CN114709384B - A flexible integrated CoxP@N-C/CC lithium-ion battery anode material, its preparation method and its application - Google Patents

A flexible integrated CoxP@N-C/CC lithium-ion battery anode material, its preparation method and its application

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CN114709384B
CN114709384B CN202210277161.XA CN202210277161A CN114709384B CN 114709384 B CN114709384 B CN 114709384B CN 202210277161 A CN202210277161 A CN 202210277161A CN 114709384 B CN114709384 B CN 114709384B
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ion battery
lithium ion
cobalt
dopamine
carbon cloth
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CN114709384A (en
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张久俊
吴倩
王琳琳
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University of Shanghai for Science and Technology
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University of Shanghai for Science and 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
    • H01M4/362—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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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
    • 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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Abstract

The invention discloses a Co x P@N-C/CC flexible integrated lithium ion battery anode material, a preparation method and application thereof, wherein a cobalt phosphide Co x P and N-C doped composite material layer is formed on the surface of a tangible flexible carbon material base material CC, the composite material layer has a line piece interweaving morphology structure, and 1< x <2 in cobalt phosphide Co x P. According to the method, a cobalt-containing precursor which grows on the carbon cloth in situ is synthesized through a hydrothermal synthesis method, the cobalt precursor coated with dopamine on the carbon cloth is subjected to low-temperature gas-phase phosphating, and simultaneously the outer-layer coated dopamine is carbonized during phosphating treatment, so that the Co x P@N-C/CC flexible integrated electrode is obtained. The Co x P@N-C/CC self-supporting flexible electrode can be directly sliced to serve as a lithium ion battery cathode, has a unique line piece interweaved morphology structure, can effectively enhance ion transmission, and the nitrogen-doped carbon coating can improve the conductivity of the material and relieve the volume expansion of the material in the charging and discharging process, so that the electrochemical performance with high capacity and high stability is realized.

Description

Co x P@N-C/CC flexible integrated lithium ion battery anode material, preparation method and application thereof
Technical Field
The invention relates to a lithium ion battery anode material with high capacity and high stability and a unique wire piece interweaving morphology structure, a method and application thereof, and belongs to the field of preparation of Co x P flexible anodes.
Background
With the rapid development of portable, flexible wearable electronic devices, flexible lithium ion batteries have received intense attention from researchers. The negative electrode material is used as one of key components of the flexible lithium ion battery, and has higher requirements on high capacity, cycle stability and flexibility.
The lithium ion battery cathode material is mainly divided into carbon-based materials, alloying reaction materials, metal oxides, metal sulfides, metal phosphides and the like. The advantages of metal phosphides, such as relatively high theoretical capacity, conductivity, and low polarization potential, have attracted attention from a large number of researchers in recent years. Among the numerous metal phosphides, cobalt phosphide (Co xPy, x=1, 2; y=1, 2,3, 4) has received high attention from researchers because of its many advantages of thermodynamically stable crystal structure, higher theoretical capacity, proper operating voltage, low cost, etc.
In recent years, several researches have reported that cobalt phosphide is prepared as a negative electrode material of a lithium ion battery, but the electrochemical performance is limited by the defects of poor conductivity and large volume expansion, and the prepared material is mostly solid powder, and the electrode prepared by the method of coating the powder material on a current collector is easy to cause the electrode material to separate from the current collector when the electrode is folded and bent, and is easy to pulverize in the process of charge-discharge reaction, so that the capacity attenuation is serious. The method for in-situ growth of the active substances through the carbon cloth substrate can not only obtain the electrode with excellent flexibility, meet the requirement of the flexible lithium ion battery, but also prevent the material from being separated from pulverization. In addition, through the shape structure of the interweaved wire pieces and the coating of the nitrogen-doped carbon outer layer, the ion transmission can be effectively enhanced, the conductivity can be improved, the volume expansion can be relieved, and the electrochemical performance can be further improved.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art, and provides a Co x P@N-C/CC flexible integrated lithium ion battery anode material, a preparation method and application thereof, the material has a unique line piece interweaving morphology structure, the material provided by the invention can be used as a lithium ion battery cathode to enhance ion transmission, improve conductivity, effectively relieve the problem of volume expansion of the material in the circulation process, and enable the material to have high capacity and high stability.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
A Co x P@N-C/CC flexible integrated lithium ion battery cathode material is characterized in that a cobalt phosphide Co x P and N-C doped composite material layer is formed on the surface of a tangible flexible carbon material base material CC, the composite material layer has a line piece interweaved morphology structure, and 1< x <2 in the cobalt phosphide Co x P.
