the carbon selenium material.
Fig. 3 is a cycle performance diagram of the carbon selenium material as an electrode material of a sodium battery in example 5; from FIG. 3, it can be seen that the cycle is more than 200 timesCapacity can be maintained at 300mAh g-1The above;
fig. 4 is a CV curve of the carbon selenium material as a sodium selenium battery in example 6; from FIG. 4, it can be seen that there is a distinct redox peak for selenium;
fig. 5 is a rate performance graph of the sodium-selenium battery assembled by the carbon-selenium material in example 6 at different current densities; fig. 5 illustrates that the carbon selenium material is used as the electrode material of the sodium selenium battery, and the rate performance of the prepared sodium selenium battery is still high under the high current density.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
With benzoselenol (C)10H6Se2) Preparation of carbon selenium material from raw materials
Keeping the benzoselenol for 0.5-2h under the inert gas atmosphere, gradually heating to 500 ℃, keeping the temperature for 1h, and naturally cooling to room temperature after the reaction is finished. Then washing the product to neutrality, and drying the substance obtained after centrifugation at 70 ℃ in vacuum for 10h to obtain the carbon selenium material shown in figure 1. It can be seen from fig. 1a that the obtained carbon selenium material is a sheet structure, it can be further seen from the high-resolution projection electron microscope image of fig. 1b that we prepared a partially graphitized selenized carbon material, and fig. 1c, element plane scanning analysis shows that each element in the material is uniformly distributed.
The procedure and conditions of example 1 were followed to select different organic materials to produce a carbon selenium material, with the results shown in table 1 below:
table 1 comparative table of reaction results of different starting materials
Figure BDA0001826948100000051
Example 2
Preparation of carbon-selenium material by using polyselenophene as raw material in sealed environment
And (3) placing the polyselenophene in a tube sealing environment, gradually heating to 650 ℃, keeping the temperature for 2 hours, and naturally cooling to room temperature after the reaction is finished. And then washing the product to be neutral, and drying the substance obtained after centrifugation for 12h at the temperature of 65 ℃ in vacuum to obtain the high-carbon selenium material. Fig. 2 shows an XPS spectrum of the material.
Example 3
In the same manner as in example 1, when the reaction temperature was set to 400 ℃, 600 ℃ and 700 ℃, the selenium content of the carbon-selenium material prepared under the same conditions was gradually reduced.
Example 4
In the same manner as in example 1, when we extended the heating time to 3 hours, the selenium content of the obtained selenized carbon material was reduced by three fifths under the same conditions.
Example 5
The material obtained in the example 1 is assembled into a sodium ion battery, the material is used as a positive electrode, metal sodium is used as a negative electrode, polypropylene is used as a diaphragm, and 1M NaClO4And (4) preparing an electrolyte. Electrochemical performance tests show that the material has better electrochemical performance when used for a sodium ion battery, and the electrochemical performance is 0.1A g-1The capacity of the capacitor is as high as 400mAh g under the current density of (1)-1(ii) a At 0.1A g-1After the current density is cycled for 200 times, the reversible specific capacity of the lithium iron phosphate is still as high as 320mAh g-1The material also exhibits good cycling performance.
Example 6
The material obtained in the example 2 is assembled into a sodium-selenium battery, the material is used as a positive electrode, metal sodium is used as a negative electrode, glass fiber is used as a diaphragm, and 1M NaClO4And (4) preparing an electrolyte. Electrochemical performance tests show that the material has better electrochemical performance when used for the sodium selenium battery, and a CV curve has an obvious oxidation-reduction peak at 0.1A g-1At a current density of (D), the capacity of the capacitor is up to 450mAh g-1(ii) a At 3.2A g-1The reversible specific capacity is still as high as 260mAh g under the current density of-1The material also shows good rate capability.

Claims (5)

1. A preparation method of a carbon selenium material is characterized by comprising the following steps: putting the selenium-containing organic matter in a protective atmosphere for carbonization treatment to obtain the selenium-containing organic matter; the ratio of selenium atoms to carbon atoms in the selenium-containing organic matter is more than or equal to 1: 6; the selenium-containing organic matter comprises at least one of benzoselenol, polyselenophenol, selenophene, 2, 5-dicarboxyl selenol, selenium ether and tetramethyl tetraseleno fulvalene.
2. The method of claim 1, wherein the carbon selenium material comprises: the carbonization conditions are as follows: and preserving the heat for 1-8 h at the temperature of 400-800 ℃ in a protective atmosphere.
3. A carbon selenium material, characterized by: the method of any one of claims 1 to 2.
4. The carbon selenium material of claim 3, wherein: selenium in the carbon selenium material is physically coated on the surface of the carbon material or is combined with carbon by a covalent bond; selenium is present in the form of seleno-seleno bonds or seleno-carbon bonds.
5. Use of the carbon selenium material of claim 3 or 4, wherein: the electrode material is applied to a sodium ion battery or a sodium selenium battery.
CN201811188854.1A 2018-10-12 2018-10-12 Carbon selenium material, preparation method thereof and application thereof in energy storage device Active CN109360959B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811188854.1A CN109360959B (en) 2018-10-12 2018-10-12 Carbon selenium material, preparation method thereof and application thereof in energy storage device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811188854.1A CN109360959B (en) 2018-10-12 2018-10-12 Carbon selenium material, preparation method thereof and application thereof in energy storage device

