CN114373906B - Honeycomb Li 3 VO 4 Preparation method of negative electrode material of/C lithium ion battery - Google Patents

Honeycomb Li 3 VO 4 Preparation method of negative electrode material of/C lithium ion battery Download PDF

Info

Publication number
CN114373906B
CN114373906B CN202111562397.XA CN202111562397A CN114373906B CN 114373906 B CN114373906 B CN 114373906B CN 202111562397 A CN202111562397 A CN 202111562397A CN 114373906 B CN114373906 B CN 114373906B
Authority
CN
China
Prior art keywords
hours
composite material
honeycomb
lithium 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.)
Active
Application number
CN202111562397.XA
Other languages
Chinese (zh)
Other versions
CN114373906A (en
Inventor
倪世兵
李道波
杨松
石嘉悦
张苗苗
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.)
China Three Gorges University CTGU
Original Assignee
China Three Gorges University CTGU
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 China Three Gorges University CTGU filed Critical China Three Gorges University CTGU
Priority to CN202111562397.XA priority Critical patent/CN114373906B/en
Publication of CN114373906A publication Critical patent/CN114373906A/en
Application granted granted Critical
Publication of CN114373906B publication Critical patent/CN114373906B/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
    • H01M4/36—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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 provides a honeycomb Li 3 VO 4 A preparation method of a negative electrode material of a C lithium ion battery. And adding polyvinyl alcohol, lithium nitrate, ammonium metavanadate and oxalic acid into a proper amount of deionized water, and stirring to obtain a uniform green solution. The mixed solution is filled into a syringe for electrostatic spraying, the syringe is connected with a steel needle with the inner diameter of 0.2-0.3 mm through a plastic pipe, a receiver is a rotatable steel roller paved with aluminum foil, when the electrostatic spraying is started, voltage of 18-20 kV is applied, the precursor solution is atomized under high pressure, mist drops with static electricity are sprayed out, and finally, the precursor composite material is formed by uniformly distributing around the aluminum foil. Drying after the spraying process is completed, pre-sintering for 2-5 hours at the temperature of 200-300 ℃, and then calcining at the temperature of 500-800 ℃ in a nitrogen environment to obtain honeycomb Li 3 VO 4 and/C composite material. The invention synthesizes the cellular Li by simple electrostatic spraying for the first time 3 VO 4 the/C composite material is used as a negative electrode material of a lithium ion battery, and the prepared honeycomb Li 3 VO 4 the/C composite material is used as a negative electrode material of a lithium ion battery.

Description

Honeycomb Li 3 VO 4 Preparation method of negative electrode material of/C lithium ion battery
Technical Field
The invention relates to a novel lithium ion battery cathode material, in particular to a method for preparing honeycomb Li by electrostatic spraying 3 VO 4 Method for using/C composite material as negative electrode material of lithium ion batteryIn the field of electrochemical power sources.
Background
Lithium ion batteries have been rapidly developed in recent decades as one of the representatives of green energy storage materials. Daily digital products such as mobile phones and notebook computers are as small as large-scale product equipment such as electric automobiles and distributed energy storage power stations, and the appearance and development of the daily digital products are closely related to the innovation and development of battery technology. In recent years, with the vigorous development of the pure electric automobile market, the demand of the market for lithium ion batteries is continuously increased, and the lithium ion battery material with high energy density, high stability and low cost is naturally the focus of current research.
Li 3 VO 4 Is a novel lithium ion battery cathode material, has higher volume specific capacity than commercialized graphite, and has higher volume specific capacity than Li 4 Ti 5 O 12 Has lower voltage platform and higher specific capacity, and is an ideal cathode candidate material for lithium ion batteries. However, li 3 VO 4 The electron conductivity and the ion conductivity of the anode material are relatively low, which may lead to a large polarization during charge/discharge, so that the electrochemical reaction kinetics is poor, and the cycle performance of the battery is poor at a large rate, and thus, research is mainly focused on enhancing Li 3 VO 4 The conductivity of the material and how to improve the recycling properties of the material.
In addition, no simple electrostatic spraying method for preparing Li by using an electrostatic spinning machine exists at present 3 VO 4 Report of electrode. Based on the background, the patent develops a method for preparing honeycomb Li based on electrostatic spraying 3 VO 4 Method of preparing a composite material. The prepared electrode material takes honeycomb carbon as a matrix, a large number of ultra-small nano particles are embedded in the surface and the inside of the electrode material, the honeycomb morphology structure has strong tolerance, the collapse of the structure caused by volume expansion in the charge and discharge process can be effectively inhibited, the ultra-small nano particles are beneficial to the permeation of electrolyte, excellent electrochemical performance is shown, and the electrode material has potential application value in lithium ion batteries.
Disclosure of Invention
Based on electrostatic spraying technology, using lithium nitrate, oxalic acid, ammonium metavanadate, polyvinyl alcohol and deionized water as raw materials to obtain honeycomb Li 3 VO 4 The steps of the composite material are as follows:
(1) Adding a certain amount of polyvinyl alcohol, lithium nitrate, ammonium metavanadate and oxalic acid into a proper amount of deionized water, and stirring to obtain a uniform green solution;
(2) Transferring the uniform solution obtained in the step (1) into a syringe, and spinning for 6-8 hours at the voltage of 18-20 kV and the temperature of 40-60 ℃ to obtain a precursor composite material;
(3) Rapidly transferring the precursor composite material obtained in the step (2) into a blast drying oven at 60-80 ℃ for drying for 10-12 hours, placing the dried precursor composite material in an air environment, heating to 200-300 ℃ for presintering for 2-5 hours, and calcining for 5 hours in a nitrogen environment at 500-800 ℃ to obtain honeycomb Li 3 VO 4 and/C composite material.
The molar ratio of lithium nitrate, oxalic acid and ammonium metavanadate in the mixed solution in the step (1) is 3-4:5-6:0.5-1, the mass of deionized water accounts for 76-80% of the total mass, and the mass of polyvinyl alcohol accounts for 6-10% of the total mass.
In the step (2), the electrostatic spraying voltage is 18-20 kV, the time is 6-8 hours, the environment temperature is 40-60 ℃ during spinning, the humidity is 20-30%, and the spinning distance is 20-30cm.
After the electrostatic spraying is finished, the aluminum foil is quickly transferred to an oven at 60-80 ℃ for drying for 10-12 hours.
In the step (3), presintering is carried out in air, the presintering temperature is 200-300 ℃, the heating rate is 5-10 ℃/min, the presintering time is 2-5 hours, and then the presintering is carried out in nitrogen atmosphere at the heating rate of 4-5 ℃/min for 5-8 hours at the temperature of 500-800 ℃.
This patent forms electrified fog drops through polymer solution atomizing in strong electric field, first utilizes simple and easy electrostatic spraying to obtain cellular Li 3 VO 4 And (3) the electrode material/C, and a large number of ultra-small nano particles are embedded in the honeycomb carbon matrix, so that the diffusion of lithium ions in the composite material is obviously enhanced.
The principle is as follows: (1) The actual structure of ammonium metavanadate is ammonium tetravanadate (NH) 4 ) 4 V 4 O 12 V in an acidic solution 4 O 12 4− VO which is changed from proton to chemical reaction is obtained 2+ （V 4 O 12 4− +16H + +4e = 4VO 2+ +12H 2 O). In the electrostatic spraying process, li due to electrostatic interaction + 、VO 2+ Mutually repel, thereby inhibiting the agglomeration of the two and the agglomeration of the two respectively - OOC-COO - Combining, and uniformly dispersing in a microscopic scale; (2) After electrostatic spraying, water in the liquid drops is atomized and mutually repulsed at the edge of the liquid drops under the action of static electricity, and Li of the core + 、VO 2+ The components remain in the center of the droplets, and the droplets are arranged in an ordered structure under the action of capillary force and convection. In the subsequent drying, the water is completely evaporated and the polymer is completely cured, whereas oxalic acid and ammonium metavanadate react chemically to form stable complexes and gases (2 NH) 4 VO 3 +4C 2 H 2 O 4 = (NH 4 ) 2 [(VO) 2 (C 2 O 4 ) 3 ]+2CO 2 +H 2 O) this gas results in the formation of honeycomb cells whose membrane cells are in a hexagonal ordered arrangement, as in honeycomb; (3) Using polyvinyl alcohol as template, through - OOC-COO - With Li + 、VO 2+ And (5) combining. The polyvinyl alcohol is presintered (preoxidized) under the air of 200-300 ℃ to generate dehydrogenation reaction and simultaneously generate conjugated C=C bond to form stable carbon skeleton, thereby being beneficial to the maintenance of honeycomb structure and simultaneously generating a large amount of free oxygen which is Li + 、VO 2+ Li formation in subsequent sintering 3 VO 4 Providing an oxidizing environment; (4) During sintering process, li + 、VO 2+ Bonding at the surface and interior of polyvinyl alcohol and forming Li in an oxidizing environment 3 VO 4 Nanoparticles, with further carbonization of the polyvinyl alcohol, to obtain Li 3 VO 4 The nano particles are embedded in the special shape of the inside and the surface of the honeycomb carbon matrix. The honeycomb carbon is beneficial to enhancing the structural stability of the material, and the ultra-small nano particles can obviously improve the activity of the composite material. Prepared byCellular Li 3 VO 4 the/C composite material shows excellent comprehensive electrochemical performance as a negative electrode of a lithium ion battery.
The invention relates to a honeycomb Li 3 VO 4 The preparation method of the/C composite material as the lithium ion battery anode material has the following obvious characteristics:
(1) The manufacturing cost is low, the method is green and pollution-free, and is environment-friendly;
(2) The synthesis process is simple, electrostatic spraying can be performed without additional high-temperature environment, and the repeatability is high;
(3) The prepared cellular Li 3 VO 4 Honeycomb structure of composite material/C, having strong bearing capacity and structure
The electrolyte is stable, can bear the volume expansion caused by charge and discharge, and the ultra-small nano particles are beneficial to the contact and permeation of the electrolyte;
(4) The prepared cellular Li 3 VO 4 the/C composite material is used as the negative electrode material of the lithium ion battery for the first time and has
Has high capacity and excellent cycle stability.
Drawings
FIG. 1 optical photograph of sample prepared in example 1: (a) after spraying, (b) after drying, (c) partial enlarged view.
Figure 2 XRD pattern of sample prepared in example 1.
Figure 3 SEM images of samples prepared in example 1.
FIG. 4 shows (a) the three previous charge and discharge graphs and (b) the cycle performance graphs of the samples prepared in example 1.
FIG. 5 is an optical photograph of the precursor solution prepared in example 2.
FIG. 6 is an optical photograph of the sample prepared in example 3.
FIG. 7 shows (a) the three previous charge and discharge graphs and (b) the cycle performance graphs of the samples prepared in example 3.
Fig. 8 SEM image of the sample prepared in example 4.
FIG. 9 shows (a) the three previous charge and discharge graphs and (b) the cycle performance graphs of the samples prepared in example 4.
Detailed Description
Example 1
Accurately weighing 7.5 mmol of lithium nitrate, 12.5 mmol of oxalic acid, 2.5 mmol of ammonium metavanadate and 1.2. 1.2 g of polyvinyl alcohol according to stoichiometric amount, adding into 15 mL of deionized water, stirring for 48 hours to obtain a uniform green solution, transferring the obtained uniform solution into a syringe, spraying for 8 hours under the conditions of voltage of 19 kV and temperature of 40 ℃, rapidly transferring the precursor material into a 80 ℃ blast drying oven for drying for 12 hours after spraying, placing in an air environment after drying is finished, presintering for 3 hours at 250 ℃, and calcining for 6 hours at 600 ℃ in a nitrogen environment to obtain honeycomb Li 3 VO 4 and/C composite material. After electrostatic spraying, first an atomized precursor material is obtained on a received aluminum foil (figure 1 a), the moisture is removed by drying and yellow particles are generated along with the reaction of oxalic acid and ammonium metavanadate (figure 1 b), the carbonized composite material is analyzed by XRD pattern, and the obtained diffraction peak and Li are obtained 3 VO 4 (PDF # 38-1247) corresponds well (FIG. 2). As can be seen from the SEM image, the composite material has a hexagonal honeycomb structure as a whole (fig. 3 a), and a large number of ultra-small nano particles are uniformly distributed on the honeycomb surface (fig. 3 b).
The materials are made into a battery according to the following method: mixing the prepared sample with acetylene black and polyvinylidene fluoride according to the weight ratio of 8:1:1, preparing slurry by using N-methyl pyrrolidone as a solvent, coating the slurry on copper foil with the thickness of 10 mu m, drying the slurry at 60 ℃ for 10 hours, cutting the slurry into wafers with the diameter of 14mm, and drying the wafers at 120 ℃ in vacuum for 12 hours. The metal lithium sheet is used as a counter electrode, the Celgard membrane is used as a diaphragm, and the LiPF is dissolved 6 (1 mmol/L) of EC+DMC+DEC (volume ratio of 1:1:1) solution was used as an electrolyte, and a CR2025 type battery was assembled in a glove box under argon protection. Standing for 8 hours after the battery is assembled, and then carrying out constant-current charge and discharge test by using a CT2001 battery test system, wherein the test voltage is 3-0.01V, and the current density is 200 mA g -1 . FIG. 4 is a honeycomb Li prepared 3 VO 4 And (3) the charge and discharge curves and the cycle performance diagrams of the first three circles of the negative electrode of the lithium ion battery. Specific capacities of 614 and 913 mAh.g respectively in initial charge and discharge -1 After 130 times of circulation, the charge and discharge capacity are 555.7 and 560.7 mAh.g respectively -1 Exhibits excellent electrochemical properties.
Example 2
In this example, the procedure was exactly the same as in example 1, except that oxalic acid was not added, 7.5 mmol lithium nitrate, 2.5 mmol ammonium metavanadate and 1.2. 1.2 g polyvinyl alcohol were weighed and added to 15 mL deionized water and stirred for 48 hours, the resulting solution was not uniform (fig. 5 a) and too viscous (fig. 5 b), so that electrostatic spraying was not possible and no battery product could be realized.
Example 3
The procedure of this example was exactly the same as that of example 1, and the material was obtained by calcining at 600℃for 6 hours at a heating rate of 5℃per minute without pre-firing, and the overall morphology of the prepared sample was not significantly changed (FIG. 6). The material obtained in example 3 was fabricated into a battery as in example 1. Specific capacities of initial charge and discharge are 268.1 mAh.g respectively -1 And 590.3 mAh.g -1 (FIG. 7 a) has obvious charge and discharge plateau, and after 130 cycles, the charge and discharge capacities are 269.1 mAh.g respectively -1 And 269.8 mAh.g -1 (FIG. 7 b), electrochemical performance is poor.
Example 4
This example was carried out in the same manner as in example 1, except that the high polymer polyvinyl alcohol used in example 1 was changed to polyvinylpyrrolidone (PVP), and 7.5 mmol of lithium nitrate, 12.5 mmol of oxalic acid, 2.5 mmol of ammonium metavanadate and 1.2. 1.2 g polyvinylpyrrolidone were added to 15 mL deionized water in stoichiometric proportions and stirred for 48 hours. And transferring the obtained uniform solution into a syringe, simply spraying at the voltage of 19 kV and the temperature of 40 ℃, finding that polyvinylpyrrolidone is stretched and thinned under the action of static electricity, finally spinning to form a fiber membrane, quickly transferring the fiber membrane into a 80 ℃ blast drying oven for drying for 12 hours after spinning, placing the dried fiber membrane in an air environment, presintering at 250 ℃ for 3 hours, and calcining at 600 ℃ for 6 hours in a nitrogen environment to obtain the fiber composite material. The prepared sample has changed morphology, is fibrous as a whole (figure 8), and has a large number of nano particles dispersed on the surface. The material obtained in example 4 was prepared as in example 1And forming a battery. Specific capacities of initial charge and discharge are 489.4 mAh.g respectively -1 And 622.2 mAh.g -1 (FIG. 9 a) has obvious charge and discharge plateau, and after 130 cycles, the charge and discharge capacities are 411.7 mAh.g respectively -1 And 413.5 mAh.g -1 (FIG. 9 b), electrochemical performance was good.

Claims (2)

1. Honeycomb Li 3 VO 4 The preparation method of the negative electrode material of the/C lithium ion battery is characterized by comprising the following specific preparation processes:
(1) Adding a certain amount of polyvinyl alcohol, lithium nitrate, ammonium metavanadate and oxalic acid into a proper amount of deionized water, and stirring to obtain a uniform green solution, wherein the molar ratio of the lithium nitrate to the oxalic acid to the ammonium metavanadate in the mixed solution is 3-4:5-6:0.5-1, the mass of the deionized water accounts for 76-80% of the total mass, and the mass of the polyvinyl alcohol accounts for 6-10% of the total mass;
(2) Transferring the uniform solution obtained in the step (1) into a syringe for electrostatic spraying, wherein the electrostatic spraying voltage is 18-20 kV, the time is 6-8 hours, the environment temperature is 40-60 ℃ during spinning, the humidity is 20-30%, the spinning distance is 20-30cm, and after the electrostatic spraying is finished, rapidly transferring the aluminum foil into a 60-80 ℃ oven for drying for 10-12 hours to obtain a precursor composite material;
(3) Rapidly transferring the precursor composite material obtained in the step (2) into a blast drying oven at 60-80 ℃ for drying for 10-12 hours, placing the dried precursor composite material in an air environment, heating to 200-300 ℃ for presintering for 2-5 hours, and calcining for 5 hours in a nitrogen environment at 500-800 ℃ to obtain honeycomb Li 3 VO 4 and/C composite material.
2. The cellular Li of claim 1 3 VO 4 The preparation method of the negative electrode material of the/C lithium ion battery is characterized in that the preparation method is firstly presintered in air in the step (3), the presintering temperature is 200-300 ℃, the heating rate is 5-10 ℃/min, the presintering time is 2-5 hours, and then the preparation method is calcined for 5-8 hours in the nitrogen atmosphere at the heating rate of 4-5 ℃/min at the temperature of 500-800 ℃.
CN202111562397.XA 2021-12-20 2021-12-20 Honeycomb Li 3 VO 4 Preparation method of negative electrode material of/C lithium ion battery Active CN114373906B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111562397.XA CN114373906B (en) 2021-12-20 2021-12-20 Honeycomb Li 3 VO 4 Preparation method of negative electrode material of/C lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111562397.XA CN114373906B (en) 2021-12-20 2021-12-20 Honeycomb Li 3 VO 4 Preparation method of negative electrode material of/C lithium ion battery

Publications (2)

Publication Number Publication Date
CN114373906A CN114373906A (en) 2022-04-19
CN114373906B true CN114373906B (en) 2024-03-15

Family

ID=81139400

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111562397.XA Active CN114373906B (en) 2021-12-20 2021-12-20 Honeycomb Li 3 VO 4 Preparation method of negative electrode material of/C lithium ion battery

Country Status (1)

Country Link
CN (1) CN114373906B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115000343B (en) * 2022-05-30 2023-11-24 三峡大学 Preparation method of flexible double-layer self-supporting electrode

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104934577A (en) * 2015-05-15 2015-09-23 武汉理工大学 Mesoporous Li3VO4/C nano ellipsoid composite material embedded into graphene network, and preparation method and application of composite material
CN106803578A (en) * 2017-01-12 2017-06-06 安徽师范大学 Hollow ball phosphoric acid vanadium lithium/carbon composite battery positive electrode and its preparation method and application
KR101779301B1 (en) * 2016-06-27 2017-09-19 경북대학교 산학협력단 Method for manufacturing for lithium-vanadium oxide having honey-comb structure, and Anode material for Lithium secondary cell using the same
CN111106335A (en) * 2019-12-20 2020-05-05 三峡大学 Preparation method of lithium ion battery composite negative electrode material
CN112018373A (en) * 2020-08-05 2020-12-01 嵊州市森拓新材料有限公司 Carbon-coated Li with shell-core structure3VO4Lithium ion battery cathode material and preparation method thereof
CN112281258A (en) * 2020-10-20 2021-01-29 三峡大学 Li3VO4Negative electrode material of/C fiber lithium ion battery and preparation method
CN113699687A (en) * 2021-08-18 2021-11-26 三峡大学 Double-needle electrostatic spinning Li3VO4Preparation method of/C fiber lithium ion battery cathode material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104934577A (en) * 2015-05-15 2015-09-23 武汉理工大学 Mesoporous Li3VO4/C nano ellipsoid composite material embedded into graphene network, and preparation method and application of composite material
KR101779301B1 (en) * 2016-06-27 2017-09-19 경북대학교 산학협력단 Method for manufacturing for lithium-vanadium oxide having honey-comb structure, and Anode material for Lithium secondary cell using the same
CN106803578A (en) * 2017-01-12 2017-06-06 安徽师范大学 Hollow ball phosphoric acid vanadium lithium/carbon composite battery positive electrode and its preparation method and application
CN111106335A (en) * 2019-12-20 2020-05-05 三峡大学 Preparation method of lithium ion battery composite negative electrode material
CN112018373A (en) * 2020-08-05 2020-12-01 嵊州市森拓新材料有限公司 Carbon-coated Li with shell-core structure3VO4Lithium ion battery cathode material and preparation method thereof
CN112281258A (en) * 2020-10-20 2021-01-29 三峡大学 Li3VO4Negative electrode material of/C fiber lithium ion battery and preparation method
CN113699687A (en) * 2021-08-18 2021-11-26 三峡大学 Double-needle electrostatic spinning Li3VO4Preparation method of/C fiber lithium ion battery cathode material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A facile spray drying route for mesoporous Li3VO4/C hollow spheres as an anode for long life lithium ion batteries;Yang Yang, etc.;《Journal of Materials Chemistry A》;第2016卷(第4期);第7165–7168页 *
Hollow−Cuboid Li3VO4/C as High-Performance Anodes for Lithium-Ion Batteries;Changkun Zhang, etc.;《ACS Applied Materials & Interfaces》;第2016卷(第8期);第680-688页 *
Spray Drying-Assisted Synthesis of Li3VO4/C/CNTs Composites for High-Performance Lithium Ion Battery Anodes;Yang Yang, etc.;《Journal of The Electrochemical Society》;第164卷(第1期);第A6001-A6006 页 *

Also Published As

Publication number Publication date
CN114373906A (en) 2022-04-19

Similar Documents

Publication Publication Date Title
CN107681091B (en) Lithium-sulfur battery functional composite diaphragm and preparation method thereof
CN110400929B (en) Phosphate-coated metal-doped ternary positive electrode active material and preparation and application thereof
CN112281258B (en) Li 3 VO 4 Negative electrode material of/C fiber lithium ion battery and preparation method
CN104900848B (en) The preparation method of long-life lithium-sulphur cell positive electrode and lithium-sulfur cell
CN107464938B (en) Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery
CN104393291B (en) A kind of vanadium phosphate cathode material of doping, cladding modification altogether and preparation method thereof
CN111430672B (en) Preparation method and application of silicon dioxide/carbon cloth self-supporting electrode material
CN110137568A (en) A kind of composite solid electrolyte, preparation method and all-solid-state battery system
CN114373906B (en) Honeycomb Li 3 VO 4 Preparation method of negative electrode material of/C lithium ion battery
CN115663157A (en) Hard carbon composite material for lithium ion battery and preparation method thereof
CN113699687B (en) Double-needle electrostatic spinning Li 3 VO 4 Preparation method of/C fiber lithium ion battery cathode material
CN111628150B (en) Carbon-coated lithium sulfide composite electrode for lithium-sulfur battery and preparation method thereof
CN109935813A (en) A kind of preparation method and application of novel cathode material for lithium ion battery
CN109037658A (en) A kind of lithium iron phosphate positive material preparation method of polymer overmold
CN115602805B (en) Nitrogen-doped hollow carbon sphere and preparation method and application thereof
CN115939361A (en) Copper phosphide-doped hard carbon composite material and preparation method thereof
CN113991104A (en) Vanadium-based material and preparation method and application thereof
CN113764672A (en) Pre-lithiation positive electrode slurry and preparation method and application thereof
CN108281632B (en) Preparation method of vanadium phosphate/carbon as cathode material of hollow spherical lithium ion battery
CN113764636A (en) Flexible self-supporting Li3VO4Preparation method of/C nanofiber lithium ion battery cathode material
CN106848293A (en) A kind of ternary cathode material of lithium ion battery and preparation method thereof
CN108183220B (en) Ternary composite negative electrode material of lithium battery and preparation method of ternary composite negative electrode material
CN112242525A (en) Nitrogen-doped carbon-coated vanadium manganese sodium phosphate composite material and preparation method and application thereof
CN111584874A (en) Sodium ion battery positive electrode material based on nanofiber framework and preparation method and application thereof
CN110649222A (en) Preparation method of lithium-sulfur battery positive electrode

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