CN113488645A - Application of ferric phosphate/carbon composite material as lithium ion battery negative electrode material - Google Patents

Application of ferric phosphate/carbon composite material as lithium ion battery negative electrode material Download PDF

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Publication number
CN113488645A
CN113488645A CN202110668590.5A CN202110668590A CN113488645A CN 113488645 A CN113488645 A CN 113488645A CN 202110668590 A CN202110668590 A CN 202110668590A CN 113488645 A CN113488645 A CN 113488645A
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iron phosphate
carbon composite
composite material
lithium ion
ion battery
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CN202110668590.5A
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李延伟
徐文翰
姚金环
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Guilin University of Technology
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Guilin University of Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses an application of an iron phosphate/carbon composite material as a lithium ion battery negative electrode material. The invention also discloses a lithium ion battery taking the iron phosphate/carbon composite material as a negative electrode material, which has the characteristics of high specific capacity, good cycle performance and rate capability and high safety. Meanwhile, the iron phosphate material has rich resources, low price and environmental friendliness, and the iron phosphate and carbon compounding method is simple, convenient and mature, has low requirements on equipment and is easy for large-scale production. Therefore, the iron phosphate/carbon composite material is a novel negative electrode material of the lithium ion battery with a good application prospect.

Description

Application of ferric phosphate/carbon composite material as lithium ion battery negative electrode material
Technical Field
The invention relates to the technical field of new energy materials, in particular to application of an iron phosphate/carbon composite material as a lithium ion battery cathode material.
Background
With the development of the times and the rapid development of products such as electric automobiles, mobile phones, computers and the like, the requirements of people on the performance and the safety of lithium ion batteries are higher and higher. Currently, a battery negative electrode material is generally usedMainly graphite material. However, the graphite material has lower theoretical specific capacity (only 372mAh g)-1) Low density and energy density (about 300W h kg)-1) Low working electrode potential (0.1V vs Li/Li)+) And low safety. In order to accelerate the development of lithium ion batteries, research and development of novel anode materials with high specific capacity, good safety and stability are urgent. The P-O bond in the iron phosphate crystal is stable and hard to decompose, and the iron phosphate crystal cannot collapse and generate heat or form a strong oxidizing substance at high temperature or during overcharge, so that the iron phosphate crystal has good safety and is favored by people. At present, the technology of iron phosphate as a positive electrode material has been studied by many researchers. However, no studies have been reported on iron phosphate as a negative electrode material for lithium ion batteries. Therefore, the invention provides an application of the iron phosphate/carbon composite material as a lithium ion battery negative electrode material.
Disclosure of Invention
The invention provides an application of an iron phosphate/carbon composite material as a lithium ion battery negative electrode material.
Preferably, the primary particle size of the iron phosphate/carbon composite is on the nanometer scale.
Preferably, the preparation method of the iron phosphate/carbon composite material adopts a chemical precipitation combined sintering technology; preferably, the carbon source of the iron phosphate/carbon composite material adopts ammonium citrate tribasic.
Preferably, the specific steps for preparing the iron phosphate/carbon composite material are as follows:
(1) 0.01mol of ammonium dihydrogen phosphate (NH) was weighed4H2PO4) Dissolving the iron oxide in 150mL of deionized water, transferring the obtained solution into a constant-temperature water bath kettle at 70 ℃, magnetically stirring for 30 minutes, and adding 0.01mol of Fe (NO) during stirring3)2·9H2And O, then, dropwise adding an ammonia water solution to adjust the pH value of the solution to 1.5, standing the obtained solution at normal temperature for 3 hours, carrying out centrifugal filtration on the obtained precipitate, washing the precipitate until the filtrate is neutral, and freeze-drying the obtained precipitate to constant weight to obtain the iron phosphate precursor.
(2) And (2) dispersing 0.2g of the iron phosphate precursor obtained in the step (1) and triammonium citrate in a mass ratio of 1: 3-1: 5 into 2mL of ethanol aqueous solution (a solution obtained by mixing absolute ethanol and deionized water in a volume ratio of 1: 1). And finally, preserving the temperature of the obtained suspension for 6h at 600 ℃ in an argon atmosphere, and increasing the temperature at a rate of 2 ℃/min to obtain the final iron phosphate/carbon composite material.
A negative electrode material of a lithium ion battery is a ferric phosphate/carbon composite material.
A lithium ion battery is composed of a positive plate, a negative plate, electrolyte and a diaphragm between the positive plate and the negative plate, wherein the negative plate comprises the negative electrode material.
The advantages of the invention are as follows:
the invention provides an application of an iron phosphate/carbon composite material as a lithium ion battery cathode material, wherein carbon in the iron phosphate/carbon composite material can improve the conductivity of the material and relieve the volume effect of the material, and the iron phosphate and Li+The iron phosphate can perform reversible redox reaction at the valence states of +3, +2 and 0, and at the same time, the iron phosphate does not generate or form a strong oxidizing substance at high temperature, and the discharge platform is high, so that the iron phosphate/carbon composite material serving as the lithium ion battery cathode material has the characteristics of high specific capacity, good cycle performance and rate capability, high safety and the like. Meanwhile, the iron phosphate material has rich resources, low price and environmental friendliness, and the iron phosphate and carbon compounding method is simple, convenient and mature, has low requirements on equipment and is easy for large-scale production. Therefore, the iron phosphate/carbon composite material is a novel negative electrode material of the lithium ion battery with a good application prospect.
Drawings
Fig. 1 is an XRD pattern of the iron phosphate/carbon composite of example 1 of the present invention.
Figure 2 is a TGA profile of the iron phosphate/carbon composite of example 1 of the present invention.
Fig. 3 is an SEM image of the iron phosphate/carbon composite of example 1 of the present invention.
