CN113782724A - Ferro-nickel phosphide-carbon composite material and preparation method and application thereof - Google Patents

Ferro-nickel phosphide-carbon composite material and preparation method and application thereof Download PDF

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CN113782724A
CN113782724A CN202111055295.9A CN202111055295A CN113782724A CN 113782724 A CN113782724 A CN 113782724A CN 202111055295 A CN202111055295 A CN 202111055295A CN 113782724 A CN113782724 A CN 113782724A
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nickel
composite material
carbon composite
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iron phosphide
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李俊哲
孙文超
汪超
陶梦琴
孔祥升
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Anhui University of Technology AHUT
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/5805—Phosphides
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

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Abstract

The invention relates to the technical field of new energy electrode material preparation, in particular to a nickel-iron phosphide-carbon composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) uniformly mixing a nickel source, an iron source, a carbon source and a surfactant according to a certain proportion, carrying out hydrothermal reaction for a period of time at a certain temperature, washing and drying a hydrothermal product to obtain a precursor; 2) and respectively placing the obtained precursor and sodium hypophosphite at the upper end and the lower end of the corundum ark according to a certain proportion, calcining for a period of time at a high temperature in argon flow with a certain flow rate, washing and drying a calcined product, and obtaining the target product, namely the nickel-iron phosphide-carbon composite material. Firstly synthesizing a precursor by a one-step hydrothermal method, then placing the precursor and sodium hypophosphite in a tubular furnace filled with argon, and calcining to obtain a nickel-iron phosphide-carbon composite material; the composite material has a large specific surface area, provides a large number of active sites for the intercalation of lithium ions, and improves the conductivity of the material.

