CN114242984A - Preparation method of iron-cobalt phosphide/carbon composite material with layered structure and button cell - Google Patents

Preparation method of iron-cobalt phosphide/carbon composite material with layered structure and button cell Download PDF

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CN114242984A
CN114242984A CN202111563183.4A CN202111563183A CN114242984A CN 114242984 A CN114242984 A CN 114242984A CN 202111563183 A CN202111563183 A CN 202111563183A CN 114242984 A CN114242984 A CN 114242984A
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cobalt
iron
composite material
button cell
carbon composite
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CN114242984B (en
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李伟伟
李俊哲
刘孝伟
秦清清
孙文超
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Chaowei Power Group Co Ltd
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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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/362—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
    • 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
    • H01M4/62—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
    • H01M2004/027—Negative 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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  • Composite Materials (AREA)
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Abstract

The invention relates to a preparation method of a layered structure iron-cobalt phosphide/carbon composite material and a button cell, belongs to the technical field of electrode material preparation, and solves the problem of poor electrochemical performance of phosphide metal as an electrode material in the prior art. The method comprises the following steps: (1) dissolving an iron source and a precipitator in a first reaction medium, stirring, transferring the obtained mixture into the lining of a high-pressure reaction kettle, preserving heat, and reacting; centrifuging, washing and drying the product to obtain the ferric oxide micron rod; (2) and (2) taking the ferric oxide micron rod obtained in the step (1) as a template, taking cobalt nitrate and/or cobalt chloride as a cobalt source, simultaneously adding a chelating agent, mixing the template, the cobalt source, the chelating agent and a second reaction medium, ultrasonically dispersing for 10-12min, stirring, centrifuging, washing and drying the obtained product, adding sodium hypophosphite in argon flow, and calcining at high temperature. The prepared composite material has better electrochemical performance.

Description

Preparation method of iron-cobalt phosphide/carbon composite material with layered structure and button cell
Technical Field
The invention relates to the technical field of new energy electrode material preparation, in particular to a preparation method of a layered structure iron-cobalt phosphide/carbon composite material and a button cell.
Background
Transition metal phosphide has many advantages as a lithium ion battery negative electrode material, and most studies show that the phosphide material has a specific capacity higher than that of a commercial graphite electrode (372 mAh/g). However, the large capacity fade during cycling due to particle aggregation during electrochemical reactions and the large volume change during charge and discharge cycling; furthermore, the formation of a solid electrolyte layer (SEI) during charging and discharging also causes a loss of capacity, limiting the further use of phosphide electrode materials.
Disclosure of Invention
In view of the foregoing analysis, embodiments of the present invention are directed to a method for preparing a layered iron-cobalt phosphide/carbon composite material and a button cell, so as to solve the problems of large capacity fading and capacity loss caused in the charging and discharging processes when the existing phosphide metal is used as an electrode material in a cyclic process.
The invention provides a preparation method of a layered structure iron-cobalt phosphide/carbon composite material, which comprises the following steps:
(1) preparing iron oxide micron rods: dissolving an iron source and a precipitator in a first reaction medium, stirring, transferring the obtained mixture into the lining of a high-pressure reaction kettle, preserving heat, and reacting; after the reaction is finished, centrifuging, washing and drying the product to obtain the ferric oxide micron rod;
(2) preparing the iron-cobalt phosphide/carbon composite material: taking the iron oxide micron rod obtained in the step (1) as a template, taking cobalt nitrate and/or cobalt chloride as a cobalt source, simultaneously adding a chelating agent, mixing the template, the cobalt source, the chelating agent and a second reaction medium, ultrasonically dispersing for 10-12min, stirring, centrifuging, washing and drying the obtained product to obtain the iron oxide micron rod Fe containing the metal cobalt and having the organic framework structure2O3@ Co-MOF; in a stream of argon, Fe2O3Mixing the @ Co-MOF and sodium hypophosphite, and calcining at high temperature to obtain the FeP @ CoP/C iron-cobalt phosphide/carbon composite material.
Preferably, in step (1), the iron source, the precipitant and the first reaction medium are used in a ratio of: 10-13 mmol: 5-13 mmol: 70-75 mL.
Preferably, the iron source is one or more of ferric chloride, ferrous sulfate and ferric nitrate; the precipitant is one or more of oxalic acid, propane diamine, sodium thiosulfate, sodium bicarbonate, sodium carbonate and ammonia water; the first reaction medium is a deionized water mixed solution containing at least two of glycerol, ethylene glycol, ethanol, methanol and dimethyl phthalate.
Preferably, in the step (1), the reaction temperature is 160-220 ℃, and the reaction time is 4-16 h.
Preferably, in the step (2), the dosage ratio of the iron oxide micron rods, the cobalt source, the chelating agent and the second reaction medium is 0.2-0.4 g: 0.1-0.2 g: 1-2 g: 70-75 mL.
