CN114039034B - Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG and application thereof - Google Patents

Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG and application thereof Download PDF

Info

Publication number
CN114039034B
CN114039034B CN202111437488.0A CN202111437488A CN114039034B CN 114039034 B CN114039034 B CN 114039034B CN 202111437488 A CN202111437488 A CN 202111437488A CN 114039034 B CN114039034 B CN 114039034B
Authority
CN
China
Prior art keywords
ion battery
mgvs
magnesium ion
anode material
magnesium
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
CN202111437488.0A
Other languages
Chinese (zh)
Other versions
CN114039034A (en
Inventor
李镇江
丁诗琦
田雨欣
戴鑫
孟阿兰
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.)
Qingdao University of Science and Technology
Original Assignee
Qingdao University of Science and Technology
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 Qingdao University of Science and Technology filed Critical Qingdao University of Science and Technology
Priority to CN202111437488.0A priority Critical patent/CN114039034B/en
Publication of CN114039034A publication Critical patent/CN114039034A/en
Application granted granted Critical
Publication of CN114039034B publication Critical patent/CN114039034B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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

The invention discloses a Mg 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG, which belongs to the technical field of battery materials. Preparing ammonium metavanadate into an aqueous solution, mixing with an excessive thioacetamide glycol solution, transferring the aqueous solution and a carbon sheet prepared by adopting a vapor deposition method and growing with N-TG into a reaction kettle, and carrying out hydrothermal reaction for 4 hours at 180 ℃; the product was dried and electrochemically dried over MgSO 4 Mg in solution 2+ Pre-embedding to obtain MgVS as the positive electrode material of the magnesium ion battery 4 N-TG. The invention uses Mg 2+ Can expand VS 4 Can also induce V 2+ And V 3+ The electrochemical performance of the magnesium ion battery is improved. The magnesium ion battery assembled by the method has high specific capacity and excellent cycle stability, and has wide application prospect.

