CN110571417A - Solvothermal preparation of VS4Polyaniline sodium ion battery cathode material - Google Patents

Solvothermal preparation of VS4Polyaniline sodium ion battery cathode material Download PDF

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Publication number
CN110571417A
CN110571417A CN201910776126.0A CN201910776126A CN110571417A CN 110571417 A CN110571417 A CN 110571417A CN 201910776126 A CN201910776126 A CN 201910776126A CN 110571417 A CN110571417 A CN 110571417A
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China
Prior art keywords
sodium
polyaniline
ion battery
cathode material
solution
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Pending
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CN201910776126.0A
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Chinese (zh)
Inventor
任慢慢
杨飞
陈谦武
钟文
刘伟良
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Qilu University of Technology
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Qilu University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—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
    • H01M4/362—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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

Abstract

The invention discloses a one-step solvothermal method for preparing VS4A method for preparing a negative electrode material of a polyaniline sodium-ion battery. Namely: adding the following components in a certain amount of methanol solution according to the ratio of vanadium: sulfur molar ratio 1: 4-10 adding a vanadium source and a sulfur source, and magnetically stirring at 20-40 ℃ for 30-180 min; then according to the aniline: the initiator molar ratio is 1-5: 1 adding aniline and an initiator into the solution, continuously stirring for 60-180 min, transferring the solution into a reaction kettle, preserving the temperature for 12-23 h at 100-180 ℃, centrifuging and washing the obtained solid product, and drying for 12-16 h at 40-70 ℃ to obtain VS4Polyaniline composite negative electrode material. The invention can increase VS4Conductivity of the Material, prepared VS4The material has good electrochemical performance. The method has the advantages of short flow, simple process, low energy consumption, low cost and the like.