Preferably, in step (2), Fe2O3The dosage ratio of the @ Co-MOF to the sodium hypophosphite is 0.1-0.3 g: 1-3 g.
Preferably, the second reaction medium is a deionized water mixed solution containing at least two of methanol, ethanol, ethylene glycol and glycerol.
Preferably, the chelating agent is one or more of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, polyvinylpyrrolidone and 2-methylimidazole.
Preferably, in the step (2), the flow rate of the argon gas flow is 25-80mL/min, and the high-temperature calcination process comprises the following steps: the calcination temperature is 300-550 ℃, the heating rate is 2-5 ℃/min, and the time is 2-3 h.
In another aspect, the invention provides a button cell, wherein the negative electrode of the button cell comprises the iron-cobalt phosphide/carbon composite material obtained by the preparation method, and a metal lithium sheet is used as a counter electrode and a reference electrode.
Preferably, the negative electrode further comprises a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF); the negative electrode is prepared by the following method: taking N-methylpyrrolidone NMP as a solvent, and mixing an active substance iron-cobalt phosphide/carbon composite material, a conductive agent acetylene black and a binder polyvinylidene fluoride PVDF according to the dosage ratio of 320-340 mg: 40-50 mg: 40-50mg of the mixed slurry is uniformly mixed until the mixed slurry has metallic luster, the prepared mixed slurry is uniformly coated on a copper foil, and the copper foil is taken out after vacuum drying for 12-14h at the temperature of 60-70 ℃ and is punched into a pole piece.
Preferably, the copper foil has the size of 6cm multiplied by 7cm, and the diameter of the punched pole piece is 8-9 mm.
Preferably, the electrolyte of the button cell is 1.0mol/L LiPF6The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the proportion of 1: 1: 1 volume ratio of the mixture.
Preferably, the button cell is composed in a glove box having a water oxygen content of less than 0.01 ppm.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
1. the preparation method is simple, efficient and convenient; in addition, the prepared iron-cobalt phosphide/carbon composite material (FeP @ CoP/C) has a multi-stage layered structure, high conductivity and excellent electrochemical performance.
2. The invention firstly proposes to utilize iron oxide (Fe)2O3) The method provides a brand new idea for preparing the bimetal phosphide composite material for the template and using the phosphide as the lithium ion battery cathode material.
3. The iron-cobalt phosphide/carbon composite material FeP @ CoP/C obtained by the preparation method is used as a lithium ion battery cathode material and assembled into a button cell for electrochemical performance test, and the button cell has the specific first-cycle discharge capacity of 400mAh/g under the current density of 200 mA/g.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is an SEM image of FeP @ CoP/C prepared in example 1.
FIG. 2 is an XRD pattern of FeP @ CoP/C prepared in example 1.
FIG. 3 is a graph showing the charge and discharge curves of the battery using FeP @ CoP/C as the electrode material in example 1.
FIG. 4 is a graph showing the cycling profile of a cell of example 1 with FeP @ CoP/C as the electrode material.
FIG. 5 is a graph of the rate performance of a cell with FeP @ CoP/C as the electrode material in example 1.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
The solution for improving the electrochemical performance of the metal phosphide can be to reasonably design the phase, the morphology and the like of the phosphide electrode material, so that the material not only can exert the unique advantages of the material, but also can weaken and improve the defects of the material.
The method for improving the electrochemical performance of the composite material is also an effective method for compounding phosphide and a functional carbon material, and firstly, the carbon material has conductivity, so that the electron transmission can be enhanced, and the conductivity of the material is improved; secondly, the carbon material can construct a complex morphology and is endowed with a large number of pores, thereby playing roles in preventing the aggregation of active substances and relieving the volume change.
Therefore, the invention provides a preparation method of a layered structure iron-cobalt phosphide/carbon composite material, which comprises the following steps:
(1) preparing iron oxide micron rods:
dissolving an iron source and a precipitator in a first reaction medium, stirring, transferring the obtained mixture into the lining of a high-pressure reaction kettle, preserving heat, and reacting; after the reaction is finished, centrifuging, washing and drying the product to obtain the ferric oxide micron rod;
(2) preparing the iron-cobalt phosphide/carbon composite material:
taking the iron oxide micron rod obtained in the step (1) as a template, taking cobalt nitrate and/or cobalt chloride as a cobalt source, simultaneously adding a chelating agent, mixing the template, the cobalt source, the chelating agent and a second reaction medium, ultrasonically dispersing for 10-12min, stirring, centrifuging, washing and drying the obtained product to obtain the iron oxide micron rod Fe containing the metal cobalt and having the organic framework structure2O3@ Co-MOF; in a stream of argon, Fe2O3Mixing the @ Co-MOF and sodium hypophosphite, and calcining at high temperature to obtain the FeP @ CoP/C iron-cobalt phosphide/carbon composite material.
