Phosphorus-metal poly phthalocyanine/carbon composite material and preparation method and application thereof
阅读说明：本技术 一种磷-金属聚酞菁/碳复合材料及其制备方法和应用 (Phosphorus-metal poly phthalocyanine/carbon composite material and preparation method and application thereof ) 是由 文钟晟 孔卫强 徐少峰 崔立英 李嵩 季世军 孙俊才 于 2021-07-30 设计创作，主要内容包括：本发明提供一种磷-金属聚酞菁/碳复合材料及其制备方法和应用,其特征在于,所述复合材料是由红磷、金属聚酞菁和碳材料构成具有良好协同效应的磷-金属聚酞菁/碳复合体系,其中,红磷作为活性中心,金属聚酞菁作为具有电化学储锂活性的电催化助剂,碳材料作为导电网络的基体材料。本发明的制备方法采用简便的高能球磨法,具有制备工艺简单,易规模化的特点,本发明的磷-金属聚酞菁/碳复合负极材料,用作锂离子电池负极,具有较高的可逆比容量、良好的电化学循环性能以及结构稳定性,具有广阔应用前景。(The invention provides a phosphorus-metal poly phthalocyanine/carbon composite material and a preparation method and application thereof, and is characterized in that the composite material is a phosphorus-metal poly phthalocyanine/carbon composite system with good synergistic effect, which is composed of red phosphorus, metal poly phthalocyanine and a carbon material, wherein the red phosphorus is used as an active center, the metal poly phthalocyanine is used as an electrocatalytic auxiliary agent with electrochemical lithium storage activity, and the carbon material is used as a matrix material of a conductive network. The preparation method adopts a simple and convenient high-energy ball milling method, has the characteristics of simple preparation process and easy scale production, and the phosphorus-metal poly phthalocyanine/carbon composite negative electrode material has higher reversible specific capacity, good electrochemical cycle performance and structural stability and wide application prospect when used as a negative electrode of a lithium ion battery.)
1. The composite material is a phosphorus-metal poly phthalocyanine/carbon composite system with good synergistic effect, which is composed of red phosphorus, metal poly phthalocyanine and a carbon material, wherein the red phosphorus is used as an active center, the metal poly phthalocyanine is used as an electrocatalytic additive with electrochemical lithium storage activity, and the carbon material is used as a matrix material of a conductive network.
2. The phosphorus-metal poly phthalocyanine/carbon composite of claim 1,
the phosphorus is elemental red phosphorus;
the metal poly phthalocyanine is poly phthalocyanine taking different metals as centers, wherein the metal refers to one of iron, cobalt, nickel and copper, and is uniformly mixed with red phosphorus and a carbon material;
the carbon material is graphene oxide or activated carbon with the granularity of 100-200 meshes, a carbon nano tube and a mixture thereof.
3. A method for preparing the phosphorus-metal polyphthalocyanine/carbon composite material according to claim 1 or 2, characterized by the steps of:
s1, grinding the elemental red phosphorus;
s2, preparing metal poly phthalocyanine;
s3, uniformly mixing products obtained in the steps S1 and S2 in proportion, and grinding to obtain a phosphorus-metal poly phthalocyanine mixture;
s4, performing ball milling treatment on the phosphorus-metal poly phthalocyanine mixture obtained in the step S3 to obtain a uniform phosphorus-metal poly phthalocyanine composite material;
s5, mixing and grinding the phosphorus-metal poly phthalocyanine composite material obtained in the step S4 and a carbon material in proportion to obtain a relatively uniform phosphorus-metal poly phthalocyanine/carbon mixture;
and S6, treating the phosphorus-metal poly phthalocyanine/carbon mixture obtained in the step S5 by a high-energy ball milling method to obtain the uniform phosphorus-metal poly phthalocyanine/carbon composite material.
4. The method according to claim 3, wherein the step S1 comprises the following steps: and (3) manually grinding the simple substance red phosphorus in an agate mortar for more than 30 minutes under the protection of argon or other inert gases.
