CN113707866A - Lifting TiO2Method for storing property of electrode material sodium ion - Google Patents

Lifting TiO2Method for storing property of electrode material sodium ion Download PDF

Info

Publication number
CN113707866A
CN113707866A CN202111003202.8A CN202111003202A CN113707866A CN 113707866 A CN113707866 A CN 113707866A CN 202111003202 A CN202111003202 A CN 202111003202A CN 113707866 A CN113707866 A CN 113707866A
Authority
CN
China
Prior art keywords
tio
electrode material
powder
sodium ion
ion battery
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.)
Pending
Application number
CN202111003202.8A
Other languages
Chinese (zh)
Inventor
李永涛
张坤
李海文
斯庭智
柳东明
张庆安
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.)
Anhui University of Technology AHUT
Original Assignee
Anhui University of Technology AHUT
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 Anhui University of Technology AHUT filed Critical Anhui University of Technology AHUT
Priority to CN202111003202.8A priority Critical patent/CN113707866A/en
Publication of CN113707866A publication Critical patent/CN113707866A/en
Pending legal-status Critical Current

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
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a titanium dioxide sulfide (S-TiO)2) Electrode material of the S-TiO2The electrode material is of a core-shell structure, and the inner core is TiO2The crystal core and the shell layer are amorphous layers formed by embedding S atoms, and the shell layer structure is isotropic. The preparation method comprises the following steps: with sulfur powder and TiO2The powder is used as raw material, sulfur powder is heated and sublimated into gaseous sulfur, and the gaseous sulfur is blown to TiO by high-temperature argon gas flow2And carrying out surface vulcanization reaction for 2 h. The S-TiO compound2The electrode material has narrow band gap and excellent ion transmission characteristic, and can be used as a negative electrodeThe electrode material is prepared into a sodium ion battery to improve TiO2The sodium ion storage capacity of the electrode material can obtain the sodium ion battery with excellent cycling stability, impedance, specific capacity and the like.