The method adopts the mixing of an iron source and a precipitator, the reaction is carried out in a high-pressure reaction kettle to obtain an iron oxide micron rod, and then the iron oxide micron rod is taken as a template and is hydrothermally treated with a cobalt source in the presence of a chelating agent to generate a cobalt-containing metal organic framework Fe2O3@ Co-MOF, and further phosphorizing the obtained product at high temperature to obtain the iron-cobalt phosphide/carbon composite material.
The product obtained by the invention is an iron-cobalt phosphide/carbon composite material with a multi-level layered structure formed by mutually stacking one-dimensional micron rods, the structure has larger specific surface area and larger reaction interface, the appearance and the function are controllable, and the proper amount of carbon coating can effectively increase the conductivity of the material and buffer the volume change of an active material in the charging and discharging process. Compared with the prior art, the iron-cobalt phosphide/carbon composite material prepared by the preparation method has the characteristics of high conductivity, long cycle life, environmental protection, simple preparation and excellent performance.
In the present invention, preferably, in step (1), the iron source, the precipitant and the first reaction medium are used in a ratio of: 10-13 mmol: 5-13 mmol: 70-75mL, such as 10 mmol: 7 mmol: 70mL, 10 mmol: 10 mmol: 70mL, 10 mmol: 5 mmol: 70mL, 11 mmol: 10 mmol: 70mL, 10 mmol: 13 mmol: 75mL, 10 mmol: 12 mmol: 70mL, 13 mmol: 13 mmol: 75mL, 13 mmol: 13 mmol: 70mL, 10-13 mmol: 10-13 mmol: 70-75 mL.
Further preferably, the iron source is one or more of ferric chloride, ferrous sulfate and ferric nitrate; the precipitant is one or more of oxalic acid, propane diamine, sodium thiosulfate, sodium bicarbonate, sodium carbonate and ammonia water; the first reaction medium is a deionized water mixed solution containing at least two of glycerol, ethylene glycol, ethanol, methanol and dimethyl phthalate.
Further preferably, in the first reaction medium, the ratio of the amount of glycerol, ethylene glycol, ethanol, methanol and dimethyl phthalate to the amount of deionized water is 40-60 mL: 10-30mL, such as 40 mL: 30mL, 50 mL: 20mL, 60 mL: 10 mL.
In the invention, the specific iron source, the precipitator, the first reaction medium and the specific dosage are adopted to ensure that the prepared product has better electrochemical performance. Further preferably, the ferric chloride is FeCl3·6H2O, ferrous sulfate is FeSO4·7H2O, Fe (NO) being ferric nitrate3)2·9H2O。
In step (1), the stirring is carried out in a rotor stirrer at a rotation speed of 160-240r/min, such as 160r/min, 180r/min, 200r/min, 220r/min and 240 r/min; stirring for 10-20min, such as 10min, 12min, 15min, 18min, and 20 min.
In order to further improve the electrochemical performance of the Fe-Co phosphide/C composite material, in the step (1), the reaction temperature is 160-220 ℃, such as 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ and 220 ℃; the reaction time is 4-16h, such as 4h, 6h, 8h, 10h, 12h, 14h and 16 h. Further preferably, the volume of the lining of the high-pressure reaction kettle is 100-110 mL.
Specifically, in the step (1), the centrifugal process is carried out in a centrifuge, and the rotating speed of the centrifuge is 7800-; the washing process comprises: washing with deionized water for 3 times, and washing with ethanol for 2 times; the drying process comprises: drying in vacuum oven at 80-90 deg.C (such as 80 deg.C and 85 deg.C) for 12-14 hr.
In the invention, the iron-cobalt phosphide/carbon composite material is prepared by using the iron oxide micron rod prepared in the step (1) as a raw material, preferably, in the step (2), the dosage ratio of the iron oxide micron rod, the cobalt source, the chelating agent and the second reaction medium is 0.2-0.4 g: 0.1-0.2 g: 1-2 g: 70-75mL, such as 0.4 g: 0.1 g: 1.8 g: 70mL, 0.3 g: 0.1 g: 1 g: 70mL, 0.2 g: 0.1 g: 1 g: 70mL, 0.2 g: 0.1 g: 1 g: 75mL, 0.4 g: 0.1 g: 1 g: 70mL, 0.4 g: 0.2 g: 1 g: 75 mL.
Further preferably, in step (2), Fe2O3The dosage ratio of the @ Co-MOF to the sodium hypophosphite is 0.1-0.3 g: 1-3g, such as 0.3 g: 3g, 0.2 g: 1.8g, 0.1 g: 1g, 0.2 g: 2g, 0.3 g: 1g of the total weight of the composition. The prepared FeP @ CoP/C composite material has a multi-level layered structure, high conductivity and excellent electrochemical performance.
