CN112768678A - Negative electrode material, preparation method thereof and lithium ion battery - Google Patents
Negative electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN112768678A CN112768678A CN201911072967.XA CN201911072967A CN112768678A CN 112768678 A CN112768678 A CN 112768678A CN 201911072967 A CN201911072967 A CN 201911072967A CN 112768678 A CN112768678 A CN 112768678A
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
Abstract
The invention discloses a negative electrode material, a preparation method thereof and a lithium ion battery. The negative electrode material comprises an inner core and an outer shell coated on the surface of the inner core, wherein the inner core comprises a first carbon material, and the outer shell comprises a second carbon material coating layer and doped nanoparticles positioned on the second carbon material coating layer. The preparation method comprises the steps of 1) coating a polymer on the surface of a first carbon material to obtain a polymer coating material; 2) doping the surface of the polymer coating material with a doping raw material to obtain the polymer coating material with a doped nano particle precursor; 3) and carbonizing the polymer coating material with the doped nano particle precursor to obtain the negative electrode material. The cathode material provided by the invention solves the problem of low specific capacity of the graphite material by using the second carbon material coating layer as the carrier and the buffer layer, and has the advantages of good conductivity, high capacity, high first coulombic efficiency and excellent cycle performance.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and relates to a negative electrode material, a preparation method thereof and a lithium ion battery.
Background
Lithium ion batteries have been widely used in portable electronic products and electric vehicles because of their advantages of high operating voltage, long cycle life, no memory effect, low self-discharge, and environmental friendliness. At present, a commercial lithium ion battery mainly adopts a graphite negative electrode material, but the theoretical specific capacity of the lithium ion battery is only 372mAh/g, and the requirement of the future lithium ion battery on high energy density cannot be met, so that the development direction of the future graphite negative electrode is considered to be the limit of how to modify graphite to break the inherent capacity.
Carbon coating is an effective method for optimizing the electrochemical performance of the graphite cathode, but the optimization effect is limited, and the carbon coating only has partial optimization functions on the cycle stability and the first charge-discharge efficiency, so that the disadvantage of low specific capacity of the graphite cannot be solved. The doping modification can fully combine materials with different lithium storage capacities, exert respective advantages, obviously improve the specific capacity of the cathode material, but reduce the rate capability and the cycling stability to a certain extent.
CN106025279A discloses a preparation method of a high-capacity porous spherical graphitized carbon negative electrode material, which comprises the steps of injecting a precursor dispersion liquid into a nanometer pore channel of a silica colloidal crystal sphere template, carrying out ultrasonic impregnation, high-temperature calcination, template removal, filtering and drying to obtain the high-capacity porous spherical graphitized carbon negative electrode material, further emulsifying a colloidal silica aqueous solution to obtain a nanometer silica mixed emulsion, and carrying out constant-temperature condensation, water evaporation, self-assembly, washing and calcination to obtain the silica colloidal crystal sphere template. However, the specific capacity of the negative electrode material obtained by the method is still to be further improved.
CN107452939A discloses a high-capacity flexible lithium ion battery negative electrode material and a preparation method thereof, wherein the flexible lithium ion battery negative electrode material is prepared by loading nanometer transition metal sulfide onto three-dimensional flexible carbon nanotube paper or three-dimensional graphene foam by adopting an electrodeposition method. Although the method improves the capacity to a certain extent, the rate capability and the cycling stability of the method are reduced to a certain extent.
CN101494286A discloses a material for secondary batteries and a method for preparing the material. The negative electrode material includes active component particles having a reversible lithium deintercalation ability or an ability to form an alloy with lithium, the active component particles having a carbon coating containing an electrically conductive, elastic carbon material having an ability to reversibly expand and contract upon electrical cycling of the negative electrode material to maintain electrical contact between the particles in an electrode matrix. But this method has a limited effect on increasing the specific capacity.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, the present invention aims to provide a negative electrode material, a preparation method thereof and a lithium ion battery. The cathode material provided by the invention has the advantages of good conductivity, high capacity, high first coulombic efficiency and excellent cycle performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an anode material, which includes an inner core and an outer shell coated on a surface of the inner core, where the inner core includes a first carbon material, and the outer shell includes a second carbon material coating layer and doped nanoparticles attached to the second carbon material coating layer.
In the cathode material provided by the invention, the second carbon material coating layer can be used as a carrier for doping nano particles and is tightly connected with the first carbon material, so that the integrity of a composite structure is maintained, and the second carbon material coating layer can also play a role of a buffer layer to improve Li+The diffusion property of (a); the nano-particles doped in the coating layer have lithium storage capacityThe lithium ion battery can form a synergistic lithium storage effect with graphite, and solves the problem of low specific capacity of the graphite material.
Through the negative electrode material structure provided by the application, the specific capacity of the carbon-based negative electrode can be effectively improved.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In a preferred embodiment of the present invention, the first carbon material includes graphite.
Preferably, the graphite comprises natural graphite and/or artificial graphite;
preferably, the graphite is subjected to a surface oxidation treatment.
Preferably, the graphite is natural graphite subjected to surface oxidation treatment.
Preferably, the graphite is spherical.
Preferably, the graphite has a median particle diameter of 5.0 to 30.0. mu.m, such as 5.0. mu.m, 8.0. mu.m, 10.0. mu.m, 15.0. mu.m, 20.0. mu.m, 25.0. mu.m, or 30.0. mu.m, etc., preferably 8.0 to 25.0. mu.m, and more preferably 10.0 to 20.0. mu.m.
In a preferred embodiment of the present invention, the second carbon material is a polymer-derived carbon.
Preferably, the polymer-derived carbon comprises polydopamine-derived carbon.
Preferably, the thickness of the second carbon material coating layer is 10 to 500nm, for example 10nm, 20nm, 50nm, 100nm, 200nm, 300nm, 400nm, 500nm or the like, preferably 10 to 30 nm. In the cathode material provided by the invention, if the second carbon material coating layer is too thick, the proportion of the shell layer in the composite material is relatively large, and the shell layer has relatively large irreversible capacity, so that the overall irreversible capacity of the coated graphite cathode material is increased, and finally the first charge-discharge efficiency is low; if the second carbon material coating layer is too thin, the shell layer is damaged, the surface of the graphite inside is exposed and reacts with a solvent in an electrolyte, and the first charge-discharge efficiency is not high.