Description

Lifting TiO2Method for storing property of electrode material sodium ion
Technical Field
The invention belongs to the technical field of energy material preparation, and particularly relates to S-TiO2An electrode material and a preparation method thereof.
Background
In recent years, power sources of electronic equipment, energy storage equipment, electric vehicles and other products which are mainstream in the market are dominated by lithium ion batteries, but the increasing demand of batteries in the market may cause serious problems such as resource exhaustion. Due to the low storage of lithium and high cost, sodium ion batteries have been gradually brought into the field of researchers and become a promising alternative to lithium ion batteries in recent years.
Although the radius of the sodium ion is larger than that of the lithium ion, many positive and negative electrode materials for lithium ion batteries are also suitable for the sodium ion battery. The same methods for improving the lithium ion conductivity can also be applied to sodium ion batteries, such as methods for introducing cation dopants or defects, and adding high-conductivity substances such as carbon nanotubes and graphene.
TiO2As a polycrystalline material, the polycrystalline material is greatly researched in the field of sodium ion batteries, and after a series of researches on documents of the sodium ion batteries, the polycrystalline material is found in TiO2In the polymorphic form, either anatase phase TiO2Rutile phase TiO2Or bronze mineral phase TiO2All show similar performance to that of the insertion type negative electrode material, and in addition, a basic theoretical research shows that the activation barrier of sodium ions inserted into anatase crystal lattices is equivalent to that of lithium ions. Crystalline phase TiO however2The conductivity is poor and the conductivity is low, which means that lithium ions or sodium ions can only be rapidly deintercalated on a thin surface layer of the host material, and the transfer rate of the sodium ions or electrons and the storage capacity of the sodium ions are very limited, thus the electrochemical performance of the electrode material is seriously influenced. Thus to TiO2Modified to provide a new electrode material and develop a new electrode material for improving TiO2Method for improving storage performance of electrode material sodium ion to improve TiO2The electrochemical properties of the electrode material are essential.
Disclosure of Invention
For crystalline phase TiO2The conductivity is poor and the conductivity is low, and the invention aims to provide a method for improving TiO2The sodium ion/electron transfer rate of the electrode material and the sodium ion storage capacity.
In order to achieve the purpose, the invention provides the following technical scheme:
one of the technical schemes of the invention is S-TiO2Electrode material of the S-TiO2The electrode material is of a core-shell structure, and the inner core is TiO2The crystal core and the shell layer are amorphous layers formed by embedding S atoms, and the shell layer structure is isotropic.
The second technical scheme of the invention is the S-TiO2Method for preparing electrode material by blowing gaseous sulfur to TiO with high temperature argon gas flow2And carrying out surface vulcanization reaction for 2 h. S-TiO2The microscopic preparation procedure of (1) is shown in FIG. 1.
Further, the TiO2Is anatase type TiO2Powder, wherein the gaseous sulfur is formed by heating and sublimating sulfur powder.
Further, the anatase type TiO2The particle size of the powder is in the nanometer scale.
Further, the anatase type TiO2The mass ratio of the powder to the sulfur powder is 1: 1.2.
The mass of the sulfur powder is larger than that of TiO2The quality of the powder ensures that gaseous sulfur generated by sublimation of the sulfur powder is fully mixed with TiO2The powders contact and react.
Further, the temperature of the high-temperature argon gas flow is 450-550 ℃.
The sulfidation temperature is higher than the boiling point of sulfur powder but not higher than 550 ℃ because the phase transition temperature range of titanium dioxide from anatase phase to rutile phase is in the range of 550 ℃ to 800 ℃ and in TiO2Among the polymorphic forms, anatase form TiO2Has the optimal sodium storage performance.
Further, the flow rate of the high temperature argon gas flow is 400ml/min, and the preferred temperature of the high temperature argon gas flow is 550 ℃.
In the third technical scheme of the invention, the improvement of TiO2The method for storing the sodium ion storage performance of the electrode material comprises the step of adding the S-TiO2And preparing a negative electrode by taking the electrode material as an active substance, and preparing a sodium ion battery by taking metal sodium as a counter electrode.
Further, the negative electrode takes graphene as a conductive agent and PVDF as a binder; the sodium ion battery takes a polypropylene microporous membrane as an electrode diaphragm and NaClO4The solution serves as an electrolyte.
Further, the mass ratio of the active material to the conductive agent to the binder is 7:2: 1; the NaClO4The concentration of the solution is 1mol/L, and the NaClO is4The solvent of the solution is a mixed solution prepared by ethylene carbonate and dimethyl carbonate according to the volume ratio of 1:1.