In the present invention, preferably, the cobalt nitrate is Co (NO)3)2·6H2O, cobalt chloride is CoCl2·6H2O。
In the present invention, the second reaction medium is preferably a deionized water mixed solution containing at least two of methanol, ethanol, ethylene glycol and glycerin. Further preferably, in the second reaction medium, the ratio of the total amount of methanol, ethanol, ethylene glycol and glycerol to the amount of deionized water is 50-60 mL: 10-20 mL. The chelating agent is preferably one or more of cetyltrimethylammonium bromide (CTAB), sodium dodecylbenzene sulfonate (SDBS), polyvinylpyrrolidone (PVP), 2-methylimidazole.
Specifically, in the step (2), the stirring process is carried out in a rotor stirrer, the rotating speed is 200-.
In step (2), the centrifugal process is carried out in a centrifuge, and the rotation speed of the centrifuge is 7800-7900 r/min; the washing process comprises the following steps: washing with deionized water for 3 times, and washing with ethanol for 2 times; the drying process comprises the following steps: drying in a vacuum drying oven at 80-90 deg.C for 12-14h to obtain Fe-containing organic frame structure ferric oxide micron rod2O3@Co-MOF。
Further preferably, in step (2), the flow rate of the argon stream is 25-80mL/min, such as 25mL/min, 30mL/min, 35mL/min, 40mL/min, 45mL/min, 50mL/min, 55mL/min, 60mL/min, 65mL/min, 70mL/min, 75mL/min, 80 mL/min; the high-temperature calcination process comprises the following steps: the calcination temperature is 300-550 deg.C, such as 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C; the heating rate is 2-5 deg.C/min, such as 2 deg.C/min, 2.5 deg.C/min, 3 deg.C/min, 3.5 deg.C/min, 4 deg.C/min, 4.5 deg.C/min, 5 deg.C/min; the time is 2-3 h. Further preferably, the high temperature calcination process comprises: heating to 350 ℃ at a heating rate of 2-3 ℃/min, preserving heat for 2-3h, then heating to 550 ℃ at a heating rate of 4-5 ℃/min, and preserving heat for 2-3 h.
On the other hand, the invention also provides a button cell, wherein the cathode of the button cell comprises the iron-cobalt phosphide/carbon composite material obtained by the preparation method, and a metal lithium sheet is used as a counter electrode and a reference electrode.
Specifically, the negative electrode further comprises a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF); the negative electrode is prepared by the following method: taking N-methylpyrrolidone NMP as a solvent, and mixing an active substance iron-cobalt phosphide/carbon composite material, a conductive agent acetylene black and a binder polyvinylidene fluoride PVDF according to the dosage ratio of 320-340 mg: 40-50 mg: 40-50mg, such as 320 mg: 40 mg: 40mg, 320 mg: 50 mg: 50mg, 340 mg: 40 mg: 40mg, 340 mg: 50 mg: 50mg, 340 mg: 40 mg: 50mg, 330 mg: 45 mg: 45mg, 330 mg: 40 mg: 40mg, 330 mg: 50 mg: 50 mg; and (3) uniformly coating the prepared mixed slurry on a copper foil until the mixed slurry has metallic luster, carrying out vacuum drying at the temperature of 60-70 ℃ for 12-14h, taking out, and stamping into a pole piece.
More preferably, the copper foil has the size of 6cm multiplied by 7cm, and the diameter of the punched pole piece is 8-9 mm.
Illustratively, the electrolyte of the button cell is 1.0mol/L LiPF6The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the proportion of 1: 1: 1 volume ratio of the mixture. Further preferably, the button cell is composed in a glove box having a water oxygen content below 0.01 ppm.
The preparation method of the iron-cobalt phosphide/carbon composite material with a layered structure and the button cell of the invention are further illustrated by the following specific examples.
Example 1
(1) Preparation of iron oxide micron rods
2.7g of FeCl were weighed out separately with a balance3·6H2O, 0.9g of oxalic acid, which was transferred into a beaker having a volume of 100mL, followed by adding 30mL of deionized water, 20mL of glycerol, and 20mL of ethylene glycol, and magnetically stirring at a rotational speed of 160r/min for 20 min. The mixture was then transferred to a 100mL kettle liner and allowed to react at 160 ℃ for 12 h. Standing the reaction kettle after the reaction is finished, removing upper-layer liquid, centrifugally washing 3 times by using deionized water and 2 times by using a centrifugal machine at the rotating speed of 7800r/min, and then drying for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain iron oxide micron rods;
(2) preparation of iron-cobalt phosphide/carbon composite material FeP @ CoP/C
0.4g of iron oxide micron rod and 0.1g of Co (NO) were weighed out separately on a balance3)2·6H2O, 1g of PVP. Transferring the mixture into a beaker with the volume of 100mL, adding 10mL of deionized water, 40mL of methanol and 20mL of ethanol, ultrasonically dispersing for 10min, and magnetically stirring at the rotating speed of 200r/min for 6 h. After the reaction is finished, removing the upper layer liquid, centrifugally washing the upper layer liquid for 3 times by deionized water by a centrifugal machine at the rotating speed of 7800r/min, and then drying the upper layer liquid for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain a product Fe2O3@ Co-MOF; 0.2g of the product Fe is taken2O3The @ Co-MOF was placed in the upper stream of a corundum ark, and 1.8g of NaH was taken2PO2Placing the corundum square boat in the lower air flow of the corundum square boat, setting the heating rate to be 2 ℃/min in argon air flow with the flow rate of 25mL/min, and preserving heat for 3 hours when the temperature is raised to 300 ℃. And then setting the heating rate to be 5 ℃/min, calcining at 550 ℃ for 2h, and then slowly cooling to room temperature along with furnace cooling to obtain the FeP @ CoP/C iron-cobalt phosphide/carbon composite material. FIGS. 1 and 2 are SEM and XRD diagrams, respectively, for FeP @ CoP/C; it can be seen from the figure that there is a multi-level hierarchy.
