CN114085377B - Preparation of polyaniline/carbon nano tube composite material and application of polyaniline/carbon nano tube composite material in sodium-based double-ion battery - Google Patents

Preparation of polyaniline/carbon nano tube composite material and application of polyaniline/carbon nano tube composite material in sodium-based double-ion battery Download PDF

Info

Publication number
CN114085377B
CN114085377B CN202111383159.2A CN202111383159A CN114085377B CN 114085377 B CN114085377 B CN 114085377B CN 202111383159 A CN202111383159 A CN 202111383159A CN 114085377 B CN114085377 B CN 114085377B
Authority
CN
China
Prior art keywords
polyaniline
carbon nano
nano tube
composite material
tube composite
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
CN202111383159.2A
Other languages
Chinese (zh)
Other versions
CN114085377A (en
Inventor
焦丽芳
孙志钦
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.)
Nankai University
Original Assignee
Nankai 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 Nankai University filed Critical Nankai University
Priority to CN202111383159.2A priority Critical patent/CN114085377B/en
Publication of CN114085377A publication Critical patent/CN114085377A/en
Application granted granted Critical
Publication of CN114085377B publication Critical patent/CN114085377B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/026—Wholly aromatic polyamines
    • C08G73/0266—Polyanilines or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • 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
    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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

Abstract

Preparation of polyaniline/carbon nano tube composite material and application in sodium-based double-ion battery. The preparation of polyaniline/carbon nano tube composite material is carried out by a simple stirring method, firstly aniline monomer and carbon nano tube are uniformly dispersed into mixed solvent containing hydrofluoric acid and hydrochloric acid, and after cooling treatment, oxidant is added for in-situ polymerization. The preparation process is simple and feasible, the reaction condition does not need high temperature and high pressure, the control is easy, the adopted raw materials are low in cost, and the preparation process is suitable for large-scale production. The excellent conductivity and structural stability of the carbon nano tube can be complemented with the high capacity advantage of polyaniline, and the electrochemical performance of the composite material for storing anions is comprehensively improved through the introduction of fluorine element and protonation.

