CN111196600A - Iron phosphate material with hollow spherical structure and preparation method thereof - Google Patents

Iron phosphate material with hollow spherical structure and preparation method thereof Download PDF

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Publication number
CN111196600A
CN111196600A CN202010023503.6A CN202010023503A CN111196600A CN 111196600 A CN111196600 A CN 111196600A CN 202010023503 A CN202010023503 A CN 202010023503A CN 111196600 A CN111196600 A CN 111196600A
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China
Prior art keywords
sodium
phosphate
parts
iron
iron phosphate
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CN202010023503.6A
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Chinese (zh)
Inventor
代汗清
陈媛媛
张国旗
郭睿倩
叶怀宇
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Shenzhen Third Generation Semiconductor Research Institute
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Shenzhen Third Generation Semiconductor Research Institute
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Priority to CN202010023503.6A priority Critical patent/CN111196600A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • 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
    • H01M4/36—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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 novel method for preparing a hollow spherical ferric phosphate material by using a hydrothermal synthesis method, and the prepared ferric phosphate material has high stability and enough initial capacity of about 280mAh g‑1. The iron phosphate material can be used as a precursor material and is subsequently compounded with other materials, and the prepared composite material can be used as an electrode material and an electrolyte material of an energy storage battery, for example, can be applied to electrodes and electrolytes of energy storage batteries such as a sodium ion battery, a lithium ion battery, a potassium ion battery, an aluminum ion battery, a lead-acid battery and a super capacitor, and can also be used as an important component of a solar battery, and can be possibly applied to the biological field in the future.