Publications (2)

Publication Number Publication Date
CN109360959A CN109360959A (en) 2019-02-19
CN109360959B true CN109360959B (en) 2021-07-27

Family

ID=65348942

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811188854.1A Active CN109360959B (en) 2018-10-12 2018-10-12 Carbon selenium material, preparation method thereof and application thereof in energy storage device

Country Status (1)

Country Link
CN (1) CN109360959B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109817920A (en) * 2019-01-22 2019-05-28 陕西科技大学 A kind of preparation method and application of selenium enveloped carbon nanometer tube/graphene

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104201349A (en) * 2014-08-13 2014-12-10 东南大学 Preparation method of selenium-carbon electrode material with porous structure and application of selenium-carbon electrode material
CN105070892A (en) * 2015-09-22 2015-11-18 中国科学院化学研究所 Preparation method and application of selenium-carbon compound
CN108183224A (en) * 2017-12-30 2018-06-19 武汉理工大学 Porous nucleocapsid carbon/selenium composite material of a kind of original position nitrating and its preparation method and application
CN108502844A (en) * 2018-04-12 2018-09-07 武汉理工大学 A kind of carbon selenium composite material, lithium selenium cell anode and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104201349A (en) * 2014-08-13 2014-12-10 东南大学 Preparation method of selenium-carbon electrode material with porous structure and application of selenium-carbon electrode material
CN105070892A (en) * 2015-09-22 2015-11-18 中国科学院化学研究所 Preparation method and application of selenium-carbon compound
CN108183224A (en) * 2017-12-30 2018-06-19 武汉理工大学 Porous nucleocapsid carbon/selenium composite material of a kind of original position nitrating and its preparation method and application
CN108502844A (en) * 2018-04-12 2018-09-07 武汉理工大学 A kind of carbon selenium composite material, lithium selenium cell anode and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Vacuum Calcination Induced Conversion of Selenium/Carbon Wires to Tubes for High-Performance Sodium-Selenium Batteries;Xuming Yang等;《Advanced Functional Materials》;20180110;第2页左栏第2段、第3节结论部分 *

Also Published As

Publication number Publication date
CN109360959A (en) 2019-02-19

Similar Documents

Publication Publication Date Title
CN107799757B (en) MoS2Nitrogen-doped carbon tube composite material and preparation method and application thereof
CN109728246B (en) Nitrogen-phosphorus co-doped ordered mesoporous carbon material and preparation method and application thereof
CN104201389B (en) A kind of preparation method of lithium selenium cell positive pole
CN109473606B (en) Self-supporting functional interlayer for lithium-sulfur battery and preparation method thereof
CN109755540B (en) Lithium-sulfur battery positive electrode material and preparation method thereof
CN108807808B (en) Preparation method of biomass carbon aerogel modified lithium-sulfur battery diaphragm
CN115417398B (en) High first-effect hard carbon negative electrode for sodium ion battery
CN110148748B (en) Preparation method of soybean protein isolate-based high-rate lithium-sulfur battery cathode carbon material
CN107140633A (en) A kind of preparation method and applications of the activated carbon with high specific surface area of biomass derived
CN105977491A (en) Nitrogen-doped hierarchical porous carbon electrode material and application thereof
CN109638260B (en) Preparation method of carbon-coated graphite negative electrode material
CN108649191B (en) Preparation method of antimony/nitrogen-doped graphene composite for sodium ion battery, and obtained material and application thereof
CN106299311A (en) A kind of preparation method and application of lithium-sulfur cell carbon/sulfur composite positive pole
CN109360959B (en) Carbon selenium material, preparation method thereof and application thereof in energy storage device
CN110336033B (en) Battery positive electrode material, preparation method thereof and lithium-sulfur battery
CN115911284B (en) Method for modifying hard carbon material by utilizing ion irradiation technology and application
CN112174119A (en) Method for preparing graphene foam from antibiotic fungi residues
CN110137494B (en) Porous hard carbon microsphere material and preparation method thereof, button cell and preparation method thereof
CN114751395B (en) Nitrogen-doped porous carbon sphere/S composite material, preparation method thereof and application thereof in lithium-sulfur battery
CN110649250A (en) Preparation method of graphene/sulfur composite material and application of graphene/sulfur composite material in lithium-sulfur battery
CN115947336A (en) Sodium ion battery and modified hard carbon cathode thereof
CN114477128B (en) Preparation of graded porous carbon and application of graded porous carbon in sodium ion battery
CN115472797A (en) Porous carbon supported interlamellar spacing expansion molybdenum disulfide compound and preparation method and application thereof
CN115178209A (en) Method for preparing vanadium sodium phosphate cathode material by microwave method
CN111924843B (en) Preparation method of cyano-modified biomass derived carbon and application of cyano-modified biomass derived carbon in potassium storage field

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