CN112397696A - Bimetallic phosphide/carbon material, negative electrode material, lithium ion battery and method - Google Patents
Bimetallic phosphide/carbon material, negative electrode material, lithium ion battery and method Download PDFInfo
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- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- 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
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Abstract
The embodiment of the application provides a bimetallic phosphide/carbon material, a negative electrode material, a lithium ion battery and a method, wherein the morphology of the bimetallic phosphide/carbon material is a uniform three-dimensional porous structure, and the molecular formula of the bimetallic phosphide/carbon material is AxByP/C, wherein A and B are different transition metal elements respectively, x is used for representing the content of the transition metal A, and y is used for representing the content of the transition metal B. The three-dimensional ordered pore bimetal phosphide/carbon lithium ion battery cathode material provided by the embodiment of the application has the advantages of high specific capacity, long cycle life and multiplying powerThe method has the advantage of good performance.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a bimetallic phosphide/carbon material, a negative electrode material, a lithium ion battery and a method.
Background
The lithium ion battery is a novel efficient chemical power supply, has the advantages of large energy density, long cycle life, high working voltage, no memory effect, small self-discharge, wide working temperature range and the like, is an ideal chemical power supply for various portable electronic products at present, is also an optimal power supply for future electric vehicles, and has wide application space and economic value.
Lithium ion batteries generally consist of a positive electrode, a negative electrode and an electrolyte. When the lithium ion battery is charged, lithium ions are generated on the positive electrode of the battery, the generated lithium ions move to the negative electrode through the electrolyte, and the lithium ions reaching the negative electrode are embedded into the negative electrode, wherein the more the number of the lithium ions embedded into the negative electrode is, the higher the charging capacity is; when the lithium ion battery is discharged, lithium ions embedded in the negative electrode are detached and return to the positive electrode through the electrolyte, wherein the more the lithium ions return to the positive electrode, the higher the discharge capacity. That is, the capacity performance of the negative electrode material in a lithium ion battery has an important influence on the energy density of the lithium ion battery.
Transition metal phosphides are often used as negative electrode materials for lithium ion batteries because of their high theoretical capacity. However, the transition metal phosphide has poor conductivity, and has a large volume change in the process of lithium ion intercalation/deintercalation, which has a certain influence on the charge and discharge performance of the lithium ion battery.
Disclosure of Invention
The embodiment of the application provides a bimetal phosphide/carbon material, a negative electrode material, a lithium ion battery and a method, which are beneficial to solving the problems that in the prior art, the conductivity of transition metal phosphide is poor, and the volume change is large in the process of lithium ion intercalation/deintercalation, so that the performance of the lithium ion battery is influenced.
In a first aspect, the present disclosure provides a bimetallic phosphide/carbon material, wherein the morphology of the bimetallic phosphide/carbon material is a uniform three-dimensional porous structure, and the molecular formula of the bimetallic phosphide/carbon material is AxByP/C, where a and B are different transition metal elements, x is used to represent the content of a transition metal a, and y is used to represent the content of a transition metal B.
Preferably, the transition metal A is cobalt, iron or nickel; the transition metal B is molybdenum or tungsten.
Preferably, 0.25. ltoreq. x.ltoreq.1, 0.25. ltoreq. y.ltoreq.1.
Preferably, the three-dimensional porous structure comprises macropores and mesopores, the diameter of the macropores is 50-500 nm, and the diameter of the mesopores is 10-30 nm.
In a second aspect, the present application provides a lithium ion battery negative electrode material, including a coating layer, where the coating layer is a mixture of the bimetallic phosphide/carbon material, the binder and the carbon black described in any one of the above first aspects.
Preferably, the ratio of bimetallic phosphide/carbon material, binder and carbon black is 7:2: 1.
In a third aspect, an embodiment of the present application provides a method for preparing a negative electrode material of a lithium ion battery, including:
mixing the bimetallic phosphide/carbon material of any one of the above first aspects, a binder and carbon black to obtain a mixture;
and coating the mixture to obtain a coating layer, wherein the coating layer is a lithium ion battery negative electrode material.