Description

Iron phosphate material with hollow spherical structure and preparation method thereof
Technical Field
The invention relates to the technical field of chemical industry, in particular to a hollow spherical ferric phosphate material and a preparation method thereof.
Background
In recent years, in the process of social development, people's overuse of fossil fuels gradually leads to increased environmental pollution. Applications of clean energy sources such as solar energy and wind energy are becoming more and more widespread. Because the consumption of the energy sources has the wave crest and trough effect, and the energy storage battery has the function of eliminating the wave crest and trough, the development of a new energy storage battery is urgently needed. However, sodium ion batteries still face the challenges of low energy density and poor cycle stability, which means that they cannot be applied in practical applications such as smart grid and large-scale energy storage.
The research and development of novel energy materials can promote the rapid development of the energy field to a certain extent, develop novel sodium ion battery materials and improve the battery capacity and the cycle stability. Although sodium ion battery materials have been abundant to date, they have poor electrochemical activity and low initial capacity. This means that these materials still need to be improved and redesigned. Therefore, the iron phosphate material with the hollow spherical structure and the preparation method thereof are provided by the invention, the iron phosphate material can be used as a precursor material and is subsequently compounded with other materials, and the prepared composite material can be used as an electrode material of an energy storage battery, and has great application potential.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides an iron phosphate material with a hollow spherical structure, which comprises the following preparation steps:
1) preparing raw materials according to the following molar ratio: 1-5 parts of iron-containing material, 1-10 parts of phosphorus-containing material, 500 parts of precipitator and 1-10 parts of surfactant;
2) fully dispersing the raw materials in a proper amount of deionized water to obtain a first mixed solution;
3) putting the first mixed solution into a polytetrafluoroethylene reaction kettle for reaction, and centrifuging to take precipitate after the reaction is finished;
4) and washing the precipitate, and drying to obtain the iron phosphate with the hollow spherical structure.
Preferably, the iron-containing material is selected from: one or more of hematite, magnetite, siderite, pyrite, ferric sulfate, ferrous sulfate, ammonium ferrous sulfate and ferric nitrate.
Preferably, the phosphorus-containing material is selected from: one or more of phosphoric acid, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphide and calcium phosphide.
Preferably, the precipitating agent is selected from: ammonia water, urea, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
Preferably, the surfactant is selected from: alcohol, ethylene glycol, polyethylene glycol, polyvinylpyrrolidone, cetyl trimethyl ammonium bromide and sodium dodecyl sulfate.
Preferably, the organic solvent is selected from: alcohol, ethylene glycol, isopropanol.
The washing solvent is organic solvent or deionized water.
Preferably, the reaction conditions of step 3) are as follows: in the air, the temperature is 60-180 ℃, and the reaction time is 1-72 h.
The iron phosphate material with the hollow spherical structure is prepared by the method, the size of the hollow sphere is 5-25 mu m, and the initial capacity is about 280mAh g-1。
The invention provides the iron phosphate material and the preparation method thereof, and the prepared iron phosphate material has high stability and initial capacity of about 280mAh g-1Has a hollow sphere structure. All of these indicate that iron phosphate materials will have potential applications in energy storage materials.
Drawings
FIG. 1 is an SEM topography of iron phosphate material prepared by a hydrothermal synthesis method;
FIG. 2 is a TEM morphology of an iron phosphate material;
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) chart of an iron phosphate material;
fig. 4 shows the battery cycle performance.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
Example 1
A preferred embodiment of the iron phosphate material with a hollow spherical structure is selected, and comprises the following preparation steps:
(1) preparing raw materials according to the following molar ratio: 2 parts of hematite, 2 parts of sodium phosphate, 300 parts of ammonia water and 5 parts of hexadecyl ammonium bromide;
(2) fully dispersing the raw materials in a proper amount of deionized water;
(3) putting the mixed solution into a polytetrafluoroethylene reaction kettle, reacting for 10 hours at 60 ℃, and centrifuging to take precipitate after the reaction is finished;
(4) washing the precipitate with deionized water, and drying to obtain the product.
Iron phosphate was not generated at 60 c, which is only a comparative experiment.
Example 2
A preferred embodiment of the iron phosphate material with a hollow spherical structure is selected, and comprises the following preparation steps:
(1) preparing raw materials according to the following molar ratio: 2 parts of ferrous sulfate, 2 parts of ammonium phosphate, 300 parts of urea and 5 parts of lauryl sodium sulfate;
(2) fully dispersing the raw materials in a proper amount of deionized water;
(3) putting the mixed solution into a polytetrafluoroethylene reaction kettle, reacting for 10 hours at 100 ℃, and centrifuging to take precipitate after the reaction is finished;
(4) washing the precipitate with deionized water, and drying to obtain the product.
The product characteristics are now shown in fig. 1a, 2a and 2 c.
Example 3
A preferred embodiment of the iron phosphate material with a hollow spherical structure is selected, and comprises the following preparation steps:
(1) preparing raw materials according to the following molar ratio: 2 parts of ferrous ammonium sulfate, 5 parts of sodium phosphate, 300 parts of urea and 5 parts of sodium dodecyl sulfate;
(2) fully dispersing the raw materials in a proper amount of deionized water;
(3) putting the mixed solution into a polytetrafluoroethylene reaction kettle, reacting for 10 hours at 180 ℃, and centrifuging to take precipitate after the reaction is finished;
(4) washing the precipitate with deionized water, and drying to obtain the product.
The product is now characterized as a hollow sphere as shown in fig. 1b, 1c, 2b and 2 d. The product was shown to exhibit a spherical structure. The XPS analysis shown in FIG. 3 shows that the product is FePO4. As shown in FIG. 4, with FePO4Button cell type CR 2032 with current density of 50mAg and cathode material composition-1At this time, the initial discharge capacity was 287.5mAhg-1Within 10 cycles, the coulombic efficiency is close to 100%, and the performance is good.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.