The invention relates to a preparation method of a Co x P@N-C/CC flexible integrated lithium ion battery anode material, which comprises the following steps:
a) Preparing a mixed solution of cobalt salt and a precipitator CO (NH 2)2) by adopting a solvent, immersing the carbon cloth into the mixed solution, and synthesizing a cobalt-containing precursor growing on the carbon cloth in situ by a hydrothermal synthesis method;
b) Immersing the obtained cobalt-containing precursor growing on the carbon cloth into a Tris-HCl buffer solution of dopamine hydrochloride, and then stirring to obtain a dopamine-coated cobalt precursor with black surface of the carbon cloth;
c) And b) placing the dopamine-coated cobalt precursor obtained in the step b) into a tube furnace, adopting sodium hypophosphite as a phosphorus source, carrying out low-temperature gas-phase phosphating, and simultaneously carbonizing the dopamine coated on the outer layer at the phosphating temperature to obtain the Co x P@N-C/CC flexible integrated lithium ion battery anode material.
Preferably, in the step a), the molar concentration ratio of the cobalt salt to the precipitant in the mixed solution is 1:2-1:6, and the solvent adopted in the mixed solution is a mixed solution of deionized water and absolute ethyl alcohol, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1:3-3:1.
Preferably, in said step a), cobalt salt is at least one of Co (NO 3)2·6H2O、CoCl2·6H2O、CoSO4·7H2 O).
Preferably, in the step a), the temperature of the hydrothermal reaction is 100-130 ℃ and the reaction time is 7-12 h.
Preferably, in the step b), the mixing ratio of the dopamine hydrochloride and the Tris-HCl buffer solution is 20-50 mg:40-100 mL, the stirring time is 10-36 h, and the concentration of the Tris-HCl buffer solution is 2-5 mM.
Preferably, in the step C), the low-temperature gas-phase phosphating is performed according to the mass ratio of the dopamine-coated cobalt precursor and the phosphorus source in the step b) of 1:10-1:40, the phosphorus source adopts sodium hypophosphite, the phosphating temperature condition is 300-400 ℃, the phosphating time is 2-4 h, and the adopted gas is any one or the mixed gas of nitrogen and argon.
The Co x P@N-C/CC flexible integrated lithium ion battery cathode material is applied to preparation of a lithium ion battery and comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that the negative electrode is prepared from the Co x P@N-C/CC flexible integrated lithium ion battery cathode material.
Preferably, the lithium ion battery is subjected to charge-discharge cycle test under the current density of 0.2A/g, and the capacity of the lithium ion battery is stably kept at not lower than 1018mAh/g after 120 cycles.
Further preferably, the lithium ion battery is subjected to a charge-discharge cycle test at a current density of 0.2A/g, and the capacity of the lithium ion battery is kept to be not lower than 1169.1mAh/g after 120 cycles.
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. The self-supporting flexible integrated electrode obtained by in-situ growth of active substances by using the carbon cloth as a substrate has excellent flexibility, meets the requirements of a flexible battery, and can prevent the active substances from being separated from a current collector in the electrochemical reaction process;
2. according to the invention, the ion transmission can be effectively enhanced through the morphology structure of the interweaved wire sheets, and the nitrogen-doped carbon outer layer is coated to improve the conductivity of the material and relieve the volume expansion of the material in the charge and discharge process, so that the high capacity and the high cycle stability are further realized;
Experiments show that the capacity is stably kept at 1169.1mAh/g after 120 circles of circulation by performing charge and discharge tests under the current density of 0.2A/g;
3. the method is simple and feasible, has low cost and is suitable for popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and of course, the drawings in the following description are merely examples of the present invention, and other drawings may be obtained according to the drawings provided without inventive effort for a person skilled in the art.
