CN113321198B - Binary metal phosphate anode material and preparation method and application thereof - Google Patents
Binary metal phosphate anode material and preparation method and application thereof Download PDFInfo
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- CN113321198B CN113321198B CN202110593262.3A CN202110593262A CN113321198B CN 113321198 B CN113321198 B CN 113321198B CN 202110593262 A CN202110593262 A CN 202110593262A CN 113321198 B CN113321198 B CN 113321198B
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- 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
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H—ELECTRICITY
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- 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
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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
- H01M4/58—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
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention discloses a binary metal phosphate anode material and a preparation method and application thereof; the preparation method comprises the following steps: (1) fully mixing phytic acid and phosphoric acid to form a solution containing phosphoric acid groups; (2) adding a transition metal salt and an alkali metal salt, and mixing thoroughly; (3) carrying out hydrothermal reaction to obtain a binary metal phosphate precursor; (4) and annealing the binary metal phosphate precursor to obtain the binary metal phosphate anode material. According to the invention, by adjusting the proportioning dosage of phytic acid and phosphoric acid, the prepared binary metal phosphate anode material has uniform particle size and obviously improved mesoporous proportion, and can realize rapid mass transfer and enhanced electron transfer when used as a battery anode material, thereby having high capacity, high multiplying power and excellent cycle stability.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a binary metal phosphate anode material and a preparation method and application thereof.
Background
With the increasing popularity of various portable electronic products, lithium ion batteries have attracted increasing attention as a portable power supply device. The physicochemical properties of sodium and lithium are similar, and the charging and discharging principles of the battery are also similar, so that the research on the sodium ion battery is increasingly paid attention. In practical applications, the energy density of sodium ion batteries is generally lower than that of lithium ion batteries, and therefore, the two batteries are suitable for different fields. However, the development of advanced anode and cathode materials becomes one of the keys for realizing the practical application of sodium and lithium ion batteries.
Lithium iron phosphate (LiFePO)4) The anode material has long cycle life, abundant resources and high environmental protection, has incomparable safety with other anode systems, and is considered as an ideal anode material of the lithium ion battery. At present, commercial lithium iron phosphate is mostly prepared by using a high-temperature solid-phase reaction technology, and has the characteristics of simple equipment, quick production, low cost and the likeDue to the limitation of high-temperature solid-phase reaction, the granularity of the product produced by the method cannot be controlled, the product has larger particles, uneven particle size distribution and insufficiently optimized pore structure.
Disclosure of Invention
The invention aims to provide a binary metal phosphate anode material and a preparation method and application thereof, the prepared binary metal phosphate anode material has uniform particle size, the mesoporous proportion is obviously improved, and the specific capacity and the cycling stability of a battery can be obviously improved.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the invention discloses a preparation method of a binary metal phosphate anode material, which comprises the following steps:
(1) fully mixing phytic acid and phosphoric acid to form a solution containing phosphoric acid groups;
(2) adding a transition metal salt and an alkali metal salt into the system obtained in the step (1), and fully mixing;
(3) carrying out hydrothermal reaction on the mixed solution obtained in the step (2) to obtain a binary metal phosphate precursor;
(4) and (4) annealing the binary metal phosphate precursor obtained in the step (3) to obtain the binary metal phosphate anode material.
As a preferable technical scheme, in the step (1), the molar ratio of the phytic acid to the phosphoric acid is 1:9-9: 1.
As a preferable technical scheme, in the step (1), the molar ratio of the phytic acid to the phosphoric acid is 4:6-6: 4.
As a preferable technical scheme, in the step (2), the molar ratio of the phosphoric acid group to the transition metal salt is 1:9-9: 1.
As a preferred technical scheme, in the step (1), phytic acid and phosphoric acid are fully mixed in a solvent; the solvent includes but is not limited to one or a mixture of water, absolute ethyl alcohol, N-methyl pyrrolidone and dimethylformamide.
As a preferred technical solution, in the step (2), the transition metal salt includes but is not limited to one or a mixture of several of iron salt, ferrous salt, manganese salt, nickel salt, cobalt salt and vanadium salt.
In a preferred embodiment, in step (2), the alkali metal salt includes, but is not limited to, one or more of lithium salt, sodium salt and potassium salt.
In a preferable embodiment, in the step (3), before the hydrothermal reaction, the PH is adjusted to 3 to 10.
As a preferable technical scheme, in the step (3), the hydrothermal reaction temperature is 100-260 ℃, and the hydrothermal reaction time is 1-48 h.
Preferably, in the step (4), a carbon material is added during annealing.
As a preferred technical solution, the carbon material includes, but is not limited to, one or a mixture of several of glucose, carbon nanotubes and graphene.
The invention also discloses the binary metal phosphate anode material prepared by the preparation method.
The invention also discloses a positive plate, which comprises the binary metal phosphate positive material, a foil, a binder and a conductive agent.