Fourth technical solution of the present invention, according to the above, TiO lifting2The sodium ion battery is prepared by the method of the sodium ion storage performance of the electrode material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the S-TiO with the core-shell structure provided by the invention2A layer of obvious para Na appears on the surface of the electrode material+The conduction is very favorable for the amorphous shell layer formed by gathering S atoms, the amorphous shell layer has isotropy, more sodium ion migration channels can be obtained on the surface layer of the material, and therefore more excellent performance is obtained. The amorphous shell layer and crystal nucleus TiO2The heterogeneous interface generated by the interaction can not only protect the electrode material from side reaction with the electrolyte in the charge-discharge cycle process, but also provide a built-in driving force to accelerate the interface charge transfer rate. The invention utilizes a one-step gas phase vulcanization method to dope S atoms on TiO2Surface, obtained TiO surface doped with S atoms2(S-TiO2) The electrode material has narrower band gap and excellent charge-discharge cycle stabilityHas excellent qualitative and ion transmission characteristics, and is superior to pure TiO in the aspects of cycle stability, impedance and specific capacity2。
(2) The preparation method provided by the invention has the advantages of simple preparation process, environmental protection and easy large-scale preparation, and is an S-TiO preparation which has popularization value and can realize batch production2The preparation method of (1).
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 shows S-TiO2A micro preparation flow chart of (1);
FIG. 2 is TiO2Fine XRD spectrum of the powder;
FIG. 3 shows S-TiO prepared in example 12Fine XRD spectrum of the powder;
FIG. 4 shows S-TiO prepared in example 12SEM and Mapping of powder wherein (a) is TiO2(ii) SEM image of (b), (c) Mapping image of Ti, (d) Mapping image of O;
FIG. 5 shows S-TiO prepared in example 12TEM and Mapping of powder, in which a and b are S-TiO2The TEM image of (a), c is a Mapping image of Ti, d is a Mapping image of O, e and f are Mapping images of S, and g, h, j and k are S-TiO2A local TEM image of; i. l is TEM analysis picture;
FIG. 6 is TiO2Powder and S-TiO from example 12The energy spectrum analysis result of the powder, wherein a is an ultraviolet visible light absorption spectrum, b is an XPS full spectrum, c is an O element high-resolution spectrum, and d is an S element high-resolution spectrum;
FIG. 7 shows S-TiO prepared in example 12Powder and TiO2Comprehensive characterization and comparison of electrochemical properties of the powder as a negative electrode material of a sodium ion battery, wherein a is TiO2Powder as negative electrode material of sodium ion batteryCyclic voltammogram of (b) S-TiO prepared in example 12Cyclic voltammetry curve of powder as negative electrode material of sodium ion battery, c is TiO2When the powder is used as the negative electrode material of a sodium ion battery/S-TiO2When the powder is used as the negative electrode material of the sodium ion battery, the constant current charge-discharge curve of the first three cycles is shown, and d is TiO in the first 200 cycles2When the powder is used as the negative electrode material of the sodium ion battery and S-TiO2The cycle performance of the powder as the negative electrode material of the sodium ion battery is compared, and e is TiO2When the powder is used as the negative electrode material of the sodium ion battery and S-TiO2The powder is used as the negative electrode material of the sodium ion battery, the multiplying power performance is compared, and f is TiO2When the powder is used as the negative electrode material of the sodium ion battery and S-TiO2Comparing the resistance values when the powder is used as a negative electrode material of a sodium-ion battery;
FIG. 8 shows S-TiO prepared in example 12The pseudocapacitance behavior analysis graph when the powder is used as an electrode material is shown, wherein a is a volt-ampere characteristic curve under different scanning speeds, b is an ion diffusion coefficient derived from the volt-ampere characteristic curve under different scanning speeds, c is the pseudocapacitance contribution rate of the volt-ampere characteristic curve, and d is the pseudocapacitance contribution rate under different scanning speeds;
FIG. 9 is TiO2Powder and S-TiO from example 12The sodium storage performance analysis chart of the powder used as an electrode material is shown, wherein a is the multiplying power performance of different materials, b is the cycle performance of different materials, and c is the constant current charge-discharge curve of different materials.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
S-TiO2Preparation of powder:
taking 100mg of anatase type TiO2Placing the powder as metal source in the middle of charging table of high-temperature high-pressure sintering resistance furnace, adding 120mg sulfur powder as sulfur source, placing at low temperature parts of two ends, heating the high-temperature high-pressure sintering resistance furnace to 550 deg.C, introducing argon gas flow (flow rate of 400ml/min), and blowing gaseous sulfur sublimated from solid sulfur powder onto TiO2Sulfurizing the surface, and continuously introducing argon to sulfurize for 2 hours to obtain light yellow S-TiO2And (3) powder.