In a fourth aspect, an embodiment of the present application provides a lithium ion battery, which includes a negative electrode, and the negative electrode is prepared by using the lithium ion battery negative electrode material described in any one of the first aspects.
In a fifth aspect, embodiments of the present application provide a method for preparing a bimetallic phosphide/carbon material, comprising:
dissolving a transition metal A salt and a transition metal B salt in water to obtain a mixed solution of the transition metal A salt and the transition metal B salt;
dissolving diammonium phosphate in water to obtain a diammonium phosphate solution;
adding the diammonium phosphate solution into the mixed solution of the transition metal A salt and the transition metal B salt, then adding citric acid, and stirring to a gel state to obtain a first gel;
dispersing silicon dioxide in ethanol, adding the silicon dioxide into the first gel, and continuously stirring to obtain a second gel;
drying the second gel and grinding into powder;
calcining the powder and removing silica with sodium hydroxide to obtain the bimetallic phosphide/carbon material of any one of the first aspect.
Preferably, the transition metal A salt is nitrate and/or chloride salt of cobalt, iron or nickel element; the transition metal B salt is ammonium salt of molybdenum or tungsten element, acetylacetone salt, isopolyacid and/or ammonium phosphate salt.
Preferably, the method satisfies one or a combination of the following conditions:
the molar ratio of the transition metal A salt to the transition metal B salt is 0.4: 1-1: 4;
the molar ratio of the transition metal A salt to the phosphorus is 0.5: 1-1: 4;
the molar ratio of the citric acid to the transition metal A salt is 0.1: 1-40: 1;
the mass ratio of the silicon dioxide to the citric acid is 1: 1-4: 1.
Preferably, the diammonium phosphate solution is added into the mixed solution of the transition metal A salt and the transition metal B salt, then citric acid is added, and the mixture is stirred to a gel state, so as to obtain a first gel, which comprises:
and adding the diammonium phosphate solution into the mixed solution of the transition metal A salt and the transition metal B salt, then adding citric acid, and stirring to a gel state under the condition of oil bath at 70-90 ℃ to obtain a first gel.
Preferably, the second gel is dried and ground into a powder comprising:
and transferring the second gel into a porcelain boat, drying at 90-120 ℃ for 10-15 h, drying, and grinding into powder.
The technical scheme provided by the embodiment of the application has the following advantages:
1. the three-dimensional porous structure in the bimetallic phosphide/carbon material improves the specific surface area of the material, thereby effectively increasing the contact area of the active substance and the electrolyte and shortening the diffusion path of lithium ions;
2. because the lithium ions are continuously inserted and removed in the battery circulation process, the three-dimensional porous structure can effectively relieve the volume expansion of the battery in the battery circulation process, so that the electrode material is not easily pulverized in the circulation process, and the circulation life of the electrode material is effectively prolonged;
3. the carbon in the bimetallic phosphide/carbon can improve the conductivity of the bimetallic phosphide/carbon and provide more active sites, so that the bimetallic phosphide/carbon material shows excellent rate capability and higher specific capacity.
Therefore, the three-dimensional ordered pore bimetal phosphide/carbon lithium ion battery cathode material provided by the embodiment of the application has the advantages of high specific capacity, long cycle life and good rate capability.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a bimetallic phosphide/carbon material provided in an example of the present application;
FIG. 2 is a schematic flow chart of a method for preparing a bimetallic phosphide/carbon material according to an embodiment of the present application;
FIG. 3 is an XRD pattern of a cobalt molybdenum phosphorus/carbon material provided in accordance with an embodiment of the present application;
fig. 4 is a schematic flow chart of a method for preparing a negative electrode material of a lithium ion battery according to an embodiment of the present disclosure;
fig. 5 is a schematic view of cycle life of a lithium ion battery provided in an embodiment of the present application.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Referring to fig. 1, a schematic structural diagram of a negative electrode material of a lithium ion battery provided in an embodiment of the present application is shown. The lithium ion battery negative electrode material shown in fig. 1 is a bimetallic phosphide/carbon material, the morphology of the bimetallic phosphide/carbon material is a uniform three-dimensional porous structure, the chemical formula of the bimetallic phosphide/carbon material is AxByP/C, wherein A and B are different transition metal elements respectively, x is used for representing the content of a transition metal A, and y is used for representing the content of a transition metal B.