Description

Preparation of polyaniline/carbon nano tube composite material and application of polyaniline/carbon nano tube composite material in sodium-based double-ion battery
Technical Field
The invention belongs to the technical field of sodium-based double-ion full batteries, and particularly relates to preparation of a positive electrode material, in particular to efficient storage of anions with larger volumes.
Background
Unlike conventional "rocking chair" metal ion batteries, a Dual Ion Battery (DIB) will achieve high energy/power density output because anions and cations can participate in the charge transfer reactions of both the anode and cathode. Due to the large volume of anions, the structural stability of the cathode material is critical for intercalation/deintercalation of anions. For example, hexafluorophosphate (PF 6 - ) The volume is larger, and when it is stored into the positive electrode active material under the action of an electric field, a larger volume expansion is caused. This significant volume expansion causes rapid performance losses while causing more irreversible electrochemical reactions to occur. To break this limitation, it is important to study a novel positive electrode with high stability, large capacity and long life.
Disclosure of Invention
The invention aims to solve the problems of low specific capacity for anion storage, poor reversibility and insufficient chemical kinetics of a double-ion battery anode material, and provides a preparation method of a polyaniline/carbon nano tube composite material and application of the composite material in a sodium-based double-ion battery. Polyaniline has been widely studied as a battery material. The organic conductor has good redox reversibility and high stability, can show different electrochemical characteristics by using doping means in different modes, and is applied to the positive electrode of the highly reversible double-ion battery. In polyaniline, nitrogen protonation is a doping process (n-type doping) that promotes uniformity of the number of electrons on the polymer chain. When polyaniline is contacted with a halogen acid, some of the nitrogen atoms are protonated, creating a positive charge that moves in the conjugated chain, while the halogen anion will dope into the conjugated chain of the polyaniline. At the end of this process, the resulting polymer is in the form of a salt and can significantly affect the cell performance for anion storage. Carbon nanotubes are attracting attention for their excellent electrical conductivity and mechanical strength. When combined as a matrix with an active material, can lead to significant performance improvements. Polyaniline is polymerized on the surface of a carbon nano tube in situ, and halogen acid is used for effective modification, so that the problems of low specific capacity, poor reversibility and insufficient electrochemical kinetics of the cathode material of the double-ion battery can be solved.
The technical scheme of the invention is as follows:
the preparation method of the polyaniline/carbon nano tube composite material comprises the following preparation steps:
(1) First, preparing a precursor solution: aniline monomer, hydrofluoric acid, hydrochloric acid and carbon nanotube (with the size of 60-100 nm) are evenly dispersed into a solvent, stirred and mixed for 5-8 hours at room temperature (20-30 ℃), and then the reaction system is cooled to below 5 ℃ in an ice bath.
(2) Adding oxidant into the dispersion liquid, controlling the temperature of the mixed solution between 3 and 5 ℃ in the whole process, and continuously stirring the mixed solution for 6 to 8 hours after the oxidant is added. And after polymerization, carrying out suction filtration and washing on the product until filtrate is colorless, clear and freeze-dried to obtain the final target product polyaniline/carbon nano tube composite material.
In the step, the mass ratio of the aniline monomer to the carbon nano tube is 1:2-3; the solvent is ultrapure water, and the total volume of the final solution is 100mL; the molar ratio of the aniline monomer to the hydrofluoric acid to the hydrochloric acid is 1:10:5; the oxidant is one of ammonium persulfate, potassium persulfate or sodium persulfate, and the molar ratio of the aniline monomer to the oxidant is 1:1-1.5.
The invention also provides application of the polyaniline/carbon nano tube composite material in the sodium-based double-ion battery, and the method comprises the following steps:
(3) And (3) battery assembly: the final target product polyaniline/carbon nano tube, conductive carbon black (super P) and Polytetrafluoroethylene (PTFE) are uniformly mixed in ethanol according to the mass ratio of 7:2:1 or 8:1:1, and stirred for 1-2 h. After the titanium mesh is prepared into uniform electrode slurry, ethanol is evaporated to dryness, the solid is rolled into a film, and the film is cut into square with the thickness of 8 multiplied by 8mm and is stamped and fixed on the surface of a titanium mesh, wherein the thickness of a titanium mesh load electrode is 75-100 mu m, and the diameter of the titanium mesh is a wafer current collector with the diameter of 12 mm. After the preparation, the mixture was dried in a vacuum oven at 60℃for 2 hours. Finally, a two-electrode system is formed by the battery and sodium metal in a glove box, and the assembled model of the battery is CR2032 button battery.
The invention has the advantages and beneficial effects that:
the preparation method has the advantages of simple preparation steps, no need of high temperature and high pressure for reaction conditions, easy control, low cost of the adopted raw materials, suitability for large-scale production and high repeatability. The mixed haloacid may be doped into the polyaniline conjugated chain during the polymerization of the monomer. The acidic environment can provide sufficient hydrogen ions, is favorable for the generation of protonated polyaniline, and plays a role in greatly improving specific capacity. Meanwhile, the existence of fluoride ions in the conjugated chain can obviously play a key role in the long cycle life of the electrode. The addition of the carbon nanotube substrate can obviously improve the conductivity of the battery active material, plays a role in dispersing the conductive polymer, avoids the aggregation of the material to a great extent, and can buffer the problem of volume expansion of the electrode in the charge and discharge process. The overall composite material exhibits a cross-linked structure which facilitates rapid kinetics of anions during charge and discharge. Electrochemical tests show that the prepared material has higher specific discharge capacity and simultaneously has excellent cycle stability and nearly 100% coulombic efficiency.
Drawings
FIG. 1 is an infrared spectrum of polyaniline and polyaniline/carbon nanotubes prepared.
Fig. 2 is an analysis of the elemental contents of the prepared polyaniline/carbon nanotubes.
Fig. 3 is a TEM topography of the prepared polyaniline/carbon nanotubes.
Fig. 4 is a TGA test of the prepared carbon nanotubes, polyaniline and polyaniline/carbon nanotubes.
Fig. 5 is a graph of the rate performance of the prepared polyaniline/carbon nanotube electrode, wherein (a) is a constant current charge-discharge curve of the polyaniline/carbon nanotube electrode at different current densities, and (b) is a graph of the rate of the electrode material.