5. The method according to claim 3, wherein the step S2 comprises the following steps:
the raw materials for preparing the metal poly phthalocyanine are as follows: the method comprises the following steps of putting the raw materials into an agate mortar according to the preset mass, grinding the raw materials into powder, uniformly mixing the powder, putting the powder into a crucible, and heating in a blast drying oven at the heating rate of 2-5 ℃ for min-1And heating to react at the temperature of 200-230 ℃, keeping the temperature for 2-5 hours, then sequentially leaching the obtained product by using deionized water, ethanol, acetone and tetrahydrofuran solvents, performing suction filtration, and drying the product in a vacuum drying oven at the temperature of 60-80 ℃ for 8-12 hours to obtain the metal poly phthalocyanine.
6. The preparation method according to claim 3, wherein in the step S3, the red phosphorus and the metal poly phthalocyanine are uniformly mixed according to a certain mass ratio of 1: 1-9: 1.
7. The preparation method according to claim 3, wherein in the step S4, the ball milling rotation speed is 300rpm to 500rpm, and the ball milling time is 10h to 30 h.
8. The method according to claim 3, wherein the step S5 comprises the following steps: and (4) manually grinding the phosphorus-metal poly phthalocyanine composite material obtained in the step (S4) and a carbon material in an agate mortar according to the proportion of 1: 1-9: 1 under the protection of argon.
9. The preparation method according to claim 3, wherein in the step S6, the high-energy ball milling method is to perform ball milling under the protection of argon or other inert gases with purity of 99% or more, the ball milling rotation speed is 300-500 rpm, and the ball milling time is 10-30 h.
10. Use of the phosphorus-metal polyphthalocyanine/carbon composite of claim 1 as a negative electrode in a lithium ion battery.
Technical Field
The invention relates to a preparation method and application of a phosphorus-metal poly phthalocyanine/carbon composite negative electrode material, belonging to the field of lithium ion batteries. In particular to a preparation method and application of a metal poly-phthalocyanine red phosphorus active negative electrode material, namely a phosphorus-based composite negative electrode material which can be used as a lithium ion battery negative electrode material and has high reversible capacity and good cycle performance.
Background
Energy is closely related to the survival and development of human society. With the increasing exhaustion of fossil energy, the realization of green sustainable development is becoming a common desire and struggle target of all mankind. The chemical power source has the advantages of excellent performance, convenient use, portability and the like as a novel energy source with the potential of replacing fossil energy, and is increasingly widely applied to various social fields. Among the commonly used chemical power sources, lithium ion batteries have been the main direction of development of secondary batteries as the most promising electrochemical batteries. Compared with other secondary batteries, the lithium ion battery is a novel green secondary battery, has the advantages of high energy density, high working voltage, long cycle life, environmental friendliness and the like, and is widely applied to the fields of various portable electronic devices, electric automobiles, energy storage and the like. In recent years, commercial lithium ion battery negative electrode materials are mainly carbon materials represented by graphite, and the carbon materials have good cycle performance, but have the problems of low theoretical capacity, poor high-rate charge and discharge performance and the like, so that the development of the carbon materials is limited. Therefore, development of a negative electrode material with high capacity, long cycle life and low cost has been a hot point of research.
The red phosphorus exists in an amorphous form in nature, and is cheap and easy to obtain. The red phosphorus is used as a nontoxic cathode material with lithium intercalation activity, and meets the requirement of green sustainable development. In addition, the red phosphorus as the lithium ion battery cathode material has higher theoretical specific capacity (2596mAh g-1), and is a novel cathode material with wide prospect. However, the disadvantages of red phosphorus itself limit its application as a negative electrode material, mainly including the following two aspects: poor electronic conductivity; and (II) the volume expansion is severe in the process of lithium intercalation and deintercalation. These two problems lead to low coulombic efficiency of the red phosphorus anode material, and cause rapid capacity fading, thereby greatly limiting the application of the red phosphorus anode material in the ion battery.