Description

Ferro-nickel phosphide-carbon composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of new energy electrode material preparation, in particular to a nickel-iron phosphide-carbon composite material and a preparation method and application thereof.
Background
Energy problems are key issues affecting the survival and development of human society. Due to the large consumption of fossil energy, resources on earth are gradually reduced, people begin to develop and utilize novel energy, and lithium ion batteries become a hotspot in the field of new energy research. Compared with the traditional lead storage battery, the lithium ion battery has the capability of long-time cyclic charge and discharge, has high energy density, and is a reliable novel energy storage device. A key component of the lithium ion battery is an electrode material, and thus development of an electrode material having good conductivity, high stability and low cost has become a key to commercialization of the lithium ion battery.
Iron-based electrode materials are emerging with unique advantages in the energy field due to the particularly large iron reserves on earth. Iron phosphide (FeP) is an excellent electrode material with a high theoretical capacity (926mAh/g), but FeP exhibits an irreversible capacity drop and poor rate performance due to aggregation of the material and pulverization of the electrode. Therefore, the carbon and the nickel are doped into the FeP, so that the conductivity and the specific surface of the material can be improved. Currently, iron phosphide is generally prepared by a hydrothermal method and a low-temperature solid-gas reaction, but the yield is small and the time is long. Therefore, the conductivity of the electrode material can be improved by doping nickel into iron phosphide and compounding the iron phosphide with carbon, the production efficiency of the electrode material is improved by a high-temperature solid phase method, and the electrode material has practical significance for improving the electrochemical performance of the nickel phosphide electrode material and improving the production efficiency.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a nickel-iron phosphide-carbon composite material and a preparation method and application thereof, wherein antimony sulfide is synthesized by solvothermal synthesis, and the antimony sulfide is used as a template to synthesize the nickel-iron phosphide-carbon composite material by secondary solvothermal synthesis and high-temperature calcination; the structure of the modified material is optimized, the conductivity is improved, and the comprehensive electrochemical performance is improved.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a preparation method of a phosphorus nickel iron-carbon composite material comprises the following steps:
1) preparing a precursor: uniformly mixing a nickel source, an iron source, a carbon source and a surfactant according to a certain proportion, carrying out hydrothermal reaction for a period of time at a certain temperature, washing and drying a hydrothermal product to obtain a precursor;
2) preparing a nickel-iron phosphide-carbon composite material: and respectively placing the obtained precursor and sodium hypophosphite at the upper end and the lower end of the corundum ark according to a certain proportion, calcining for a period of time at a high temperature in argon flow with a certain flow rate, washing and drying a calcined product, and obtaining the target product, namely the nickel-iron phosphide-carbon composite material.
Further, in the preparation method of the nickel phosphide iron-carbon composite material, in the step 1), the nickel source is at least one of nickel nitrate, nickel sulfate and nickel acetate; the iron source is at least one of ferric nitrate, ferric oxalate, ferrocene, ferrous chloride and ferric chloride; the carbon source is at least one of urea, sucrose and glucose; the surfactant is at least one of polyvinylpyrrolidone, polyvinyl alcohol and cetyl trimethyl ammonium bromide.
Further, the preparation method of the nickel iron phosphide-carbon composite material as described above, step 1), the nickel source, the iron source, the carbon source and the surfactant are according to FeNi (OOH)2The addition amount of the carbon source is 5-10 wt.% of the total mass.
Further, in the preparation method of the nickel-iron phosphide-carbon composite material, in the step 1), the temperature of the hydrothermal reaction is 150-180 ℃ and the time is 8-12 h.
Further, in the preparation method of the nickel-iron phosphide-carbon composite material, in the step 2), the mass ratio of the phosphorus content in the precursor to the phosphorus content in the sodium hypophosphite is 1: 5-10.
Further, in the preparation method of the nickel iron phosphide-carbon composite material, in the step 2), the flow rate of the argon gas flow is 50-150 mL/min.
Further, in the preparation method of the nickel iron phosphide-carbon composite material, step 2), the high-temperature calcination is carried out at a temperature rise rate of 2-5 ℃/min to 300-500 ℃, and then the calcination is carried out at the temperature for 2-6 h.