FIG. 6 shows the cycle life performance of the polyaniline/carbon nanotubes prepared, wherein (a) is the polyaniline/carbon nanotube electrode at 0.2 A.g -1 Performance for 250 weeks at cycling conditions, (b) is a TEM topography after cycling of the electrode material.
Detailed Description
Example 1
In the step of preparing the polymerization precursor, the size of the carbon nanotube may be 60nm to 100nm. Before aniline, hydrofluoric acid and hydrochloric acid are added, the mass fraction of the carbon nano tube in the solvent is not more than 15%, and the inventor finds that the composite material is easier to agglomerate and has poor effect when being prepared at the concentration.
(1) Precursor solution configuration: the total volume of the precursor mixed solution is 100mL, hydrofluoric acid, concentrated hydrochloric acid, aniline monomer and carbon nano tube are uniformly dispersed into ultrapure water, and after uniform mixing, mixing and stirring are carried out at room temperature (20-30 ℃), and the treatment time is 6h. Compared with other temperatures, the temperature range can be more favorable for electrostatic attraction of the aniline monomer and the carbon tube. After stirring uniformly, it was ice-bathed and the temperature was reduced to 5 ℃. The mass ratio of the aniline monomer to the carbon nano tube is 1:2; the molar ratio of the aniline monomer to the hydrofluoric acid to the hydrochloric acid is 1:10:5.
(2) Preparation of polyaniline/carbon nano tube composite material: in the polymerization step of preparing polyaniline/carbon nano tube, ammonium persulfate oxidant is added when the temperature of the precursor solution is reduced to 3 ℃. Studies have shown that polymerization at lower temperatures is advantageous for increasing the molecular weight of polyaniline and for obtaining polymers with narrower molecular weight distribution. The molar ratio of the ammonium persulfate to the aniline monomer is 1:1. The whole reaction temperature is 3-5 ℃ and the reaction time is 6h.
Example 2
(1) Precursor solution configuration: the total volume of the precursor mixed solution is 100mL, hydrofluoric acid, concentrated hydrochloric acid, aniline monomer and carbon nano tube are uniformly dispersed into ultrapure water, and after uniform mixing, mixing and stirring are carried out at room temperature (20-30 ℃), and the treatment time is 6h. Compared with other temperatures, the temperature range can be more favorable for electrostatic attraction of the aniline monomer and the carbon tube. After stirring uniformly, it was ice-bathed and the temperature was reduced to 5 ℃. The mass ratio of the aniline monomer to the carbon nano tube is 1:2; the molar ratio of the aniline monomer to the hydrofluoric acid to the hydrochloric acid is 1:10:5.
(2) Preparation of polyaniline/carbon nano tube composite material: in the polymerization step of preparing polyaniline/carbon nano tube, when the temperature of the precursor solution is reduced to 3 ℃, adding potassium persulfate oxidant. The molar ratio of the potassium persulfate to the aniline monomer was 1.25:1. The whole reaction temperature is 3-5 ℃ and the reaction time is 6h.
Example 3
(1) Precursor solution configuration: the total volume of the precursor mixed solution is 100mL, hydrofluoric acid, concentrated hydrochloric acid, aniline monomer and carbon nano tube are uniformly dispersed into ultrapure water, and after uniform mixing, mixing and stirring are carried out at room temperature (20-30 ℃), and the treatment time is 6h. Compared with other temperatures, the temperature range can be more favorable for electrostatic attraction of the aniline monomer and the carbon tube. After stirring uniformly, it was ice-bathed and the temperature was reduced to 5 ℃. The mass ratio of the aniline monomer to the carbon nano tube is 1:2; the molar ratio of the aniline monomer to the hydrofluoric acid to the hydrochloric acid is 1:10:5.
(2) Preparation of polyaniline/carbon nano tube composite material: in the polymerization step of preparing polyaniline/carbon nano tube, ammonium persulfate sodium oxidant is added when the temperature of the precursor solution is reduced to 3 ℃. The molar ratio of the added sodium persulfate to the aniline monomer was 1.5:1. The whole reaction temperature is 3-5 ℃ and the reaction time is 6h.
Battery assembly
Example 4:
(1) Preparing electrode slurry, uniformly mixing final target products polyaniline/carbon nano tube, conductive carbon black (super P) and Polytetrafluoroethylene (PTFE) in ethanol according to the mass ratio of 7:2:1, and stirring for 1h. After the titanium mesh is prepared into uniform electrode slurry, ethanol is evaporated to dryness, the solid is rolled into a film, and the film is cut into square with the thickness of 8 multiplied by 8mm and is stamped and fixed on the surface of a titanium mesh, and a titanium mesh loading electrode is 100 mu m, and a wafer current collector with the diameter of 12mm is used for the titanium mesh. After the preparation, the mixture was dried in a vacuum oven at 60℃for 2 hours.
(2) 5mmol of NaPF was added to 5mL of Propylene Carbonate (PC) as a solvent for the electrolyte 6 . Glass fiber with a diameter of 16mm is used as a diaphragm, and a metal sodium sheet with a diameter of 14mm is used as a counter electrode. The whole process of assembling the CR2032 button battery is in a glove box with argon atmosphere, and the voltage test range is 2.2-4.2V.
FIG. 1 is an infrared spectrum of polyaniline and polyaniline/carbon nanotubes showing the correspondence of infrared characteristic peaks for both materials. At 1600 and 1500cm -1 The positions correspond to the stretching vibration of the nitrogen-quinone ring and the nitrogen-benzene ring respectively. At 1100 and 1300cm -1 The corresponding protonated imine can prove that the prepared polyaniline composite material has a reduced state, which is favorable for improving specific capacity.
Fig. 2 is an X-ray spectroscopy (EDS) of the polyaniline/carbon nanotubes prepared, from which it can be seen that fluorine was successfully doped into the conjugated backbone after aniline polymerization.
Fig. 3 is a TEM morphology of polyaniline/carbon nanotubes, and it can be seen that polyaniline is uniformly coated on the surface of the carbon nanotubes, and the thickness is about 100nm.
Fig. 4 shows TGA test of polyaniline/carbon nanotubes, and the mass fraction of polyaniline in the polyaniline/carbon nanotube composite material can be calculated to be 78% according to the test result.
FIG. 5 is a graph showing the constant current density of sodium ion batteries assembled with metallic sodiumCurrent charge-discharge graph (a in fig. 5). The rate capability of polyaniline/carbon nano tube shows that the current density is 0.2 A.g -1 When the reversible capacity reaches 127 mAh.g -1 The method comprises the steps of carrying out a first treatment on the surface of the When the current density is increased to 3 A.g -1 When the reversible capacity is maintained at about 75 mAh.g -1 (b in FIG. 5).
FIG. 6 shows the current density of the polyaniline/carbon nanotubes prepared at 0.2 A.g -1 The cycle life is lower, and the prepared electrode material has better cycle stability, namely, the coulombic efficiency is more stable after 250 cycles, and the capacity can be maintained at about 101 mAh.g -1 。