Preferably, the doped nanoparticles comprise ZnO nanoparticles. The ZnO nanoparticles have lithium storage capacity, can form a synergistic lithium storage effect with the first carbon material, and solve the problem of low specific capacity inherent in the carbon-based material (such as a graphite material). In the cathode material provided by the invention, if the doped nano particles are too much, the composite material has poor conductivity and the irreversible capacity is increased, and finally the first charge-discharge efficiency is low; if the doped nano particles are too few, the capacity of the composite material is not obviously improved.
Preferably, the particle size of the doped nanoparticles is 10-50nm, such as 10nm, 20nm, 30nm, 40nm or 50nm, etc.
Preferably, the mass fraction of the first carbon material is 30-80 wt%, such as 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, or 80 wt%, etc., the mass fraction of the second carbon material is 10-50 wt%, such as 10 wt%, 20 wt%, 30 wt%, 40 wt%, or 50 wt%, etc., and the mass fraction of the doped nanoparticles is 1-40 wt%, such as 1 wt%, 5 wt%, 10 wt%, 20 wt%, 30 wt%, or 40 wt%, etc., based on 100% of the total mass of the anode material.
In a second aspect, the present invention provides a method for preparing the anode material according to the first aspect, the method comprising the steps of:
(1) coating a polymer on the surface of the first carbon material to obtain a polymer coating material;
(2) doping the surface of the polymer coating material in the step (1) with a doping raw material to obtain a polymer coating material with a doped nanoparticle precursor;
(3) and (3) carbonizing the polymer coating material with the doped nano particle precursor in the step (2) to obtain the cathode material.
In the preparation method provided by the invention, the negative electrode material of the first aspect is successfully prepared by combining a coating modification technology and a doping technology. The method comprises the steps of coating a polymer on the surface of a first carbon material (graphite), utilizing the adsorption effect of groups on the polymer on metal ions to enable the metal ions in a doping raw material to be gathered on a polymer coating layer to form a nano particle precursor, carbonizing at high temperature in an inert atmosphere, pyrolyzing the polymer coating layer to form a second carbon material coating layer (polymer derived carbon), and pyrolyzing the nano particle precursor attached to the polymer coating layer to form doped nano particles to finally form the negative electrode material of the first aspect.
In a preferred embodiment of the present invention, in step (1), the method for coating the polymer is a liquid phase coating method;
preferably, the liquid phase coating method comprises: and adding a first carbon material and a polymer precursor into the alkaline buffer solution, and heating for reaction to obtain the polymer coating material.
In the invention, the alkaline buffer solution is used in the liquid phase coating method because the dopamine hydrochloride can generate self-polymerization reaction under the alkalescent condition to generate the polydopamine.
Preferably, the buffer solvent is tris-aqueous solution.
Preferably, the aqueous solution of tris-hcl is prepared by adding dilute hydrochloric acid to an aqueous solution of tris.
Preferably, the concentration of the tris aqueous solution is 0.5-5.0mg/mL, preferably 2.0-4.0 mg/mL.
Preferably, the concentration of the dilute hydrochloric acid is 0.1 mol/L.
Preferably, the pH of the buffer solution is 8.0-9.0, such as 8.0, 8.2, 8.4, 8.6, 8.8, or 9.0, and the like.
Preferably, the polymer precursor is dopamine hydrochloride.
The polydopamine can be coated on the surface of the first carbon material by using dopamine salt, and the adsorption effect of nitrogen and phenol groups of the polydopamine on metal ions is utilized to dope the metal ions (such as Zn) in the raw material2+) The precursor is connected with a first carbon material due to strong adhesiveness of the polydopamine, and the polydopamine is carbonized at high temperature in inert atmosphere and pyrolyzed to form polydopamine-derived carbonThe precursor attached to the polydopamine coating is pyrolysed to form doped nanoparticles (e.g. ZnO) and finally a negative electrode material as described in the first aspect is formed.
Preferably, the mass ratio of the first carbon material and the polymer precursor is 0.5 to 4, such as 0.5, 1, 2, 3 or 4, etc., preferably 1 to 2.
Preferably, the temperature of the heating reaction is 40-80 ℃, such as 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, preferably 60-65 ℃. In the invention, if the heating reaction temperature of the liquid phase coating method is too high, the self-polymerization reaction speed of the dopamine hydrochloride is too high, and the coating is not uniform; if the temperature is too low, the self-polymerization reaction of dopamine hydrochloride is abnormally slow.
Preferably, the heating reaction time is 6-48h, such as 6h, 12h, 18h, 24h, 30h, 36h, 42h or 48h, etc., preferably 18-24 h.
Preferably, the heating is accompanied by stirring.
As a preferred technical scheme of the invention, the method for doping by using the doping raw material in the step (2) is an in-situ precipitation method.
Preferably, the in situ precipitation method comprises: and (2) placing the polymer coating material obtained in the step (1) in a solvent, performing ultrasonic dispersion, adding a doping raw material and a precipitator, and stirring and mixing to obtain the polymer coating material with the doped nano particle precursor.
Preferably, the solvent is an aqueous solution of ethanol.
Preferably, the volume fraction of ethanol in the aqueous ethanol solution is 5-40%, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, etc., preferably 10-20%.
Preferably, the time of the ultrasonic dispersion is 10-30min, such as 10min, 15min, 20min, 25min or 30min and the like.
Preferably, the doping material comprises a zinc salt.
Preferably, the zinc salt comprises any one of zinc chloride, zinc sulfate or zinc acetate or a combination of at least two of them.
Preferably, the precipitant comprises any one of, or a combination of at least two of, aqueous ammonia, ammonium bicarbonate or ammonium oxalate.
Preferably, the molar ratio of the doping raw material to the precipitant is 1:1 to 1:2, such as 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, or 1:2, etc. In the invention, if the molar ratio of the doping raw material to the precipitator is too large (i.e. the doping raw material is too much) in the in-situ precipitation process, the particle size of the precursor of the doped nanoparticles is too large, and finally the particle size of the doped nanoparticles is too large, thereby affecting the doping effect; if the molar ratio of the doping raw material to the precipitant is too small (i.e., the doping raw material is too small), the particle size of the precursor of the doped nanoparticles is too small, and finally the particle size of the doped nanoparticles is too small, thereby causing agglomeration, and thus causing uneven doping.