In order to relieve volume expansion and improve conductivity, the following two strategies are mainly adopted for improving the electrochemical performance of the red phosphorus anode material: firstly, preparing a nano-structure red phosphorus material; second, the carbon material is bonded to the carbon material having good conductivity. The nano material can provide a higher specific surface area, shorten the diffusion path of lithium ions in the material and effectively improve the electrochemical performance of the red phosphorus material. The red phosphorus and the carbon material are compounded, so that the conductivity of the red phosphorus can be improved, the volume expansion in the circulation process is effectively relieved, and the structural damage of the active substance is effectively relieved.
The metal poly phthalocyanine is an artificially synthesized metal macrocyclic chelate, the polymer material contains different types of transition metals, nitrogen atoms and carbon atoms, has a graphite-like pi-pi stacking structure, has good chemical and physical stability, can be used as a high-efficiency electrocatalyst with stable performance, improves an electron transmission mechanism, and improves the electrochemical activity of red phosphorus; the poly phthalocyanine can be anchored on the surface of the red phosphorus through a path of surface engineering, so that the direct contact of the red phosphorus and electrolyte is reduced, and the stability of the phosphorus-based material electrode is improved.
Up to now, metal polyphthalocyanines have not been used in electrode materials for lithium ion batteries. According to the invention, a large number of systematic researches at the early stage discover that the electrochemical activity of red phosphorus can be effectively improved by adding a proper amount of metal poly-phthalocyanine as a cocatalyst into the red phosphorus material, and the method has a pioneering significance for improving the performance of the red phosphorus anode material.
Therefore, there is a need to provide a phosphorus-metal poly phthalocyanine/carbon composite material for improving the electrochemical performance of a carbon material or a red phosphorus and carbon composite material as a negative electrode material.
Disclosure of Invention
According to the technical problems of fast capacity attenuation, poor electrode stability and the like of the lithium ion battery cathode material in the prior art, the preparation method and the application of the phosphorus-metal poly phthalocyanine/carbon composite material are provided. The invention relates to a phosphorus-metal poly phthalocyanine/carbon composite system with good synergistic effect, which is composed of red phosphorus, metal poly phthalocyanine and carbon material. In the system, phosphorus is used as an active center, metal poly phthalocyanine is used as an important electrocatalytic assistant, and carbon is used as a matrix material. The metal poly phthalocyanine is compounded with phosphorus through chemical bonding and is used as an electrocatalytic assistant on the surface of the phosphorus to improve the electron transfer performance on the surface of the phosphorus. The addition of the carbon material creates a basic conductive network. The metal poly phthalocyanine has highly conjugated pi electrons, can be attached to carbon materials such as graphene oxide sheet layers and the like through pi-pi stacking, and shows a good synergistic effect.
The technical means adopted by the invention are as follows:
the composite material is a phosphorus-metal poly phthalocyanine/carbon composite system with good synergistic effect, which is composed of red phosphorus, metal poly phthalocyanine and a carbon material, wherein the red phosphorus is used as an active center, the metal poly phthalocyanine is used as an electrocatalytic additive with electrochemical lithium storage activity, and the carbon material is used as a matrix material of a conductive network.
Further, the phosphorus is simple substance red phosphorus, and is used as an electrochemical active lithium desorption center in the charge-discharge process of the phosphorus-metal poly phthalocyanine/carbon negative electrode material to play a main electrochemical reversible lithium storage role;
the metal poly phthalocyanine is poly phthalocyanine taking different metals as centers, wherein the metal refers to one metal element of iron, cobalt, nickel and copper, and is uniformly mixed with red phosphorus and a carbon material, and the metal poly phthalocyanine is uniformly dispersed in the phosphorus-metal poly phthalocyanine/carbon composite material and is chemically bonded with the red phosphorus, so that the electron transfer performance of the surface of the red phosphorus is improved, and the electrochemical activity and the cycle stability of the red phosphorus are improved;
the carbon material is one or a mixture of graphene oxide, activated carbon and carbon nano tubes with the granularity of 100-200 meshes, so that the activity of the metal poly phthalocyanine can be improved, the lithium ion and electronic conductivity of the material can be obviously enhanced, and the mechanical stability of the phosphorus-based negative electrode material can be improved.