(3) Preparation of button cell
Assembling the FeP @ CoP/C composite material prepared in the step (2) into an electrode, which specifically comprises the following steps: uniformly mixing 320mg of active substance FeP @ CoP/C composite material, 40mg of conductive agent acetylene black and 40mg of PVDF, uniformly mixing with NMP as a solvent until the mixed slurry has metallic luster, uniformly coating the prepared electrode slurry on a copper foil with the thickness of 6cm multiplied by 7cm, drying in vacuum at 60 ℃ for 12 hours, taking out, and stamping into a pole piece with the diameter of 8 mm.
The prepared pole piece containing the FeP @ CoP/C composite material is used as a negative electrode of a battery, a metal lithium piece is used as a counter electrode and a reference electrode, and the electrolyte is 1.0mol/L LiPF6The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the proportion of 1: 1: 1, in a glove box with a water oxygen content below 0.01 ppm.
(4) Electrochemical performance detection
And (3) carrying out cycle and rate performance tests on the battery at 0.1-3V by using a blue charge-discharge tester. The results are shown in FIGS. 3-5.
As can be seen from FIGS. 3-5, the battery using the FeP @ CoP/C composite material obtained by the preparation method of the invention as the negative electrode has good charge-discharge performance, cycle performance and rate capability.
Example 2
(1) Preparation of iron oxide micron rods
2.78g of FeSO were weighed out separately on a balance4·7H2O, 0.84g NaHCO3. It was transferred to a beaker having a volume of 100mL, followed by addition of 20mL of deionized water, 20mL of DMP, 30mL of ethanol and magnetic stirring at 200r/min for 15 min. The mixture was then transferred to a 100mL kettle liner and allowed to react at 180 ℃ for 8 h. Standing the reaction kettle after the reaction is finished, removing upper-layer liquid, centrifugally washing 3 times by using deionized water and 2 times by using a centrifugal machine at the rotating speed of 7800r/min, and then drying for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain iron oxide micron rods;
(2) preparation of iron-cobalt phosphide/carbon composite material FeP @ CoP/C
0.3g of iron oxide micron rod and 0.1g of CoCl were weighed out separately on a balance2·6H2O, 1g of 2-methylimidazole.Transferring the mixture into a beaker with the volume of 100mL, adding 20mL of deionized water, 30mL of methanol and 20mL of ethylene glycol, ultrasonically dispersing for 10min, and magnetically stirring for 3h at the rotating speed of 200 r/min. After the reaction is finished, removing the upper layer liquid, centrifugally washing the upper layer liquid for 3 times by deionized water by a centrifugal machine at the rotating speed of 7800r/min, and then drying the upper layer liquid for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain a product Fe2O3@ Co-MOF; 0.1g of the product Fe is taken2O3The @ Co-MOF was placed in the upper air stream of a corundum ark, and 1g of NaH was taken2PO2Placing the corundum square boat in lower air flow of the corundum square boat, setting the heating rate to be 3 ℃/min in argon air flow with the flow rate of 50mL/min, and preserving heat for 2h when the temperature is raised to 350 ℃. And then setting the heating rate to be 4 ℃/min, calcining at the high temperature of 500 ℃ for 3h, and then slowly cooling to room temperature along with furnace cooling to obtain the FeP @ CoP/C iron-cobalt phosphide/carbon composite material.
(3) Preparation of button cell
Assembling the FeP @ CoP/C composite material prepared in the step (2) into an electrode, which specifically comprises the following steps: uniformly mixing 320mg of active substance FeP @ CoP/C composite material, 40mg of conductive agent acetylene black and 40mg of PVDF, uniformly mixing with NMP as a solvent until the mixed slurry has metallic luster, uniformly coating the prepared electrode slurry on a copper foil with the thickness of 6cm multiplied by 7cm, drying in vacuum at 60 ℃ for 12 hours, taking out, and stamping into a pole piece with the diameter of 8 mm.
