CN108539132B - Preparation method of zinc oxide composite lithium iron phosphate cathode material - Google Patents

Preparation method of zinc oxide composite lithium iron phosphate cathode material Download PDF

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CN108539132B
CN108539132B CN201810077440.5A CN201810077440A CN108539132B CN 108539132 B CN108539132 B CN 108539132B CN 201810077440 A CN201810077440 A CN 201810077440A CN 108539132 B CN108539132 B CN 108539132B
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iron phosphate
zinc oxide
lithium iron
oxide composite
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CN108539132A (en
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沈学如
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Aoyang Group
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/58—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention discloses a preparation method of a zinc oxide composite lithium iron phosphate anode material, which comprises the following steps: (1) adding ferrous nitrate and lithium nitrate into (NH)4)2HPO4‑NH4H2PO4Stirring the acid buffer solution for 10-30 min under the heating condition to obtain a mixed solution; (2) under the condition of stirring, adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to be alkaline, then dropwise adding a proper amount of zinc salt solution, stirring, and stopping reaction after precipitation is finished to obtain a mixture of precipitate and solution; (3) and carrying out vacuum filtration on the mixture of the precipitate and the solution, carrying out vacuum drying for 10-15 h at 75-80 ℃, grinding into powder, presintering the obtained powder for 5-10 h at 300-400 ℃ in an inert atmosphere, calcining for 8-12 h at 600-800 ℃, and grinding to obtain the zinc oxide composite lithium iron phosphate cathode material. The preparation method is simple and has uniform phase, and the prepared zinc oxide composite lithium iron phosphate anode material has the advantages of small and uniform particle size.

Description

Preparation method of zinc oxide composite lithium iron phosphate cathode material
Technical Field
The invention relates to the technical field of battery electrode materials, in particular to a preparation method of a zinc oxide composite lithium iron phosphate anode material.
Background
Lithium iron phosphate (LiFePO)4) The material can be used as a lithium ion battery anode material, and has the remarkable advantages of high theoretical capacity, good safety performance, environmental friendliness, wide raw material source, low raw material cost and the like. However, the material also has the obvious disadvantages of low electronic and ionic conductivity and the like, and the commercial development of the material is limited to a certain extent. The theory proves that the electron and ion conductivity of the material can be obviously improved by doping a certain amount of metal cations in the lithium iron phosphate cathode material. Zn2+With Fe2+The ion radius is similar, a small amount of zinc ions and zinc oxide particles are doped in the lithium iron phosphate material, the integrity of lithium iron phosphate crystal lattices can be supported in the charge-discharge cycle process, meanwhile, the n-type ZnO semiconductor material can remarkably improve the electronic conductivity of the lithium iron phosphate, and the attenuation of the lithium iron phosphate anode material in the charge-discharge cycle process is reduced.
The method for preparing the zinc oxide composite lithium iron phosphate powder material in the prior art has the defects of complex preparation process and uneven phase, and the prepared powder material has larger particle size.
Therefore, in order to solve the above problems, it is necessary to provide a method for preparing a zinc oxide composite lithium iron phosphate positive electrode material, which can solve the problems in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of a zinc oxide composite lithium iron phosphate positive electrode material, which overcomes the defects in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a zinc oxide composite lithium iron phosphate cathode material comprises the following steps:
(1) adding ferrous nitrate and lithium nitrate into (NH)4)2HPO4-NH4H2PO4Stirring the acid buffer solution for 10-30 min under the heating condition to obtain a mixed solution;
(2) under the condition of stirring, adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to be alkaline, then dropwise adding a proper amount of zinc salt solution, stirring, and stopping reaction after precipitation is finished to obtain a mixture of precipitate and solution;
(3) and carrying out vacuum filtration on the mixture of the precipitate and the solution, carrying out vacuum drying for 10-15 h at 75-80 ℃, grinding into powder, presintering the obtained powder for 5-10 h at 300-400 ℃ in an inert atmosphere, calcining for 8-12 h at 600-800 ℃, and grinding to obtain the zinc oxide composite lithium iron phosphate cathode material.
Preferably, in the step (1), the molar ratio of the ferrous nitrate to the lithium nitrate is 1: 2-5.
Preferably, in step (1), the (NH)4)2HPO4-NH4H2PO4The pH value of the acidic buffer solution is 3.98-5.80.
Preferably, in the step (2), the pH value of the mixed solution is adjusted to be alkaline, and the pH value is 9-12.
Preferably, in the step (2), a proper amount of zinc salt solution is dropwise added, specifically: and (4) dropwise adding the zinc salt solution until the precipitate does not increase any more, and stopping the dropwise adding process.
Preferably, in the step (3), the inert atmosphere is an argon atmosphere or a nitrogen atmosphere.
Compared with the prior art, the invention has the advantages that: the preparation method is simple and has uniform phase, and the prepared zinc oxide composite lithium iron phosphate anode material has the advantages of small and uniform particle size.
Detailed Description
The invention is further illustrated by the following examples: the invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the specific material ratios, process conditions and results thereof described in the examples are illustrative only and should not be taken as limiting the invention as detailed in the claims.
The invention discloses a preparation method of a zinc oxide composite lithium iron phosphate anode material, which comprises the following steps:
(1) adding ferrous nitrate and lithium nitrate into (NH)4)2HPO4-NH4H2PO4Stirring the acid buffer solution for 10-30 min under the heating condition to obtain a mixed solution;
(2) under the condition of stirring, adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to be alkaline, then dropwise adding a proper amount of zinc salt solution, stirring, and stopping reaction after precipitation is finished to obtain a mixture of precipitate and solution;
(3) and carrying out vacuum filtration on the mixture of the precipitate and the solution, carrying out vacuum drying for 10-15 h at 75-80 ℃, grinding into powder, presintering the obtained powder for 5-10 h at 300-400 ℃ in an inert atmosphere, calcining for 8-12 h at 600-800 ℃, and grinding to obtain the zinc oxide composite lithium iron phosphate cathode material.
In the step (1), the molar ratio of the ferrous nitrate to the lithium nitrate is 1: 2-5, and preferably, the molar ratio of the ferrous nitrate to the lithium nitrate is 1: 3.
In the above step (1), the (NH)4)2HPO4-NH4H2PO4The pH value of the acidic buffer solution is 3.98-5.80.
In the step (2), the pH value of the mixed solution is adjusted to be alkaline, the pH value is 9-12, and preferably the pH value is 10.
In the step (2), dropwise adding a proper amount of zinc salt solution, specifically: and (4) dropwise adding the zinc salt solution until the precipitate does not increase any more, and stopping the dropwise adding process.
In the step (3), the inert atmosphere is an argon atmosphere or a nitrogen atmosphere, and preferably, the inert atmosphere is an argon atmosphere.
The following description will be given with specific examples to prepare the zinc oxide composite lithium iron phosphate positive electrode material of the present invention.
Example 1
(1) Adding ferrous nitrate and lithium nitrate into (NH) solution with pH value of 3.98-5.80 at a molar ratio of 1:24)2HPO4-NH4H2PO4Stirring in an acidic buffer solution for 10min under a heating condition to obtain a mixed solution;
(2) under the condition of stirring, adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to be 9, dropwise adding a proper amount of zinc salt solution until the precipitate is not increased any more, and stopping the reaction to obtain a mixture of the precipitate and the solution;
(3) and (3) carrying out vacuum filtration on the mixture of the precipitate and the solution, carrying out vacuum drying for 10h at 75 ℃, grinding into powder, presintering the obtained powder for 5h at 300 ℃ in an argon atmosphere, then calcining for 8h at 600 ℃, and grinding to obtain the zinc oxide composite lithium iron phosphate cathode material.
Example 2
(1) Adding ferrous nitrate and lithium nitrate into (NH) solution with pH value of 3.98-5.80 according to the molar ratio of 1:34)2HPO4-NH4H2PO4Stirring in an acidic buffer solution for 20min under a heating condition to obtain a mixed solution;
(2) under the condition of stirring, adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to 10, dropwise adding a proper amount of zinc salt solution until the precipitate is not increased any more, and stopping the reaction to obtain a mixture of the precipitate and the solution;
(3) and (3) carrying out vacuum filtration on the mixture of the precipitate and the solution, carrying out vacuum drying for 12h at 78 ℃, grinding into powder, presintering the obtained powder for 8h at 350 ℃ in an argon atmosphere, calcining for 10h at 700 ℃, and grinding to obtain the zinc oxide composite lithium iron phosphate cathode material.
Example 3
(1) Adding ferrous nitrate and lithium nitrate into (NH) solution with pH value of 3.98-5.80 at a molar ratio of 1:54)2HPO4-NH4H2PO4Stirring in an acidic buffer solution for 30min under a heating condition to obtain a mixed solution;
(2) under the condition of stirring, adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to be 12, dropwise adding a proper amount of zinc salt solution until the precipitate is not increased any more, and stopping the reaction to obtain a mixture of the precipitate and the solution;
(3) and (3) carrying out vacuum filtration on the mixture of the precipitate and the solution, carrying out vacuum drying for 15h at the temperature of 80 ℃, grinding into powder, presintering the obtained powder for 10h at the temperature of 400 ℃ in an argon atmosphere, then calcining for 12h at the temperature of 800 ℃, and grinding to obtain the zinc oxide composite lithium iron phosphate cathode material.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Claims (2)