In an alternative embodiment, the transition metal a is cobalt Co, iron Fe, or nickel Ni element; the transition metal B is molybdenum Mo or tungsten W.
In an alternative embodiment, the transition metal a and transition metal B are present in the following amounts: x is more than or equal to 0.25 and less than or equal to 1, and y is more than or equal to 0.25 and less than or equal to 1.
In an optional embodiment, the three-dimensional porous structure comprises macropores and mesopores, the diameter of the macropores is 50-500 nm, and the diameter of the mesopores is 10-30 nm.
The lithium ion battery negative electrode material provided by the embodiment of the application has the following advantages:
1. the three-dimensional porous structure in the bimetallic phosphide/carbon material improves the specific surface area of the material, thereby effectively increasing the contact area of the active substance and the electrolyte and shortening the diffusion path of lithium ions;
2. because the lithium ions are continuously inserted and removed in the battery circulation process, the three-dimensional porous structure can effectively relieve the volume expansion of the battery in the battery circulation process, so that the electrode material is not easily pulverized in the circulation process, and the circulation life of the electrode material is effectively prolonged;
3. the carbon in the bimetallic phosphide/carbon can improve the conductivity of the bimetallic phosphide/carbon and provide more active sites, so that the bimetallic phosphide/carbon material shows excellent rate capability and higher specific capacity.
Therefore, the three-dimensional ordered pore bimetal phosphide/carbon lithium ion battery cathode material provided by the embodiment of the application has the advantages of high specific capacity, long cycle life and good rate capability.
Corresponding to the lithium ion battery negative electrode material, the embodiment of the present application further provides a preparation method of a lithium ion battery negative electrode material, specifically, the lithium ion battery negative electrode material is prepared by using a sol-gel method, using transition metal salt, diammonium hydrogen phosphate (NH4)2HPO4, and citric acid as raw materials, and using silica SiO2 as a template, and the following detailed description is provided with reference to the accompanying drawings.
Referring to fig. 2, a schematic flow chart of a preparation method of a negative electrode material of a lithium ion battery provided in an embodiment of the present application is shown in fig. 2, which mainly includes the following steps.
Step S201: and dissolving the transition metal A salt and the transition metal B salt in water to obtain a mixed solution of the transition metal A salt and the transition metal B salt.
Specifically, the transition metal A salt is nitrate and/or chloride of cobalt Co, iron Fe or nickel Ni element; the transition metal B salt is ammonium salt, acetylacetone salt, isopolyacid and/or ammonium phosphate salt of molybdenum Mo or tungsten W element.
In an optional embodiment, the molar ratio of the transition metal A salt to the transition metal B salt is 0.4:1 to 1: 4. Among them, the transition metal A is beneficial to improve the theoretical lithium storage capacity of the material, but too high content thereof can reduce the conductivity of the material, and too low content thereof can result in lower theoretical capacity of the material, so that, in a preferred embodiment, the molar ratio of the transition metal A salt to the transition metal B salt is 1: 1.
Step S202: dissolving diammonium phosphate in water to obtain a diammonium phosphate solution.
Step S203: and adding the diammonium phosphate solution into the mixed solution of the transition metal A salt and the transition metal B salt, then adding citric acid, and stirring to a gel state to obtain a first gel.
Specifically, the diammonium phosphate solution is added into the mixed solution of the transition metal A salt and the transition metal B salt, then citric acid is added, and the mixture is stirred to be in a gel state under the condition of oil bath at the temperature of 70-90 ℃ to obtain a first gel.
Wherein the molar ratio of the transition metal A salt to the phosphorus P is 0.5: 1-1: 4. Because the bimetallic phosphide material mainly stores electrons and charges by the reaction of P and Li, if the proportion of P is too low, the transferred electrons are less, the stored lithium is less, and the theoretical capacity is reduced, therefore, the preferred molar ratio of the transition metal A salt to the phosphorus P is 1: 1.