A nickel-iron phosphide-carbon composite material is prepared by the preparation method. The application of the nickel iron phosphide-carbon composite material in the lithium ion battery is as follows: uniformly mixing 80 wt.% of active substance ferronickel phosphide-carbon composite material, 10 wt.% of conductive agent acetylene black and 10 wt.% of binder polyvinylidene fluoride; and uniformly coating the prepared electrode slurry on a copper foil current collector, baking the electrode in a constant-temperature oven at 60 ℃ for 12 hours, taking out, cutting into small round pieces with the diameter of 12mm by using a tablet press, and keeping the mass of the active substance on each working electrode between 0.8 and 1.2mg approximately. According to the application, the prepared nickel-iron phosphide-carbon composite material is used as the positive electrode of the button cell, and the lithium sheet is used as the negative electrode of the button cell, so that the button cell can be assembled for electrochemical performance test.
The invention has the beneficial effects that:
1. the invention uses iron source and nickel source with grain size of 0.5-2 μm and carbon coating layer on the surface to compose the material for manufacturing electrode, the electrode material has discharge specific capacitance of 300-400 mAh/g; firstly synthesizing a precursor by a one-step hydrothermal method, then placing the precursor and sodium hypophosphite in a tubular furnace filled with argon, and calcining to obtain a nickel phosphide-carbon composite material; compared with the prior art, the nickel-iron-carbon composite material has the characteristics of higher conductivity, longer cycle life, environmental protection, low cost and excellent performance.
2. The method has simple process, high efficiency and convenience, and the prepared product has smaller charge transfer and ion diffusion resistance and shows excellent electrochemical performance; compared with other preparation methods of ferronickel phosphide/carbon, the preparation method of ferronickel phosphide/carbon is prepared by compounding an iron source, a nickel source and carbon for the first time, provides a brand new thought for the ferronickel phosphide as an electrode material of a lithium ion battery, and provides a wider research field for scientific research work.
Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM photograph of an electrode material FeNiP/C-PVP in example 1;
FIG. 2 is a constant current charge and discharge curve of FeNiP/C-PVP as the electrode material in example 1;
FIG. 3 is a first-turn charge-discharge curve diagram of the electrode material FeNiP/C-PVP in example 1;
FIG. 4 is a graph of the rate at different current densities for the electrode material FeNiP/C-PVP in example 1;
FIG. 5 is a CV curve of the electrode material FeNiP/C-PVP in example 1;
FIG. 6 is an SEM photograph of the electrode material FeNiP/C-PVA in example 2;
FIG. 7 is a constant current charge and discharge curve of FeNiP/C-PVA as an electrode material in example 2;
FIG. 8 is a first-turn charge-discharge curve diagram of the electrode material FeNiP/C-PVA in example 2;
FIG. 9 is a graph showing the rate curves at different current densities for the electrode material FeNiP/C-PVA of example 2;
FIG. 10 is a CV curve of the electrode material FeNiP/C-PVA in example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be 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 protection scope of the present invention.
A preparation method of a phosphorus nickel iron-carbon composite material comprises the following steps:
1) preparing a precursor: uniformly mixing a nickel source, an iron source, a carbon source and a surfactant according to a certain proportion, carrying out hydrothermal reaction for 8-12h at the temperature of 150-180 ℃, washing and drying a hydrothermal product to obtain a precursor; the nickel source is at least one of nickel nitrate, nickel sulfate and nickel acetate; the iron source is at least one of ferric nitrate, ferric oxalate, ferrocene, ferrous chloride and ferric chloride; the carbon source is at least one of urea, sucrose and glucose; the surfactant is at least one of polyvinylpyrrolidone, polyvinyl alcohol and cetyl trimethyl ammonium bromide. A nickel source, an iron source, a carbon source and a surfactant according to FeNi (OOH)2The addition amount of the carbon source is 5-10 wt.% of the total mass.
2) Preparing a nickel-iron phosphide-carbon composite material: weighing materials according to the mass ratio of the phosphorus content in the precursor to the sodium hypophosphite of 1:5-10, respectively placing the precursor and the sodium hypophosphite at the upper end and the lower end of a corundum ark, calcining at a high temperature in an argon flow of 50-150mL/min, heating the high-temperature calcination to 500 ℃ at a heating rate of 2-5 ℃/min, then calcining at the temperature for 2-6h, washing and drying the calcined product, and obtaining the target product, namely the ferronickel phosphide-carbon composite material.
The specific embodiment of the invention is as follows:
example 1
100ml of deionized water was weighed into a beaker by a measuring cylinder, 1.616g (4mmol) of ferric nitrate, 1.16g (4mmol) of nickel nitrate and 1.44g of urea were weighed into the beaker by a balance, and stirred for 30min until completely dissolved. Then, 1g of PVP is weighed by a balance and added into the mixed solution, and the mixture is continuously stirred until the solid is completely dissolved. Transferring the solution into a 100ml polytetrafluoroethylene linerHydrothermal in an autoclave at 150 ℃ for 8 h. And centrifugally washing the suspension after the hydrothermal reaction by using a centrifugal machine at the rotating speed of 7500r/min, wherein the suspension is washed by deionized water for 3 times and ethanol for 2 times. After 5 centrifugal washes, the resulting powder was dried at 80 ℃ for 12h to give FeNi (OOH)2And (3) precursor.