The invention also discloses a preparation method for preparing the phosphorus-metal poly phthalocyanine/carbon composite material, which is characterized by comprising the following steps:
s1, grinding the elemental red phosphorus;
s2, preparing metal poly phthalocyanine;
s3, uniformly mixing products obtained in the steps S1 and S2 in proportion, and grinding to obtain a phosphorus-metal poly phthalocyanine mixture;
s4, performing ball milling treatment on the phosphorus-metal poly phthalocyanine mixture obtained in the step S3 to obtain a uniform phosphorus-metal poly phthalocyanine composite material;
s5, mixing and grinding the phosphorus-metal poly phthalocyanine composite material obtained in the step S4 and a carbon material in proportion to obtain a relatively uniform phosphorus-metal poly phthalocyanine/carbon mixture;
s6, performing ball milling treatment on the relatively uniform phosphorus-metal poly phthalocyanine/carbon composite material obtained in the step S5 by a high-energy ball milling method, ensuring that the phosphorus-metal poly phthalocyanine composite material is fully mixed with the carbon material, and uniformly dispersing the phosphorus-metal poly phthalocyanine composite material in the carbon material, wherein the obtained ball milling product is the phosphorus-metal poly phthalocyanine/carbon composite material under certain conditions.
Further, the specific steps of step S1 are as follows: and (3) manually grinding the simple substance red phosphorus in an agate mortar for more than 30 minutes under the protection of argon or other inert gases.
Further, the specific steps of step S2 are as follows:
the raw materials and the mass thereof for preparing the metal poly phthalocyanine are as follows: 4.1g of urea, 0.025g of ammonium molybdate, 1.0g of ammonium chloride and 1g of pyromellitic anhydride74g, 0.3g phthalic anhydride, about 0.005mol metal chloride. The metal chloride can be ferric chloride, cobalt chloride hexahydrate, nickel chloride hexahydrate, copper chloride dihydrate and the like which are soluble in water. Placing the raw materials in an agate mortar, grinding into powder, uniformly mixing, placing in a crucible, and heating in a blast drying oven at a heating rate of 2-5 ℃ for min-1And heating to react at the temperature of 200-230 ℃, keeping the temperature for 2-5 hours, then sequentially leaching the obtained product by using solvents such as deionized water, ethanol, acetone, tetrahydrofuran and the like, performing suction filtration, and drying the product in a vacuum drying oven at the temperature of 60-80 ℃ for 8-12 hours to obtain the metal poly phthalocyanine.
Further, in the step S3, the metal phthalocyanine prepared in the step S2 and the ground simple substance red phosphorus obtained in the step S1 are ground manually in an agate mortar for more than 30 minutes in a certain ratio of 1:1 to 9:1 (different ratios are determined according to the capacity and the stability requirement) under the protection of argon or other inert gases, so that the metal phthalocyanine and the ground simple substance red phosphorus obtained in the step S1 are premixed uniformly, and the phosphorus-metal phthalocyanine premix is obtained.
Further, in the step S4, the ball milling rotation speed is 300rpm to 500rpm, and the ball milling time is 10h to 30 h.
Further, the specific steps of step S5 are as follows: and (4) manually grinding the phosphorus-metal poly phthalocyanine composite material obtained in the step (S4) and a carbon material in a ratio of 1: 1-9: 1 (different ratios are determined according to the capacity and stability requirements) in an agate mortar under the protection of argon.
Further, in the step S6, the high-energy ball milling method is to perform ball milling under the protection of argon or other inert gases with a purity of 99% or more, wherein the ball milling rotation speed is 300rpm to 500rpm, and the ball milling time is 10h to 30 h.
The invention also discloses an application of the phosphorus-metal poly phthalocyanine/carbon composite material as a lithium ion battery cathode.
Compared with the prior art, the invention has the following advantages:
the invention adopts metal poly phthalocyanine as an effective electrocatalytic additive of a phosphorus-based material and an effective component with lithium storage performance, and prepares the phosphorus-metal poly phthalocyanine/carbon composite material with high electrochemical activity and long-term electrochemical stability by adopting a simple ball milling method.