The molar ratio of the citric acid to the transition metal A salt is 0.1: 1-40: 1. Wherein if the ratio is too high, too high a content of citric acid derived carbon will reduce the specific capacity of the overall material, and if the ratio is too low, citric acid will not complex the transition metal a salt and the transition metal B salt well, so the preferred molar ratio of citric acid to transition metal a salt is 4: 1.
Step S204: dispersing silicon dioxide in ethanol, adding the silicon dioxide into the first gel, and continuously stirring to obtain a second gel.
Wherein the mass ratio of the silicon dioxide SiO2 to the citric acid is 1: 1-4: 1. If the using amount of the SiO2 is too small, a uniform ordered three-dimensional pore structure cannot be formed; if the amount of SiO2 is too high, it will be costly to remove it in a later step. Thus, the preferred mass ratio of silica SiO2 to citric acid is 1.2: 1. In an alternative embodiment, the diameter of the SiO2 is preferably 50-500 nm.
Step S205: the second gel was dried and ground to a powder.
Specifically, the second gel is transferred to a porcelain boat, dried for 10-15 hours at 90-120 ℃, and ground into powder. Preferably, the drying temperature is controlled to be 60-110 ℃.
Step S206: calcining the powder, and removing silica with sodium hydroxide to obtain the bimetallic phosphide/carbon material.
Specifically, if the calcination temperature is too high or too low, the synthesized material is not a pure phase, and therefore, the calcination temperature is controlled to be 500-900 ℃. In addition, the heating rate is 2-5 ℃/min, the calcination time is 1-8H, and the used protective gas is Ar/H2.
In order to facilitate understanding, the embodiment of the application provides a specific implementation mode of a preparation method of a cobalt-molybdenum-phosphorus/carbon material. It should be noted that the following is only a specific implementation manner, and should not be taken as a limitation of the protection scope of the present application, and the person skilled in the art can make appropriate adjustments according to actual needs, and all should fall within the protection scope of the present application.
The first embodiment is as follows:
1.164g of Co (NO3) 2. H2O was dissolved in 5mL of water, and 0.7062g of (NH4)2MoO4 was dissolved in 5mL of water, and the two solutions were mixed. 0.524g (NH4)2HPO4 was weighed out and dissolved in 15mL of water, and then the above mixed solution was added. Magnetic stirring was continued and 1.5288g of citric acid were added. The solution was stirred in an oil bath at 90 ℃ until it became a gel. 1.56g of SiO2 was dispersed in 5mL of ethanol and added to the above gel and stirring was continued in the oil bath until a homogeneous gel was obtained. The gel was transferred to a porcelain boat, dried at 110 ℃ for 12h, and ground to a powder. 0.8g of the powder is taken and transferred into a tube furnace, and is calcined for 5h at 850 ℃ in the argon-hydrogen atmosphere, and the temperature rising rate of the calcination is 5 ℃/min. And finally, removing SiO2 by using sodium hydroxide to obtain the three-dimensional ordered pore cobalt molybdenum phosphorus/carbon material.
Fig. 3 is an XRD pattern of cobalt molybdenum phosphorus/carbon material provided in the present application, wherein XRD refers to X-ray diffraction, and the diffraction signal of X-ray in the crystal is used to analyze the crystal structure. The abscissa 2 θ (degree) in fig. 3 is the 2 θ position of the diffraction peak, representing the diffraction angle, in degrees; intensity of diffraction for each angle is given by the ordinate (a.u.); the lowest vertical line in fig. 3 is a standard card of cobalt molybdenum phosphorus; the upper curve in fig. 3 is the peak position and diffraction intensity of the tested material. As can be seen from the figure, the peak goodness of fit of the material prepared by the method and a standard card is higher, which indicates that the prepared cobalt-molybdenum-phosphorus/carbon material is a pure phase.