Description

Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG and application thereof
Technical Field
The invention relates to the technical field of battery materials, in particular to a Mg 2+ Pre-embedded magnesium ion battery anode material MgVS 4 /N-TG。
Background
With the increase in energy consumption and the increase in environmental pollution, development and popularization of renewable energy storage devices are urgently required. Because of high safety, low cost and high theoretical volume capacity (3833 mAh cm) -3 ) And similar principles of operation as lithium ion batteries, have received great attention. However, in the intercalation/deintercalation process of the magnesium working ion, there is a large polarization between the magnesium working ion and the positive electrode material, resulting in poor stability of the positive electrode material, reaction kineticsLow school. VS (virtual switch) 4 As an energy storage material, the material has a one-dimensional linear chain structure, extends along a c-axis, and has a V center at two S 2 2- Between dimers, and having a diameter greater than the diameter of the magnesium working ionIs beneficial to the intercalation and deintercalation of magnesium working ions. In addition, VS 4 The interaction between adjacent atomic chains by van der Waals forces and the weak forces are of great benefit in improving the mobility kinetics of magnesium working ions. Although VS 4 Has very encouraging structural advantages, but VS 4 Low conductivity of (2) and magnesium working ion and VS 4 The larger electrostatic interactions between the two do not yet enable VS 4 Satisfactory levels are achieved in magnesium ion batteries. Therefore, to improve VS 4 Application potential in magnesium ion batteries, VS is required 4 Modifications were made to overcome these problems.
Among methods capable of relieving strong electrostatic interactions between magnesium working ions and a positive electrode material and enhancing reaction kinetics, an interlayer regulation method can effectively improve conductivity and prevent structural collapse, thereby improving electrochemical performance of a magnesium ion battery (see literature: guest-features-incorporation in manganese/vanadium-based oxides: towards high performance aqueous zinc-ion batteries, li et al nano Energy,2021,85,105969). Cation pre-intercalation is a typical interlayer regulating method, which is to intercalate part of cations into the crystal lattice of an electrode material before cycling of the battery, and these pre-intercalated cations react with the host framework through chemical and physical interactions, with a significant promoting effect on the structural stability of the electrode material and the mobility kinetics of carriers (see documents: preintercalation Strategy in Manganese Oxides for Electrochemical Energy Storage: review and Prospects, adv. Mater.,2020,32, e 2002450). However, regarding Mg 2+ Pre-intercalating VS grown on the surface of Nitrogen doped tubular graphene (N-TG) 4 Research for improving the electrochemical performance of the magnesium ion battery has not been reported yet.
The invention realizes Mg by an electrochemical method 2+ Pre-embedded VS 4 N-TG and studied MgVS 4 The N-TG is used as a positive electrode material to be applied to the electrochemical performance of the magnesium ion battery. The research result shows that VS due to the fact that the pre-intercalated magnesium ions have the same ionic radius and ionic valence as the working ions 4 The chain spacing of the V element is enlarged, and the valence state change of the V element is induced, so that MgVS 4 The specific capacity and the cycling stability of the N-TG are improved. At 0.05A g –1 MgVS at current density of (2) 4 N-TG showed 170mAh g –1 Is a high specific capacity of (a). When the current density is from 0.05 to 0.05A g -1 To 1A g -1 In the process of (2), the specific capacity is 169mAh g -1 Changing to 107mAh g -1 And when the current density drops back to 0.05A g -1 When the specific capacity is restored to 145mAh g -1 And shows excellent multiplying power performance. At 1A g –1 MgVS at current density of (2) 4 After 1500 cycles of/N-TG, the capacity retention was approximately 100%.
Disclosure of Invention
The invention aims to provide a magnesium ion battery anode material, in particular to a magnesium ion battery anode material 2+ Pre-embedded magnesium ion battery anode material MgVS 4 /N-TG。
To achieve the aim, the invention provides a magnesium ion battery anode material MgVS 4 The preparation process of the N-TG is as follows:
1. according to the mass ratio of 9:1, weighing melamine and silicon powder in proportion, fully grinding, putting the melamine and the silicon powder and a carbon sheet dropwise added with a catalyst into a vertical vacuum atmosphere furnace for calcination, and obtaining nitrogen doped tubular graphene (N-TG) uniformly growing on the surface of the carbon sheet after the carbon sheet is cooled to normal temperature;
2. ammonium metavanadate is dissolved in deionized water under the condition of stirring at 60 ℃ to obtain a solution A with the concentration of 0.167M;
3. weighing excessive thioacetamide to be dissolved in glycol with the volume equal to that of the solution A, and stirring until the thioacetamide is completely dissolved to obtain a solution B;
4. mixing the solution A and the solution B, and stirring at 60 ℃ until the two solutions are completely mixed;
5. transferring the fully mixed solution and the carbon sheet growing with the N-TG into a 100ml reaction kettle, heating to 180 ℃, reacting for 4 hours, and cooling to room temperature along with a furnace after the reaction is finished;
6. taking out the reacted sample, washing with deionized water and absolute ethyl alcohol for 3 times, respectively, placing the obtained product into a vacuum drying oven, and drying at 60 ℃ for 12h to obtain VS 4 /N-TG。
7. Electrochemical method was used with 1M MgSO 4 Is a solution with a current density of 20mA cm –2 VS under the condition of 0-1.2V voltage window 4 Mg by N-TG 2+ Pre-embedding to obtain MgVS as the positive electrode material of magnesium ion battery 4 /N-TG。
The invention also provides MgVS 4 The N-TG is used as a positive electrode material in a magnesium ion battery, and the positive electrode material, a magnesium metal negative electrode, a glass fiber diaphragm and an APC-THF electrolyte are assembled into a button cell. Standing the assembled battery for 24 hours, and then performing electrochemical performance test on a CT2001A battery program-controlled tester, wherein the test voltage window is 0.2-2.1V, and the current density is 0.05-1A g -1 。
