CN112811409A - Method for preparing hard carbon negative electrode material and high-specific-capacity lithium ion battery by using salix purpurea as carbon source - Google Patents
Method for preparing hard carbon negative electrode material and high-specific-capacity lithium ion battery by using salix purpurea as carbon source Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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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
- 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
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
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Abstract
The invention provides a method for preparing a hard carbon negative electrode material and a high-specific-capacity lithium ion battery by using salix purpurea as a carbon source, and relates to the technical field of new energy. The preparation method has the advantages of reproducibility, greenness, low cost, no pollution and the like, provides a new way and effective measures for the preparation and large-scale production of green new energy storage materials, and the hard carbon anode material obtained by the invention has unique initial discharge specific capacity, cycling stability and rate capability.
Description
Technical Field
The invention relates to the technical field of new energy, in particular to a method for preparing a hard carbon negative electrode material and a high-specific-capacity lithium ion battery by using salix purpurea as a carbon source.
Background
To meet the needs of modern society and to solve the emerging ecological problems, the search for new, low-cost and environmentally friendly energy conversion and storage systems is a hot and difficult point of current research in this field.
At present, graphite has the advantages of low charge-discharge voltage platform, high cycle stability, low cost and the like, and is considered to be an ideal negative electrode material for current LIBs. However, the graphite powder hinders the development of lithium ion batteries in energy storage due to the problems of low power density, slow energy transfer, potential safety hazard and the like caused by large specific surface area, anisotropy, small interlayer spacing and rapid charge and discharge.
The biomass-based hard carbon material has attracted extensive attention in LIBs anode materials due to its advantages of low cost, abundant resources, fast regeneration speed, environmental friendliness, and the like. Currently studied biomass such as rice hulls, egg white, walnut shells, almond shells, grapefruit peels, straw, and the like. Xiao et al successfully prepare a birth-material-based carbon material by using waste chaff as a raw material and utilizing an etching method. Jiang et al extracted 3D rod-like structures and 2D carbon nanosheets from ramie and corncobs by heat treatment to apply to lithium ion batteries. Sun et al have demonstrated that shaddock peel-based carbon materials have a stable reversible capacity of 452mAhg-1 after 200 cycles in a lithium ion battery using a heat treatment process. However, in addition to the key steps for preparing the biomass-based hard carbon material, the subsequent chemical activation and physical activation are also one of the important influencing factors of the electrochemical performance, and the further development of the hard carbon material in the field of lithium battery energy storage materials is limited due to the complexity and high cost of the synthesis process. Therefore, the preparation of green, recyclable and high performance through direct carbonization and simple post-treatment of biomass is of great importance.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a hard carbon negative electrode material, and provide a new way for preparation and large-scale production of green new energy storage materials.
The invention also aims to provide a hard carbon negative electrode material which has unique initial discharge specific capacity, cycling stability and rate capability.
It is a further object of the present invention to provide an anode comprising said hard carbon anode material having the same advantages as said hard carbon anode material.
The fourth purpose of the invention is to provide a preparation method of the cathode.
The fifth object of the present invention is to provide a lithium ion battery comprising the negative electrode.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, a method for preparing a hard carbon anode material comprises the following steps:
and carrying out thermal decomposition by using the red willow branches as a carbon source to obtain the hard carbon cathode material.
Further, the preparation method comprises the following steps:
and sequentially carrying out primary annealing treatment, crushing and screening treatment and secondary annealing treatment on the red willow branches, and then carrying out acid soaking treatment and deacidification treatment to obtain the hard carbon negative electrode material.
Further, the temperature rise rate of the primary annealing treatment is 1-3 ℃/min;
further preferably, the temperature of the primary annealing treatment is 350-450 ℃;
further, the temperature of the primary annealing treatment is 350-450 ℃;
further preferably, the time for heat preservation of the primary annealing treatment is 1-3 hours.