Preferably, the time for stirring and mixing is 30-60min, such as 30min, 35min, 40min, 45min, 50min, 55min or 60min, etc.
As a preferred embodiment of the present invention, the carbonization method in the step (3) comprises: carbonizing the polymer coating material with the doped nano particle precursor in the step (2) in a tubular furnace, and introducing protective gas in the whole carbonization process to obtain the cathode material.
Preferably, the temperature of the carbonization is 600-1000 ℃, such as 600 ℃, 700 ℃, 800 ℃, 900 ℃ or 1000 ℃ and the like. In the invention, if the carbonization temperature is too high, the structure of the coating layer is unstable, and the doped nano particles are agglomerated; if the carbonization temperature is too low, insufficient carbonization of polydopamine may result.
Preferably, the carbonization time is 10-14 h.
Preferably, the protective gas comprises any one of nitrogen, helium, neon, argon or xenon, or a combination of at least two thereof.
Preferably, the protective gas is introduced at a constant speed.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1) adding graphite and dopamine hydrochloride into a trihydroxymethyl aminomethane-hydrochloric acid aqueous solution, heating and stirring at 60-65 ℃, and reacting for 18-24h to obtain polydopamine-coated graphite;
wherein the pH of the tris-hydroxymethyl aminomethane-hydrochloric acid aqueous solution is 8.0-9.0; the mass ratio of the graphite to the dopamine hydrochloride is 1-2;
(2) placing the polydopamine-coated graphite obtained in the step (1) in an ethanol water solution, performing ultrasonic dispersion for 10-30min, adding zinc salt and a precipitator, and stirring and mixing for 30-60min to obtain polydopamine-coated graphite with a zinc oxide precursor;
wherein the volume fraction of ethanol in the ethanol aqueous solution is 10-20%, and the molar ratio of the zinc salt to the precipitator is 1:1-1: 2;
(3) carbonizing the polydopamine-coated graphite with the zinc oxide precursor in the step (2) in a tubular furnace at the temperature of 600-1000 ℃ for 10-14h, and introducing protective gas at a constant speed in the whole carbonization process to obtain the cathode material.
The further preferable technical scheme is that the polydopamine is firstly coated on the surface of the graphite, and the adsorption effect of nitrogen and phenol groups of the polydopamine on metal ions is utilized to ensure that Zn is coated2+The poly dopamine is gathered on the poly dopamine coating layer, a ZnO precursor is generated in situ under the action of a precipitator, the poly dopamine has strong adhesion, the ZnO precursor and graphite can be connected together, the poly dopamine is subjected to high-temperature carbonization in inert atmosphere, the poly dopamine is pyrolyzed to become poly dopamine-derived carbon, meanwhile, the ZnO precursor attached to the poly dopamine coating layer is pyrolyzed to ZnO, and finally, the ZnO-doped poly dopamine-derived carbon coated graphite is formed.
In a third aspect, the present invention provides a lithium ion battery comprising the negative electrode material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the second carbon material coating layer (polydopamine-derived carbon coating layer) of the cathode material provided by the invention can be used as a carrier of doped nanoparticles (ZnO nanoparticles) on one hand, and is tightly connected with the first carbon material (graphite) so as to be beneficial to maintaining the integrity of a composite structureOn the other hand, the second carbon material coating layer itself can also function as a buffer layer to improve Li+The diffusion property of (a); the nano particles doped in the coating layer have lithium storage capacity, can form a synergistic lithium storage effect with graphite, and solve the problem of low specific capacity of the graphite material. The negative electrode material provided by the invention can increase the first charge specific capacity of a graphite negative electrode from 365mAh/g to 482mAh/g, the capacity increase rate reaches 32%, the first discharge specific capacity of the negative electrode material provided by the invention can reach 585mAh/g, the first coulombic efficiency can reach 87%, and the capacity retention rate after 100 charge-discharge cycles can reach 97.7%.
(2) The preparation method provided by the invention successfully prepares the cathode material by combining a coating modification technology and a doping technology. The method comprises the steps of coating a polymer on the surface of graphite, utilizing the adsorption effect of groups on the polymer on metal ions to enable the metal ions in a doping raw material to be gathered on a polymer coating layer to form a nano particle precursor, carbonizing at high temperature in an inert atmosphere, pyrolyzing the polymer to form polymer derived carbon, pyrolyzing the nano particle precursor attached to the polymer coating layer to form doped nano particles, and finally forming the cathode material.
Drawings
FIG. 1 is a scanning electron micrograph of a negative electrode material prepared in example 1 of the present invention;
fig. 2 is a graph showing cycle characteristics of the negative electrode material prepared in example 1 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
This example prepares a negative electrode material as follows:
weighing 300mg of trihydroxymethyl ammoniaAdding methyl methane into deionized water with the volume of 100mL, then adding dilute hydrochloric acid with the concentration of 0.1mol/L, stirring for 20min, adjusting the pH value to 8.5, then soaking 1000mg of natural graphite into aqueous solution of tris (hydroxymethyl) aminomethane, then adding 500mg of dopamine hydrochloride, and stirring for 12h at 60 ℃ to obtain poly-dopamine-coated natural graphite; adding 1000mg of the polydopamine-coated natural graphite into a mixed solution of 100ml of deionized water and 10ml of alcohol, performing ultrasonic dispersion for 20min, and then adding 400mg of ZnCl2And 300mg of (NH)4)2C2O4Stirring for 45min, then placing the precipitate in a tube furnace, carbonizing at 800 ℃ for 12h, and introducing nitrogen at a constant speed in the whole carbonization process to obtain the cathode material (ZnO-doped polydopamine-derived carbon-coated graphite).
Fig. 1 is a scanning electron micrograph of the negative electrode material prepared in this example. As can be seen from fig. 1, a layer of ZnO nanoparticles is densely attached to the surface of the graphite, so that the ZnO nanoparticles can be firmly combined with the graphite, mainly because the polydopamine-derived carbon coating layer can be used as a carrier of the ZnO nanoparticles, which plays a role in connection, and maintains the integrity of the composite structure.
Fig. 2 is a graph showing cycle performance of the anode material prepared in this example. It can be seen from fig. 2 that the material has good cycling properties: under the current density of 360mA/g, the initial discharge specific capacity is 567mAh/g, the initial charge specific capacity is 483mAh/g, the initial coulombic efficiency is 85%, the specific charge capacity of 472mAh/g can be still maintained after 100 cycles, the capacity retention rate is 97.7%, and the cycling stability is good. The high charging specific capacity is mainly benefited from the fact that the ZnO nano particles doped in the coating layer have lithium storage capacity, can form a synergistic lithium storage effect with graphite, solves the problem of low inherent specific capacity of graphite materials, and can play a role in buffering and maintain the stability of circulation through the poly-dopamine derived carbon coating.