Claims (8)

1. The preparation method of the iron phosphate material with the hollow spherical structure is characterized by comprising the following preparation steps:
1) preparing raw materials according to the following molar ratio: 1-5 parts of iron-containing material, 1-10 parts of phosphorus-containing material, 500 parts of precipitator and 1-10 parts of surfactant;
2) fully dispersing the raw materials in a proper amount of deionized water to obtain a first mixed solution;
3) putting the first mixed solution into a polytetrafluoroethylene reaction kettle for reaction, and centrifuging to take precipitate after the reaction is finished;
4) and washing the precipitate, and drying to obtain the iron phosphate with the hollow spherical structure.
2. The method of claim 1, wherein the iron-containing material is selected from the group consisting of: one or more of hematite, magnetite, siderite, pyrite, ferric sulfate, ferrous sulfate, ammonium ferrous sulfate and ferric nitrate.
3. The method of claim 1, wherein the phosphorus-containing material is selected from the group consisting of: one or more of phosphoric acid, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphide and calcium phosphide.
4. The method of claim 1, wherein the precipitating agent is selected from the group consisting of: one or more of ammonia water, urea, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
5. The method of claim 1, wherein the surfactant is selected from the group consisting of: alcohol, ethylene glycol, polyethylene glycol, polyvinylpyrrolidone, cetyl trimethyl ammonium bromide and sodium dodecyl sulfate.
6. The method of claim 1, wherein the organic solvent is selected from the group consisting of: alcohol, ethylene glycol, isopropanol.
7. The method of claim 1, wherein the reaction conditions in step 3) are: in the air, the temperature is 60-180 ℃, and the reaction time is 1-72 h.
8. A hollow sphere structured iron phosphate material prepared by the method of any one of claims 1 to 7, wherein the hollow spheres have a size of 5 to 25 μm in length.
CN202010023503.6A 2020-01-09 2020-01-09 Iron phosphate material with hollow spherical structure and preparation method thereof Pending CN111196600A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111362243A (en) * 2020-05-27 2020-07-03 湖南雅城新材料有限公司 Preparation method of iron phosphate for lithium battery
CN112436132A (en) * 2020-12-10 2021-03-02 桂林理工大学 Method for preparing in-situ carbon-coated porous ferric phosphate material by adopting sweet osmanthus
CN114361425A (en) * 2022-01-17 2022-04-15 中南大学 Method for directly preparing pyrophosphate sodium iron phosphate composite material from pyrite, pyrophosphate sodium iron phosphate composite material and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102185154A (en) * 2011-04-15 2011-09-14 南京师范大学 Nano ferric phosphate hollow sphere lithium ion battery and preparation method thereof
CN102849702A (en) * 2012-09-07 2013-01-02 浙江振华新能源科技有限公司 Preparation method for nanometer spherical ferric phosphate
CN103887498A (en) * 2014-03-31 2014-06-25 广西大学 Nanometer ferric phosphate hollow microsphere and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102185154A (en) * 2011-04-15 2011-09-14 南京师范大学 Nano ferric phosphate hollow sphere lithium ion battery and preparation method thereof
CN102849702A (en) * 2012-09-07 2013-01-02 浙江振华新能源科技有限公司 Preparation method for nanometer spherical ferric phosphate
CN103887498A (en) * 2014-03-31 2014-06-25 广西大学 Nanometer ferric phosphate hollow microsphere and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111362243A (en) * 2020-05-27 2020-07-03 湖南雅城新材料有限公司 Preparation method of iron phosphate for lithium battery
CN112436132A (en) * 2020-12-10 2021-03-02 桂林理工大学 Method for preparing in-situ carbon-coated porous ferric phosphate material by adopting sweet osmanthus
CN114361425A (en) * 2022-01-17 2022-04-15 中南大学 Method for directly preparing pyrophosphate sodium iron phosphate composite material from pyrite, pyrophosphate sodium iron phosphate composite material and application thereof
CN114361425B (en) * 2022-01-17 2023-12-12 深圳市津工能源有限公司 Method for directly preparing ferric sodium pyrophosphate composite material from pyrite, ferric sodium pyrophosphate composite material and application of ferric sodium pyrophosphate composite material

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Application publication date: 20200526

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