The magnesium ion battery anode material MgVS provided by the invention 4 The advantages of N-TG are:
1. the magnesium ion battery anode material MgVS prepared by the invention 4 N-TG, pre-embedded Mg 2+ Expand VS 4 Chain spacing of MgVS is improved 4 The conductivity of the/N-TG promotes diffusion kinetics of the magnesium working ion and acts as a "leg" to weaken the electrostatic interaction between the magnesium working ion and the positive electrode material to maintain structural stability, thus MgVS 4 The positive electrode material of the N-TG magnesium ion battery can show enhanced rate performance and cycle stability.
2. The magnesium ion battery anode material MgVS prepared by the invention 4 /N-TG，Mg 2+ Pre-embedding induction V 2+ And V 3+ Generating, optimizing MgVS 4 Electronic structure of N-TG and provides higher electrochemical reactivity, thus MgVS 4 The positive electrode material of the N-TG magnesium ion battery can show higher specific capacity.
3. The magnesium ion battery anode material MgVS prepared by the invention 4 N-TG exhibits excellent electrochemical properties: at 0.05Ag -1 MgVS at current density of (2) 4 N-TG showed 170mAh g -1 Is a high specific capacity of (a). When the current density is from 0.05 to 0.05A g -1 Is increased to 1Ag -1 In the process of (2), the specific capacity is 169mAh g -1 Changing to 107mAh g -1 And when the current density drops back to 0.05Ag -1 When the specific capacity is restored to 145mAh g -1 And shows excellent multiplying power performance. At 1A g -1 The electrode material showed excellent cycle stability with a capacity retention of approximately 100% after 1500 cycles.
The conception, structure and technical effects of the present invention will be further described with reference to the accompanying drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is a schematic diagram of a magnesium ion battery positive electrode material MgVS obtained in the example 4 XRD pattern of N-TG;
FIG. 2 is a schematic diagram of MgVS as a cathode material of a magnesium ion battery obtained in the example 4 (110) crystal plane HRTEM picture of N-TG;
FIG. 3 is a schematic diagram of MgVS as a cathode material of a magnesium ion battery obtained in the example 4 XPS profile of N-TG;
FIG. 4 is a schematic diagram of MgVS as a cathode material of a magnesium ion battery obtained in the example 4 V high resolution XPS spectrum of N-TG;
FIG. 5 is a schematic diagram of MgVS as a cathode material of a magnesium ion battery obtained in the example 4 Electrochemical performance curve of N-TG;
FIG. 6 is a schematic diagram of MgVS as a cathode material of a magnesium ion battery obtained in the example 4 N-TG at 1A g -1 Cycling performance curve at current density.
Detailed Description
The present invention is described in further detail below in connection with specific examples, which, however, do not limit the scope of the invention in any way.
Examples
Weighing 12.6g of melamine and 1.4g of silicon powder, fully grinding, then placing the mixture and a carbon sheet dropwise added with a nickel nitrate catalyst into a vertical vacuum atmosphere furnace, reacting at 1250 ℃ for 30min, and cooling the mixture along with the furnace to room temperature to obtain N-TG uniformly growing on the carbon sheet; 0.5814g of ammonium metavanadate is weighed and dissolved in 30ml of deionized water, and stirred at 60 ℃ until the ammonium metavanadate is completely dissolved, so as to obtain a solution A; weighing excessive thioacetamide to be dissolved in 30ml of ethylene glycol, and stirring at normal temperature until the thioacetamide is completely dissolved to obtain a solution B; thoroughly mixing the solution B and the solution A at 60 ℃; transferring the mixed solution and the carbon sheet growing with the N-TG into a 100ml reaction kettle, reacting for 4 hours at 180 ℃, and cooling to room temperature along with a furnace; taking out the sample, washing with deionized water and absolute ethyl alcohol for 3 times respectively, putting into a vacuum drying oven, and drying at 60 ℃ for 12h to obtain VS 4 N-TG; the obtained VS 4 N-TG was used as working electrode, saturated calomel electrode and platinum wire electrode were used as reference electrode and counter electrode, respectively, at 1M MgSO 4 The solution is electrochemically treated at 20mA cm –2 Three-stage circulation is carried out within the range of 0-1.2V voltage window, after the reaction is finished, the sample is washed 3 times by deionized water, and the magnesium ion battery anode material MgVS is obtained by drying 4 /N-TG。
After hydrothermal reaction and electrochemical reaction, mg 2+ Successfully embed into VS 4 In the case of N-TG, it can be observed in XRD results (FIG. 1), except for VS 4 And N-TG, no new phase is generated, and VS 4 Low angular shift of diffraction peaks of (2) relative to the standard spectrum, can prove that Mg 2+ Pre-embedding of (a) enlarges VS 4 Chain spacing of (2) and this result can also be found in MgVS 4 In the HRTEM images of (a), the expansion of the (110) interplanar spacing was confirmed (fig. 2). Mg, V, S, C, N element was observed simultaneously in XPS (FIG. 3), further demonstrating that Mg 2+ Pre-embedding into VS 4 In the N-TG lattice. The high resolution XPS spectrum of V (FIG. 4) shows that the V element has V in addition to V 4+ In addition to the peak, V was also shown 2+ And V 3+ The peaks of (1) indicate Mg 2+ Is pre-embedded to induce V 2+ And V 3+ Is generated.
The MgVS obtained by the preparation method 4 And (3) taking the N-TG as a magnesium ion battery anode material, taking the polished magnesium foil as a cathode material, taking a glass fiber filter membrane as a diaphragm of the magnesium ion battery, taking 0.4M APC-THF as an electrolyte, and assembling the button cell in a glove box filled with high-purity argon. Standing the assembled magnesium ion battery for 24 hours, and then performing electrochemical performance test on a CT2001A battery program-controlled tester, wherein the test voltage window is 0.2-2.1V, and the current density is 0.05-1A g -1 。
The obtained magnesium ion battery anode material MgVS 4 N-TG at a current density of 0.05A g -1 At the time, 170mAh g was exhibited -1 And when the current density is from 0.05 to 0.05A g -1 To 1A g -1 In the process of (2), the specific capacity is 169mAh g -1 Changing to 107mAh g -1 And when the current density drops back to 0.05A g -1 When the specific capacity is restored to 145mAh g -1 Exhibits excellent rate performance (fig. 5). At a current density of 1A g -1 At the time of MgVS 4 The positive electrode material of the N-TG magnesium ion battery has a capacity retention rate close to 100% after 1500 cycles, and shows excellent cycle stability (FIG. 6).