The negative electrode material prepared in the embodiment comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core is made of natural graphite, and the shell is composed of a polydopamine-derived carbon coating layer and ZnO nanoparticles positioned on the polydopamine-derived carbon coating layer. The graphite has a median particle size of 15 mu m, the polydopamine-derived carbon coating layer has a thickness of 20nm, and the ZnO nanoparticles have a particle size range of 10-15 nm. Based on the total mass of the negative electrode material as 100%, the mass fraction of graphite is 75 wt%, the mass fraction of polydopamine-derived carbon is 15 wt%, and the mass fraction of ZnO nanoparticles is 10 wt%.
The performance test results of the negative electrode material prepared in this example are shown in table 1.
Example 2
This example prepares a negative electrode material as follows:
weighing 300mg of trihydroxymethyl aminomethane, adding the trihydroxymethyl aminomethane into 100mL of deionized water, adding dilute hydrochloric acid with the concentration of 0.1mol/L, stirring for 20min, adjusting the pH value to 8.5, immersing 1000mg of natural graphite into an aqueous solution of the trihydroxymethyl aminomethane, then adding 300mg of dopamine hydrochloride, and stirring at 60 ℃ for 12h to obtain poly-dopamine coated natural graphite; adding 1000mg of the polydopamine-coated natural graphite into a mixed solution of 100ml of deionized water and 10ml of alcohol, performing ultrasonic dispersion for 20min, and then adding 400mg of ZnCl2And 300mg of (NH)4)2C2O4Stirring for 45min, then placing the precipitate in a tube furnace, carbonizing at 800 ℃ for 12h, and introducing nitrogen at a constant speed in the whole carbonization process to obtain the cathode material (ZnO-doped polydopamine-derived carbon-coated graphite).
The negative electrode material prepared in the embodiment comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core is made of natural graphite, and the shell is composed of a polydopamine-derived carbon coating layer and ZnO nanoparticles positioned on the polydopamine-derived carbon coating layer. The graphite has a median particle size of 15 mu m, the thickness of the polydopamine-derived carbon coating layer is 10nm, and the particle size range of the ZnO nanoparticles is 10-15 nm. Based on the total mass of the negative electrode material as 100%, the mass fraction of graphite is 80 wt%, the mass fraction of polydopamine-derived carbon is 10 wt%, and the mass fraction of ZnO nanoparticles is 10 wt%.
The performance test results of the negative electrode material prepared in this example are shown in table 1.
Example 3
This example prepares a negative electrode material as follows:
weighing 300mg of trihydroxymethyl aminomethane, adding the trihydroxymethyl aminomethane into 100mL of deionized water, adding dilute hydrochloric acid with the concentration of 0.1mol/L, stirring for 20min, adjusting the pH value to 8.5, immersing 1000mg of natural graphite into an aqueous solution of the trihydroxymethyl aminomethane, then adding 700mg of dopamine hydrochloride, and stirring at 60 ℃ for 12h to obtain poly-dopamine coated natural graphite; adding 1000mg of the polydopamine-coated natural graphite into a mixed solution of 100ml of deionized water and 10ml of alcohol, performing ultrasonic dispersion for 20min, and then adding 400mg of ZnCl2And 300mg of (NH)4)2C2O4Stirring for 45min, then placing the precipitate in a tube furnace, carbonizing at 800 ℃ for 12h, and introducing nitrogen at a constant speed in the whole carbonization process to obtain the cathode material (ZnO-doped polydopamine-derived carbon-coated graphite).
The negative electrode material prepared in the embodiment comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core is made of natural graphite, and the shell is composed of a polydopamine-derived carbon coating layer and ZnO nanoparticles positioned on the polydopamine-derived carbon coating layer. The graphite has a median particle size of 15 mu m, the polydopamine-derived carbon coating layer has a thickness of 30nm, and the ZnO nanoparticles have a particle size range of 10-15 nm. Based on the total mass of the negative electrode material as 100%, the mass fraction of graphite is 70 wt%, the mass fraction of polydopamine-derived carbon is 20 wt%, and the mass fraction of ZnO nanoparticles is 10 wt%.
The performance test results of the negative electrode material prepared in this example are shown in table 1.
Example 4
This example prepares a negative electrode material as follows:
weighing 300mg of tris (hydroxymethyl) aminomethane, adding into 100mL of deionized water, adding dilute hydrochloric acid with concentration of 0.1mol/L, stirring for 20min, adjusting pH to 8.5, and adding 1000mg of natural amino methaneImmersing graphite into a water solution of tris (hydroxymethyl) aminomethane, then adding 500mg of dopamine hydrochloride, and stirring at 60 ℃ for 12h to obtain natural graphite coated with polydopamine; adding 1000mg of the polydopamine-coated natural graphite into a mixed solution of 100ml of deionized water and 10ml of alcohol, performing ultrasonic dispersion for 20min, and then adding 200mg of ZnCl2And 150mg of (NH)4)2C2O4Stirring for 45min, then placing the precipitate in a tube furnace, carbonizing at 800 ℃ for 12h, and introducing nitrogen at a constant speed in the whole carbonization process to obtain the cathode material (ZnO-doped polydopamine-derived carbon-coated graphite).
The negative electrode material prepared in the embodiment comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core is made of natural graphite, and the shell is composed of a polydopamine-derived carbon coating layer and ZnO nanoparticles positioned on the polydopamine-derived carbon coating layer. The graphite has a median particle size of 15 mu m, the polydopamine-derived carbon coating layer has a thickness of 20nm, and the ZnO nanoparticles have a particle size range of 10-15 nm. The mass fraction of graphite is 78 wt%, the mass fraction of polydopamine-derived carbon is 15 wt%, and the mass fraction of ZnO nanoparticles is 7 wt%, based on 100% of the total mass of the negative electrode material.
The performance test results of the negative electrode material prepared in this example are shown in table 1.