Further, the temperature rise rate of the secondary annealing treatment is 1-3 ℃/min;
further preferably, the temperature of the secondary annealing treatment is 500-800 ℃;
preferably, the temperature of the secondary annealing treatment is 500-800 ℃;
further preferably, the time for heat preservation of the secondary annealing treatment is 1-3 hours.
Further, the temperature of the acid soaking treatment is 60-80 ℃;
preferably, the time of the acid soaking treatment is more than 5 hours;
further preferably, the concentration of the acid liquor for the acid soaking treatment is 0.08-0.1mol/L, preferably 0.1 mol/L;
preferably, the acid of the acid soaking treatment includes at least one of hydrochloric acid and hydrofluoric acid.
Further, the preparation method comprises the following steps:
(a) cleaning, namely ultrasonically cleaning the red willow branches with the length less than 10cm for several times by using polar liquid, and drying to obtain the cleaned red willow branches;
(b) performing primary annealing treatment, namely heating the cleaned red willow branches obtained in the step (a) to 350-450 ℃ at a heating rate of 1-3 ℃/min in an inert gas atmosphere, and preserving heat at 350-450 ℃ for 1-3h to obtain the red willow branches subjected to primary annealing treatment;
(c) crushing and screening, namely mixing the primarily annealed salix purpurea hassk branches obtained in the step (b) with ball-milled beads according to the mass ratio of 1: 7-15 to obtain a mixture, adding an organic solvent to cover the surface of the mixture, crushing at the rotation speed of 200-400 rpm for more than 70h, and screening to obtain carbonized salix purpurea hassk branch powder;
(d) performing secondary annealing treatment, namely putting the carbonized red willow branch powder obtained in the step (c) in an inert gas atmosphere, heating to 500-800 ℃ at the heating rate of 1-3 ℃/min, and preserving heat at 500-800 ℃ for 1-3h to obtain the carbonized red willow branch powder subjected to secondary annealing treatment;
(e) acid soaking treatment:
immersing the carbonized red willow branch powder subjected to secondary annealing treatment obtained in the step (d) into 0.1mol/L hydrochloric acid solution, and stirring for more than 5 hours at the temperature of 60-80 ℃ to obtain acid-immersed carbonized red willow branch powder;
(f) acid removal treatment:
and (e) ultrasonically cleaning the carbonized red willow branch powder subjected to acid soaking and obtained in the step (e) by using ethanol and/or water to remove acid, then centrifugally removing the acid, wherein the acid removal treatment is performed for more than 4 times to ensure that the pH value is more than 6, and finally, drying is more than 8 hours to obtain the hard carbon negative electrode material.
In a second aspect, a hard carbon anode material prepared by the preparation method.
In a third aspect, an anode includes the hard carbon anode material.
In a fourth aspect, a method for preparing the anode includes the steps of:
mixing the hard carbon negative electrode material with a conductive agent and a binder, then dropwise adding a solvent, grinding the mixture into pasty liquid, then coating the pasty liquid on a wafer, drying and tabletting to obtain a negative electrode;
further, the mass ratio of the hard carbon negative electrode material to the mixture of the conductive agent and the binder is 8:1: 1;
preferably, the solvent comprises N-methylpyrrolidone;
further preferably, the conductive agent includes Super P;
preferably, the binder comprises PVDF.
In a fifth aspect, a lithium ion battery includes the anode.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the hard carbon cathode material, the biomass resource of the salix purpurea is used as a carbon source, and the hard carbon cathode material is obtained through heat treatment, so that the method has the advantages of being renewable, green, low in cost, free of pollution and the like, and provides a new way and effective measures for preparation and large-scale production of green new energy storage materials.
The hard carbon negative electrode material provided by the invention has unique initial discharge specific capacity, cycling stability and rate capability.
The cathode provided by the invention has the same advantages as the hard carbon cathode material, and the details are not repeated.
The preparation method of the cathode provided by the invention has the same advantages as the preparation method of the hard carbon cathode material, and is not repeated herein.