Weighing sodium hypophosphite in a ratio of 1:8 with the precursor, placing the sodium hypophosphite at the upper airflow end of the tube furnace, placing the precursor in the lower airflow of the tube furnace, calcining for 2 hours at 350 ℃ at a heating rate of 2 ℃/min under the atmosphere of argon, and naturally cooling to room temperature to obtain a target product, namely, ferronickel phosphide/carbon, which is recorded as FeNiP/C-PVP.
The prepared FeNiP/C-PVP is used as an active substance, conductive carbon black (SP) is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a binder, and the mass ratio of the FeNiP/C-PVP to the conductive agent is 80: 10: 10 to a total of 100mg, and a certain amount of dispersant N-methylpyrrolidone (NMP) was added to prepare an electrode slurry. And (3) placing the slurry on a magnetic stirring table, stirring for 12h, uniformly mixing, uniformly coating the paste on a copper foil with the coating thickness of 100 mu m, then placing the copper foil in a vacuum drying oven for vacuum drying at 60 ℃ for 12h, cutting into small round pieces with the diameter of 12mm by using a tablet press, and sealing and storing the self-sealing bags.
In the system, copper foil is used as a current collector, an active material is used as a button cell positive electrode, a lithium sheet is used as a button cell negative electrode, and the main component of electrolyte is LiPF6. The electrochemical performance of the FeNiP/C-PVP electrode material in a button cell is tested as shown in the figure. FIG. 2 is a constant-current charge-discharge curve of an electrode plate with a capacity of 0.8mg of electrode material, which shows that FeNiP/C-PVP has good stability, and the FeNiP/C-PVP can still maintain the discharge specific capacity of 150mAh/g after circulating for 200 circles under the current density of 200 mA/g. As shown in the multiplying power of the electrode plate in figure 4, the specific capacity of the FeNiP/C-PVP electrode is 500mAh/g under the current density of 20mA/g, and the specific discharge capacity of the FeNiP/C-PVP electrode material can still reach 200mAh/g under the current density of 500mA/g, which indicates that the material has better multiplying power charge-discharge performance and better electrochemical stability.
Example 2
Measuring 100ml of deionized water in a beaker by using a measuring cylinder, and usingA balance weighing 1.616g (4mmol) of ferric nitrate, 1.16g (4mmol) of nickel nitrate and 1.44g of glucose respectively into the beaker and stirring continuously for 30min until complete dissolution. Then 1g of PVA is weighed by a balance and added into the mixed solution, and the mixture is continuously stirred until the solid is completely dissolved. The solution was transferred to a 100ml teflon lined autoclave and hydrothermal treated at 180 ℃ for 6 h. And centrifugally washing the suspension after the hydrothermal reaction by using a centrifugal machine at the rotating speed of 7500r/min, wherein the suspension is washed by deionized water for 3 times and ethanol for 2 times. After 5 times of centrifugal washing, the obtained powder is dried for 12h at 60 ℃ to obtain FeNi (OOH)2And (3) precursor.
Weighing sodium hypophosphite with a ratio of 1:10 to the precursor, placing the sodium hypophosphite at the upper airflow end of the tube furnace, placing the precursor in the lower airflow of the tube furnace, calcining for 2 hours at 350 ℃ at a heating rate of 2 ℃/min under the atmosphere of argon, heating to 500 ℃ at a heating rate of 5 ℃/min, and calcining for 3 hours. And naturally cooling to room temperature to obtain a target product of ferronickel phosphide/carbon, which is recorded as FeNiP/C-PVA.
The prepared FeNiP/C-PVA is used as an active substance, conductive carbon black (SP) is used as a conductive agent, polyvinylidene fluoride (PVDF) is used as a binder, and the mass ratio of the FeNiP/C-PVA to the conductive carbon black is 80: 10: 10 to a total of 100mg, and a certain amount of dispersant N-methylpyrrolidone (NMP) was added to prepare an electrode slurry. And (3) placing the slurry on a magnetic stirring table, stirring for 12h, uniformly mixing, uniformly coating the paste on a copper foil with the coating thickness of 100 mu m, then placing the copper foil in a vacuum drying oven for vacuum drying at 60 ℃ for 12h, cutting into small round pieces with the diameter of 12mm by using a tablet press, and sealing and storing the self-sealing bags.
In the system, copper foil is used as a current collector, an active material is used as a button cell positive electrode, a lithium sheet is used as a button cell negative electrode, and the main component of electrolyte is LiPF6. The electrochemical performance of the FeNiP/C-PVA electrode material in the button cell is tested as shown in the figure. FIG. 6 is a constant-current charge-discharge curve of an electrode plate of an electrode material with a capacity of 0.8mg, which shows that FeNiP/C-PVA has good stability, the discharge specific capacity of the first circle reaches 450mAh/g under the current density of 200mA/g, and the discharge specific capacity of 70mAh/g can still be maintained after 200 circles of circulation. As shown in fig. 9, the magnification of the electrode sheet isUnder the current density of 20mA/g, the specific capacity of the FeNiP/C-PVA electrode is 550mAh/g, and under the current density of 500mA/g, the discharge specific capacity of the FeNiP/C-PVA electrode material can still reach 70mAh/g, which shows that the material has better rate charge-discharge performance and better electrochemical stability.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (10)