Example 5
This example prepares a negative electrode material as follows:
weighing 300mg of trihydroxymethyl aminomethane, adding the trihydroxymethyl aminomethane into 100mL of deionized water, adding dilute hydrochloric acid with the concentration of 0.1mol/L, stirring for 20min, adjusting the pH value to 8.5, immersing 1000mg of natural graphite into an aqueous solution of the trihydroxymethyl aminomethane, then adding 500mg of dopamine hydrochloride, and stirring at 60 ℃ for 12h to obtain poly-dopamine coated natural graphite; adding 1000mg of the polydopamine-coated natural graphite into a mixed solution of 100ml of deionized water and 10ml of alcohol, performing ultrasonic dispersion for 20min, and then adding 100mg of ZnCl2And 75mg of (NH)4)2C2O4Stirring 4And 5min, then placing the precipitate in a tube furnace, carbonizing at 800 ℃ for 12h, and introducing nitrogen at a constant speed in the whole carbonization process to obtain the cathode material (ZnO-doped polydopamine-derived carbon-coated graphite).
The negative electrode material prepared in the embodiment comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core is made of natural graphite, and the shell is composed of a polydopamine-derived carbon coating layer and ZnO nanoparticles positioned on the polydopamine-derived carbon coating layer. The graphite has a median particle size of 15 mu m, the polydopamine-derived carbon coating layer has a thickness of 20nm, and the ZnO nanoparticles have a particle size range of 10-15 nm. Based on the total mass of the negative electrode material as 100%, the mass fraction of graphite is 80 wt%, the mass fraction of polydopamine-derived carbon is 15 wt%, and the mass fraction of ZnO nanoparticles is 5 wt%.
The performance test results of the negative electrode material prepared in this example are shown in table 1.
Example 6
This example prepares a negative electrode material as follows:
weighing 300mg of trihydroxymethyl aminomethane, adding the trihydroxymethyl aminomethane into 100mL of deionized water, adding dilute hydrochloric acid with the concentration of 0.1mol/L, stirring for 20min, adjusting the pH value to 8.5, immersing 1000mg of artificial graphite into aqueous solution of the trihydroxymethyl aminomethane, then adding 500mg of dopamine hydrochloride, and stirring at 60 ℃ for 12h to obtain polydopamine-coated artificial graphite; adding 1000mg of the polydopamine-coated natural graphite into a mixed solution of 100ml of deionized water and 10ml of alcohol, performing ultrasonic dispersion for 20min, and then adding 400mg of ZnCl2And 300mg of (NH)4)2C2O4Stirring for 45min, then placing the precipitate in a tube furnace, carbonizing at 800 ℃ for 12h, and introducing nitrogen at a constant speed in the whole carbonization process to obtain the cathode material (ZnO-doped polydopamine-derived carbon-coated graphite).
The negative electrode material prepared in the embodiment comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core is made of natural graphite, and the shell is composed of a polydopamine-derived carbon coating layer and ZnO nanoparticles positioned on the polydopamine-derived carbon coating layer. The graphite has a median particle size of 20 μm, the polydopamine-derived carbon coating layer has a thickness of 20nm, and the ZnO nanoparticles have a particle size ranging from 10nm to 15 nm. Based on the total mass of the negative electrode material as 100%, the mass fraction of graphite is 75 wt%, the mass fraction of polydopamine-derived carbon is 15 wt%, and the mass fraction of ZnO nanoparticles is 10 wt%.
The performance test results of the negative electrode material prepared in this example are shown in table 1.
Example 7
This example prepares a negative electrode material as follows:
adding 300mg of weighed trihydroxymethyl aminomethane into 100mL of deionized water, then adding dilute hydrochloric acid with the concentration of 0.1mol/L, stirring for 20min, adjusting the pH value to 8.0, then soaking 1000mg of natural spherical graphite into an aqueous solution of the trihydroxymethyl aminomethane, then adding 1000mg of dopamine hydrochloride, and stirring for 24h at 60 ℃ to obtain poly-dopamine coated natural graphite; adding 1000mg of the polydopamine-coated natural graphite into a mixed solution of 95ml of deionized water and 5ml of alcohol, performing ultrasonic dispersion for 10min, and then adding 270mg of ZnCl2And 250mg of (NH)4)2C2O4Stirring for 30min, then placing the precipitate in a tube furnace, carbonizing at 600 ℃ for 14h, and introducing nitrogen at a constant speed in the whole carbonization process to obtain the cathode material (ZnO-doped polydopamine-derived carbon-coated graphite).
The negative electrode material prepared in the embodiment comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core is natural spherical graphite, and the shell consists of a polydopamine-derived carbon coating layer and ZnO nanoparticles positioned on the polydopamine-derived carbon coating layer. The graphite has a median particle size of 10 μm, the polydopamine-derived carbon coating layer has a thickness of 40nm, and the ZnO nanoparticles have a particle size range of 15-30 nm. Based on the total mass of the negative electrode material as 100%, the mass fraction of graphite is 70 wt%, the mass fraction of polydopamine-derived carbon is 25 wt%, and the mass fraction of ZnO nanoparticles is 5 wt%.
The performance test results of the negative electrode material prepared in this example are shown in table 1.
Example 8
This example prepares a negative electrode material as follows:
adding 300mg of weighed trihydroxymethyl aminomethane into 100mL of deionized water, then adding 0.1mol/L diluted hydrochloric acid, stirring for 20min, adjusting the pH value to 9.0, then soaking 1000mg of natural graphite subjected to surface oxidation treatment into an aqueous solution of the trihydroxymethyl aminomethane, then adding 800mg of dopamine hydrochloride, and stirring at 65 ℃ for 18h to obtain natural graphite coated with polydopamine; adding 1000mg of the polydopamine-coated natural graphite into a mixed solution of 60ml of deionized water and 40ml of alcohol, performing ultrasonic dispersion for 30min, and then adding 270mg of ZnCl2And 500mg of (NH)4)2C2O4Stirring for 60min, then placing the precipitate in a tube furnace, carbonizing at 1000 ℃ for 10h, and introducing nitrogen at a constant speed in the whole carbonization process to obtain the cathode material (ZnO-doped polydopamine-derived carbon-coated graphite).
The negative electrode material prepared by the embodiment comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core is natural graphite subjected to surface oxidation treatment, and the shell consists of a polydopamine-derived carbon coating layer and ZnO nanoparticles positioned on the polydopamine-derived carbon coating layer. The graphite has a median particle size of 20 μm, the polydopamine-derived carbon coating layer has a thickness of 35nm, and the ZnO nanoparticles have a particle size range of 15-30 nm. Based on the total mass of the negative electrode material as 100%, the mass fraction of graphite is 70 wt%, the mass fraction of polydopamine-derived carbon is 22 wt%, and the mass fraction of ZnO nanoparticles is 8 wt%.
The performance test results of the negative electrode material prepared in this example are shown in table 1.
Example 9
This example prepares a negative electrode material as follows:
300mg of tris (hydroxymethyl) aminomethane is weighed and added into deionized water with the volume of 100mL, and then the deionized water is added into the deionized water with the concentration of 0.1mol/L diluted hydrochloric acid is stirred for 20min, the pH value is adjusted to 9.0, 1000mg of natural graphite with oxidized surface is immersed into the aqueous solution of tris (hydroxymethyl) aminomethane, then 250mg of dopamine hydrochloride is added, and the mixture is stirred for 48h at 40 ℃ to obtain poly-dopamine-coated natural graphite; adding 1000mg of the polydopamine-coated natural graphite into a mixed solution of 90ml of deionized water and 10ml of alcohol, performing ultrasonic dispersion for 25min, and then adding 400mg of ZnCl2And 300mg of (NH)4)2C2O4Stirring for 45min, then placing the precipitate in a tube furnace, carbonizing at 800 ℃ for 12h, and introducing argon gas at a constant speed in the whole carbonization process to obtain the cathode material (ZnO-doped polydopamine-derived carbon-coated graphite).
The negative electrode material prepared by the embodiment comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core is natural graphite subjected to surface oxidation treatment, and the shell consists of a polydopamine-derived carbon coating layer and ZnO nanoparticles positioned on the polydopamine-derived carbon coating layer. The graphite has a median particle size of 8 μm, the polydopamine-derived carbon coating layer has a thickness of 10nm, and the ZnO nanoparticles have a particle size range of 10-15 nm. Based on the total mass of the negative electrode material as 100%, the mass fraction of graphite is 82 wt%, the mass fraction of polydopamine-derived carbon is 8 wt%, and the mass fraction of ZnO nanoparticles is 10 wt%.
The performance test results of the negative electrode material prepared in this example are shown in table 1.
Example 10
This example prepares a negative electrode material as follows:
adding 300mg of weighed trihydroxymethyl aminomethane into 100mL of deionized water, then adding 0.1mol/L dilute hydrochloric acid, stirring for 20min, adjusting the pH value to 9.0, then soaking 1000mg of artificial graphite subjected to surface oxidation treatment into aqueous solution of the trihydroxymethyl aminomethane, then adding 2000mg of dopamine hydrochloride, and stirring for 6h at 80 ℃ to obtain natural polydopamine-coated graphite; 1000mg of the polydopamine-coated natural graphite obtained above was added to a mixed solution of 80ml of deionized water and 20ml of alcoholIn the process, ultrasonic dispersion is carried out for 25min, and then 400mg of ZnCl is added2And 300mg of (NH)4)2C2O4Stirring for 45min, then placing the precipitate in a tube furnace, carbonizing at 800 ℃ for 12h, and introducing argon gas at a constant speed in the whole carbonization process to obtain the cathode material (ZnO-doped polydopamine-derived carbon-coated graphite).
The negative electrode material prepared in the embodiment comprises an inner core and a shell coated on the surface of the inner core, wherein the inner core is artificial graphite subjected to surface oxidation treatment, and the shell consists of a polydopamine-derived carbon coating layer and ZnO nanoparticles positioned on the polydopamine-derived carbon coating layer. The graphite has a median particle size of 25 μm, the polydopamine-derived carbon coating layer has a thickness of 60nm, and the ZnO nanoparticles have a particle size ranging from 10nm to 15 nm. Based on the total mass of the negative electrode material as 100%, the mass fraction of graphite is 55 wt%, the mass fraction of polydopamine-derived carbon is 35 wt%, and the mass fraction of ZnO nanoparticles is 10 wt%.
The performance test results of the negative electrode material prepared in this example are shown in table 1.
Comparative example 1
The comparative example prepared a negative electrode material as follows:
weighing 300mg of trihydroxymethyl aminomethane, adding the trihydroxymethyl aminomethane into 100mL of deionized water, adding dilute hydrochloric acid with the concentration of 0.1mol/L, stirring for 20min, adjusting the pH value to 8.5, immersing 1000mg of natural graphite into an aqueous solution of the trihydroxymethyl aminomethane, then adding 500mg of dopamine hydrochloride, and stirring at 60 ℃ for 12h to obtain poly-dopamine coated natural graphite; and (3) putting the obtained natural graphite coated with the polydopamine into a tubular furnace, carbonizing at 800 ℃ for 12h, and introducing nitrogen at a constant speed in the whole carbonization process to obtain the graphite coated with the polydopamine-derived carbon.
The anode material product of this comparative example was not doped with ZnO nanoparticles compared to example 1.
The results of the performance test of the negative electrode material prepared in this comparative example are shown in table 1.
Comparative example 2
The comparative example prepared a negative electrode material as follows:
1000mg of natural graphite was added to a mixed solution of 100ml of deionized water and 10ml of alcohol, and 400mg of ZnCl was then added2And 300mg of (NH)4)2C2O4Stirring for 45min, then placing the precipitate in a tube furnace, carbonizing at 800 ℃ for 12h, and introducing nitrogen at a constant speed in the whole carbonization process to obtain the ZnO particle and graphite composite material.
The negative electrode material product of this comparative example had no dopamine-derived carbon coating layer compared to example 1.
The results of the performance test of the negative electrode material prepared in this comparative example are shown in table 1.
Test method
The anode materials of the respective examples and comparative examples were tested by the following methods:
the surface appearance, particle size and the like of the sample were observed by a scanning electron microscope of Hitachi S4800.
Electrochemical cycling performance was tested using the following method: dissolving a negative electrode material, a conductive agent (acetylene black) and a binder (PVDF) in a solvent according to the mass percentage of 94:1:5, mixing, controlling the solid content to be 50%, coating the mixture on a copper foil current collector to be used as a test electrode, assembling a button cell by using a metal lithium sheet as a comparison electrode, and adopting an electrolytic liquid system of LiPF with the concentration of 1mol/L6/EC + DMC + EMC (v/v ═ 1:1: 1). The button cell is tested on a LAND cell test system of Wuhanjinnuo electronics, and under the condition of normal temperature, constant current charging and discharging are carried out at 0.1C, the charging and discharging voltage is limited to 0.01-2.5V, and various electrochemical performance tests are carried out.