The lithium ion battery provided by the invention has the same advantages as the hard carbon cathode material, and is not repeated herein.
Drawings
In order to more clearly illustrate the embodiments of the present invention 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 that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a process flow diagram for preparing a negative electrode according to an embodiment of the present invention;
fig. 2 is an SEM image of a hard carbon negative electrode material obtained in an experimental example of the present invention;
FIG. 3 is an XRD pattern of CRN obtained in an experimental example of the present invention;
FIG. 4 is a Raman spectrum of CRN obtained in the experimental example of the present invention;
FIG. 5 is a charge-discharge cycle curve of CRN obtained in the experimental example of the present invention at different carbonization temperatures;
FIG. 6 shows the current rates at 50, 100, 200 and 500mAg obtained in the experimental examples of the present invention-1After charging and discharging, the material recovers to 50mAg-1Specific capacity graph of time.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
At present, graphite powder hinders the development of lithium ion batteries in energy storage due to the problems of low power density, slow energy transmission, potential safety hazards and the like caused by large specific surface area, anisotropy, small interlayer spacing and rapid charge and discharge.
The biomass-based hard carbon material has attracted extensive attention in LIBs anode materials due to its advantages of low cost, abundant resources, fast regeneration speed, environmental friendliness, and the like. However, the preparation of biomass-based hard carbon materials is complicated and expensive due to the synthesis process, which limits the further development of the hard carbon materials in the field of lithium battery energy storage materials.
Therefore, the preparation of green, recyclable and high performance through direct carbonization and simple post-treatment of biomass is of great importance.
In view of the above, the invention particularly provides a preparation method of a hard carbon negative electrode material, which takes red willow branches as a carbon source and obtains the hard carbon negative electrode material after heat treatment and acid treatment. The method has the advantages of reproducibility, greenness, low cost, no pollution and the like, and provides a new way and effective measures for the preparation and the large-scale production of green new energy storage materials.
According to an aspect of the present invention, there is provided a method for preparing a hard carbon anode material, comprising the steps of:
and carrying out thermal decomposition by using the red willow branches as a carbon source to obtain the hard carbon cathode material.
In a preferred embodiment, the method for preparing the hard carbon anode material comprises the following steps:
and sequentially carrying out primary annealing treatment, crushing and screening treatment and secondary annealing treatment on the red willow branches, and then carrying out acid soaking treatment and deacidification treatment to obtain the hard carbon negative electrode material.
In the preparation method of the hard carbon cathode material, the primary annealing treatment has the effect of completely carbonizing the branches of the salix chinensis and is used for preparing for grinding into nano particles at the early stage;
in a preferred embodiment, the temperature rise rate of the primary annealing treatment is 1-3 ℃/min, and typical but non-limiting temperature rise rates are 1 ℃/min, 2 ℃/min and 3 ℃/min;
in a preferred embodiment, the temperature of the primary annealing treatment is raised to 350-450 ℃, and the temperature is raised to 350 ℃, 400 ℃ and 450 ℃ as a typical but non-limiting example;
in a preferred embodiment, the temperature of the primary annealing treatment is 350-450 ℃, and typical but non-limiting temperature of the primary annealing treatment is 350 ℃, 400 ℃ and 450 ℃;
in a preferred embodiment, the primary annealing treatment is performed for 1-3 hours, and typical but non-limiting holding times are 1 hour, 2 hours and 3 hours.
In the preparation method of the hard carbon negative electrode material, the secondary annealing has the effect that the hard carbon negative electrode material with high specific performance is prepared under the specific condition of the secondary annealing, particularly at a specific temperature;
in a preferred embodiment, the temperature rise rate of the secondary annealing treatment is 1-3 ℃/min, and typical but non-limiting temperature rise rates are 1 ℃/min, 2 ℃/min and 3 ℃/min;
in a preferred embodiment, the temperature of the secondary annealing is 500 to 800 ℃, and the typical but non-limiting temperature of the secondary annealing is 500 ℃, 600 ℃, 700 ℃, 800 ℃;
in a preferred embodiment, the temperature of the secondary annealing treatment is 500 to 800 ℃, and typical but non-limiting temperature of the secondary annealing treatment is 500 ℃, 600 ℃, 700 ℃, 800 ℃;
in a preferred embodiment, the time for the secondary annealing treatment is 1-3h, and typical but non-limiting holding times are 1h, 2h and 3 h.