Claims (3)

1. Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG, characterized by the following preparation process:
ammonium metavanadate is dissolved in water under magnetic stirring at 60 ℃ to prepare an aqueous solution with the concentration of 0.167M; weighing excessive thioacetamide and dissolving in glycol with the volume equal to that of the aqueous solution; the two solutions are completely mixed and then transferred to a reaction kettle together with a carbon sheet growing with N-TG, the reaction is carried out for 4 hours at 180 ℃, after the reaction is finished, deionized water and absolute ethyl alcohol are respectively used for cleaning the carbon sheet for 3 times, and the carbon sheet is dried in vacuum; electrochemical method is adopted at 20mA cm –2 In the range of 0 to 1.2V, at a concentration of 1M MgSO 4 Mg in solution 2+ Pre-embedding, after the reaction is finishedWashing the sample with deionized water for 3 times, and vacuum drying to obtain Mg 2+ Pre-embedded magnesium ion battery anode material MgVS 4 /N-TG；
The obtained magnesium ion battery anode material MgVS 4 And assembling the N-TG to form a button magnesium ion battery for electrochemical performance test.
2. An Mg according to claim 1 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG characterized by pre-embedded Mg 2+ Can expand VS 4 And induces V 2+ And V 3+ Is an occurrence of (2).
3. An Mg according to claim 1 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG, characterized in that when the obtained material is used as the positive electrode of a magnesium ion battery, the current density is 0.05A g -1 When the specific capacity is stabilized at 170mAh g -1 Left and right; when the current density is from 0.05 to 0.05A g -1 To 1A g -1 In the process of (2), the specific capacity is 169mAh g -1 Changing to 107mAh g -1 And when the current density drops back to 0.05A g -1 When the specific capacity is restored to 145mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 1A g -1 MgVS at current density 4 After 1500 cycles of/N-TG, the capacity retention was approximately 100%.
CN202111437488.0A 2021-11-29 2021-11-29 Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG and application thereof Active CN114039034B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111437488.0A CN114039034B (en) 2021-11-29 2021-11-29 Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111437488.0A CN114039034B (en) 2021-11-29 2021-11-29 Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG and application thereof