1. A preparation method of a zinc oxide composite lithium iron phosphate cathode material is characterized by comprising the following steps:
(1) adding ferrous nitrate and lithium nitrate into (NH)4)2HPO4-NH4H2PO4Stirring the acidic buffer solution for 10-30 min under the heating condition to obtain a mixed solution, wherein the molar ratio of the ferrous nitrate to the lithium nitrate is 1: 2-5, and the (NH)4)2HPO4-NH4H2PO4The pH value of the acidic buffer solution is 3.98-5.80;
(2) under the condition of stirring, adding ammonia water into the mixed solution, adjusting the pH value of the mixed solution to be 9-12, then dropwise adding a proper amount of zinc salt solution, stopping the dropwise adding process when the zinc salt solution is dropwise added until the precipitate is not increased any more, stirring, and stopping the reaction after the precipitation is finished to obtain a mixture of the precipitate and the solution;
(3) and carrying out vacuum filtration on the mixture of the precipitate and the solution, carrying out vacuum drying for 10-15 h at 75-80 ℃, grinding into powder, presintering the obtained powder for 5-10 h at 300-400 ℃ in an inert atmosphere, calcining for 8-12 h at 600-800 ℃, and grinding to obtain the zinc oxide composite lithium iron phosphate cathode material.
2. The preparation method of the zinc oxide composite lithium iron phosphate positive electrode material according to claim 1, wherein in the step (3), the inert atmosphere is an argon atmosphere or a nitrogen atmosphere.
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CN112938916B (en) * 2021-03-05 2023-09-19 四川优源新能源有限公司 Synthesis method for preparing lithium iron phosphate precursor with high cost performance by controlling crystallization
CN112938927B (en) * 2021-05-12 2021-10-12 蜂巢能源科技有限公司 Preparation method of lithium iron phosphate

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