Claims (2)

1. The application of the polyaniline/carbon nano tube composite material in the sodium-based double-ion battery is characterized in that the preparation method of the polyaniline/carbon nano tube composite material comprises the following preparation steps:
(1) First, preparing a precursor solution: uniformly dispersing hydrofluoric acid, hydrochloric acid, aniline monomer and carbon nano tube into a solvent, uniformly mixing, stirring at room temperature for 5-8 hours, uniformly stirring, and then carrying out ice bath to reduce the temperature to below 5 ℃;
(2) And (3) after the temperature of the dispersion liquid in the step (1) is reduced to below 5 ℃, adding an oxidant, enabling the whole-process reaction temperature to be below 5 ℃ and the reaction time to be 6-8 hours, performing suction filtration and washing for multiple times by using ultrapure water, and performing freeze drying to obtain the polyaniline/carbon nano tube composite material.
2. The application of the polyaniline/carbon nano tube composite material in the sodium-based double-ion battery according to claim 1, wherein in the step (1), the mass ratio of the aniline monomer to the carbon nano tube is 1:2-3, and the molar ratio of the aniline monomer to the hydrofluoric acid to the hydrochloric acid is 1:10:5; the solvent is ultrapure water, the total volume of the reaction solution is 100mL, and the mass fraction of the carbon nano tube in the solvent is not more than 15%.
CN202111383159.2A 2021-11-22 2021-11-22 Preparation of polyaniline/carbon nano tube composite material and application of polyaniline/carbon nano tube composite material in sodium-based double-ion battery Active CN114085377B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111383159.2A CN114085377B (en) 2021-11-22 2021-11-22 Preparation of polyaniline/carbon nano tube composite material and application of polyaniline/carbon nano tube composite material in sodium-based double-ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111383159.2A CN114085377B (en) 2021-11-22 2021-11-22 Preparation of polyaniline/carbon nano tube composite material and application of polyaniline/carbon nano tube composite material in sodium-based double-ion battery

Publications (2)

Publication Number Publication Date
CN114085377A CN114085377A (en) 2022-02-25
CN114085377B true CN114085377B (en) 2023-05-26

Family

ID=80302610

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111383159.2A Active CN114085377B (en) 2021-11-22 2021-11-22 Preparation of polyaniline/carbon nano tube composite material and application of polyaniline/carbon nano tube composite material in sodium-based double-ion battery

Country Status (1)