Fig. 4 is a graph of cycle performance and rate performance of a battery assembled according to example 1 of the present invention.
Fig. 5 is a graph of the cycling performance and rate performance of the assembled battery of example 2 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Preparing an iron phosphate/carbon composite material:
(1) 0.01mol of ammonium dihydrogen phosphate (NH) was weighed4H2PO4) Dissolving the iron oxide in 150mL of deionized water, transferring the obtained solution into a constant-temperature water bath kettle at 70 ℃, magnetically stirring for 30 minutes, and adding 0.01mol of Fe (NO) during stirring3)2·9H2And O, then, dropwise adding an ammonia water solution to adjust the pH value of the solution to 1.5, standing the obtained solution at normal temperature for 3 hours, carrying out centrifugal filtration on the obtained precipitate, washing the precipitate until the filtrate is neutral, and freeze-drying the obtained precipitate to constant weight to obtain the iron phosphate precursor.
(2) 0.2g of the iron phosphate precursor obtained in the step (1) and triammonium citrate are dispersed in 2mL of ethanol aqueous solution (solution obtained by mixing absolute ethanol and deionized water in a volume ratio of 1:1) according to a mass ratio of 1: 5. And finally, preserving the temperature of the obtained suspension for 6h at 600 ℃ in an argon atmosphere, and increasing the temperature at a rate of 2 ℃/min to obtain the final iron phosphate/carbon composite material.
Example 2
(1) 0.01mol of ammonium dihydrogen phosphate (NH) was weighed4H2PO4) Dissolving the iron oxide in 150mL of deionized water, transferring the obtained solution into a constant-temperature water bath kettle at 70 ℃, magnetically stirring for 30 minutes, and adding 0.01mol of Fe (NO) during stirring3)2·9H2And O, then, dropwise adding an ammonia water solution to adjust the pH value of the solution to 1.5, standing the obtained solution at normal temperature for 3 hours, carrying out centrifugal filtration on the obtained precipitate, washing the precipitate until the filtrate is neutral, and freeze-drying the obtained precipitate to constant weight to obtain the iron phosphate precursor.
(2) 0.2g of the iron phosphate precursor obtained in the step (1) and triammonium citrate are dispersed in 2mL of ethanol aqueous solution (solution obtained by mixing absolute ethanol and deionized water in a volume ratio of 1:1) according to a mass ratio of 1: 3. And finally, preserving the temperature of the obtained suspension for 6h at 600 ℃ in an argon atmosphere, and increasing the temperature at a rate of 2 ℃/min to obtain the final iron phosphate/carbon composite material.
And (3) electrochemical performance testing: the iron phosphate/carbon composite materials prepared in the examples 1 and 2 are used as electrode active materials, conductive carbon black (Super P) is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a binder, the materials are mixed and ground uniformly according to the mass ratio of 7:2:1, a proper amount of N-methyl-2-pyrrolidone (NMP) is added, the mixture is mixed uniformly to form slurry, the slurry is coated on a copper foil uniformly, the vacuum drying is carried out for 12 hours at the temperature of 80 ℃, and the iron phosphate/carbon composite material electrode plate is obtained after blanking. Taking the prepared iron phosphate/carbon composite electrode plate as a working electrode, a metal lithium plate as a counter electrode, a polypropylene porous membrane (Celgard 2400) as a diaphragm and 1mol/L LiPF6The mixed solution of Ethylene Carbonate (EC), dimethyl carbonate (DMC) and diethyl carbonate (DEC) (v (EC): v (DMC): v (DEC): 1:1:1) was used as an electrolyte, and assembled into a CR2016 type button half cell in a glove box filled with argon gas. The constant current charge-discharge performance and the rate capability of the assembled button half cell are tested by adopting a BTS-5V/10mA type charge-discharge tester of Shenzhen Xinwei company, and the charge-discharge voltage range is 0.01-3.0V (vs+/Li). In the cycle performance test, the catalyst is firstly activated for 10 circles at a current density of 0.2A/g, and then the cycle is continuously cycled to 200 circles at a current density of 0.5A/g. The current density of the rate performance test is 0.2, 0.5, 1, 2, 3 and 5A/g respectively.
As shown in fig. 1, the XRD pattern of the iron phosphate/carbon composite of example 1 of the present invention is shown. As can be seen from the figure, the main phase of the material is iron phosphate.
As shown in fig. 2, a TGA profile of the iron phosphate/carbon composite of example 1 of the present invention is shown. As can be seen from the figure, the carbon in the iron phosphate/carbon composite material is burnt and removed after being heated to more than 300 ℃ under the air atmosphere, so that the material is subjected to weight loss.
Fig. 3 shows an SEM image of the iron phosphate/carbon composite material according to example 1 of the present invention. As can be seen from the figure, the iron phosphate/carbon composite material is composed of blocks with different sizes formed by tightly agglomerating small nano-scale particles.
As shown in fig. 4, the left graph is a cycle performance curve, and the right graph is a rate performance curve. As can be seen from the left graph of FIG. 4, the initial specific discharge capacity of the electrode can reach 1290mAh/g at the current density of 0.2A/g, after 10 cycles of charge and discharge, the electrode continues to cycle at the current density of 0.5A/g, the specific discharge capacity is 513mAh/g (namely, the 11 th cycle in the graph), and then the electrode always keeps good reversible charge and discharge performance and cycle stability, the coulomb efficiency is close to 100%, and the specific discharge capacity and the specific charge capacity after 200 cycles of cycle are respectively kept at 505mAh/g and 503 mAh/g. As can be seen from the right graph of FIG. 4, the discharge specific capacity of the electrode can still reach 258mAh/g and 191mAh/g at high current densities of 3A/g and 5A/g, respectively.
As shown in fig. 5, the left graph is a cycle performance curve, and the right graph is a rate performance curve. As can be seen from the left graph of FIG. 5, the initial specific discharge capacity of the electrode can reach 1265mAh/g at the current density of 0.2A/g, after 10 cycles of charge and discharge, the electrode continues to cycle at the current density of 0.5A/g, the specific discharge capacity is 579mAh/g (namely, the 11 th cycle in the graph), and then the electrode always keeps good reversible charge and discharge performance and cycle stability, the coulomb efficiency is close to 100%, and the specific discharge capacity and the specific charge capacity after 200 cycles of cycle are respectively kept at 444mAh/g and 442 mAh/g. As can be seen from the right graph of FIG. 5, the specific discharge capacity of the electrode can still reach 302mAh/g and 236mAh/g at high current densities of 3A/g and 5A/g, respectively.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (5)