The metal poly phthalocyanine is used as a component similar to a graphite layered structure, is uniformly mixed with red phosphorus by a high-energy ball milling method, and is partially chemically bonded with the red phosphorus, so that the decomposition of an electrolyte on the surface of the phosphorus can be effectively reduced, and the electron transfer rate of the red phosphorus can be remarkably improved. The metal poly phthalocyanine synthesized by the invention has electrochemical lithium-intercalation activity, and the active sites of the metal poly phthalocyanine are distributed on the surface of phosphorus, so that the reactivity of red phosphorus can be effectively enhanced, and the electrochemical activity and the electrochemical cycling stability of the phosphorus-based negative electrode material are further improved.
In addition, metal polyphthalocyanine has highly conjugated pi electrons and is easily attached to a carbon material such as a graphene oxide sheet layer by a strong pi-pi stacking effect, and thus the carbon material and the metal polyphthalocyanine also exhibit an excellent synergistic effect.
In conclusion, the synergistic effect of the phosphorus, the carbon material and the metal poly phthalocyanine obviously improves the electrochemical performance of the phosphorus-metal poly phthalocyanine/carbon composite material, so that the phosphorus-metal poly phthalocyanine/carbon composite material constructed and prepared by the invention has good electrochemical cycle performance.
The preparation method provided by the invention is very simple, and the composite material prepared by the method has excellent compatibility and structural stability and can exert a good synergistic effect among components. The material has high batch stability, is easy to realize mass production, and can be widely popularized in the fields of lithium ion batteries and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an XRD pattern of the phosphorus-cobalt polyphthalocyanine/graphene oxide composite prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the phosphorus-cobalt polyphthalocyanine/graphene oxide composite material prepared in example 1 of the present invention, wherein the scale is 200 nm.
FIG. 3 is a charge-discharge curve diagram of an assembled negative electrode sheet of the phosphorus-cobalt poly-phthalocyanine/graphene oxide composite prepared in example 1 of the present invention, wherein the abscissa is the specific capacity (mAh g) of the material-1) And the ordinate is the voltage (V).
FIG. 4 is a cycle life test chart of an assembled negative electrode sheet of the phosphorus-cobalt poly-phthalocyanine/graphene oxide composite material prepared in example 1 of the present invention, wherein the abscissa is the cycle number, and the left ordinate represents the specific charge-discharge capacity (mAh g) of the material-1) The right ordinate represents the coulombic efficiency (%) of the cycle.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the following examples, the method for preparing the negative electrode sheet by using the phosphorus-metal poly phthalocyanine/graphene oxide composite negative electrode material of the present invention is as follows:
dissolving polyvinylidene fluoride (binder) in N-methyl pyrrolidone to prepare a 0.03 g/ml N-methyl pyrrolidone solution of polyvinylidene fluoride; phosphorus-metal poly phthalocyanine/graphene oxide composite negative electrode material (active substance), acetylene black (conductive agent) and polyvinylidene fluoride solution are mixed according to the following active substance: conductive agent: uniformly mixing the binder in a mass ratio of 6:2:2, coating the mixture on a copper foil with the thickness of 9 microns, transferring the copper foil into a vacuum oven, and drying the copper foil in vacuum for 10 hours at 80 ℃ and then taking out the copper foil; and cutting the dried copper foil into a wafer with the diameter of 16mm to obtain the phosphorus-metal poly phthalocyanine/graphene oxide composite negative electrode material negative electrode sheet for electrochemical test. The cathode plate and metal Li are directly used as counter electrodes to assemble a button cell to test the electrochemical performance, and the electrolyte is LiPF6/EC: DEC (1:1, volume ratio). The current density of the charge and discharge is tested to be 200mA g-1And the cut-off charge-discharge voltage is 0.02V-2.5V. The discharging process corresponds to the process of lithium ion intercalation into the phosphorus-based material composite electrode, and the charging process corresponds to the process of lithium ion deintercalation.