The test results are shown in Table 1.
TABLE 1
It can be seen from the above examples and comparative examples that in examples 1-10, poly-dopamine is coated on the surface of graphite by combining the coating modification technique and the doping technique,zn is made to adsorb metal ions by utilizing the nitrogen and phenol groups of polydopamine2+The poly dopamine-doped carbon-coated graphite is finally formed, and the product has good conductivity, high capacity, high first coulombic efficiency and excellent cycle performance.
The first reversible capacity of the negative electrode material prepared by the method in example 1 is much higher than that of the negative electrode material prepared by the method in comparative example 1, but the first coulombic efficiency is also reduced, mainly because the doping of the ZnO nanoparticles can improve the specific capacity of the graphite, but a new side reaction also occurs in the lithium storage process of the ZnO, so that the first coulombic efficiency is reduced. The negative electrode material prepared by the method of comparative example 1 has no ZnO particles, so that the synergistic lithium storage effect does not exist, and the capacity is not obviously improved.
The negative electrode material prepared by the method in example 1 is superior to the negative electrode material prepared by the method in comparative example 2 in the first reversible charge specific capacity, the first coulombic efficiency and the cycle capacity retention rate, mainly because the negative electrode material prepared by the method in comparative example 2 is only formed by simply combining ZnO particles and graphite, lacks a polydopamine-derived carbon coating layer as a connection, is easy to damage in structure and poor in cycle performance.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The negative electrode material is characterized by comprising an inner core and an outer shell coated on the surface of the inner core, wherein the inner core comprises a first carbon material, and the outer shell comprises a second carbon material coating layer and doped nanoparticles positioned on the second carbon material coating layer.
2. The anode material according to claim 1, wherein the first carbon material comprises graphite;
preferably, the graphite comprises natural graphite and/or artificial graphite;
preferably, the graphite is subjected to surface oxidation treatment;
preferably, the graphite is natural graphite subjected to surface oxidation treatment;
preferably, the graphite is spherical;
preferably, the graphite has a median particle diameter of 5.0 to 30.0. mu.m, preferably 8.0 to 25.0. mu.m, and more preferably 10.0 to 20.0. mu.m.
3. The anode material according to claim 1 or 2, wherein the second carbon material is a polymer-derived carbon;
preferably, the polymer-derived carbon comprises polydopamine-derived carbon;
preferably, the thickness of the second carbon material coating layer is 10-500nm, preferably 10-30 nm;
preferably, the doped nanoparticles comprise ZnO nanoparticles;
preferably, the particle size of the doped nanoparticles is 10-50 nm;
preferably, the mass fraction of the first carbon material is 30-80 wt%, the mass fraction of the second carbon material is 10-50 wt%, and the mass fraction of the doped nanoparticles is 1-40 wt%, based on 100% of the total mass of the negative electrode material.
4. A method for preparing the negative electrode material according to any one of claims 1 to 3, comprising the steps of:
(1) coating a polymer on the surface of the first carbon material to obtain a polymer coating material;
(2) doping the surface of the polymer coating material in the step (1) with a doping raw material to obtain a polymer coating material with a doped nanoparticle precursor;
(3) and (3) carbonizing the polymer coating material with the doped nano particle precursor in the step (2) to obtain the cathode material.
5. The method according to claim 4, wherein in the step (1), the method for coating the polymer is a liquid phase coating method;
preferably, the liquid phase coating method comprises: adding a first carbon material and a polymer precursor into an alkaline buffer solution, and heating for reaction to obtain a polymer coating material;
preferably, the buffer solvent is a tris-aqueous solution;
preferably, the pH of the buffer solution is 8.0 to 9.0;
preferably, the polymer precursor is dopamine hydrochloride;
preferably, the mass ratio of the first carbon material to the polymer precursor is 0.5 to 4, preferably 1 to 2;
preferably, the temperature of the heating reaction is 40-80 ℃, preferably 60-65 ℃;
preferably, the heating reaction time is 6-48h, preferably 18-24 h;
preferably, the heating is accompanied by stirring.
6. The method according to claim 4 or 5, wherein the doping with the doping material in step (2) is an in-situ precipitation method;
preferably, the in situ precipitation method comprises: placing the polymer coating material obtained in the step (1) in a solvent, performing ultrasonic dispersion, adding a doping raw material and a precipitator, and stirring and mixing to obtain the polymer coating material with a doped nanoparticle precursor;
preferably, the solvent is an aqueous solution of ethanol;
preferably, the volume fraction of ethanol in the ethanol aqueous solution is 5-40%, preferably 10-20%;
preferably, the time of ultrasonic dispersion is 10-30 min;
preferably, the doping raw material comprises a zinc salt;
preferably, the zinc salt comprises any one of zinc chloride, zinc sulfate or zinc acetate or a combination of at least two of the foregoing;
preferably, the precipitant comprises any one of ammonia, ammonium bicarbonate or ammonium oxalate or a combination of at least two thereof;
preferably, the molar ratio of the doping raw material to the precipitating agent is 1:1-1: 2;
preferably, the time for stirring and mixing is 30-60 min.
7. The production method according to any one of claims 4 to 6, wherein the carbonization in the step (3) comprises: carbonizing the polymer coating material with the doped nano particle precursor in the step (2) in a tubular furnace, and introducing protective gas in the whole carbonization process to obtain the cathode material.
8. The method as claimed in claim 7, wherein the carbonization temperature is 600-1000 ℃;
preferably, the carbonization time is 10-14 h;
preferably, the protective gas comprises any one of nitrogen, helium, neon, argon or xenon or a combination of at least two thereof;
preferably, the protective gas is introduced at a constant speed.