The invention also discloses a battery, which comprises the positive plate, the negative plate, the diaphragm and the electrolyte.
The invention has the beneficial effects that:
according to the invention, phytic acid and phosphoric acid are utilized to form a phosphate group, metal ions are adsorbed on the phosphate group, and a hydrothermal method is utilized to prepare a binary metal phosphate anode material; according to the invention, by adjusting the proportioning dosage of phytic acid and phosphoric acid, the prepared binary metal phosphate anode material has uniform particle size and obviously improved mesoporous proportion, and can realize rapid mass transfer and enhanced electron transfer when used as a battery anode material, thereby having high capacity, high multiplying power and excellent cycle stability.
Drawings
FIG. 1 is a LiFePO prepared in example 14SEM picture of (1);
FIG. 2 shows LiFePO obtained in examples 1 to 2 and comparative examples 1 to 24The aperture distribution map of (a);
FIG. 3 is a photograph obtained in example 1LiFePO4A discharge specific capacity performance diagram of the button cell prepared by the anode material under the charge-discharge rate of 1C;
FIG. 4 shows LiFePO obtained in example 14Efficiency chart of button cell made of anode material under 1C charge-discharge rate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described with reference to the accompanying drawings.
Example 1
(1) Fully stirring and mixing phytic acid and phosphoric acid in water according to a molar ratio of 6:4 to form a solution containing phosphoric acid groups;
(2) adding FeSO into the system obtained in the step (1)4And LiOH and mixing thoroughly;
(3) adjusting the pH value of the mixed solution obtained in the step (2) to 7.5, and then carrying out hydrothermal reaction at the hydrothermal temperature of 230 ℃ for 6 hours;
(4) filtering and drying the product obtained in the step (3), adding 5% of glucose by mass, and annealing at 760 ℃ to obtain the material LiFePO4。
Example 2
(1) Fully stirring and mixing phytic acid and phosphoric acid in water according to a molar ratio of 4:6 to form a solution containing phosphoric acid groups;
(2) adding FeSO into the system obtained in the step (1)4And LiOH and mixing thoroughly;
(3) adjusting the pH value of the mixed solution obtained in the step (2) to 7.5, and then carrying out hydrothermal reaction at the hydrothermal temperature of 230 ℃ for 6 hours;
(4) filtering and drying the product obtained in the step (3), adding 5% of glucose by mass, and annealing at 760 ℃ to obtain the material LiFePO4。
Comparative example 1
(1) Fully stirring pure phytic acid in water to form a solution containing phosphoric acid groups;
(2) adding FeSO into the system obtained in the step (1)4And LiOH and mixing thoroughly;
(3) adjusting the pH value of the mixed solution obtained in the step (2) to 7.5, and then carrying out hydrothermal reaction at the hydrothermal temperature of 230 ℃ for 6 hours;
(4) filtering and drying the product obtained in the step (3), adding 5% of glucose by mass, and annealing at 760 ℃ to obtain the material LiFePO4。
Then annealing treatment is carried out to obtain the material LiFePO4。
Comparative example 2
(1) Fully stirring pure phosphoric acid in water to form a solution containing phosphoric acid groups;
(2) adding FeSO into the system obtained in the step (1)4And LiOH and mixing thoroughly;
(3) adjusting the pH value of the mixed solution obtained in the step (2) to 7.5, and then carrying out hydrothermal reaction at the hydrothermal temperature of 230 ℃ for 6 hours;
(4) filtering and drying the product obtained in the step (3), adding 5% of glucose by mass, and annealing at 760 ℃ to obtain the material LiFePO4。
FIG. 1 is a LiFePO prepared in example 14From the SEM image, the LiFePO obtained in example 1 can be seen4The particle size is uniform.
FIG. 2 shows LiFePO obtained in examples 1 to 2 and comparative examples 1 to 24Pore size distribution of (1) from the graph, it can be seen that LiFePO obtained in examples 1-2 is compared with that obtained in comparative examples 1-24The mesoporous ratio is obviously improved, in particular the LiFePO prepared in the embodiment 14The mesoporous proportion of (A) is highest. Thus, the present invention produces LiFePO4When the proportion of the phytic acid to the phosphoric acid is adjusted, compared with pure phytic acid or pure phosphoric acid, the proportion of the mesopores can be obviously improved, and the lithium ion can be rapidly diffused in the material.
LiFePO obtained in example 14As a positive electrode material, a positive electrode plate is firstly manufactured: carrying out anode batching on an anode material, a binder and a conductive agent to obtain uniform anode slurry, and uniformly coating the prepared anode slurry on an anodeAnd obtaining the positive plate on the polar current collector aluminum foil. And winding the positive plate, the negative plate and the diaphragm to prepare a lithium ion cell, and injecting electrolyte to prepare the button cell.