Example 1
(1) Grinding red phosphorus in a glove box, and refining particles;
(2) weighing 4.1g of urea, 0.025g of ammonium molybdate, 1.0g of ammonium chloride, 1.74g of pyromellitic anhydride, 0.3g of phthalic anhydride and 1.2g of cobalt chloride hexahydrate, putting the raw materials into an agate mortar, grinding the raw materials into powder, uniformly mixing the powder, putting the powder into a crucible, and heating the mixture in a blast drying oven at the heating rate of 5 ℃ for min-1And heating to react at 220 ℃ for 3h, leaching the obtained product for multiple times by using solvents such as deionized water, ethanol, acetone, tetrahydrofuran and the like, performing suction filtration, and drying the product in a vacuum drying oven at 80 ℃ for 12h to obtain the cobalt phthalocyanine.
(3) Grinding 1.4g of red phosphorus and 0.6g of metal cobalt poly phthalocyanine in a mortar according to the mass ratio of 7:3, and uniformly mixing to obtain a uniform phosphorus-cobalt poly phthalocyanine mixture for later use;
(4) adding 2g of phosphorus-cobalt poly phthalocyanine mixture into a ball milling tank, and carrying out ball milling treatment under the following ball milling conditions: the ball milling speed is 480rpm, the ball milling time is 10 hours, and the phosphorus-cobalt phthalocyanine and the composite material are prepared for standby;
(5) adding 0.7g of phosphorus-cobalt poly phthalocyanine composite material and 0.3g of graphene oxide into a mortar, and grinding and mixing uniformly;
(6) adding the mixture of the phosphorus-cobalt poly phthalocyanine and the graphene oxide in the step (5) into a ball milling tank for ball milling treatment, wherein the ball milling conditions are as follows: the ball milling speed is 480rpm, the ball milling time is 10 hours, and the phosphorus-cobalt poly phthalocyanine/graphene oxide composite material (shown in figures 1 and 2) is prepared for later use;
the phosphorus-cobalt phthalocyanine/graphene oxide composite negative electrode material under the auxiliary catalysis of cobalt phthalocyanine prepared in the embodiment comprises a phosphorus active center and graphene oxide, and a proper amount of cobalt phthalocyanine is used as an auxiliary catalyst.
The process of assembling the target product obtained in the embodiment into the electrode sheet is as follows: dissolving polyvinylidene fluoride (binder) in N-methyl pyrrolidone to prepare a 0.03 g/ml N-methyl pyrrolidone solution of polyvinylidene fluoride; uniformly mixing a phosphorus-cobalt poly phthalocyanine/graphene oxide composite negative electrode material (active substance), acetylene black (conductive agent) and a polyvinylidene fluoride solution according to the mass ratio of the active substance to the conductive agent to a binder of 6:2:2, coating the mixture on a copper foil with the thickness of 9 microns, and taking out the copper foil after the copper foil is placed into a vacuum oven and is dried for 10 hours in vacuum at the temperature of 80 ℃; and cutting the dried copper foil into a wafer with the diameter of 16mm to obtain the phosphorus-cobalt poly phthalocyanine/graphene oxide composite negative electrode material negative electrode sheet for the electrochemical test. The cathode plate and metal Li are directly used as counter electrodes to assemble a button cell to test the electrochemical performance, and the electrolyte is LiPF6/EC: DEC (1:1, volume ratio). The current density of the charge and discharge is tested to be 200mA g-1And the cut-off charge-discharge voltage is 0.02V-2.5V. The discharging process corresponds to the process of lithium ion intercalation into the phosphorus-based material composite electrode, and the charging process corresponds to the process of lithium ion deintercalation.
The first reversible capacity of the prepared electrode reaches 3393.6mAh g-1. Fig. 3 is a charge-discharge curve diagram of a negative electrode sheet assembled with the target product prepared in this example.