Example 2
Preparation of 2032 type button cell:
weighing 120mg of the extract by using a full-automatic electronic analytical balance (Quintix 35-1CN, Sartorius)S-TiO prepared in example 12Preparing a negative electrode by tabletting with the powder as a negative electrode active material (wherein graphene is used as a conductive agent, PVDF is used as a binder, the mass ratio of the active material, the conductive agent and the binder is 7:2:1), taking high-purity (more than 99.9%) sodium metal as a counter electrode (punching with a punch to a diameter of 10 mm), taking a polypropylene microporous membrane (Celgard 2400) as a diaphragm, and taking 50 muL of 1mol/L NaClO4The S-TiO prepared in example 1 was assembled using a solution (EC: DMC (1:1) as a solvent) as an electrolyte for sodium batteries2A 2032 type button cell with the powder as the negative active material. The whole battery assembling process is carried out in an argon glove box (O)2<0.1ppm；H2O<0.1 ppm).
Comparative example 1
The difference from example 2 is that TiO is used2Powder instead of S-TiO2Powder, assembled with TiO2A 2032 type button cell with the powder as the negative active material.
Performance testing
(1) Diffraction by X-ray
Taking TiO2Powder and S-TiO from example 12Powder by X-ray diffraction, TiO2The XRD fine-modification spectrum of the powder is shown in figure 2, and S-TiO2The XRD refinement of the powder is shown in FIG. 3, where White in FIG. 2 represents TiO before sulfiding2Powder, FIG. 3Yellow represents TiO after vulcanization2And (3) powder. After the refinement fitting, the variance value is lower, and the conclusion can be drawn: TiO after sulphurization under a stream of argon containing S atoms2The powder does dope the S atom in TiO2On the surface, S-TiO is formed2And (3) powder.
(2) Scanning by electron microscope
Scanning Electron Microscope (SEM) was used to measure S-TiO prepared in example 12The powder was scanned and the results are shown in FIG. 4, where (a) is TiO2The SEM image of (a), (b) is a Mapping image of S, (c) is a Mapping image of Ti, and (d) is a Mapping image of O, it can be seen that S element is uniformly distributed in TiO2A surface.
Transmission Electron Microscope (TEM) was used for the S-TiO prepared in example 12Scanning the powder and obtaining the resultAs shown in FIG. 5, wherein a and b are S-TiO2The TEM image of (a), c is a Mapping image of Ti, d is a Mapping image of O, e and f are Mapping images of S, and g, h, j and k are S-TiO2A local TEM image of; i. l is TEM analysis image. It can be seen that the S atom is in TiO2The S atoms are gathered on the TiO with a certain thickness2The molecular groups form shell layers on the surfaces (as shown in FIG. 5 f), and the S atoms form shell layers which are amorphous and isotropic (as shown in FIG. 5 i).
(3) Energy spectrum analysis
For TiO using X-ray photoelectron spectrometer (XPS)2Powder and S-TiO from example 12The powder was analyzed, and the results are shown in FIG. 6, where a is an ultraviolet-visible absorption spectrum, b is an XPS full spectrum, c is an O element high-resolution spectrum, and d is an S element high-resolution spectrum, because of TiO2Powder and S-TiO from example 12The powder has different absorption capacities for visible light with different wavelengths, and can identify that: s atom doped in TiO2S-O bonds and S-Ti bonds are formed on the surface.
(4) Electrical Performance testing
The S-TiO compound prepared in example 2 was used22032 type button cell using powder as negative active material and TiO prepared in comparative example 12The 2032 button cell with powder as the negative active material was tested for electrical properties. Wherein the cyclic voltammetry test and the AC impedance test are both performed on an electrochemical workstation with a test system of Solartron Mobrey England SI 1287. The constant current charge and discharge test is carried out under the New electrochemical test system. The ambient temperature measured for all samples was 25 ℃ at ambient temperature. Considering anatase type TiO2Has a theoretical specific capacity of 335mAh/g, so we specify an applied current density of 335mA/g as 1C in charge-discharge rate. S-TiO prepared in example 12Powder and TiO2The comprehensive characterization and comparison of electrochemical properties of the powder as a negative electrode material of sodium ion battery are shown in FIG. 7, in which a is TiO2The cyclic voltammetry curve of the powder as a negative electrode material of a sodium ion battery, b is S-TiO prepared in example 12Cyclic voltammetry when the powder is used as the cathode material of a sodium ion battery,c is TiO2When the powder is used as the negative electrode material of a sodium ion battery/S-TiO2When the powder is used as the negative electrode material of the sodium ion battery, the constant current charge-discharge curve of the first three cycles is shown, and d is TiO in the first 200 cycles2When the powder is used as the negative electrode material of the sodium ion battery and S-TiO2The cycle performance of the powder as the negative electrode material