CN110350191B - Preparation method of sodium/lithium ion battery phosphate anode material - Google Patents

Preparation method of sodium/lithium ion battery phosphate anode material Download PDF

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CN110350191B
CN110350191B CN201910628119.6A CN201910628119A CN110350191B CN 110350191 B CN110350191 B CN 110350191B CN 201910628119 A CN201910628119 A CN 201910628119A CN 110350191 B CN110350191 B CN 110350191B
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lithium ion
ion battery
sodium
phosphate
metal ions
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CN110350191A (en
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李长明
吴超
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QINGDAO JIUHUAN XINYUE NEW ENERGY TECHNOLOGY Co.,Ltd.
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Southwest University
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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
    • 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
    • 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
    • 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
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/028—Positive 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

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

The invention discloses a preparation method of a sodium/lithium ion battery phosphate anode material, which comprises the following steps: (1) fully stirring and mixing phytic acid and a carbon material in a solvent to enable phosphate radicals to be adsorbed on the carbon material to form phosphate groups; (2) and (2) adding metal salt containing metal ions into the system obtained in the step (1) and fully mixing to enable the metal ions to be electrostatically adsorbed on the phosphate groups, and crystallizing the metal ions according to the distribution of the phosphate groups on the carbon material to form the material with the pore structure. The phytic acid is uniformly adsorbed on the carbon material to form phosphate groups, and then metal ions are distributed and crystallized on the carbon material according to the arrangement of the phosphate groups, so that a uniform and controllable specific pore structure for mass transfer is formed, and the phytic acid is used as a positive electrode material of a sodium/lithium ion battery, can realize rapid mass transfer and strengthen electron transfer, and has high capacity, high multiplying power and excellent cycle stability.

Description

Preparation method of sodium/lithium ion battery phosphate anode material
Technical Field
The invention relates to the technical field of sodium/lithium ion batteries, in particular to a preparation method of a sodium/lithium ion battery anode material.
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 lithium ion battery cathode material is considered to be an ideal cathode material for a lithium ion battery as a new generation of lithium ion battery cathode material. With LiFePO4Compared with FePO4The method has the advantages of simple synthesis process, wide raw material source, lower cost and the like, but the low electronic conductivity of the lithium ion battery still needs to be overcome at present, which directly influences the specific capacity of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a preparation method of a sodium/lithium ion battery phosphate anode material, which can obviously improve the specific capacity and the cycling stability of a sodium/lithium ion battery.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the invention discloses a preparation method of a sodium/lithium ion battery phosphate anode material, which comprises the following steps:
(1) fully stirring and mixing phytic acid and a carbon material in a solvent to enable phosphate radicals to be adsorbed on the carbon material to form phosphate groups;
(2) and (2) adding metal salt containing metal ions into the system obtained in the step (1) and fully mixing to enable the metal ions to be electrostatically adsorbed on the phosphate groups, and crystallizing the metal ions according to the distribution of the phosphate groups on the carbon material to form a material with a pore structure, namely the sodium/lithium ion battery phosphate anode material.
Preferably, in step (1), the carbon material includes, but is not limited to, carbon nanotubes.
In the step (1), the solvent includes, but is not limited to, one or more of water, absolute ethanol, N-methylpyrrolidone and dimethylformamide.
Preferably, in the step (2), the metal ion includes, but is not limited to, Fe3+、Mn2+、Ni2+And Co2+One or a mixture of several of them.
As a preferred technical scheme, in the step (2), the metal salt containing metal ions includes but is not limited to Fe3+、Mn2+、Ni2+And Co2+And (3) one or more of nitrate, sulfate and chloride.
As a preferable technical scheme, in the step (2), metal salt containing metal ions is added to the system obtained in the step (1) and fully mixed, the supersaturation degree of the metal salt and the temperature of the solution are regulated, so that the metal ions are electrostatically adsorbed on the phosphate groups, and the metal ions are crystallized according to the distribution of the phosphate groups on the carbon material, so as to form a material with a pore structure, namely the sodium/lithium ion battery phosphate positive electrode material.
Preferably, in the step (2), the mass ratio of the carbon material, the phytic acid and the metal salt is 1: 1-10: 10-30.
As a preferable technical scheme, in the step (2), the temperature of the solution is regulated to be-20-40 ℃.
As a preferable technical scheme, the product obtained in the step (2) is filtered, and the obtained solid material is dried.
As a preferred technical scheme, the dried solid material is placed in an environment of 25-1000 ℃ for annealing treatment.
The invention has the beneficial effects that:
the phytic acid is uniformly adsorbed on the carbon material to form phosphate groups, and then metal ions are distributed and crystallized on the carbon material according to the arrangement of the phosphate groups, so that a uniform and controllable specific pore structure for mass transfer is formed, and the phytic acid can be used as a positive electrode material of a sodium/lithium ion battery to realize rapid mass transfer and enhanced electron transfer, so that the phytic acid has high capacity, high multiplying power and excellent cycle stability.
Drawings
FIG. 1 shows FePO prepared in example 14SEM photograph of (slurry);
FIG. 2 shows FePO prepared in example 14SEM photograph of (powder);
FIG. 3 shows FePO prepared in example 14A performance diagram of the sodium ion battery as the anode material under the charge-discharge rate of 0.5C;
FIG. 4 shows FePO prepared in example 14A performance diagram of the lithium ion battery as the anode material under the charge-discharge rate of 0.5C;
FIG. 5 shows Mn obtained in example 23(PO4)2SEM photograph of (slurry);
FIG. 6 shows Mn obtained in example 23(PO4)2Performance diagram of lithium ion battery as positive electrode 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 the carbon nano tube in water to enable phosphate radicals to be adsorbed on the carbon nano tube to form phosphate groups;
(2) adding Fe (NO) into the system obtained in the step (1)3)3And mixing them fully to control the carbon nano tube, phytic acid and Fe (NO)3)3The mass ratio of (1: 5: 25) and the temperature of the solution is 0-5 ℃ to ensure that Fe is contained3+Electrostatic adsorption on the phosphate group, Fe3+Distributed crystals on the carbon nanotubes according to the arrangement of phosphate groups; the SEM photograph of the prepared slurry is shown in FIG. 1, and the uniform and controllable pore structure for mass transfer can be seen from the SEM photograph;
(3) filtering the product obtained in the step (2), drying the obtained solid material, and then annealing the solid material at 200 ℃; the SEM photograph of the prepared powder is shown in FIG. 2, from which a uniform and controllable pore structure for mass transfer can be seen.
FIG. 3 shows FePO prepared in example 14From the performance graph of the sodium ion battery as the cathode material at the charge and discharge rate of 0.5C, it can be seen that the battery maintains a high specific capacity even after 300 cycles, and shows excellent stability.
FIG. 4 shows FePO prepared in example 14From the performance graph of the lithium ion battery as the cathode material at the charge-discharge rate of 0.5C, it can be seen that the battery maintains a high specific capacity even after 120 cycles, and shows excellent stability.
Example 2
(1) Fully stirring and mixing phytic acid and the carbon nano tube in N-methyl pyrrolidone to enable phosphate radicals to be adsorbed on the carbon nano tube to form phosphate groups;
(2) adding MnSO into the system obtained in the step (1)4And mixing thoroughly to control the carbon nano tube, the phytic acid and the MnSO4The mass ratio of (1: 8: 20) and the temperature of the solution is 20-25 ℃ so that Mn is added2+Electrostatic adsorption on the phosphate group, Mn2+Distributed crystals on the carbon nanotubes according to the arrangement of phosphate groups; the SEM photograph of the resulting slurry is shown in FIG. 5, from which it can be seen that the slurry is uniformControlled pore structure available for mass transfer.
FIG. 6 shows Mn obtained in example 23(PO4)2As can be seen from the performance graph of the lithium ion battery as the cathode material at a charge/discharge rate of 1C, the battery maintains a high specific capacity even after 100 cycles, and exhibits excellent stability.
Reference is made to the processes of examples 1 and 2, using a catalyst containing Fe3+、Mn2+、Ni2+、Co2+One or more mixed metal salts can also achieve the aim of the invention.
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 (7)