As shown in FIG. 4, the prepared electrode still maintains good electrochemical performance after 50 times of circulation, and the reversible capacity is 1367.2mAh/g-1。
Example 2
(1) Grinding red phosphorus in a glove box, and refining particles;
(2) weighing 4.1g of urea, 0.025g of ammonium molybdate, 1.0g of ammonium chloride, 1.74g of pyromellitic anhydride, 0.3g of phthalic anhydride and 1.2g of nickel chloride hexahydrate, putting the raw materials into an agate mortar, grinding the raw materials into powder, uniformly mixing the powder, putting the powder into a crucible, and heating the mixture in a blast drying oven at the heating rate of 5 ℃ for min-1And heating to react at 220 ℃ for 3h, leaching the obtained product for multiple times by using solvents such as deionized water, ethanol, acetone, tetrahydrofuran and the like, performing suction filtration, and drying the product in a vacuum drying oven at 80 ℃ for 12h to obtain the nickel poly phthalocyanine.
(3) Grinding 1.0g of phosphorus and 1.0g of nickel poly phthalocyanine in a mortar according to the mass ratio of 1:1, and uniformly mixing to obtain a uniform phosphorus-cobalt poly phthalocyanine mixture for later use;
(4) adding 2g of phosphorus-nickel poly phthalocyanine mixture into a ball milling tank, and carrying out ball milling treatment under the following ball milling conditions: the rotating speed of a motor is 450rpm, the ball milling time is 15 hours, and the phosphorus-cobalt phthalocyanine composite material is prepared for standby;
(5) adding 0.9g of phosphorus-nickel poly phthalocyanine composite material and 0.1g of carbon nano tube into a mortar, grinding and mixing uniformly;
(6) adding the mixture of the phosphorus-nickel poly phthalocyanine and the carbon nano tube in the step (5) into a ball milling tank for ball milling treatment, wherein the ball milling conditions are as follows: the rotating speed of a motor is 450rpm, the ball milling time is 15 hours, and the phosphorus-nickel poly phthalocyanine/carbon nano tube composite material is prepared for later use;
the process of assembling the obtained product into an electrode plate and the electrochemical test process are the same as those of example 1, and the first reversible capacity of the prepared electrode reaches 1548.6mAh g-1(ii) a The prepared electrode has reversible capacity of 657.9mAh g after being circulated for 50 times-1。
Example 3
(1) Grinding red phosphorus in a glove box, and refining particles;
(2) weighing 4.1g of urea, 0.025g of ammonium molybdate, 1.0g of ammonium chloride, 1.74g of pyromellitic anhydride, 0.3g of phthalic anhydride and 0.85g of copper chloride dihydrate, placing the above raw materials in an agate mortar, grinding into powder,mixing, placing in a crucible, and heating in a forced air drying oven at a heating rate of 5 deg.C for min-1And heating to react at 220 ℃ for 3h, leaching the obtained product for multiple times by using solvents such as deionized water, ethanol, acetone, tetrahydrofuran and the like, performing suction filtration, and drying the product in a vacuum drying oven at 80 ℃ for 12h to obtain the cobalt phthalocyanine.
(3) Grinding 1.8g of phosphorus and 0.2g of copper poly phthalocyanine in a mortar according to the mass ratio of 9:1, and uniformly mixing to obtain a uniform phosphorus-cobalt poly phthalocyanine mixture for later use;
(4) adding 2g of phosphorus-copper poly phthalocyanine mixture into a ball milling tank, and carrying out ball milling treatment under the following ball milling conditions: the rotating speed of a motor is 400rpm, the ball milling time is 20 hours, and the phosphorus-cobalt poly phthalocyanine composite material is prepared for later use;
(5) adding 0.5g of phosphorus-copper poly phthalocyanine composite material and 0.5g of activated carbon into a mortar, and grinding and mixing uniformly;
(6) adding the mixture of the phosphorus-copper poly phthalocyanine and the activated carbon in the step (5) into a ball milling tank for ball milling treatment, wherein the ball milling conditions are as follows: the rotating speed of a motor is 400rpm, the ball milling time is 20 hours, and the phosphorus-copper poly phthalocyanine/activated carbon composite material is prepared for later use;
the process of assembling the obtained product into an electrode plate and the electrochemical test process are the same as those of example 1, and the first reversible capacity of the prepared electrode reaches 1883.5mAh g-1。
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.