Example two:
0.7768g (NH4)2MoO4 was weighed out and dissolved in 5mL of water, 1.2804g Co (NO3) 2. H2O was weighed out and dissolved in 5mL of water, and the above solutions were mixed. 0.5764g (NH4)2HPO4 was dissolved in 15mL of water, and the above mixed solution was added. The solution was mixed well by magnetic stirring, 1.6817g of citric acid was added, the mixture was oil-bathed at 90 ℃ until it became a gel, 1.716g of SiO2 was dispersed in 5mL of ethanol and then added to the gel, and stirring was continued in the oil bath until it became a homogeneous gel. The gel was transferred to a porcelain boat, dried at 110 ℃ for 12h, and ground to a powder. 0.8g of the powder is taken and transferred into a tube furnace, and is calcined for 5h at 850 ℃ in the argon-hydrogen atmosphere, and the temperature rising rate of the calcination is 5 ℃/min. And finally, removing SiO2 by using sodium hydroxide to obtain the three-dimensional ordered pore cobalt molybdenum phosphorus/carbon material. The obtained cobalt molybdenum phosphorus/carbon material sample is tested by SEM (scanning electron microscope), and as shown in figure 1, the prepared cobalt molybdenum phosphorus has uniform three-dimensional ordered pore diameter.
The difference between the examples of the present application and the first example is that the concentration of each raw material aqueous solution is increased, which indicates that the same proportion of increase in concentration within a certain range does not affect the preparation result.
Example three:
1.3968g of Co (NO3) 2. H2O was dissolved in 5.5mL of water, and 0.8474g of (NH4)2MoO4 was dissolved in 5.5mL of water, and the above solutions were mixed. 0.6288g of (NH4)2HPO4 was dissolved in 16mL of water, and the (NH4)2HPO4 solution was added to the above mixed solution. The solution was homogenized by magnetic stirring and 1.8346g of citric acid were added. The solution was oil-bathed at 90 ℃ to a gel state, 1.872g of SiO2 was dispersed in 6mL of ethanol, and then added to the gel, and stirring was continued in the oil bath until a uniform gel was obtained. The gel was transferred to a porcelain boat, dried at 110 ℃ for 12h, and ground to a powder. 0.8g of the powder is taken and transferred into a tube furnace, and is calcined for 5h at 850 ℃ in the argon-hydrogen atmosphere, and the temperature rising rate of the calcination is 5 ℃/min. And finally, removing SiO2 by using sodium hydroxide to obtain the three-dimensional ordered pore cobalt molybdenum phosphorus/carbon material.
The difference between the examples of the present application and the first example is that the amount of each raw material is increased, which indicates that the amount of raw material expanded in equal proportion has no influence on the preparation result.
Based on the above bimetallic phosphide/carbon material, an embodiment of the present application further provides a lithium ion battery negative electrode material, where the lithium ion battery negative electrode material includes a coating layer, and the coating layer is a mixture of the bimetallic phosphide/carbon material, a binder and carbon black shown in fig. 1. Preferably, the ratio of bimetallic phosphide/carbon material, binder and carbon black is 7:2: 1.
Corresponding to the lithium ion battery cathode material, the embodiment of the application also provides a preparation method of the lithium ion battery cathode material. Referring to fig. 4, a schematic flow chart of a preparation method of a negative electrode material of a lithium ion battery provided in an embodiment of the present application is shown in fig. 4, which mainly includes the following steps.
Step S401: the bimetallic phosphide/carbon material, binder and carbon black are mixed to obtain a mixture.
Specifically, the bimetallic phosphide/carbon material is the bimetallic phosphide/carbon material shown in fig. 1, and preferably, the ratio of the bimetallic phosphide/carbon material, the binder and the carbon black is 7:2: 1.
Step S402: and coating the mixture to obtain a coating layer, wherein the coating layer is a lithium ion battery negative electrode material.
Based on the lithium ion battery cathode material, the embodiment of the application also provides a lithium ion battery, the lithium ion battery comprises a cathode, and the cathode is prepared from the lithium ion battery cathode material of the embodiment.
Fig. 5 is a schematic diagram of Cycle life of a lithium ion battery provided in an embodiment of the present application, and a lithium ion battery assembled from the lithium ion battery negative electrode material has a Cycle performance as shown in fig. 5 at a current density of 1000mA/g, where a Cycle number on an abscissa is a number of cycles of the battery, one Cycle of discharge and charge is one Cycle, and a Specific capacity on an ordinate is a Specific capacity corresponding to each Cycle of the battery, and a unit is mAh/g. As shown in fig. 5, the lithium ion battery still maintains the specific capacity of 696mAh/g after 900 cycles of cycling, shows high specific capacity and excellent cycling performance, and shows that the three-dimensional ordered pore cobalt molybdenum phosphorus/carbon material is an excellent lithium storage material.