1. A preparation method of a sodium/lithium ion battery phosphate anode material is characterized by comprising the following steps: the method comprises the following steps:
(1) fully stirring and mixing phytic acid and a carbon material in a solvent to enable phosphate radicals to be adsorbed on the carbon material to form phosphate groups;
(2) adding metal salt containing metal ions into the system obtained in the step (1), fully mixing, regulating and controlling the supersaturation degree of the metal salt and the temperature of the solution, wherein the mass ratio of the carbon material, the phytic acid and the metal salt is 1: 1-10: 10-30, the temperature of the solution is regulated and controlled to be-20-40 ℃, so that the metal ions are electrostatically adsorbed on the phosphate groups, and the metal ions are distributed and crystallized on the carbon material according to the arrangement of the phosphate groups to form a material with a pore structure, namely the sodium/lithium ion battery phosphate anode material.
2. The method for preparing the phosphate positive electrode material of the sodium/lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (1), the carbon material includes, but is not limited to, carbon nanotubes.
3. The method for preparing the phosphate positive electrode material of the sodium/lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (1), the solvent includes but is not limited to one or more of water, absolute ethyl alcohol, N-methyl pyrrolidone and dimethylformamide.
4. The method for preparing the phosphate positive electrode material of the sodium/lithium ion battery according to claim 1, wherein the method comprises the following steps: in the step (2), the metal ions include but are not limited to Fe3+、Mn2+、Ni2+And Co2+One or a mixture of several of them.
5. The method for preparing the phosphate positive electrode material of the sodium/lithium ion battery according to claim 4, wherein the method comprises the following steps: in the step (2), the metal salt containing metal ions includes, but is not limited to, Fe3+、Mn2+、Ni2+And Co2+And (3) one or more of nitrate, sulfate and chloride.
6. The method for preparing the phosphate positive electrode material of the sodium/lithium ion battery according to claim 1, wherein the method comprises the following steps: and (3) filtering the product obtained in the step (2), and drying the obtained solid material.
7. The method for preparing the phosphate positive electrode material of the sodium/lithium ion battery according to claim 6, wherein the method comprises the following steps: and (3) annealing the dried solid material at the temperature of 25-1000 ℃.
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WO2018068035A1 (en) * 2016-10-07 2018-04-12 Kratos LLC Graphite and group iva composite particles and methods of making
CN109449426A (en) * 2018-11-29 2019-03-08 华南理工大学 A method of lithium ion battery negative material is prepared using chromium slag

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CN103915626A (en) * 2014-04-21 2014-07-09 上海电力学院 Sodium ion battery composite positive material and preparation method thereof
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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
CN106384808B (en) * 2016-11-29 2019-09-06 湖南三迅新能源科技有限公司 A kind of based lithium-ion battery positive plate and preparation method thereof, lithium ion battery
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WO2018068035A1 (en) * 2016-10-07 2018-04-12 Kratos LLC Graphite and group iva composite particles and methods of making
CN107579234A (en) * 2017-09-11 2018-01-12 长沙小新新能源科技有限公司 A kind of graphene battery material of magnetic conductive and preparation method thereof
CN109449426A (en) * 2018-11-29 2019-03-08 华南理工大学 A method of lithium ion battery negative material is prepared using chromium slag

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