In the preparation method of the hard carbon cathode material, the acid soaking treatment has the effects of removing ash on the surface of a carbon source, increasing the adsorption capacity of biomass charcoal and also increasing the specific surface area of the biomass charcoal;
wherein, the acid for acid soaking treatment includes but is not limited to hydrochloric acid, hydrofluoric acid;
in a preferred embodiment, the temperature of the acid soaking treatment is 60 to 80 ℃, and typical but non-limiting treatment temperatures are, for example, 60 ℃, 70 ℃, 80 ℃;
in a preferred embodiment, the acid soaking treatment is carried out for a period of > 5h, typical but not limiting treatment periods being for example 6h, 7h, 8h, 9 h;
in a preferred embodiment, the acid solution for the acid pickling treatment has a concentration of 0.08 to 0.1mol/L, and further 0.1 mol/L.
In a preferred embodiment, the method for preparing the hard carbon anode material comprises the following steps:
(a) cleaning, namely ultrasonically cleaning the red willow branches with the length less than 10cm for several times by using polar liquid, and drying to obtain the cleaned red willow branches;
(b) performing primary annealing treatment, namely heating the cleaned red willow branches obtained in the step (a) to 350-450 ℃ at a heating rate of 1-3 ℃/min in an inert gas atmosphere, and preserving heat at 350-450 ℃ for 1-3h to obtain the red willow branches subjected to primary annealing treatment;
(c) crushing and screening, namely mixing the primarily annealed salix purpurea hassk branches obtained in the step (b) with ball-milled beads according to the mass ratio of 1: 7-15 to obtain a mixture, adding an organic solvent to cover the surface of the mixture, crushing at the rotation speed of 200-400 rpm for more than 70h, and screening to obtain carbonized salix purpurea hassk branch powder;
(d) performing secondary annealing treatment, namely putting the carbonized red willow branch powder obtained in the step (c) in an inert gas atmosphere, heating to 500-800 ℃ at the heating rate of 1-3 ℃/min, and preserving heat at 500-800 ℃ for 1-3h to obtain the carbonized red willow branch powder subjected to secondary annealing treatment;
(e) acid soaking treatment:
immersing the carbonized red willow branch powder subjected to secondary annealing treatment obtained in the step (d) into 0.1mol/L hydrochloric acid solution, and stirring for more than 5 hours at the temperature of 60-80 ℃ to obtain acid-immersed carbonized red willow branch powder;
(f) acid removal treatment:
and (e) ultrasonically cleaning the carbonized red willow branch powder subjected to acid soaking and obtained in the step (e) by using ethanol and/or water to remove acid, then centrifugally removing the acid, wherein the acid removal treatment is performed for more than 4 times to ensure that the pH value is more than 6, and finally, drying is more than 8 hours to obtain the hard carbon negative electrode material.