The prepared pole piece containing the FeP @ CoP/C composite material is used as a negative electrode of a battery, a metal lithium piece is used as a counter electrode and a reference electrode, and the electrolyte is 1.0mol/L LiPF6The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the proportion of 1: 1: 1, and forming the button cell in a glove box with the water oxygen content lower than 0.01 ppm.
(4) Electrochemical performance detection
And (3) carrying out cycle and rate performance tests on the battery at 0.1-3V by using a blue charge-discharge tester. The result shows that the battery using the FeP @ CoP/C composite material prepared in example 2 as the negative electrode has good charge and discharge performance, cycle performance and rate capability.
Example 3
(1) Preparation of iron oxide micron rods
1.35g of FeCl was weighed out separately with a balance3 6H2O, 1.39g of FeSO4·7H2O, 0.53g of NaCO31mL of concentrated ammonia water is measured by a measuring cylinder, transferred into a beaker with the volume of 100mL, and then added with 20mL of deionized water, 20mL of glycerol, 20mL of methanol and 10mL of ethylene glycol, and magnetically stirred for 10min at the rotating speed of 240 r/min. The mixture was then transferred to a 100mL reactor liner and reacted at 200 ℃ for 6 h. Standing the reaction kettle after the reaction is finished, removing upper-layer liquid, centrifugally washing the reaction kettle for 3 times by using deionized water and 2 times by using an ethanol at the rotating speed of 7800r/min by using a centrifugal machine, and then drying the reaction kettle for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the iron oxide micron rod;
(2) preparation of iron-cobalt phosphide/carbon composite material FeP @ CoP/C
0.2g of iron oxide micron rod and 0.05g of Co (NO) were weighed out separately on a balance3)2·6H2O, 0.05g of CoCl2·6H2O, 1g CTAB. Transferring the mixture into a beaker with the volume of 100mL, adding 20mL of deionized water, 30mL of methanol and 20mL of glycerol, ultrasonically dispersing for 10min, and magnetically stirring at the rotating speed of 200r/min for 8 h. After the reaction is finished, removing the upper layer liquid, centrifugally washing the upper layer liquid for 3 times by deionized water by a centrifugal machine at the rotating speed of 7800r/min, and then drying the upper layer liquid for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain a product Fe2O3@ Co-MOF; 0.2g of the product Fe is taken2O3The @ Co-MOF was placed in the upper stream of a corundum ark, and 1.8g of NaH was taken2PO2Placing the corundum square boat in lower air flow of the corundum square boat, setting the heating rate to be 3 ℃/min in argon air flow with the flow rate of 70mL/min, and preserving heat for 2h when the temperature is raised to 300 ℃. And then setting the heating rate to be 5 ℃/min, calcining at 500 ℃ for 2h, and then slowly cooling to room temperature along with furnace cooling to obtain the FeP @ CoP/C iron-cobalt phosphide/carbon composite material.
(3) Preparation of button cell
Assembling the FeP @ CoP/C composite material prepared in the step (2) into an electrode, which specifically comprises the following steps: uniformly mixing 320mg of active substance FeP @ CoP/C composite material, 40mg of conductive agent acetylene black and 40mg of PVDF, uniformly mixing with NMP as a solvent until the mixed slurry has metallic luster, uniformly coating the prepared electrode slurry on a copper foil with the thickness of 6cm multiplied by 7cm, drying in vacuum at 60 ℃ for 12 hours, taking out, and stamping into a pole piece with the diameter of 8 mm.
The prepared pole piece containing the FeP @ CoP/C composite material is used as a negative electrode of a battery, a metal lithium piece is used as a counter electrode and a reference electrode, and the electrolyte is 1.0mol/L LiPF6The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the proportion of 1: 1: 1, and forming the button cell in a glove box with the water oxygen content lower than 0.01 ppm.
(4) Electrochemical performance detection
And (3) carrying out cycle and rate performance test on the battery by using a blue charge-discharge tester at 0.1-3V. The result shows that the battery using the FeP @ CoP/C composite material prepared in example 3 as the negative electrode has good charge and discharge performance, cycle performance and rate capability.
Example 4
(1) Preparation of iron oxide micron rods
4.04g of Fe (NO) were weighed out separately on a balance3)2·9H2O, 1.58g of sodium thiosulfate, and 1mL of concentrated ammonia water is measured in a measuring cylinder. It was transferred into a beaker having a volume of 100mL, followed by addition of 10mL of deionized water, 20mL of glycerol, 20mL of ethanol, and 20mL of DMP. Stirring for 20min by magnetic force at the rotating speed of 160 r/min. The mixture was then transferred to a 100mL kettle liner and allowed to react at 220 ℃ for 4 h. And (3) standing the reaction kettle after the reaction is finished, removing upper-layer liquid, centrifugally washing the reaction kettle for 3 times by using deionized water and 2 times by using ethanol at the rotating speed of 7800r/min by using a centrifugal machine, and drying the reaction kettle for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the iron oxide micron rod.