Fig. 1 is an XRD pattern of the negative electrode material in example 1 of the present invention.
Fig. 2 is an SEM image of the anode material in example 1 of the present invention.
Fig. 3 is a flexible representation of the negative electrode material in example 1 of the present invention.
FIG. 4 is a Raman spectrum of the anode material in example 1 of the present invention.
Fig. 5 is a charge-discharge cycle test of the lithium ion battery of example 1 of the present invention at a current density of 0.2A/g.
Fig. 6 is a charge-discharge cycle test of the lithium ion battery of example 2 of the present invention at a current density of 0.2A/g.
Fig. 7 is a charge-discharge cycle test of the lithium ion battery of example 3 of the present invention at a current density of 0.2A/g.
Detailed Description
The invention provides a method for preparing a Co x P@N-C/CC (1 < x < 2) flexible integrated negative electrode with a unique line piece interweaving morphology structure and high-capacity and high-stability lithium ion battery performance. The method comprises the following steps:
a) Preparing a mixed solution of cobalt salt (Co (NO 3)2·6H2O、CoCl2·6H2O、CoSO4·7H2 O and the like) and precipitator CO (NH 2)2) with a certain molar concentration ratio, immersing the carbon cloth into the mixed solution, and synthesizing a cobalt-containing precursor growing on the carbon cloth in situ by a hydrothermal synthesis method, wherein the cobalt salt in the mixed solution comprises all the cobalt salts.
B) And immersing the obtained cobalt-containing precursor growing on the carbon cloth into a Tris-HCl buffer solution of dopamine hydrochloride with a certain mass, and stirring for a certain time to obtain the dopamine-coated cobalt precursor with black surface of the carbon cloth.
C) And C) placing the dopamine-coated cobalt precursor obtained in the step b) into a tube furnace, carrying out low-temperature gas-phase phosphating by taking sodium hypophosphite as a phosphorus source according to a certain mass ratio, and simultaneously carbonizing the dopamine coated on the outer layer at the phosphating temperature to obtain the Co x P@N-C/CC (1 < x < 2) flexible integrated lithium ion battery cathode.
The invention provides a method for preparing a Co x P@N-C/CC (1 < x < 2) flexible integrated negative electrode with a unique wire piece interweaving morphology structure and high-capacity and high-stability lithium ion battery performance.
The self-supporting flexible integrated electrode prepared by the invention has excellent flexibility, meets the requirements of flexible batteries, and can prevent active substances from being separated from a current collector. In addition, the ion transmission can be effectively enhanced through the morphology structure of the interweaved wire sheets, and the coating of the nitrogen-doped carbon outer layer can improve the conductivity of the material and relieve the volume expansion of the material in the charge and discharge process, so that the high capacity and the high cycle stability are further realized.
The invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode comprises the self-supporting flexible lithium ion battery negative electrode material.
The kind of the electrode, separator and electrolyte is not particularly limited in the present invention. The cathode can be a lithium sheet, the anode can be a self-supporting flexible integrated electrode directly, the diaphragm can be a polypropylene microporous membrane, and the electrolyte can be a mixed solution of three components of the LiPF 6 of 1M, namely DMC, namely EMC=1:1:1, and adding 1% of FEC, so that the CR2016 analog battery is assembled.
According to the invention, a constant-current charge-discharge experiment is carried out by using 0.2A/g current, and the cycle performance of the lithium ion battery is tested, wherein the charge-discharge voltage range is 0.01-3V. The electrochemical performance of the cells was tested using the CT2001A cell test system from Wuhan City blue electric Co., ltd, and at room temperature. The result shows that the lithium ion battery is charged and discharged at the current density of 0.2A/g, the capacity is stably kept at 1169.1mAh/g after 120 circles of circulation, and the lithium ion battery has ultrahigh capacity and excellent stability.