FIG. 3 shows LiFePO obtained in example 14The discharge specific capacity performance graph of the button cell made of the anode material under the charge-discharge rate of 1C shows that the 1C discharge specific capacity can reach 150mAh/g, and the battery still maintains higher specific capacity even after 200 cycles and shows excellent stability.
FIG. 4 shows LiFePO obtained in example 14The efficiency chart of the button cell made of the anode material under the charge-discharge rate of 1C shows that the residual capacity of the cell is kept about 99.8 percent even after 200 cycles, and the cell shows excellent cycling stability.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (11)
1. A preparation method of a binary metal phosphate anode material is characterized by comprising the following steps: the method comprises the following steps:
(1) fully mixing phytic acid and phosphoric acid to form a solution containing phosphoric acid groups;
(2) adding a transition metal salt and an alkali metal salt into the system obtained in the step (1), and fully mixing;
(3) carrying out hydrothermal reaction on the mixed solution obtained in the step (2) to obtain a binary metal phosphate precursor;
(4) annealing the binary metal phosphate precursor obtained in the step (3) to obtain a binary metal phosphate anode material;
in the step (1), the mol ratio of the phytic acid to the phosphoric acid is 4:6-6: 4;
in the step (2), the molar ratio of the phosphate group to the transition metal salt is 1:9-9: 1.
2. The method for producing a binary metal phosphate positive electrode material according to claim 1, characterized in that: in the step (1), fully mixing phytic acid and phosphoric acid in a solvent; the solvent comprises one or more of water, absolute ethyl alcohol, N-methyl pyrrolidone and dimethylformamide.
3. The method for producing a binary metal phosphate positive electrode material according to claim 1, characterized in that: in the step (2), the transition metal salt includes one or a mixture of more of ferric salt, ferrous salt, manganese salt, nickel salt, cobalt salt and vanadium salt.
4. The method for producing a binary metal phosphate positive electrode material according to claim 1, characterized in that: in the step (2), the alkali metal salt comprises one or a mixture of more of lithium salt, sodium salt and potassium salt.
5. The method for producing a binary metal phosphate positive electrode material according to claim 1, characterized in that: in the step (3), before the hydrothermal reaction, the pH value is adjusted to 3-10.
6. The method for producing a binary metal phosphate positive electrode material according to claim 1, characterized in that: in the step (3), the hydrothermal reaction temperature is 100-260 ℃, and the hydrothermal reaction time is 1-48 h.
7. The method for producing a binary metal phosphate positive electrode material according to claim 1, characterized in that: in the step (4), a carbon material is added during annealing.
8. The method for producing a binary metal phosphate positive electrode material according to claim 7, characterized in that: the carbon material comprises one or a mixture of glucose, carbon nanotubes and graphene.
9. The binary metal phosphate positive electrode material prepared by the preparation method of any one of claims 1 to 8.
10. A positive electrode sheet characterized in that: the positive electrode sheet comprises the binary metal phosphate positive electrode material according to claim 9, a foil, a binder, and a conductive agent.
11. A battery, characterized by: the battery comprises the positive electrode sheet according to claim 10, a negative electrode sheet, a separator, and an electrolyte.
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| CN114105115B (en) * | 2021-11-22 | 2023-09-19 | 青岛九环新越新能源科技股份有限公司 | Production method and application of ferric phosphate and lithium iron phosphate |
| CN115583642B (en) * | 2022-10-25 | 2024-05-10 | 西安合升汇力新材料有限公司 | LiFexMnyDzPO4Preparation and application of @ C and precursor thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2098483A1 (en) * | 2008-03-05 | 2009-09-09 | High Power Lithium S.A. | Synthesis of lithium metal phosphate/carbon nanocomposites with phytic acid |
| CN104393293A (en) * | 2014-11-20 | 2015-03-04 | 中物院成都科学技术发展中心 | Positive pole lithium iron phosphate/carbon composite material for low-temperature battery and preparation method of composite material |
| CN109205586A (en) * | 2018-09-07 | 2019-01-15 | 高延敏 | A kind of industrialized LiFePO4 manufacturing method and its composite ferric lithium phosphate material of preparation |
| CN110350191A (en) * | 2019-07-12 | 2019-10-18 | 西南大学 | Sodium/lithium ion battery phosphate cathode material preparation method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2098483A1 (en) * | 2008-03-05 | 2009-09-09 | High Power Lithium S.A. | Synthesis of lithium metal phosphate/carbon nanocomposites with phytic acid |
| CN104393293A (en) * | 2014-11-20 | 2015-03-04 | 中物院成都科学技术发展中心 | Positive pole lithium iron phosphate/carbon composite material for low-temperature battery and preparation method of composite material |
| CN109205586A (en) * | 2018-09-07 | 2019-01-15 | 高延敏 | A kind of industrialized LiFePO4 manufacturing method and its composite ferric lithium phosphate material of preparation |
| CN110350191A (en) * | 2019-07-12 | 2019-10-18 | 西南大学 | Sodium/lithium ion battery phosphate cathode material preparation method |
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