(2) Preparation of iron-cobalt phosphide/carbon composite material FeP @ CoP/C
0.3g of iron oxide micron rod and 0.1g of Co (NO) were weighed out separately on a balance3)2·6H2O, 1g of SDBS. Transferring into a beaker with a volume of 100mL, adding 20mL of deionized water, 30mL of methanol, 10mL of ethanol and 10mL of ethylene glycol, ultrasonically dispersing for 10min, and rotating at a speed of 200r/minAnd magnetically stirring for 10 hours. After the reaction is finished, removing the upper layer liquid, centrifugally washing the upper layer liquid for 3 times by deionized water by a centrifugal machine at the rotating speed of 7800r/min, and then drying the upper layer liquid for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain a product Fe2O3@ Co-MOF; 0.3g of the product Fe is taken2O3The @ Co-MOF was placed in the upper air stream of a corundum ark, 3g of NaH was taken2PO2Placing the corundum square boat in the lower air flow of the corundum square boat, setting the heating rate to be 3 ℃/min in the argon air flow with the flow rate of 80mL/min, and preserving heat for 2h when the temperature is raised to 300 ℃. And then setting the heating rate to be 5 ℃/min, calcining at 550 ℃ for 3h, and then slowly cooling to room temperature along with furnace cooling to obtain the FeP @ CoP/C iron-cobalt phosphide/carbon composite material.
(3) Preparation of button cell
Assembling the FeP @ CoP/C composite material prepared in the step (2) into an electrode, which specifically comprises the following steps: uniformly mixing 320mg of active substance FeP @ CoP/C composite material, 40mg of conductive agent acetylene black and 40mg of PVDF, uniformly mixing with NMP as a solvent until the mixed slurry has metallic luster, uniformly coating the prepared electrode slurry on a copper foil with the thickness of 6cm multiplied by 7cm, drying in vacuum at 60 ℃ for 12 hours, taking out, and stamping into a pole piece with the diameter of 8 mm.
The prepared pole piece containing the FeP @ CoP/C composite material is used as a negative electrode of a battery, a metal lithium piece is used as a counter electrode and a reference electrode, and the electrolyte is 1.0mol/L LiPF6The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the proportion of 1: 1: 1, and forming the button cell in a glove box with the water oxygen content lower than 0.01 ppm.
(4) Electrochemical performance detection
And (3) carrying out cycle and rate performance tests on the battery at 0.1-3V by using a blue charge-discharge tester. The battery using the FeP @ CoP/C composite material prepared in the embodiment 4 as the negative electrode has good charge and discharge performance, cycle performance and rate capability.
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 changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (14)

1. A preparation method of a layered structure iron-cobalt phosphide/carbon composite material is characterized by comprising the following steps:
(1) preparing iron oxide micron rods: dissolving an iron source and a precipitator in a first reaction medium, stirring, transferring the obtained mixture into the lining of a high-pressure reaction kettle, preserving heat, and reacting; after the reaction is finished, centrifuging, washing and drying the product to obtain the ferric oxide micron rod;
(2) preparing the iron-cobalt phosphide/carbon composite material: taking the iron oxide micron rod obtained in the step (1) as a template, taking cobalt nitrate and/or cobalt chloride as a cobalt source, simultaneously adding a chelating agent, mixing the template, the cobalt source, the chelating agent and a second reaction medium, ultrasonically dispersing for 10-12min, stirring, centrifuging, washing and drying the obtained product to obtain the iron oxide micron rod Fe containing the metal cobalt and having the organic framework structure2O3@ Co-MOF; in a stream of argon, Fe2O3Mixing the @ Co-MOF and sodium hypophosphite, and calcining at high temperature to obtain the FeP @ CoP/C iron-cobalt phosphide/carbon composite material.
2. The method according to claim 1, wherein in the step (1), the iron source, the precipitant and the first reaction medium are used in a ratio of: 10-13 mmol: 5-13 mmol: 70-75 mL.
3. The preparation method according to claim 2, wherein the iron source is one or more of ferric chloride, ferrous sulfate and ferric nitrate; the precipitant is one or more of oxalic acid, propane diamine, sodium thiosulfate, sodium bicarbonate, sodium carbonate and ammonia water; the first reaction medium is a deionized water mixed solution containing at least two of glycerol, ethylene glycol, ethanol, methanol and dimethyl phthalate.
4. The method as claimed in claim 2, wherein the reaction temperature in step (1) is 160-220 ℃ and the reaction time is 4-16 h.
5. The method according to claim 1, wherein in the step (2), the iron oxide micro-rods, the cobalt source, the chelating agent, and the second reaction medium are used in a ratio of 0.2 to 0.4 g: 0.1-0.2 g: 1-2 g: 70-75 mL.
6. The method according to claim 5, wherein in the step (2), Fe2O3The dosage ratio of the @ Co-MOF to the sodium hypophosphite is 0.1-0.3 g: 1-3 g.