A typical preparation method of a hard carbon negative electrode material is shown in a flow chart of figure 1 and comprises the following steps:
(1) ultrasonic cleaning, namely cutting the red willow branches into branches with the length less than 10cm, cleaning the branches for several times in an ultrasonic cleaning machine by using deionized water and absolute ethyl alcohol, and cleaning dust and stains on the surface;
(2) performing primary annealing treatment, namely putting the red willow branch knots obtained by cleaning in the step (1) into an oven at the temperature of 60-80 ℃ for drying, then putting the dried red willow branch knots into a GSL-1600X tube furnace, heating to 350-450 ℃ at the heating rate of 1-3 ℃/min in the atmosphere of inert gas argon (Ar), preserving the heat for 1-3 hours, then cooling to room temperature, and taking out the red willow branch knots to obtain the red willow branch knots subjected to primary annealing treatment;
(3) crushing and sieving, namely mixing the primarily annealed salix purpurea knots obtained in the step (2) with ball milling beads according to the mass ratio of 1: 7-15 to obtain a mixture, adding absolute ethyl alcohol to cover the surface of the mixture, then performing unidirectional operation on a ball mill at the rotating speed of 200-400 rpm for more than 70h, and finally sieving to obtain carbonized salix purpurea powder;
(4) secondary annealing, namely putting the carbonized red willow branch powder obtained in the step (3) into a GSL-1600X tubular furnace in an inert gas (Ar) atmosphere again, heating to 500-800 ℃ at a heating rate of 1-3 ℃/min, preserving heat for 1-3h, cooling to room temperature, and taking out to obtain the carbonized red willow branch powder subjected to secondary annealing;
(5) acid soaking, namely soaking the carbonized rose willow powder obtained in the step (4) after secondary annealing treatment into 0.1mol/L hydrochloric acid solution, then placing the carbonized rose willow powder in a water bath kettle at the temperature of 60-80 ℃ for magnetic stirring and constant temperature treatment for more than 5 hours to fully contact and react, and taking out the carbonized rose willow branch powder after acid soaking after the reaction is finished;
(6) and (3) centrifugal deacidification treatment, namely washing the carbonized red willow branch powder obtained in the step (5) after acid leaching in an ultrasonic cleaning machine by using alcohol solution and deionized water, separating the solution from a product by using a centrifugal machine, wherein the circulation frequency of deacidification is more than 4 times, the pH value of the solution is more than 6, and finally drying in a blast drying oven for more than 8 hours to obtain the hard carbon cathode material.
The preparation method of the hard carbon cathode material takes the red willow branches as a carbon source, and the hard carbon cathode material is obtained after heat treatment and acid treatment. The method has the advantages of reproducibility, greenness, low cost, no pollution and the like, and provides a new way and effective measures for the preparation and the large-scale production of green new energy storage materials.
According to a second aspect of the present invention, there is provided a hard carbon anode material having unique specific initial discharge capacity, cycling stability and rate capability.
According to a third aspect of the present invention, there is provided a negative electrode prepared from the hard carbon negative electrode material, which has the same advantages as the hard carbon negative electrode material and will not be described herein again.
According to a fourth aspect of the present invention, there is provided a method for producing the anode, comprising the steps of:
mixing the hard carbon negative electrode material with a conductive agent and a binder, dripping a solvent, grinding the mixture into pasty liquid, coating the pasty liquid on a wafer, drying and tabletting to obtain a negative electrode;
wherein, the solvent includes but is not limited to N-methyl pyrrolidone, the conductive agent includes but is not limited to Super P, and the binder includes but is not limited to PVDF.
In a preferred embodiment, the mass ratio of the hard carbon negative electrode material to the conductive agent to the binder is 8:1: 1.
A typical preparation method of a negative electrode includes the steps of:
mixing the hard carbon negative electrode material, a conductive agent Super P and a binder PVDF in a mortar according to the mass ratio of 8:1:1, stirring the mixture till the mixture is fully mixed, dripping an NMP solvent, and continuously grinding the mixture till pasty liquid is obtained. And then uniformly coating the slurry on a cut nickel foam wafer with the diameter of 14mm by using a medicine spoon, then putting the nickel foam wafer into a vacuum drying oven with the temperature of 120 ℃ for vacuum drying for 12 hours to remove the NMP solvent, taking out the nickel foam wafer, and compacting the nickel foam wafer by using a tablet press to obtain the cathode with neat edge and good shape.
The method has the same advantages as the preparation method of the hard carbon cathode material, and is not described in detail herein.
In a fifth aspect, a lithium ion battery is provided, which has the same advantages as the hard carbon negative electrode material, and is not described herein again.