Description

solvothermal preparation of VS4Polyaniline sodium ion battery cathode material
Technical Field
The invention belongs to the field of preparation of sodium-ion battery electrode materials, and relates to a method for preparing VS by using a solvothermal method4Polyaniline sodium ion battery cathode material. VS prepared by this method4Polyaniline negative electrode material has higher electronic conductivity and good electrochemistryAnd (4) performance.
Background
Sodium ion batteries have attracted researchers' interest as rechargeable secondary battery systems due to their advantages of low cost, abundant sodium resources, and the like. V-based sulfides have a high theoretical capacity due to their multiple valence states (from +5 to + 1), and thus have attracted considerable attention. VS4Can be described as V4+(S2 2-)2. It is a linear chain compound consisting of S2 2-The dimer is attached to two adjacent V atoms. VS4Has a unique linear chain structure with weak inter-chain van der waals forces, thus providing a loose stacking framework. VS4The interchain distance of (A) is 0.583 nm, far greater than Na+(0.196 nm) ion diameter. The large channels between and in the chains provide potential sites for diffusion and storage of alkali metals, and are considered to be promising sodium-ion battery negative electrode materials. VS reported by Sun et al4When the material is used for a negative electrode of a sodium ion battery, the reversible specific capacity after 50 cycles is about 320 mAh/g under 0.1A/g and is far less than the theoretical specific capacity, which is because the material cannot be reversed in the desulfurization process. Li et al prepared VS with controllable assembly of three nano-units with different crystallinities by simple template-free hydrothermal method4Microspheres, found to reduce the crystallinity of the nano-units may promote VS4Pseudo-capacitive behavior of microspheres to greatly increase VS4Electrochemical properties of the microspheres. Wang et al prepared VS by in-situ rGO template hydrothermal method4Composite material of/rGO, nano VS4The synergistic effect between the particles and the highly conductive graphene network, and the flexible porous structure of the nanocomposite is Na+And a large area contact area between the electrolyte and the electrodes provides a short diffusion path. Thus by lowering VS4Crystallinity of particles and increase of VS4can improve its electrochemical dynamic performance to make VS4The electrode has excellent electrochemical performance.
Disclosure of Invention
The invention aims to prepare VS by a one-step solvothermal method4Polyaniline sodium ion battery cathodea material. The method has the advantages of short flow, simple process, low energy consumption and low cost, and the prepared material has high reversible specific capacity and good electrochemical cycle performance.
The invention provides a solvothermal method for preparing VS4The preparation process of the polyaniline sodium-ion battery negative electrode material comprises the following steps:
(1) Measuring a certain amount of methanol solution;
(2) Mixing a vanadium source and a sulfur source according to a molar ratio of 1: 4-10 ℃, dissolving the mixture in the solution obtained in the step (1) at the temperature of 20-40 ℃, and magnetically stirring the mixture for 30-180 min at the temperature of 20-40 ℃;
(3) adding aniline and an initiator into the solution obtained in the step (2) according to the mol ratio of 1 ~ 5: 1, continuously stirring for 60 ~ 180 min, transferring the solution into a stainless steel reaction kettle, preserving the temperature for 12 ~ 23 h at 100 ~ 180 ℃, centrifuging and washing the obtained product, and drying at 40 ~ 70 ℃ for 12 ~ 16 h to obtain VS4Solid polyaniline product.
Further, the vanadium source in the step is at least one of vanadium pentoxide, ammonium metavanadate, sodium metavanadate or sodium orthovanadate.
Further, the sulfur source in the step is at least one of thiourea, thioacetamide, sulfur powder or L-cysteine.
further, in the step, the initiator is at least one of ammonium persulfate and potassium persulfate.
The invention is characterized in that: the method has the advantages of simple preparation process, short flow and low production cost; prepared VS4The polyaniline composite material has uniform particles and good electrochemical performance.
Description of the drawings:
Figure 1 is the XRD pattern of the sample in example 1.
FIG. 2 is a graph showing charge and discharge curves of the sample in example 1.
Detailed Description
The invention is further described with reference to the following figures and detailed description. The following examples are intended to illustrate the invention without further limiting it.
example 1: ammonium metavanadate and thioacetamide are used as initial raw materials. Weighing ammonium metavanadate (0.17 g) and thioacetamide (0.56 g) according to a molar ratio of 1:5, adding the ammonium metavanadate and thioacetamide into 32 mL of methanol, and magnetically stirring and mixing the mixture at 30 ℃ to form a uniform solution; to this solution was then added the following aniline: adding aniline (60 mu L) and ammonium persulfate (0.15 g) into the initiator according to the molar ratio of 1:1, continuously mixing for 120 min, pouring into a 40 mL reaction kettle, and preserving heat for 15 h at 170 ℃; centrifuging and washing the product for many times, and drying at 60 ℃ for 14 h to obtain a solid product; VS4The first discharge capacity of the polyaniline composite negative electrode material under the current density of 1A/g is 578.6 mAh/g.
Example 2: vanadium pentoxide and thiourea are used as initial raw materials. Firstly, weighing vanadium pentoxide (0.18 g) and thiourea (0.30 g) according to the molar ratio of 1:4, adding the vanadium pentoxide and the thiourea into 25 mL of methanol, and magnetically stirring and mixing the mixture at the temperature of 20 ℃ to form a uniform solution; to this solution was then added the following aniline: adding aniline (90 mu L) and potassium persulfate (0.13 g) into the initiator at a molar ratio of 2:1, continuously mixing for 60 min, pouring into a 40 mL reaction kettle, and preserving heat at 150 ℃ for 20 h; centrifuging and washing the product for multiple times, and drying at 50 ℃ for 16 h to obtain a solid product; VS4The first discharge capacity of the polyaniline composite negative electrode material under the current density of 1A/g is 561.8 mAh/g.
Example 3: sodium metavanadate and thioacetamide are used as initial raw materials. Weighing sodium metavanadate (0.12 g) and thioacetamide (0.60 g) according to the mol ratio of 1:8, adding the sodium metavanadate and the thioacetamide into 28 mL of methanol, and magnetically stirring and mixing the mixture at 40 ℃ to form a uniform solution; to this solution was then added the following aniline: adding aniline (100 mu L) and ammonium persulfate (0.25 g) into the initiator according to the molar ratio of 3:1, continuously mixing for 180 min, pouring into a 40 mL reaction kettle, and preserving heat for 23 h at 120 ℃; centrifuging and washing the product for many times, and drying at 70 ℃ for 12 h to obtain a solid product; VS4The first discharge capacity of the polyaniline composite negative electrode material under the current density of 1A/g is 570.2 mAh/g.