Publications (2)

Publication Number Publication Date
CN114039034A CN114039034A (en) 2022-02-11
CN114039034B true CN114039034B (en) 2023-10-10

Family

ID=80145991

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111437488.0A Active CN114039034B (en) 2021-11-29 2021-11-29 Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG and application thereof

Country Status (1)

Country Link
CN (1) CN114039034B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111029172A (en) * 2019-12-31 2020-04-17 青岛科技大学 Two-dimensional layered supercapacitor electrode material Ti3C2Interlayer structure regulation and control method of MXene
CN112242526A (en) * 2020-10-20 2021-01-19 青岛科技大学 Mo-doped VS4Magnesium ion battery positive electrode material and application thereof
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111029172A (en) * 2019-12-31 2020-04-17 青岛科技大学 Two-dimensional layered supercapacitor electrode material Ti3C2Interlayer structure regulation and control method of MXene
CN112242526A (en) * 2020-10-20 2021-01-19 青岛科技大学 Mo-doped VS4Magnesium ion battery positive electrode material and application thereof
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Alkali ions pre-intercalated layered vanadium oxide nanowires for stable magnesium ions storage;Han Tang;《Nano Energy》;20190116;第347-354页 *

Also Published As

Publication number Publication date
CN114039034A (en) 2022-02-11

Similar Documents

Publication Publication Date Title
CN111180709B (en) Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof
CN112242526B (en) Mo-doped VS4 magnesium ion battery positive electrode material
CN103151522A (en) Mixed crystal form ferric fluoride cathode material and preparation method thereof
CN109873140B (en) Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material
CN112490438B (en) Mo-VS4Positive electrode material of/N-GNTs magnesium ion battery
CN103435104B (en) A kind of preparation method of lithium ion battery negative electrode material-nano zinc ferrite
CN104993125A (en) Preparation method of lithium ion battery novel cathode material Fe3O4/Ni/C
CN112886004A (en) Cathode material of water-based zinc ion battery and matched electrolyte
CN107394204B (en) Preparation method of layered lithium manganate serving as lithium ion battery anode material
CN103606672A (en) Rod-shaped nano iron oxide electrode material, and preparation method and application thereof
CN104701517A (en) Method for preparing NH4V3O8 anode material for lithium ion battery
CN102751489B (en) Method for preparing anode material of lithium ion battery
CN105826524B (en) A kind of synthetic method of graphene original position forming core LiFePO4
CN103346323A (en) Preparation method of carbon-coated lithium iron phosphate material with polystyrene microspheres and polyethylene glycol as carbon sources
CN113903884A (en) Positive electrode active material, preparation method thereof, positive electrode and lithium ion battery
CN108232186A (en) A kind of preparation method of single crystal grain and its application in the secondary battery
CN113644274B (en) O2 type lithium ion battery anode material and preparation method and application thereof
CN108117103A (en) A kind of vanadic acid cobalt compound and preparation method and application
CN106992295A (en) A kind of preparation method of single dispersing α ferric oxide nano pieces
CN106784803A (en) A kind of cobalt acid nickel nanocube material and its preparation method and application
CN108217725B (en) Hydrated basic zinc pyrovanadate (Zn)3V2O7(OH)2·2H2Preparation method and application of O) material
CN110233251A (en) A kind of preparation method and applications of porous silicon/carbon composite material
CN112467069A (en) Battery negative electrode material and preparation method and application thereof
CN114039034B (en) Mg (magnesium) 2+ Pre-embedded magnesium ion battery anode material MgVS 4 N-TG and application thereof
CN107265514A (en) A kind of rhombus Fe2O3Nano material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant