CN111048778B - Doped modified lithium ion battery vanadate anode material and preparation method thereof - Google Patents

Doped modified lithium ion battery vanadate anode material and preparation method thereof Download PDF

Info

Publication number
CN111048778B
CN111048778B CN201911028862.4A CN201911028862A CN111048778B CN 111048778 B CN111048778 B CN 111048778B CN 201911028862 A CN201911028862 A CN 201911028862A CN 111048778 B CN111048778 B CN 111048778B
Authority
CN
China
Prior art keywords
vanadate
lithium ion
source compound
doped
anode material
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
CN201911028862.4A
Other languages
Chinese (zh)
Other versions
CN111048778A (en
Inventor
袁正勇
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.)
Ningbo Polytechnic
Original Assignee
Ningbo Polytechnic
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 Ningbo Polytechnic filed Critical Ningbo Polytechnic
Priority to CN201911028862.4A priority Critical patent/CN111048778B/en
Publication of CN111048778A publication Critical patent/CN111048778A/en
Application granted granted Critical
Publication of CN111048778B publication Critical patent/CN111048778B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/58—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a doped modified vanadate anode material for a lithium ion battery and a preparation method thereof, belonging to the lithium ion batteryThe field of material preparation. The vanadate anode material of the doped modified lithium ion battery is prepared from an iron source compound, an antimony source compound, a vanadate source compound and a fluorine source compound according to the mol ratio of Fe: sb: VO (vacuum vapor volume)4 3‑: f ═ x: y: 1: z, wherein x is 0.5 to 0.9, y is 0.1 to 0.5, and z is 0.01 to 0.1. The vanadate is taken as a main framework, iron ions and antimony ions with different ionic radiuses and electronic structures and fluoride ions with smaller radiuses and stronger electronegativity are doped with each other, the electric field distribution in a unit cell is changed, a lithium ion insertion and extraction channel in a crystal is enlarged, the migration rate of the lithium ions is improved, and the impact of the lithium ions on the crystal structure due to the change of the crystal volume in the insertion and extraction process is buffered, so that the lithium storage performance of the material is improved, and the cycle life of the vanadate-doped negative electrode material lithium ion battery is greatly prolonged.

Description

Doped modified lithium ion battery vanadate anode material and preparation method thereof
Technical Field
The invention belongs to the field of preparation of lithium ion battery materials, and particularly relates to a doped modified vanadate negative electrode material for a lithium ion battery and a preparation method thereof.
Background
With the increasing energy crisis and environmental pollution, more alternative new environmentally friendly energy sources are required for human beings. As an environment-friendly renewable energy source, a lithium ion battery has the advantages of high energy density, good safety performance, environmental protection and the like, and has attracted general attention in recent years.
The cathode material is a key component material of the lithium ion battery. At present, lithium storage negative electrode materials which have been practically applied to lithium ion batteries are basically carbon materials such as artificial graphite, natural graphite, mesocarbon microbeads, petroleum coke, carbon fibers, pyrolytic resin carbon and the like. Although the carbon material has low intercalation potential and excellent intercalation and deintercalation performance, potential safety hazard exists in the use process, when the charge-discharge potential reaches 0V or lower, lithium is deposited on the graphite electrode, and the possibility of explosion of the battery is caused by the generation of active lithium metal; and the specific capacity of lithium storage quality and the specific capacity of volume are both lower.
The transition metal oxide and the salt thereof are used as the lithium ion battery cathode material, have high safety performance, high volume specific capacity and mass specific capacity, and are a lithium ion battery cathode material with great development prospect. However, the cathode materials generally have the problems of low electronic conductivity and large volume expansion effect. In order to effectively solve the problem, besides a morphology control method of nanocrystallization, porous hollow construction and the like, the method is also an effective method for compounding and doping with other substances.
As a novel lithium ion battery cathode material, an iron vanadate cathode material has high lithium storage capacity and safety, and a great deal of research is carried out in recent years. As a mixed transition metal oxide, the material also has problems like other transition metal oxides, the material has low conductivity, and the volume expansion and contraction are severe as lithium is intercalated and deintercalated in the material during charge and discharge. Introducing other metal ions into the ferric vanadate negative electrode material to form composite metal salt, improving the conductivity of the material by utilizing the synergistic effect of different metal ions, and buffering the expansion and contraction of the volume of the material in the charging and discharging processes; other non-metal ions are doped into the ferric vanadate negative electrode material, so that the crystal of the material is distorted, and the insertion and extraction channels of lithium ions in the material are enlarged, thereby improving the electrochemical performance of the material.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a doped modified ferric vanadate negative electrode material which can improve the reversible lithium storage capacity and the cycle life of the material by expanding and contracting the volume of a ferric vanadate doped modified buffer material in the charging and discharging processes.
The above object of the present invention can be achieved by the following technical solutions: a modified vanadate anode material for a lithium ion battery is prepared from an iron source compound, an antimony source compound, a vanadate source compound and a fluorine source compound according to the mol ratio of Fe: sb: VO (vacuum vapor volume)4 3-: f ═ x: y: 1: z, wherein x is 0.5 to 0.9, y is 0.1 to 0.5, and z is 0.01 to 0.1.
According to the invention, vanadate is used as a main framework, and iron ions and antimony ions with different ionic radii and electronic structures are mutually doped, so that the electric field distribution in a unit cell is changed, and the impact of the lithium ions on the crystal structure due to the change of the crystal volume in the insertion and extraction process is buffered, thereby improving the lithium storage performance of the material. The vanadic acid is treated by fluoride ions with smaller radius and stronger electronegativityThe doping modification is carried out on the roots, so that partial distortion of a main skeleton of vanadate in the crystal is promoted, lithium ion intercalation and deintercalation channels in the crystal are enlarged, the migration rate of lithium ions is improved, and the lithium storage performance and the cycle life of the vanadate-doped negative electrode material are greatly improved. Meanwhile, in the cathode material, Fe is a main central ion, and the structure of the material can be damaged when the content of Sb exceeds 0.5; f as negative ion to replace VO4 3-The doping effect cannot be realized when the content of ions and F is less than 0.01, and the ions and the F cannot be effectively doped when the content of the ions and the F exceeds 0.1.
Preferably, the chemical general formula of the doped modified vanadate anode material of the lithium ion battery is FexSbyVO4FzWherein x is 0.5 to 0.9, y is 0.1 to 0.5, and z is 0.01 to 0.1.
Preferably, the iron source compound is one or more of iron oxide, iron hydroxide, ferrous oxalate, ferrous acetate, and the like.
Preferably, the antimony source compound is one or more of antimony oxide, antimony hydroxide and antimony carboxylate. The antimony in the antimony source compounds has the same valence with the central ion Fe and certain difference in ionic radius, and is easy to be mixed with VO4 3-The ions combine to form a complex and can cause some deformation of the crystal. In addition, antimony is easy to form an alloy with lithium, and has strong lithium storage capacity
Preferably, the vanadate source compound is one or two of vanadium oxide and vanadates.
Further preferably, the vanadium oxide is vanadium pentoxide, and the vanadium oxoacid salt is ammonium metavanadate.
Preferably, the fluorine source compound is one or both of hydrofluoric acid and ammonium fluoride. The invention takes hydrofluoric acid and ammonium fluoride as fluorine source compounds, and impurity ions can not be brought into a target product in the subsequent treatment stage, thereby being convenient for obtaining the cathode material with better conductivity.
The invention also provides a preparation method of the doped modified vanadate anode material for the lithium ion battery, which comprises the following specific steps:
s1: an iron source compound, an antimony source compound,Vanadate source compound and fluorine source compound, wherein the molar ratio of Fe: sb: VO (vacuum vapor volume)4 3-: f ═ x: y: 1: z, accurately weighing and ball-milling to obtain a rheological phase mixture;
s2: adding oxalic acid solution into the rheological phase mixture, adjusting the pH value of the mixture system to be kept at 5-7, fully stirring, placing the mixture into a stainless steel high-pressure tank for reaction, and after the reaction is finished, drying and grinding reactants to obtain precursor powder;
s3: heating the precursor powder to 500-1000 ℃, and reacting for 1-10 hours to obtain the doped and modified FexSbyVO4FzVanadate anode materials.
Preferably, the concentration of the oxalic acid solution in the step S2 is 0.5-1.5 mol/L. The oxalic acid solution in the concentration range not only ensures that enough acid enters the reaction system to adjust the pH value of the system, but also does not bring too much water into the system to influence the reaction process.
Preferably, the reaction temperature in step S2 is 150-220 ℃, and the reaction time is 8-60 hours. Repeated tests show that the reaction efficiency is higher under the condition, the composite reaction is more thorough, and the obtained composite material has better electrical property.
Preferably, the heating rate in the step S2 is 3-7 ℃/min. The heating speed is too slow, the composite reaction efficiency is low, and the doping effect is not obvious; the heating speed is too high, the crystallization of the material is incomplete, and the electrical property and the cycle life are influenced.
Compared with the prior art, the invention has the beneficial effects that: in the crystal formed by taking vanadate as a main framework, iron ions and antimony ions with different ionic radii and electronic structures are doped with each other, so that the electric field distribution in a unit cell is changed, and the impact of the lithium ions on the crystal structure due to the change of the crystal volume in the insertion and extraction process is buffered, thereby improving the lithium storage performance of the material. The vanadate is doped and modified by the fluoride ions with smaller radius and stronger electronegativity, so that partial distortion of the main skeleton of the vanadate in the crystal is caused, lithium ion intercalation and deintercalation channels in the crystal are enlarged, the migration rate of lithium ions is improved, and the lithium storage performance and the cycle life of the vanadate-doped negative electrode material are greatly improved. The preparation process is simple to operate, easy to control and beneficial to realizing large-scale industrial production.
Drawings
FIG. 1 shows Fe synthesized in example 10.85Sb0.14VO4F0.03SEM image of vanadate anode material.
FIG. 2 shows Fe synthesized in example 10.85Sb0.14VO4F0.03And the charge-discharge curve of the vanadate negative electrode material in the previous two weeks when the charge-discharge current is 0.1C.
FIG. 3 shows Fe synthesized in example 10.85Sb0.14VO4F0.03And the discharge capacity curve of the vanadate negative electrode material at the first 50 weeks when the charge-discharge current is 0.1C.
Detailed Description
The following are specific examples of the present invention and illustrate the technical solutions of the present invention for further description, but the present invention is not limited to these examples.
Example 1
Accurately weigh 0.85mol Fe (OH)3、0.14molSb(OH)3、1.0molNH4VO3、0.03mol NH4And F, filling the mixture into a ball milling tank of a planetary ball mill, adding deionized water, and performing ball milling to obtain a rheological phase mixture. While stirring, 1.0mol/L oxalic acid solution was added dropwise to the rheological phase mixture to adjust the pH of the mixture to 5.8, followed by sufficient stirring. Transferring the mixture into a stainless steel high-pressure tank, reacting for 24 hours at a constant temperature of 220 ℃, taking out and drying, and grinding the solid mixture to obtain precursor powder. Heating the precursor powder in a programmed electric furnace at a heating rate of 5 ℃/min to 720 ℃, and keeping the temperature for 8 hours to obtain the doped modified Fe0.85Sb0.14VO4F0.03Vanadate anode materials.
Fe to be synthesized0.85Sb0.14VO4F0.03Mixing vanadate negative electrode material, acetylene black and polytetrafluoroethylene according to a mass ratio of 85: 10: 5 mixing uniformly, pressing into film with thickness of about 1mm by film pressing machine, placing in oven, drying at 120 deg.C, and cutting to obtain surface area of 1cm2Is of a circleThe membrane was pressed on a stainless steel mesh to make a research electrode. A research electrode is used as a cathode, metal lithium is used as a counter electrode, a Celgard2400 microporous polypropylene membrane is used as a diaphragm, 1mol/LLiPF6 dissolved in EC (ethylene carbonate)/DMC (1, 2-dimethyl carbonate) with the volume ratio of 1: 1 is used as electrolyte, and the electrolyte is assembled into a CR2032 type button cell in a glove box filled with argon. The button cell is placed on a cell test system to test the charge and discharge performance at room temperature, the charge and discharge voltage range is 0.02V-3.0V (vs. Li), the charge and discharge current is 0.1C, and the first reversible discharge specific capacity is 1475 mAh/g; after 50 cycles, the discharge capacity still remained 1296 mAh/g.
Example 2
Accurately weighing 0.25mol Fe2O3、0.05molSb2O3、1.0molNH4VO3、0.01mol NH4And F, filling the mixture into a ball milling tank of a planetary ball mill, adding deionized water, and performing ball milling to obtain a rheological phase mixture. While stirring, 0.5mol/L oxalic acid solution was added dropwise to the rheological phase mixture to adjust the pH of the mixture to 5.1, followed by sufficient stirring. Transferring the mixture into a stainless steel high-pressure tank, reacting for 60 hours at a constant temperature of 150 ℃, taking out and drying, and grinding the solid mixture to obtain precursor powder. Heating the precursor powder in a programmed electric furnace at a heating rate of 3 ℃/min to 500 ℃ and keeping the temperature for 1 hour to obtain the doped modified Fe0.5Sb0.1VO4F0.01Vanadate anode materials.
Fe to be synthesized0.5Sb0.1VO4F0.01The vanadate negative electrode material, acetylene black and polytetrafluoroethylene are mixed according to the mass ratio of 85: 10: 5 mixing uniformly, pressing into film with thickness of about 1mm by film pressing machine, placing in oven, drying at 120 deg.C, and cutting to obtain surface area of 1cm2The round membrane of (a) was pressed on a stainless steel mesh to make a research electrode. A research electrode is used as a cathode, metal lithium is used as a counter electrode, a Celgard2400 microporous polypropylene membrane is used as a diaphragm, 1mol/LLiPF6 dissolved in EC (ethylene carbonate)/DMC (1, 2-dimethyl carbonate) with the volume ratio of 1: 1 is used as electrolyte, and the electrolyte is assembled into a CR2032 type button cell in a glove box filled with argon. Placing the button cellTesting the charge and discharge performance at room temperature on a battery test system, wherein the charge and discharge voltage range is 0.02V-3.0V (vs. Li), the charge and discharge current is 0.1C, and the first reversible discharge specific capacity is 1285 mAh/g; after 50 cycles, the discharge capacity remained 1126 mAh/g.
Example 3
Accurately weighing 0.6mol Fe (OH)3、0.19molmolSb2O3、1.0mol NH4VO3And 0.015mol of HF, filling the mixture into a ball milling tank of a planetary ball mill, adding a proper amount of deionized water, and carrying out ball milling to obtain a rheological phase mixture. While stirring, 1.0mol/l oxalic acid solution was added dropwise to the rheological phase mixture to adjust the pH of the mixture to 5.5, followed by sufficient stirring. Transferring the mixture into a stainless steel high-pressure tank, reacting at the constant temperature of 160 ℃ for 56 hours, taking out and drying, and grinding the solid mixture to obtain precursor powder. Heating the precursor powder in a programmed electric furnace at a heating rate of 4 ℃/min to 600 ℃, and keeping the temperature for 3 hours to obtain the doped modified Fe0.6Sb0.38VO4F0.015Vanadate anode materials.
Fe to be synthesized0.6Sb0.38VO4F0.015Mixing vanadate negative electrode material with acetylene black and polytetrafluoroethylene according to the weight ratio of about 85: 10: 5, pressing into a film with the thickness of about 1mm by a film pressing machine, fully drying in an oven at 120 ℃, and intercepting the film with the surface area of 1cm2The round membrane of (a) was pressed on a stainless steel mesh to make a research electrode. A research electrode is used as a cathode, metal lithium is used as a counter electrode, a Celgard2400 microporous polypropylene membrane is used as a diaphragm, 1mol/LLiPF6 dissolved in EC (ethylene carbonate)/DMC (1, 2-dimethyl carbonate) with the volume ratio of 1: 1 is used as electrolyte, and the electrolyte is assembled into a CR2032 type button cell in a glove box filled with argon. The button cell is placed on a cell test system to test the charge and discharge performance at room temperature, the charge and discharge voltage range is 0.02V-3.0V (vs. Li), the charge and discharge current is 0.1C, and the first reversible discharge specific capacity is 1328 mAh/g; after 50 cycles, the discharge capacity still remained 1224 mAh/g.
Example 4
Accurately weighing 0.7mol C4H6FeO4、0.28mol Sb(OH)3、1.0mol NH4VO3、0.06mol NH4And F, filling the mixture into a ball milling tank of a planetary ball mill, adding a proper amount of deionized water, and performing ball milling to obtain a rheological phase mixture. While stirring, 0.8mol/l oxalic acid solution was added dropwise to the rheological phase mixture to adjust the pH of the mixture to 5.6, followed by sufficient stirring. Transferring the mixture into a stainless steel high-pressure tank, reacting for 48 hours at a constant temperature of 180 ℃, taking out and drying, and grinding the solid mixture to obtain precursor powder. Heating the precursor powder in a programmed electric furnace at a heating rate of 6 ℃/min to 800 ℃, and keeping the temperature for 6 hours to obtain the doped modified Fe0.7Sb0.28VO4F0.06Vanadate anode materials.
Fe to be synthesized0.7Sb0.28VO4F0.06Mixing vanadate negative electrode material with acetylene black and polytetrafluoroethylene according to the weight ratio of about 85: 10: 5, pressing into a film with the thickness of about 1mm by a film pressing machine, fully drying in an oven at 120 ℃, and intercepting the film with the surface area of 1cm2The round membrane of (a) was pressed on a stainless steel mesh to make a research electrode. A research electrode is used as a cathode, metal lithium is used as a counter electrode, a Celgard2400 microporous polypropylene membrane is used as a diaphragm, 1mol/LLiPF6 dissolved in EC (ethylene carbonate)/DMC (1, 2-dimethyl carbonate) with the volume ratio of 1: 1 is used as electrolyte, and the electrolyte is assembled into a CR2032 type button cell in a glove box filled with argon. The button cell is placed on a cell test system to test the charge and discharge performance at room temperature, the charge and discharge voltage range is 0.02V-3.0V (vs. Li), the charge and discharge current is 0.1C, and the first reversible discharge specific capacity is 1362 mAh/g; after 50 cycles, the discharge capacity remained 1170 mAh/g.
Example 5
Accurately weighing 0.8mol C4H6FeO4、0.4mol Sb(OH)3、0.5mol V2O5、0.08mol NH4And F, putting the mixture into a ball milling tank of a planetary ball mill, adding a proper amount of deionized water, and performing ball milling to obtain a rheological phase mixture. While stirring, 1.2mol/l oxalic acid solution was added dropwise to the rheological phase mixture to adjust the pH of the mixture to 6.4, followed by sufficient stirring.Transferring the mixture into a stainless steel high-pressure tank, reacting for 12 hours at the constant temperature of 200 ℃, taking out and drying, and grinding the solid mixture to obtain precursor powder. Heating the precursor powder in a programmed electric furnace to 900 ℃ at the heating rate of 6 ℃/min, and keeping the temperature for 8 hours to obtain the doped modified Fe0.8Sb0.4VO4F0.08Vanadate anode materials.
Fe to be synthesized0.8Sb0.4VO4F0.08Mixing vanadate negative electrode material with acetylene black and polytetrafluoroethylene according to the weight ratio of about 85: 10: 5, pressing into a film with the thickness of about 1mm by a film pressing machine, fully drying in an oven at 120 ℃, and intercepting the film with the surface area of 1cm2The circular membrane of (2) was pressed on a stainless steel mesh to make a research electrode. A research electrode is used as a cathode, metal lithium is used as a counter electrode, a Celgard2400 microporous polypropylene membrane is used as a diaphragm, 1mol/LLiPF6 dissolved in EC (ethylene carbonate)/DMC (1, 2-dimethyl carbonate) with the volume ratio of 1: 1 is used as electrolyte, and the electrolyte is assembled into a CR2032 type button cell in a glove box filled with argon. The button cell is placed on a cell test system to test the charging and discharging performance at room temperature, the charging and discharging voltage range is 0.02V-3.0V (vs. Li), the charging and discharging current is 0.1C, and the first reversible discharging specific capacity is 1235 mAh/g; after 50 cycles, the discharge capacity remained 1090 mAh/g.
Example 6
Accurately weighing 0.9mol FeC2O4·2H2O、0.5mol Sb(CH3COO)3、1.0mol NH4VO3、0.1mol NH4And F, putting the mixture into a ball milling tank of a planetary ball mill, adding a proper amount of deionized water, and performing ball milling to obtain a rheological phase mixture. While stirring, 1.5mol/l oxalic acid solution was added dropwise to the rheological phase mixture to adjust the pH of the mixture to 7, followed by sufficient stirring. Transferring the mixture into a stainless steel high-pressure tank, reacting for 8 hours at a constant temperature of 220 ℃, taking out and drying, and grinding the solid mixture to obtain precursor powder. Heating the precursor powder in a programmed electric furnace at a heating rate of 7 ℃/min to 1000 ℃, and keeping the temperature for 10 hours to obtain the doped modified Fe0.9Sb0.5VO4F0.1Vanadate anode materials.
The synthesized Fe0.9Sb0.5VO4F0.1Mixing vanadate negative electrode material with acetylene black and polytetrafluoroethylene according to the weight ratio of about 85: 10: 5, pressing into a film with the thickness of about 1mm by using a film pressing machine, fully drying in an oven at 120 ℃, and cutting out the film with the surface area of 1cm2The circular membrane of (2) was pressed on a stainless steel mesh to make a research electrode. A research electrode is used as a cathode, metal lithium is used as a counter electrode, a Celgard2400 microporous polypropylene membrane is used as a diaphragm, 1mol/LLiPF6 dissolved in EC (ethylene carbonate)/DMC (1, 2-dimethyl carbonate) with the volume ratio of 1: 1 is used as electrolyte, and the electrolyte is assembled into a CR2032 type button cell in a glove box filled with argon. The button cell is placed on a cell test system to test the charge-discharge performance at room temperature, the charge-discharge voltage range is 0.02V-3.0V (vs. Li), the charge-discharge current is 0.1C, and the first reversible discharge specific capacity is 1258 mAh/g; after 50 cycles, the discharge capacity was still maintained at 1105 mAh/g.
Comparative example 1
This comparative example differs from example 1 only in that the negative electrode material weighed did not contain Sb (OH)3. The procedure was as in example 1. Placing the prepared button cell on a cell test system to test the charge-discharge performance at room temperature, wherein the charge-discharge voltage range is 0.02V-3.0V (vs. Li), the charge-discharge current is 0.1C, and the first reversible discharge specific capacity is 825 mAh/g; after 50 cycles, the discharge capacity remained 642 mAh/g.
Comparative example 2
The comparative example differs from example 1 only in that the weighed anode material does not contain NH4F. The procedure was as in example 1. Placing the prepared button cell on a cell test system to test the charge-discharge performance at room temperature, wherein the charge-discharge voltage range is 0.02V-3.0V (vs. Li), the charge-discharge current is 0.1C, and the first reversible discharge specific capacity is 738 mAh/g; after 50 cycles, the discharge capacity remained 567 mAh/g.
Comparative example 3
The comparative example differs from example 1 only in that the weighed anode material does not contain Sb(OH)3And NH4F. The procedure is as in example 1. Placing the prepared button cell on a cell test system to test the charge-discharge performance at room temperature, wherein the charge-discharge voltage range is 0.02V-3.0V (vs. Li), the charge-discharge current is 0.1C, and the first reversible discharge specific capacity is 558 mAh/g; after 50 cycles, the discharge capacity still remained 372 mAh/g.
Comparative example 4
This comparative example differs from example 1 only in that the concentration of the oxalic acid solution added during the preparation process was 0.3 mol/L. The prepared button cell is placed on a cell test system to test the charge and discharge performance at room temperature, the charge and discharge voltage range is 0.02V-3.0V (vs. Li), the charge and discharge current is 0.1C, and the first reversible discharge specific capacity is 1068 mAh/g; after 50 cycles, the discharge capacity was still at 942 mAh/g.
Comparative example 5
The comparative example differs from example 1 only in that the heating rate during the preparation of the precursor was 2 c/min. Placing the prepared button cell on a cell test system to test the charge-discharge performance at room temperature, wherein the charge-discharge voltage range is 0.02V-3.0V (vs. Li), the charge-discharge current is 0.1C, and the first reversible discharge specific capacity is 892 mAh/g; after 50 cycles, the discharge capacity remained 705 mAh/g.
Comparative example 6
The comparative example differs from example 1 only in that the heating rate during the preparation of the precursor was 8 deg.c/min. The prepared button cell is placed on a cell test system to test the charge-discharge performance at room temperature, the charge-discharge voltage range is 0.02V-3.0V (vs. Li), the charge-discharge current is 0.1C, and the first reversible discharge specific capacity is 827 mAh/g; after 50 cycles, the discharge capacity was still maintained at 650 mAh/g.
In view of the numerous embodiments of the present invention, the experimental data of each embodiment is huge and is not suitable for being listed and explained herein one by one, but the contents to be verified and the final conclusions obtained by each embodiment are close. While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims (9)

1. The doped modified vanadate anode material for the lithium ion battery is characterized by comprising an iron source compound, an antimony source compound, a vanadate source compound and a fluorine source compound in a molar ratio of Fe: sb: VO (vacuum vapor volume)4 3-: f = x: y: 1: z, wherein x = 0.5-0.9, y = 0.1-0.5, and z = 0.01-0.1; the chemical general formula of the cathode material is FexSbyVO4FzWherein x = 0.5-0.9, y = 0.1-0.5, and z = 0.01-0.1.
2. The doped and modified vanadate anode material for lithium ion batteries according to claim 1, wherein the iron source compound is one or more of ferric oxide, ferric hydroxide, ferrous oxalate and ferrous acetate.
3. The doping modified vanadate anode material for lithium ion batteries according to claim 1, wherein the antimony source compound is one or more of antimony oxide, antimony hydroxide and antimony carboxylate.
4. The doped and modified vanadate anode material for lithium ion batteries according to claim 1, wherein the vanadate source compound is one or two of vanadium oxide and vanadates.
5. The doping modified vanadate anode material for lithium ion batteries according to claim 1, wherein the fluorine source compound is one or both of hydrofluoric acid and ammonium fluoride.
6. The preparation method of the vanadate anode material of the doped modified lithium ion battery according to claim 1, wherein the preparation method comprises the following steps:
s1: mixing an iron source compound, an antimony source compound, a vanadate source compound and a fluorine source compound according to a molar ratio of Fe: sb:VO4 3-: f = x: y: 1: z, accurately weighing and ball milling to obtain a rheological phase mixture;
s2: adding oxalic acid solution into the rheological phase mixture, adjusting the pH value of the mixture system to be 5-7, fully stirring, placing the mixture into a stainless steel high-pressure tank for reaction, and after the reaction is finished, drying and grinding reactants to obtain precursor powder;
s3: heating the precursor powder to 500-1000 ℃, and reacting for 1-10 hours to obtain the doped and modified FexSbyVO4FzVanadate anode materials.
7. The preparation method of the vanadate anode material for the doped modified lithium ion battery according to claim 6, wherein the concentration of the oxalic acid solution in the step S2 is 0.5-1.5 mol/L.
8. The preparation method of the doped modified vanadate anode material for lithium ion batteries according to claim 6, wherein the reaction temperature in the step S2 is 150-220 ℃, and the reaction time is 8-60 hours.
9. The preparation method of the doped modified vanadate anode material for lithium ion batteries according to claim 6, wherein the heating rate in the step S3 is 3-7 ℃/min.
CN201911028862.4A 2019-10-28 2019-10-28 Doped modified lithium ion battery vanadate anode material and preparation method thereof Active CN111048778B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911028862.4A CN111048778B (en) 2019-10-28 2019-10-28 Doped modified lithium ion battery vanadate anode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911028862.4A CN111048778B (en) 2019-10-28 2019-10-28 Doped modified lithium ion battery vanadate anode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111048778A CN111048778A (en) 2020-04-21
CN111048778B true CN111048778B (en) 2022-06-24

Family

ID=70232770

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911028862.4A Active CN111048778B (en) 2019-10-28 2019-10-28 Doped modified lithium ion battery vanadate anode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111048778B (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT1033767E (en) * 1998-09-18 2010-07-13 Canon Kk Electrode material for negative pole of lithium secondary cell, electrode structure using said electrode material, lithium secondary cell using said electrode structure, and method for manufacturing said electrode structure and said lithium secondary
KR100805875B1 (en) * 2006-12-29 2008-02-20 한양대학교 산학협력단 Olivine type positive active material precursor for lithium battery, and method for preparing the same
CN104766975B (en) * 2015-04-15 2017-04-12 深圳市德睿新能源科技有限公司 Method for preparing ferric vanadate-graphene negative electrode composite material
CN105958068B (en) * 2016-07-21 2017-06-27 中南大学 A kind of preparation method of nano bar-shape lithium ion battery negative material ferric vandate
CN107512740B (en) * 2017-08-29 2019-01-18 合肥国轩电池材料有限公司 A kind of lithium ion battery negative material FeVO4The preparation method of nano wire
CN108400329A (en) * 2018-01-30 2018-08-14 昆明理工大学 A kind of preparation method of precious metal simple substance adulterated vanadate nano-electrode material

Also Published As

Publication number Publication date
CN111048778A (en) 2020-04-21

Similar Documents

Publication Publication Date Title
CN103151510B (en) A kind of lithium ion battery cathode material and its preparation method
CN109449379B (en) Nitrogen-doped carbon composite SnFe2O4Lithium ion battery cathode material and preparation method and application thereof
CN110875490B (en) Lithium ion battery and preparation method thereof
CN103078113A (en) Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof
CN107437617A (en) A kind of surface modification method, gained richness lithium material and application for improving rich lithium material chemical property
CN107546372B (en) Anion-doped lithium titanium phosphate negative electrode material and preparation and application thereof
CN107204426A (en) A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property
CN108598378A (en) A kind of lithium/anode material of lithium-ion battery Fe1-xThe preparation method of S/C
CN114242968A (en) Carbon-coated sodium iron fluorophosphate material and preparation method and application thereof
CN109560284A (en) A kind of high performance doping type lithium manganate positive electrode and preparation method thereof
CN104600262B (en) A kind of LiFePO4/ C composite positive poles and preparation method thereof
CN105185978A (en) Manganese-containing oxygen compound used as negative active substance, and preparation method and use thereof
CN115064670A (en) Preparation method of doped coated modified sodium nickel manganese oxide cathode material
CN110649263A (en) Nickel-ion battery lithium vanadium phosphate positive electrode material, sol-gel preparation method and application
CN109037652B (en) Preparation method and application of nitrogen-doped carbon-coated graded germanium structure
CN112777611B (en) Rhombohedral phase Prussian blue derivative and preparation method and application thereof
CN107230779B (en) Preparation method of high-temperature stable phase-change type lithium iron fluorosulfate battery material, electrode plate and use method of lithium ion battery
CN116826014A (en) Coated sodium-based layered oxide composite material, preparation method thereof and sodium ion battery
CN107069026A (en) A kind of rich lithium manganese oxide anode material of effective stratiform for suppressing capacity/voltage attenuation in cyclic process and its preparation method and application
CN114843459B (en) Antimony pentasulfide-based material and preparation method and application thereof
CN109659536A (en) A kind of anode of magnesium ion battery material and its preparation method and application
CN111048778B (en) Doped modified lithium ion battery vanadate anode material and preparation method thereof
CN114142010B (en) Magnesium oxide and cerium fluoride composite coated lithium ion battery positive electrode material and preparation method thereof
CN111653736B (en) Preparation method of double-coating-layer positive electrode composite material
CN105958043B (en) A kind of doping Ti4+、Cr3+Borontrifluoride iron composite material and preparation method thereof, lithium ion battery

Legal Events

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