According to the invention, the cobalt salt is preferably Co (NO 3)2·H2 O, the substance which plays a role of a precipitant is CO (NH 2)2), the molar concentration ratio is preferably 1:4, the ratio of the solvent deionized water to the absolute ethanol is preferably 1:1, the temperature condition of the hydrothermal reaction is preferably 100 ℃, the time condition is preferably 6h, the molar concentration of the Tris-HCl buffer solution is preferably 2.5mM, the volume is 50mL, the mass of dopamine hydrochloride is 25mg, the stirring time is 14h, the ratio of the dopamine-coated cobalt precursor to the phosphorus source is preferably 1:20, the temperature condition is preferably 350 ℃, the time condition is preferably 3h, and the gas is preferably nitrogen.
In order to further illustrate the invention, the following embodiment is provided for a method for preparing a Co x P@N-C/CC (1 < x < 2) flexible integrated negative electrode with a unique wire sheet interweaving morphology and the performance of a high-capacity and high-stability lithium ion battery, but the method cannot be understood as limiting the protection scope of the invention.
Example 1:
In the embodiment, a Co x P@N-C/CC flexible integrated lithium ion battery anode material is formed by forming a cobalt phosphide Co x P and an N-C doped composite material layer on the surface of a tangible flexible carbon material base material CC, wherein the composite material layer has a wire sheet interweaved morphology structure, and 1< x <2 in the cobalt phosphide Co x P.
The preparation method of the Co x P@N-C/CC flexible integrated lithium ion battery anode material comprises the following steps:
a) Preparing Co (mixed solution of NO 3)2·H2 O and CO (NH 2)2) with a molar concentration ratio of 1:4, wherein the solvent is deionized water and absolute ethyl alcohol with a volume ratio of 1:1, uniformly stirring, transferring into a reaction kettle liner, obliquely placing the pretreated carbon cloth into the reaction kettle liner, and performing hydrothermal reaction for 8 hours at 100 ℃ by a hydrothermal synthesis method to synthesize a cobalt-containing precursor growing on the carbon cloth in situ;
b) Weighing 25mg of dopamine hydrochloride, dispersing into 50mL of prepared Tris-HCl buffer solution with the concentration of 2.5mM, immersing the obtained cobalt-containing precursor growing on the carbon cloth into the Tris-HCl buffer solution of dopamine hydrochloride, and stirring for 14h to obtain a dopamine-coated cobalt precursor with black carbon cloth surface;
c) Taking out the product dopamine-coated cobalt precursor obtained in the step b), repeatedly washing and drying the dopamine-coated cobalt precursor by deionized water, then placing the dopamine-coated cobalt precursor in a tube furnace, reacting for 3 hours in a nitrogen atmosphere at 350 ℃ by adopting sodium hypophosphite as a phosphorus source according to the mass ratio of the dopamine-coated cobalt precursor to the phosphorus source of 1:20, carrying out low-temperature gas-phase phosphating, and simultaneously carbonizing the dopamine coated on the outer layer at the phosphating temperature to obtain the Co x P@N-C/CC self-supporting flexible integrated electrode material with a unique line piece interweaving morphology structure.
Experimental test analysis:
XRD of the final product of this example is shown in FIG. 1, and characteristic peaks correspond to CoP (JCPDS: 29-0497) and Co 2 P (JCPDS: 32-0306). The scanning electron microscope image is shown in fig. 2, and the view field shows a structure of interweaving line slices. The self-supporting flexible electrode was subjected to bending test, and as shown in fig. 3, the material was found to have good flexibility characteristics. Raman testing of the product produced, as can be seen in fig. 4, shows a D/AG =3.34, indicating a number of defects in the material. The product was subjected to a charge-discharge cycle test, and the result thereof was shown in FIG. 5, and after 120 cycles of cycle at 0.2A/g, the capacity was maintained at 1169.1mAh/g, exhibiting an ultra-high capacity and excellent cycle stability.
The self-supporting flexible integrated electrode obtained by in-situ growth of active substances by using carbon cloth as a substrate has excellent flexibility, meets the requirements of a flexible battery, and can prevent the active substances from being separated from a current collector in the electrochemical reaction process. In addition, the ion transmission can be effectively enhanced through the morphology structure of the interweaved wire sheets, the nitrogen-doped carbon coating can improve the conductivity of the material and relieve the volume expansion of the material in the charge and discharge process, so that the high capacity and the high cycle stability are further realized.
Example 2
This embodiment is substantially the same as embodiment 1, except that:
in this embodiment, a preparation method of the Co x P@N-C/CC flexible integrated lithium ion battery anode material of this embodiment includes the following steps:
a) Preparing Co (mixed solution of NO 3)2·H2 O and CO (NH 2)2) with a molar concentration ratio of 1:5, wherein the solvent is deionized water and absolute ethyl alcohol with a volume ratio of 1:1, uniformly stirring, transferring into a reaction kettle liner, obliquely placing the pretreated carbon cloth into the reaction kettle liner, and performing hydrothermal reaction for 9 hours at 110 ℃ to synthesize a cobalt-containing precursor growing on the carbon cloth in situ by a hydrothermal synthesis method;
b) Weighing 20mg of dopamine hydrochloride, dispersing into 40mL of prepared Tris-HCl buffer solution with the concentration of 2.0mM, immersing the obtained cobalt-containing precursor growing on the carbon cloth into the Tris-HCl buffer solution of the dopamine hydrochloride, and stirring for 16 hours to obtain a dopamine-coated cobalt precursor with black carbon cloth surface;
c) Taking out the product dopamine-coated cobalt precursor obtained in the step b), repeatedly washing and drying the dopamine-coated cobalt precursor by deionized water, then placing the dopamine-coated cobalt precursor in a tube furnace, reacting for 2 hours in a nitrogen atmosphere at 400 ℃ by adopting sodium hypophosphite as a phosphorus source according to the mass ratio of the dopamine-coated cobalt precursor to the phosphorus source of 1:15, carrying out low-temperature gas-phase phosphating, and simultaneously carbonizing the dopamine coated on the outer layer at the phosphating temperature to obtain the Co x P@N-C/CC self-supporting flexible integrated electrode material with a unique line piece interweaving morphology structure.
Experiments show that the capacity is stably maintained at 1088mAh/g after 120 cycles by performing charge and discharge tests at a current density of 0.2A/g as shown in FIG. 6. The self-supporting flexible integrated electrode obtained by in-situ growth of active substances by using carbon cloth as a substrate has excellent flexibility, meets the requirements of a flexible battery, and can prevent the active substances from being separated from a current collector in the electrochemical reaction process. In addition, the ion transmission can be effectively enhanced through the morphology structure of the interweaved wire sheets, the nitrogen-doped carbon coating can improve the conductivity of the material and relieve the volume expansion of the material in the charge and discharge process, so that the high capacity and the high cycle stability are further realized.
Example 3
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a preparation method of the Co x P@N-C/CC flexible integrated lithium ion battery anode material of this embodiment includes the following steps:
a) Preparing Co (mixed solution of NO 3)2·H2 O and CO (NH 2)2) with a molar concentration ratio of 1:3, wherein the solvent is deionized water and absolute ethyl alcohol with a volume ratio of 1.5:1, uniformly stirring, transferring into a reaction kettle liner, obliquely placing the pretreated carbon cloth therein, and performing hydrothermal reaction for 10 hours at 120 ℃ to synthesize a cobalt-containing precursor growing on the carbon cloth in situ by a hydrothermal synthesis method;
b) 30mg of dopamine hydrochloride is weighed and dispersed into 80mL of prepared Tris-HCl buffer solution with the concentration of 3.0mM, the obtained cobalt-containing precursor growing on the carbon cloth is immersed into the Tris-HCl buffer solution of the dopamine hydrochloride, and then stirring is carried out for 18 hours, so that the dopamine-coated cobalt precursor with black carbon cloth surface is obtained;
c) Taking out the product dopamine-coated cobalt precursor obtained in the step b), repeatedly washing and drying the dopamine-coated cobalt precursor by deionized water, then placing the dopamine-coated cobalt precursor in a tube furnace, reacting for 4 hours in a nitrogen atmosphere at 300 ℃ by adopting sodium hypophosphite as a phosphorus source according to the mass ratio of the dopamine-coated cobalt precursor to the phosphorus source of 1:25, carrying out low-temperature gas-phase phosphating, and simultaneously carbonizing the dopamine coated on the outer layer at the phosphating temperature to obtain the Co x P@N-C/CC self-supporting flexible integrated electrode material with a unique line piece interweaving morphology structure.
Experiments show that the capacity is stably maintained at 1018mAh/g after 120 cycles by performing charge and discharge tests at a current density of 0.2A/g as shown in FIG. 7. The self-supporting flexible integrated electrode obtained by in-situ growth of active substances by using carbon cloth as a substrate has excellent flexibility, meets the requirements of a flexible battery, and can prevent the active substances from being separated from a current collector in the electrochemical reaction process. In addition, the ion transmission can be effectively enhanced through the morphology structure of the interweaved wire sheets, the nitrogen-doped carbon coating can improve the conductivity of the material and relieve the volume expansion of the material in the charge and discharge process, so that the high capacity and the high cycle stability are further realized.
The Co x P@N-C/CC flexible integrated cathode with the unique wire piece interweaving morphology structure is prepared by the embodiment of the invention, and has high capacity and high stability of lithium ion battery performance. Preparing a mixed solution of cobalt salt and precipitant CO (NH 2)2) in a certain molar concentration ratio, immersing carbon cloth into the mixed solution, and synthesizing a cobalt-containing precursor growing on the carbon cloth in situ by a hydrothermal synthesis method, wherein the cobalt salt comprises all cobalt compounds; the cobalt-containing precursor growing on carbon cloth is immersed into Tris-HCl buffer solution of dopamine hydrochloride with a certain mass, stirred for a certain time to obtain the dopamine-coated cobalt precursor on the carbon cloth, and then the obtained dopamine-coated cobalt precursor on the carbon cloth is subjected to low-temperature gas-phase phosphating according to a certain mass ratio by adopting sodium hypophosphite as a phosphorus source, and simultaneously the outer layer-coated dopamine is carbonized to obtain a Co x P@N-C/CC flexible integrated electrode which is used for a lithium ion electrode negative electrode, the Co x P@N-C/CC self-supported flexible electrode prepared by the embodiment of the invention can be directly sliced to serve as the lithium ion battery negative electrode and has a unique linear piece interweaved morphology structure, the structure can effectively enhance ion transmission, and the coated nitrogen-doped carbon outer layer can improve the conductivity of the material and relieve the volume expansion of the material in the charging and discharging process, so that the electrochemical performance experiment of high capacity and high stability is realized, the lithium ion battery assembled by the Co x P@N-C/CC flexible integrated electrode is tested at a current density of 0.2A/g, the current density of the lithium ion battery is tested for a circle of 120 h/1018 m, the capacity of the lithium ion battery is kept at a constant capacity of 348 g/1018 h after the current of the test example is carried out, the current density of the lithium ion battery is kept at a constant capacity of 120 h/3/16/m/3, has high capacity and good stability. Compared with the prior art, the preparation method is simple to operate and low in cost, and the obtained Co x P@N-C/CC flexible integrated electrode is excellent in electrochemical performance, has good flexibility, meets the requirements of flexible batteries, and can be widely applied to other flexible electronic devices.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the embodiments described above, and various changes, modifications, substitutions, combinations or simplifications made under the spirit and principles of the technical solution of the present invention can be made according to the purpose of the present invention, and all the changes, modifications, substitutions, combinations or simplifications should be equivalent to the substitution, so long as the purpose of the present invention is met, and all the changes are within the scope of the present invention without departing from the technical principles and the inventive concept of the present invention.

Claims (10)

1. A Co x P@N-C/CC flexible integrated lithium ion battery anode material is characterized in that a cobalt phosphide Co x P and N-C doped composite material layer is formed on the surface of a tangible flexible carbon material base material CC, the composite material layer is provided with a wire piece interweaved morphology structure, 1< x <2 in cobalt phosphide Co x P, the Co x P@N-C/CC flexible integrated lithium ion battery anode material is prepared by the following steps of preparing a mixed solution of cobalt salt and a precipitator CO (NH 2)2), immersing carbon cloth in the mixed solution, synthesizing a cobalt-containing precursor growing on the carbon cloth in situ through a hydrothermal synthesis method, immersing the obtained cobalt-containing precursor growing on the carbon cloth in a Tris-HCl buffer solution of dopamine hydrochloride, stirring to obtain a dopamine-coated cobalt precursor on the carbon cloth, and carbonizing the obtained dopamine-coated cobalt precursor on the carbon cloth by adopting sodium hypophosphite as a phosphorus source, carrying out low-temperature gas phase phosphating, and carbonizing the dopamine-coated cobalt precursor on the outer layer by using the carbon cloth as a phosphorus source, so as to obtain the integrated lithium ion battery anode electrode, wherein the anode is used for the anode electrode x P@N-C flexible.