of the sodium ion battery is compared, and e is TiO2When the powder is used as the negative electrode material of the sodium ion battery and S-TiO2The powder is used as the negative electrode material of the sodium ion battery, the multiplying power performance is compared, and f is TiO2When the powder is used as the negative electrode material of the sodium ion battery and S-TiO2Comparison of the resistance values of the powders when used as negative electrode materials for sodium ion batteries revealed from FIG. 7 that the sulfidation treatment was applied to anatase TiO2The electrochemical performance (such as specific capacity, cycling stability, first coulombic efficiency, impedance, rate capability, electrode reversibility and the like) of the electrode is improved. S-TiO prepared in example 12Pseudocapacitance behavior analysis when the powder is used as an electrode material is shown in fig. 8, wherein a is a volt-ampere characteristic curve at different scanning speeds, b is an ion diffusion coefficient derived from the volt-ampere characteristic curve at different scanning speeds, c is a pseudocapacitance contribution rate of the volt-ampere characteristic curve, and d is a pseudocapacitance contribution rate at different scanning speeds; from FIG. 8, it can be seen that S-TiO2The pseudocapacitance contribution rate increases with the increase of the sweep rate, and the pseudocapacitance behavior is beneficial to the multiplying power performance and the cycling stability of the electrode material. This indicates the formation of S-TiO2The cathode material has a remarkable effect on improving the electrochemical performance. TiO 22Powder and S-TiO from example 12Sodium storage performance analysis when the powder is used as an electrode material is shown in fig. 9, wherein a is rate performance of different materials, b is cycle performance of different materials, and c is constant current charge and discharge curve of different materials; white stands for TiO before unvulcanized2Powder, Yellow represents S-TiO 2 hours after vulcanization as obtained in example 12Powder, FIG. 9 shows that sulfidation improves TiO2The electrode material has high cycling stability and Yellow with high cycling capacity, coulombic efficiency and multiplying power performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. S-TiO2Electrode material, characterized in that the S-TiO2The electrode material is of a core-shell structure, and the inner core is TiO2The crystal core and the shell layer are amorphous layers formed by embedding S atoms, and the shell layer structure is isotropic.
2. An S-TiO according to claim 12A process for the preparation of an electrode material, characterized in that gaseous sulfur is blown to TiO with a high temperature argon gas stream2And carrying out surface vulcanization reaction for 2 h.
3. S-TiO according to claim 22A method for preparing an electrode material, characterized in that the TiO is2Is anatase type TiO2Powder, wherein the gaseous sulfur is formed by heating and sublimating sulfur powder.
4. S-TiO according to claim 32A method for preparing an electrode material, characterized in that the anatase TiO is2The mass ratio of the powder to the sulfur powder is 1: 1.2.
5. S-TiO according to claim 22The preparation method of the electrode material is characterized in that the temperature of the high-temperature argon gas flow is 450-550 ℃.
6. S-TiO according to claim 22The preparation method of the electrode material is characterized in that the flow rate of the high-temperature argon gas flow is 400ml/min, and the temperature of the high-temperature argon gas flow is 550 ℃.
7. Lifting TiO2A method for the sodium ion storage property of an electrode material, characterized in that the S-TiO according to claim 1 is used2The electrode material is used as an active substance to prepare a negative electrode, the metal sodium is used as a counter electrode,and (5) preparing the sodium ion battery.
8. Lifting TiO according to claim 72The method for the sodium ion storage performance of the electrode material is characterized in that graphene is used as a conductive agent and PVDF is used as a binder for the negative electrode; the sodium ion battery takes a polypropylene microporous membrane as an electrode diaphragm and NaClO4The solution serves as an electrolyte.
9. Lifting TiO according to claim 82The method for storing the sodium ion storage performance of the electrode material is characterized in that the mass ratio of an active substance, a conductive agent and a binder is 7:2: 1; the NaClO4The concentration of the solution is 1mol/L, and the NaClO is4The solvent of the solution is a mixed solution prepared by ethylene carbonate and dimethyl carbonate according to the volume ratio of 1:1.
10. A sodium ion battery prepared according to the method of any one of claims 7-9.
CN202111003202.8A 2021-08-30 2021-08-30 Lifting TiO2Method for storing property of electrode material sodium ion Pending CN113707866A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111003202.8A CN113707866A (en) 2021-08-30 2021-08-30 Lifting TiO2Method for storing property of electrode material sodium ion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111003202.8A CN113707866A (en) 2021-08-30 2021-08-30 Lifting TiO2Method for storing property of electrode material sodium ion