7. The method of claim 5, wherein the second reaction medium is a deionized water mixed solution containing at least two of methanol, ethanol, ethylene glycol, and glycerol.
8. The method according to claim 6, wherein the chelating agent is one or more of cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, and 2-methylimidazole.
9. The method according to claim 8, wherein in the step (2), the flow rate of the argon gas stream is 25-80mL/min, and the high-temperature calcination process comprises: the calcination temperature is 300-550 ℃, the heating rate is 2-5 ℃/min, and the time is 2-3 h.
10. Button cell, characterized in that the negative electrode of the button cell comprises the iron-cobalt-phosphide/carbon composite obtained by the preparation method of claims 1-9, with metallic lithium sheets as counter and reference electrodes.
11. The button cell according to claim 10, wherein the negative electrode further comprises a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF); the negative electrode is prepared by the following method: taking N-methylpyrrolidone NMP as a solvent, and mixing an active substance iron-cobalt phosphide/carbon composite material, a conductive agent acetylene black and a binder polyvinylidene fluoride PVDF according to the dosage ratio of 320-340 mg: 40-50 mg: 40-50mg of the mixed slurry is uniformly mixed until the mixed slurry has metallic luster, the prepared mixed slurry is uniformly coated on a copper foil, and the copper foil is taken out after vacuum drying for 12-14h at the temperature of 60-70 ℃ and is punched into a pole piece.
12. The button cell according to claim 11, wherein the copper foil has dimensions of 6cm x 7cm and the punched pole piece has a diameter of 8-9 mm.
13. The button cell according to claim 11, wherein the electrolyte of the button cell is 1.0mol/L LiPF6The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the proportion of 1: 1: 1 volume ratio of the mixture.
14. The button cell according to claim 13, characterized in that it is composed in a glove box with a water oxygen content lower than 0.01 ppm.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107275622A (en) * 2017-07-11 2017-10-20 西北大学 A kind of preparation method and application of graphene@metal phosphides@C nano composites
WO2018194263A1 (en) * 2017-04-19 2018-10-25 서울대학교산학협력단 Method for preparing fuel cell catalyst iron phosphide nanoparticles, and iron phosphide nanoparticles prepared thereby
CN111569914A (en) * 2020-04-29 2020-08-25 国电新能源技术研究院有限公司 Bimetal phosphide composite material and preparation method and application thereof
CN113101955A (en) * 2021-03-02 2021-07-13 中国长江三峡集团有限公司 Preparation method of iron phosphide nano material and application of iron phosphide nano material as electrocatalyst
CN113233514A (en) * 2021-05-14 2021-08-10 扬州大学 Preparation method and application of vesicular phosphate radical ion functionalized cobalt oxide nano material
CN113782724A (en) * 2021-09-09 2021-12-10 安徽工业大学 Ferro-nickel phosphide-carbon composite material and preparation method and application thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105895886B (en) * 2016-06-21 2018-09-14 中南大学 A kind of sodium-ion battery transition metal phosphide/porous anode composite and preparation method thereof
CN106099106B (en) * 2016-08-22 2019-06-18 上海工程技术大学 It is ultrafast to fill lithium ion battery negative material, preparation method and lithium ion battery
CN110176360B (en) * 2019-04-22 2020-09-18 山东大学 Hollow core-shell structure supercapacitor material Fe-Co-S/NF as well as preparation method and application thereof
CN112635738B (en) * 2020-12-22 2021-09-21 江西理工大学 Preparation method of FeNiP/C @ MXene composite anode material for lithium ion battery
CN113735181B (en) * 2021-09-06 2022-10-11 安徽工业大学 Antimony-cobalt sulfide-carbon composite nanorod and preparation method and application thereof
CN113782738A (en) * 2021-09-09 2021-12-10 安徽工业大学 MOF-derived nickel iron phosphide-carbon electrode material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018194263A1 (en) * 2017-04-19 2018-10-25 서울대학교산학협력단 Method for preparing fuel cell catalyst iron phosphide nanoparticles, and iron phosphide nanoparticles prepared thereby
CN107275622A (en) * 2017-07-11 2017-10-20 西北大学 A kind of preparation method and application of graphene@metal phosphides@C nano composites
CN111569914A (en) * 2020-04-29 2020-08-25 国电新能源技术研究院有限公司 Bimetal phosphide composite material and preparation method and application thereof
CN113101955A (en) * 2021-03-02 2021-07-13 中国长江三峡集团有限公司 Preparation method of iron phosphide nano material and application of iron phosphide nano material as electrocatalyst
CN113233514A (en) * 2021-05-14 2021-08-10 扬州大学 Preparation method and application of vesicular phosphate radical ion functionalized cobalt oxide nano material
CN113782724A (en) * 2021-09-09 2021-12-10 安徽工业大学 Ferro-nickel phosphide-carbon composite material and preparation method and application thereof

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