Country Link
CN (1) CN114085377B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114622105B (en) * 2022-04-08 2023-11-10 内蒙古科技大学 Composite material for extracting niobium and preparation method and application method thereof
CN115642237A (en) * 2022-10-28 2023-01-24 无锡零一未来新材料技术研究院有限公司 Sodium ion composite cathode material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101235199A (en) * 2007-12-26 2008-08-06 华东理工大学 Method for preparing carbon nano-tube modified polyaniline nano fiber composite material
CN109755553A (en) * 2019-03-20 2019-05-14 北京航空航天大学 A kind of magnesium lithium Dual-ion cell composite positive pole and its preparation method and application, battery system
CN109904452A (en) * 2019-02-21 2019-06-18 三峡大学 The preparation method of sodium base Dual-ion cell based on carbon fiber negative electrode material
WO2021203086A1 (en) * 2020-04-03 2021-10-07 Sila Nanotechnologies Inc. Lithium-ion battery with anode comprising blend of intercalation-type anode material and conversion-type anode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101235199A (en) * 2007-12-26 2008-08-06 华东理工大学 Method for preparing carbon nano-tube modified polyaniline nano fiber composite material
CN109904452A (en) * 2019-02-21 2019-06-18 三峡大学 The preparation method of sodium base Dual-ion cell based on carbon fiber negative electrode material
CN109755553A (en) * 2019-03-20 2019-05-14 北京航空航天大学 A kind of magnesium lithium Dual-ion cell composite positive pole and its preparation method and application, battery system
WO2021203086A1 (en) * 2020-04-03 2021-10-07 Sila Nanotechnologies Inc. Lithium-ion battery with anode comprising blend of intercalation-type anode material and conversion-type anode material

Also Published As

Publication number Publication date
CN114085377A (en) 2022-02-25

Similar Documents

Publication Publication Date Title
US9437870B2 (en) Nano-silicon composite lithium ion battery anode material coated with poly (3,4-ethylenedioxythiophene) as carbon source and preparation method thereof
Tang et al. An aqueous rechargeable lithium battery of excellent rate capability based on a nanocomposite of MoO 3 coated with PPy and LiMn 2 O 4
CN107256956B (en) Nitrogen-doped carbon-coated vanadium nitride electrode material and preparation method and application thereof
CN110993908A (en) Vertical graphene/manganese dioxide composite material and preparation method and application thereof
CN107492655B (en) molybdenum disulfide/carbon composite material and preparation method and application thereof
CN114085377B (en) Preparation of polyaniline/carbon nano tube composite material and application of polyaniline/carbon nano tube composite material in sodium-based double-ion battery
CN108598390A (en) A kind of preparation method and lithium-sulfur cell of positive material for lithium-sulfur battery
CN109326768B (en) Sodium ion battery cathode, preparation method thereof and sodium ion battery
CN114883559B (en) Naphthoquinone-quinoxaline organic electrode material and application thereof in water-based zinc ion battery
CN111211273A (en) Lithium-sulfur battery with iron nitride nanoparticles growing in situ on reduced graphene oxide as modified diaphragm material and preparation method thereof
CN105185989B (en) A kind of sodium-ion battery conducting polymer/SnSexNano flower anode material and preparation method thereof
CN109786690B (en) Lithium-sulfur battery positive electrode material and preparation method thereof
CN113809303A (en) Elm-shaped molybdenum diselenide @ nitrogen-doped carbon nanofiber and preparation method and application thereof
CN114335531A (en) Sulfur-doped hard carbon material and preparation method and application thereof
WO2017197675A1 (en) Lithium titanate-modified material and manufacturing method thereof
CN112047325A (en) Sodium-ion battery negative electrode material and preparation method thereof, and sodium-ion battery
CN111370783A (en) High-performance water-based chloride ion battery and preparation method thereof
CN113921812B (en) Ultra-high power density sodium ion battery and preparation method thereof
CN107845798B (en) Preparation method of lithium ion battery anode material
CN114057180A (en) Preparation method and application of carbon quantum dot modified PTCDA-based carbon material
CN115000426B (en) Two-dimensional titanium carbide supported double-component efficient zinc-air battery catalyst and preparation method and application thereof
CN114361391B (en) Polymer modified nano silicon negative electrode material and preparation method and application thereof
CN113782742B (en) Tungsten oxide composite nitrogen-doped carbon nanofiber negative electrode material of lithium battery and preparation method thereof
Su et al. Preparation of the nanocarbon/polypyrrole composite electrode by in situ electrochemical polymerization and its electrochemical performances as the cathode of the lithium ion battery
CN114804117B (en) Silicon oxide/carbon composite material, preparation method thereof and lithium ion battery

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