Claims (5)

1. Solvothermal preparation of VS4Polyaniline sodium ion battery cathode material. The method is characterized by comprising the following steps:
(1) Measuring a certain amount of methanol solution;
(2) Mixing a vanadium source and a sulfur source according to a molar ratio of 1: 4-10 ℃, dissolving the mixture in the solution obtained in the step (1) at the temperature of 20-40 ℃, and magnetically stirring the mixture for 30-180 min at the temperature of 20-40 ℃;
(3) adding aniline and an initiator into the solution obtained in the step (2) according to the mol ratio of 1 ~ 5: 1, continuously stirring for 60 ~ 180 min, transferring the solution into a stainless steel reaction kettle, preserving the temperature for 12 ~ 23 h at 100 ~ 180 ℃, centrifuging and washing the obtained product, and drying at 40 ~ 70 ℃ for 12 ~ 16 h to obtain VS4solid polyaniline product.
2. The solvothermal preparation of VS according to claim 14The polyaniline sodium-ion battery cathode material is characterized in that the certain amount of methanol solution in the step (1) is 20-40 mL.
3. The solvothermal preparation of VS according to claim 14The polyaniline sodium-ion battery cathode material is characterized in that the vanadium source in the step (2) is at least one of vanadium pentoxide, ammonium metavanadate, sodium metavanadate or sodium orthovanadate.
4. The solvothermal preparation of VS according to claim 14The polyaniline sodium-ion battery cathode material is characterized in that the sulfur source in the step (2) is at least one of thiourea, thioacetamide, sulfur powder or L-cysteine.
5. the solvothermal preparation of VS according to claim 14The polyaniline sodium-ion battery negative electrode material is characterized in that the initiator in the step (3) is at least one of ammonium persulfate and potassium persulfate.
CN201910776126.0A 2019-08-22 2019-08-22 Solvothermal preparation of VS4Polyaniline sodium ion battery cathode material Pending CN110571417A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112421028A (en) * 2020-12-02 2021-02-26 齐鲁工业大学 Preparation method of novel water-based zinc ion battery positive electrode material
CN112490438A (en) * 2020-11-27 2021-03-12 青岛科技大学 Magnesium ion battery positive electrode material Mo-VS4N-GNTs and uses thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170207448A1 (en) * 2014-06-06 2017-07-20 Robert Bosch Gmbh Cathode material for lithium sulphur cells
CN107381636A (en) * 2017-07-11 2017-11-24 陕西科技大学 A kind of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four and its preparation method and application
CN107706405A (en) * 2017-11-23 2018-02-16 齐鲁工业大学 A kind of method for preparing nitrogen or the bar-shaped Zinc ion battery positive electrode of nitrogen sulfur doping carbon coating manganese dioxide composite Nano
CN109713304A (en) * 2019-01-02 2019-05-03 齐鲁工业大学 A kind of preparation method of Carbon negative electrode material of sodium ion battery derived from potato peel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170207448A1 (en) * 2014-06-06 2017-07-20 Robert Bosch Gmbh Cathode material for lithium sulphur cells
CN107381636A (en) * 2017-07-11 2017-11-24 陕西科技大学 A kind of vanadic sulfide powder of nano-particles self assemble three dimensional micron cauliflower-shaped four and its preparation method and application
CN107706405A (en) * 2017-11-23 2018-02-16 齐鲁工业大学 A kind of method for preparing nitrogen or the bar-shaped Zinc ion battery positive electrode of nitrogen sulfur doping carbon coating manganese dioxide composite Nano
CN109713304A (en) * 2019-01-02 2019-05-03 齐鲁工业大学 A kind of preparation method of Carbon negative electrode material of sodium ion battery derived from potato peel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YANLI ZHOU 等: "Conductive polymer-Coated VS4 submicrospheres As Advanced Electrode Materials in Lithium-Ion Batteries", 《ACS APPLIED MATERIALS & INTERFACES》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112490438A (en) * 2020-11-27 2021-03-12 青岛科技大学 Magnesium ion battery positive electrode material Mo-VS4N-GNTs and uses thereof
CN112421028A (en) * 2020-12-02 2021-02-26 齐鲁工业大学 Preparation method of novel water-based zinc ion battery positive electrode material

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