Publications (1)

Publication Number Publication Date
CN113707866A true CN113707866A (en) 2021-11-26

Family

ID=78656697

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111003202.8A Pending CN113707866A (en) 2021-08-30 2021-08-30 Lifting TiO2Method for storing property of electrode material sodium ion

Country Status (1)

Country Link
CN (1) CN113707866A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080286656A1 (en) * 2007-05-15 2008-11-20 Kumoh National Institute Of Technology Industry- Academic Cooperation Negative active material for lithium secondary battery, method of preparing thereof, and lithium secondary battery including same
CN105591075A (en) * 2015-12-18 2016-05-18 苏州大学 Preparation method of titanium oxide negative pole of sodium-ion battery
CN107337233A (en) * 2017-06-05 2017-11-10 陕西科技大学 A kind of method of one step vulcanization method synthesis of titanium dioxide and titanium disulfide composite
CN108134065A (en) * 2017-12-22 2018-06-08 华中科技大学 A kind of TiO for storing up lithium and being adulterated with S2/ C composite, preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080286656A1 (en) * 2007-05-15 2008-11-20 Kumoh National Institute Of Technology Industry- Academic Cooperation Negative active material for lithium secondary battery, method of preparing thereof, and lithium secondary battery including same
CN105591075A (en) * 2015-12-18 2016-05-18 苏州大学 Preparation method of titanium oxide negative pole of sodium-ion battery
CN107337233A (en) * 2017-06-05 2017-11-10 陕西科技大学 A kind of method of one step vulcanization method synthesis of titanium dioxide and titanium disulfide composite
CN108134065A (en) * 2017-12-22 2018-06-08 华中科技大学 A kind of TiO for storing up lithium and being adulterated with S2/ C composite, preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HANNA HE等: "Plasma-Induced Amorphous Shell and Deep Cation-Site S Doping Endow TiO 2 with Extraordinary Sodium Storage Performance", 《ADVANCED MATERIALS》 *
连芳: "《电池储能器件及关键材料》", 31 July 2019, 冶金工业出版社 *

Similar Documents

Publication Publication Date Title
Li et al. Controllable synthesis of uniform mesoporous H-Nb 2 O 5/rGO nanocomposites for advanced lithium ion hybrid supercapacitors
Cheng et al. Graphene-like-graphite as fast-chargeable and high-capacity anode materials for lithium ion batteries
Tian et al. High-rate and cycling-stable nickel-rich cathode materials with enhanced Li+ diffusion pathway
JP7470043B2 (en) Silicon-carbon nanomaterials, their production method and their uses
Liu et al. Synthesis of Mo 2 N nanolayer coated MoO 2 hollow nanostructures as high-performance anode materials for lithium-ion batteries
Pham-Cong et al. Enhanced cycle stability of polypyrrole-derived nitrogen-doped carbon-coated tin oxide hollow nanofibers for lithium battery anodes
Li et al. High performance porous MnO@ C composite anode materials for lithium-ion batteries
CN109659540B (en) Preparation method of porous carbon-coated antimony telluride nanosheet and application of porous carbon-coated antimony telluride nanosheet as negative electrode material of metal ion battery
CN108448057B (en) CoO/CoMoO4Preparation of composite material and application of composite material in lithium ion battery
WO2017034093A1 (en) Ultra-high output, ultra-long-lifespan lithium secondary battery negative electrode material using layered structure of porous graphene and metal oxide nanoparticles, and method for preparing same
Şahan et al. A novel and green synthesis of mixed phase CoO@ Co 3 O 4@ C anode material for lithium ion batteries
Han et al. A scalable synthesis of N-doped Si nanoparticles for high-performance Li-ion batteries
Santhoshkumar et al. Hierarchically structured mesoporous bimetallic oxides as a potential anode material for rechargeable lithium batteries
Zhou et al. Encapsulated SnSe in carbon nanofibers as anode of sodium ion batteries with improved properties
JP2024517230A (en) Uniformly modified silicon monoxide anode material and its preparation method and application
Priyadharshini et al. Electrochemical performance of TiO 2–C nanocomposite as an anode material for lithium-ion battery
Wu et al. Promoting electrochemical performances of vanadium carbide nanodots via N and P co-doped carbon nanosheets wrapping
Sovizi et al. Effect of praseodymium doping on structural and electrochemical performance of lithium titanate oxide (Li4Ti5O12) as new anode material for lithium-sulfur batteries
CN114497707A (en) High-performance low-cost composite solid electrolyte and preparation method and application thereof
KR102522173B1 (en) Anode active material coated with nitrogen-doped carbon for sodium ion secondary battery and method of preparing the same
Ji et al. Electrospinning preparation of one-dimensional Co 2+-doped Li 4 Ti 5 O 12 nanofibers for high-performance lithium ion battery
CN113410459A (en) Embedded MoSxThree-dimensional ordered macroporous graphene carbon material of nanosheet, preparation and application
EP4016673A1 (en) Negative electrode, electrochemical device containing same and electronic device
Sun et al. Simple synthesis of TiNb6O17/C composite toward high-rate lithium storage
Xu et al. Facile preparation of porous erythrocyte-like CuCo 2 O 4 as active material of lithium ion batteries anode

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20211126

RJ01 Rejection of invention patent application after publication