9. Method for preparing a negative electrode material according to any of claims 4 to 8, characterized in that it comprises the following steps:
(1) adding graphite and dopamine hydrochloride into a trihydroxymethyl aminomethane-hydrochloric acid aqueous solution, heating and stirring at 60-65 ℃, and reacting for 18-24h to obtain polydopamine-coated graphite;
wherein the pH of the tris-hydroxymethyl aminomethane-hydrochloric acid aqueous solution is 8.0-9.0; the mass ratio of the graphite to the dopamine hydrochloride is 1-2;
(2) placing the polydopamine-coated graphite obtained in the step (1) in an ethanol water solution, performing ultrasonic dispersion for 10-30min, adding zinc salt and a precipitator, and stirring and mixing for 30-60min to obtain polydopamine-coated graphite with a zinc oxide precursor;
wherein the volume fraction of ethanol in the ethanol aqueous solution is 10-20%, and the molar ratio of the zinc salt to the precipitator is 1:1-1: 2;
(3) carbonizing the polydopamine-coated graphite with the zinc oxide precursor in the step (2) in a tubular furnace at the temperature of 600-1000 ℃ for 10-14h, and introducing protective gas at a constant speed in the whole carbonization process to obtain the cathode material.
10. A lithium ion battery comprising the negative electrode material according to any one of claims 1 to 3.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113839003A (en) * | 2021-09-17 | 2021-12-24 | 超威电源集团有限公司 | Preparation method of nickel-zinc battery negative plate |
| CN113972363A (en) * | 2021-09-28 | 2022-01-25 | 惠州锂威新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN114725323A (en) * | 2022-05-16 | 2022-07-08 | 湖北亿纬动力有限公司 | Preparation method and application of negative pole piece |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569755A (en) * | 2011-11-03 | 2012-07-11 | 青岛瀚博电子科技有限公司 | Graphite carbon negative electrode material for lithium ion battery, and preparation method thereof |
| CN104022268A (en) * | 2014-05-30 | 2014-09-03 | 陕西科技大学 | Preparation method of zinc oxide /graphene composite material for lithium ion battery |
| CN104091934A (en) * | 2014-07-17 | 2014-10-08 | 深圳市贝特瑞新能源材料股份有限公司 | Multi-component composite negative electrode material, preparation method of multi-component composite negative electrode material and lithium ion battery comprising multi-component composite negative electrode material |
| CN104617281A (en) * | 2015-02-12 | 2015-05-13 | 中南大学 | Method for preparing sodium-ion battery antimony/nitrogen-doped carbon nanosheet negative electrode composite material |
| CN104617256A (en) * | 2015-01-21 | 2015-05-13 | 上海轻丰新材料科技有限公司 | Nano-zinc oxide-graphite-graphene composite material as well as preparation method and application thereof |
| CN106340626A (en) * | 2016-10-05 | 2017-01-18 | 复旦大学 | High-capacity lithium-stored oxide nano-film composite expanded graphite material and preparation method thereof |
| CN107910515A (en) * | 2017-11-07 | 2018-04-13 | 大连理工大学 | A kind of Fe available for negative electrode of lithium ion battery3O4The preparation method of/nitrogen-doped graphene material |
| CN108336311A (en) * | 2017-08-16 | 2018-07-27 | 中天储能科技有限公司 | A kind of preparation method of the silicon-carbon cathode material of doping Argent grain |
| CN108511719A (en) * | 2018-03-29 | 2018-09-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material |
| WO2018188772A1 (en) * | 2017-04-13 | 2018-10-18 | Eckart Gmbh | Zno nanoparticle coated exfoliated graphite composite, method of producing composite and use in li-ion battery |
| CN109935662A (en) * | 2017-12-15 | 2019-06-25 | Tcl集团股份有限公司 | Electron transport material and preparation method thereof, light emitting diode |
-
2019
- 2019-11-05 CN CN201911072967.XA patent/CN112768678A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569755A (en) * | 2011-11-03 | 2012-07-11 | 青岛瀚博电子科技有限公司 | Graphite carbon negative electrode material for lithium ion battery, and preparation method thereof |
| CN104022268A (en) * | 2014-05-30 | 2014-09-03 | 陕西科技大学 | Preparation method of zinc oxide /graphene composite material for lithium ion battery |
| CN104091934A (en) * | 2014-07-17 | 2014-10-08 | 深圳市贝特瑞新能源材料股份有限公司 | Multi-component composite negative electrode material, preparation method of multi-component composite negative electrode material and lithium ion battery comprising multi-component composite negative electrode material |
| CN104617256A (en) * | 2015-01-21 | 2015-05-13 | 上海轻丰新材料科技有限公司 | Nano-zinc oxide-graphite-graphene composite material as well as preparation method and application thereof |
| CN104617281A (en) * | 2015-02-12 | 2015-05-13 | 中南大学 | Method for preparing sodium-ion battery antimony/nitrogen-doped carbon nanosheet negative electrode composite material |
| CN106340626A (en) * | 2016-10-05 | 2017-01-18 | 复旦大学 | High-capacity lithium-stored oxide nano-film composite expanded graphite material and preparation method thereof |
| WO2018188772A1 (en) * | 2017-04-13 | 2018-10-18 | Eckart Gmbh | Zno nanoparticle coated exfoliated graphite composite, method of producing composite and use in li-ion battery |
| CN108336311A (en) * | 2017-08-16 | 2018-07-27 | 中天储能科技有限公司 | A kind of preparation method of the silicon-carbon cathode material of doping Argent grain |
| CN107910515A (en) * | 2017-11-07 | 2018-04-13 | 大连理工大学 | A kind of Fe available for negative electrode of lithium ion battery3O4The preparation method of/nitrogen-doped graphene material |
| CN109935662A (en) * | 2017-12-15 | 2019-06-25 | Tcl集团股份有限公司 | Electron transport material and preparation method thereof, light emitting diode |
| CN108511719A (en) * | 2018-03-29 | 2018-09-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of bivalve layer structural composite material, preparation method and the lithium ion battery comprising the composite material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113839003A (en) * | 2021-09-17 | 2021-12-24 | 超威电源集团有限公司 | Preparation method of nickel-zinc battery negative plate |
| CN113839003B (en) * | 2021-09-17 | 2023-05-26 | 超威电源集团有限公司 | Preparation method of nickel-zinc battery negative plate |
| CN113972363A (en) * | 2021-09-28 | 2022-01-25 | 惠州锂威新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN113972363B (en) * | 2021-09-28 | 2023-01-31 | 惠州锂威新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN114725323A (en) * | 2022-05-16 | 2022-07-08 | 湖北亿纬动力有限公司 | Preparation method and application of negative pole piece |
| CN114725323B (en) * | 2022-05-16 | 2024-04-02 | 湖北亿纬动力有限公司 | Preparation method and application of negative electrode plate |
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