1. The preparation method of the nickel-iron phosphide-carbon composite material is characterized by comprising the following steps of:
1) preparing a precursor: uniformly mixing a nickel source, an iron source, a carbon source and a surfactant according to a certain proportion, carrying out hydrothermal reaction for a period of time at a certain temperature, washing and drying a hydrothermal product to obtain a precursor;
2) preparing a nickel-iron phosphide-carbon composite material: and respectively placing the obtained precursor and sodium hypophosphite at the upper end and the lower end of the corundum ark according to a certain proportion, calcining for a period of time at a high temperature in argon flow with a certain flow rate, washing and drying a calcined product, and obtaining the target product, namely the nickel-iron phosphide-carbon composite material.
2. The method of preparing a nickel iron phosphide-carbon composite material according to claim 1, characterized in that: in the step 1), the nickel source is at least one of nickel nitrate, nickel sulfate and nickel acetate; the iron source is at least one of ferric nitrate, ferric oxalate, ferrocene, ferrous chloride and ferric chloride; the carbon source is at least one of urea, sucrose and glucose; the surfactant is at least one of polyvinylpyrrolidone, polyvinyl alcohol and cetyl trimethyl ammonium bromide.
3. The method for preparing a nickel iron phosphide-carbon composite material according to claim 2, characterized in that: in the step 1), the nickel source, the iron source, the carbon source and the surfactant are FeNi (OOH)2The addition amount of the carbon source is 5-10 wt.% of the total mass.
4. The method of preparing a nickel iron phosphide-carbon composite material according to claim 1, characterized in that: in the step 1), the temperature of the hydrothermal reaction is 150-180 ℃, and the time is 8-12 h.
5. The method of preparing a nickel iron phosphide-carbon composite material according to claim 1, characterized in that: in the step 2), the mass ratio of the phosphorus content in the precursor to the phosphorus content in the sodium hypophosphite is 1: 5-10.
6. The method of preparing a nickel iron phosphide-carbon composite material according to claim 1, characterized in that: in the step 2), the flow rate of the argon gas flow is 50-150 mL/min.
7. The method of preparing a nickel iron phosphide-carbon composite material according to claim 1, characterized in that: in the step 2), the high-temperature calcination is heated to 500 ℃ at the heating rate of 2-5 ℃/min, and then the calcination is carried out for 2-6h at the temperature.
8. A nickel iron phosphide-carbon composite material produced by the production method according to any one of claims 1 to 7.
9. Use of the nickel iron phosphide-carbon composite material according to claim 8 in lithium ion batteries.
10. Use according to claim 9, characterized in that: uniformly mixing 80 wt.% of active substance ferronickel phosphide-carbon composite material, 10 wt.% of conductive agent acetylene black and 10 wt.% of binder polyvinylidene fluoride; and uniformly coating the prepared electrode slurry on a copper foil current collector, baking the electrode in a constant-temperature oven at 60 ℃ for 12 hours, taking out, cutting into small round pieces with the diameter of 12mm by using a tablet press, and keeping the mass of the active substance on each working electrode between 0.8 and 1.2mg approximately.
CN202111055295.9A 2021-09-09 2021-09-09 Ferro-nickel phosphide-carbon composite material and preparation method and application thereof Pending CN113782724A (en)

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CN114256444A (en) * 2021-12-23 2022-03-29 永高股份有限公司 Phosphorus-nickel-germanium composite negative electrode material, and preparation method and application thereof

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Application publication date: 20211210