The technical scheme provided by the embodiment of the application has the following advantages:
1. the three-dimensional porous structure in the bimetallic phosphide/carbon material improves the specific surface area of the material, thereby effectively increasing the contact area of the active substance and the electrolyte and shortening the diffusion path of lithium ions;
2. because the lithium ions are continuously inserted and removed in the battery circulation process, the three-dimensional porous structure can effectively relieve the volume expansion of the battery in the battery circulation process, so that the electrode material is not easily pulverized in the circulation process, and the circulation life of the electrode material is effectively prolonged;
3. the carbon in the bimetallic phosphide/carbon can improve the conductivity of the bimetallic phosphide/carbon and provide more active sites, so that the bimetallic phosphide/carbon material shows excellent rate capability and higher specific capacity.
Therefore, the three-dimensional ordered pore bimetal phosphide/carbon lithium ion battery cathode material provided by the embodiment of the application has the advantages of high specific capacity, long cycle life and good rate capability.
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above description is merely exemplary of the present application and is presented to enable those skilled in the art to understand and practice the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The bimetal phosphide/carbon material is characterized in that the shape of the bimetal phosphide/carbon material is a uniform three-dimensional porous structure, and the molecular formula of the bimetal phosphide/carbon material is AxByP/C, wherein A and B are different transition metal elements respectively, x is used for representing the content of the transition metal A, and y is used for representing the content of the transition metal B.
2. The bimetallic phosphide/carbon material according to claim 1, wherein the transition metal A is an element of cobalt, iron or nickel; the transition metal B is molybdenum or tungsten.
3. The bimetallic phosphide/carbon material of claim 1, wherein x is 0.25. ltoreq. x.ltoreq.1 and y is 0.25. ltoreq. y.ltoreq.1.
4. The bimetallic phosphide/carbon material of claim 1, wherein the three-dimensional porous structure comprises macropores and mesopores, the macropores having a diameter of 50-500 nm, and the mesopores having a diameter of 10-30 nm.
5. A lithium ion battery negative electrode material, characterized by comprising a coating layer, wherein the coating layer is a mixture of the bimetallic phosphide/carbon material as defined in any one of claims 1 to 4, a binder and carbon black.
6. The lithium ion battery anode material of claim 5, wherein the ratio of the bimetallic phosphide/carbon material, binder and carbon black is 7:2: 1.
7. A preparation method of a lithium ion battery negative electrode material is characterized by comprising the following steps:
mixing the bimetallic phosphide/carbon material of any one of claims 1 to 4, a binder and carbon black to obtain a mixture;
and coating the mixture to obtain a coating layer, wherein the coating layer is a lithium ion battery negative electrode material.
8. A lithium ion battery, which is characterized by comprising a negative electrode, wherein the negative electrode is prepared by the lithium ion battery negative electrode material of any one of claims 1 to 4.
9. A method of making a bimetallic phosphide/carbon material, comprising:
dissolving a transition metal A salt and a transition metal B salt in water to obtain a mixed solution of the transition metal A salt and the transition metal B salt;
dissolving diammonium phosphate in water to obtain a diammonium phosphate solution;
adding the diammonium phosphate solution into the mixed solution of the transition metal A salt and the transition metal B salt, then adding citric acid, and stirring to a gel state to obtain a first gel;
dispersing silicon dioxide in ethanol, adding the silicon dioxide into the first gel, and continuously stirring to obtain a second gel;
drying the second gel and grinding into powder;
calcining the powder and removing silica with sodium hydroxide to obtain the bimetallic phosphide/carbon material of any one of claims 1 to 4.
10. The method according to claim 9, characterized in that the transition metal a salt is a nitrate and/or chloride salt of the elements cobalt, iron or nickel; the transition metal B salt is ammonium salt of molybdenum or tungsten element, acetylacetone salt, isopolyacid and/or ammonium phosphate salt.
Priority Applications (1)
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