1. An application of an iron phosphate/carbon composite material as a negative electrode material of a lithium ion battery.
2. Use according to claim 1, characterized in that: (1) the primary particle size of the iron phosphate/carbon composite material is nano-scale; (2) preferably, the preparation method of the iron phosphate/carbon composite material adopts a chemical precipitation combined sintering technology; preferably, the carbon source of the iron phosphate/carbon composite material adopts ammonium citrate tribasic.
3. The lithium ion battery negative electrode material is characterized in that the negative electrode material is an iron phosphate/carbon composite material.
4. The lithium ion battery anode material according to claim 3, wherein the primary particle size of the anode material is nano-scale; the preparation method of the cathode material adopts a chemical precipitation and sintering technology, and the carbon source adopts triammonium citrate.
5. A lithium ion battery, which is characterized by comprising a positive plate, a negative plate, electrolyte and a diaphragm between the positive plate and the negative plate, wherein the negative plate comprises the negative electrode material of claim 3 or 4.
CN202110668590.5A 2021-06-16 2021-06-16 Application of ferric phosphate/carbon composite material as lithium ion battery negative electrode material Withdrawn CN113488645A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335693A (en) * 2021-12-28 2022-04-12 盐城工学院 High-safety iron-based phosphate sodium ion full cell and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114335693A (en) * 2021-12-28 2022-04-12 盐城工学院 High-safety iron-based phosphate sodium ion full cell and preparation method thereof
CN114335693B (en) * 2021-12-28 2023-09-12 盐城工学院 High-safety iron-based phosphate sodium ion full battery and preparation method thereof

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Application publication date: 20211008