2. A method for preparing the Co x P@N-C/CC flexible integrated lithium ion battery anode material according to claim 1, which is characterized by comprising the following steps:
a) Preparing a mixed solution of cobalt salt and a precipitator CO (NH 2)2) by adopting a solvent, immersing the carbon cloth into the mixed solution, and synthesizing a cobalt-containing precursor growing on the carbon cloth in situ by a hydrothermal synthesis method;
b) Immersing the obtained cobalt-containing precursor growing on the carbon cloth into a Tris-HCl buffer solution of dopamine hydrochloride, and then stirring to obtain a dopamine-coated cobalt precursor with black surface of the carbon cloth;
c) And b) placing the dopamine-coated cobalt precursor obtained in the step b) into a tube furnace, adopting sodium hypophosphite as a phosphorus source, carrying out low-temperature gas-phase phosphating, and simultaneously carbonizing the dopamine coated on the outer layer at the phosphating temperature to obtain the Co x P@N-C/CC flexible integrated lithium ion battery anode material.
3. The preparation method of the Co x P@N-C/CC flexible integrated lithium ion battery anode material according to claim 2 is characterized in that in the step a), in the mixed solution, the molar concentration ratio of cobalt salt to precipitant is 1:2-1:6, and the solvent adopted in the mixed solution is a mixed solution of deionized water and absolute ethyl alcohol, wherein the volume ratio of the deionized water to the absolute ethyl alcohol is 1:3-3:1.
4. The method for preparing a cathode material for a Co x P@N-C/CC flexible integrated lithium ion battery according to claim 2, wherein in the step a), at least one of Co (NO 3)2·6H2O、CoCl2·6H2O、CoSO4·7H2 O) is used as the cobalt salt.
5. The method for preparing the Co x P@N-C/CC flexible integrated lithium ion battery anode material according to claim 2, wherein in the step a), the hydrothermal reaction temperature is 100-130 ℃, and the reaction time is 7-12 h.
6. The preparation method of the Co x P@N-C/CC flexible integrated lithium ion battery anode material according to claim 2 is characterized in that in the step b), the mixing ratio of dopamine hydrochloride and Tris-HCl buffer solution is 20~50 mg:40~100 mL, the stirring time is 10-36 h, and the concentration of Tris adopted Tris-HCl buffer solution is 2-5 mM.
7. The method for preparing the Co x P@N-C/CC flexible integrated lithium ion battery anode material according to claim 2, wherein in the step C), low-temperature gas-phase phosphating is carried out according to the mass ratio of the dopamine-coated cobalt precursor obtained in the step b) to a phosphorus source of 1:10-1:40, the phosphorus source adopts sodium hypophosphite, the phosphating temperature condition is 300-400 ℃, the phosphating time is 2-4h, and the adopted gas is any one or the mixed gas of nitrogen and argon.
8. The application of the Co x P@N-C/CC flexible integrated lithium ion battery anode material disclosed in claim 1 in preparing a lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that the negative electrode is prepared from the Co x P@N-C/CC flexible integrated lithium ion battery anode material disclosed in claim 1.
9. The method of claim 8, wherein the lithium ion battery is subjected to a charge-discharge cycle test at a current density of 0.2A/g, and the capacity of the lithium ion battery is kept at not less than 1018 mAh/g after 120 cycles.
10. The method of claim 9, wherein the lithium ion battery is subjected to a charge-discharge cycle test at a current density of 0.2A/g, and the capacity of the lithium ion battery is kept at 1169.1 mAh/g or more after 120 cycles.
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