The invention is further illustrated by the following examples. The materials in the examples are prepared according to known methods or are directly commercially available, unless otherwise specified.
Example 1
A preparation method of a hard carbon negative electrode material comprises the following steps:
(1) ultrasonic cleaning, namely cutting the red willow branches into branches with the length of 9cm, cleaning the branches for a plurality of times in an ultrasonic cleaning machine by using deionized water and absolute ethyl alcohol, and cleaning dust and stains on the surface;
(2) performing primary annealing treatment, namely putting the red willow branch sections obtained by cleaning in the step (1) into an oven at 80 ℃ for drying, then putting the dried red willow branch sections into a GSL-1600X tube furnace, heating to 400 ℃ at a heating rate of 2 ℃/min in an atmosphere of inert gas argon (Ar), preserving heat for 2 hours, then cooling to room temperature, and taking out to obtain the red willow branch sections subjected to primary annealing treatment;
(3) crushing and sieving, namely mixing the primarily annealed salix purpurea segments obtained in the step (2) with ball milling beads according to the mass ratio of 1:15 to obtain a mixture, adding absolute ethyl alcohol to cover the surface of the mixture, then performing unidirectional operation on a ball mill at the rotating speed of 300rpm for 90 hours, and finally sieving to obtain carbonized salix purpurea powder;
(4) secondary annealing, namely putting the carbonized red willow branch powder obtained in the step (3) into a GSL-1600X tubular furnace in an inert gas (Ar) atmosphere again, heating to 500 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, and taking out after cooling to room temperature to obtain the carbonized red willow branch powder subjected to secondary annealing;
(5) acid soaking, namely soaking the carbonized rose willow powder obtained in the step (4) after secondary annealing treatment into 0.1mol/L hydrochloric acid solution, then placing the carbonized rose willow powder in a water bath kettle at the temperature of 80 ℃ for magnetic stirring and constant temperature treatment for 12 hours to fully contact and react, and taking out after the reaction is finished to obtain carbonized rose willow branch powder after acid leaching;
(6) and (3) centrifugal deacidification treatment, namely washing the carbonized red willow branch powder obtained in the step (5) after acid leaching in an ultrasonic cleaning machine by using alcohol solution and deionized water, separating the solution from a product by using a centrifugal machine, wherein the circulation time of deacidification is 5 times to ensure that the pH value is 7, and finally drying in a forced air drying oven for 12 hours to obtain the hard carbon cathode material, wherein the process flow diagram is shown in figure 1 and is marked as CRN 500.
A method for preparing a negative electrode:
mixing the hard carbon negative electrode material CRN500 obtained in the step with a conductive agent Super P and a binder PVDF in a weight ratio of 8:1:1 in a mortar, stirring the mixture fully, dripping an NMP solvent, and continuously grinding the mixture to form pasty liquid to obtain slurry. And then uniformly coating the slurry on a cut nickel foam wafer with the diameter of 14mm by using a medicine spoon, then putting the nickel foam wafer into a vacuum drying oven with the temperature of 120 ℃ for vacuum drying for 12 hours to remove the NMP solvent, taking out the nickel foam wafer, and compacting the nickel foam wafer by using a tablet press to obtain the cathode with neat edge and good shape.
Example 2
The difference between this example and example 1 is that the temperature of the secondary annealing treatment in step (4) of this example is 600 ℃, the remaining steps and parameters are the same as those in example 1, and a hard carbon anode material is obtained, the process flow diagram of which is shown in fig. 1 and labeled as CRN600, and a cathode is prepared from the hard carbon anode material CRN600, the steps and parameters are the same as those in example 1.
Example 3
The difference between this example and example 1 is that the temperature of the secondary annealing treatment in step (4) of this example is 700 ℃, the remaining steps and parameters are the same as those in example 1, and a hard carbon anode material is obtained, the process flow diagram of which is shown in fig. 1 and labeled as CRN700, and a cathode is prepared from the hard carbon anode material CRN700, and the steps and parameters are the same as those in example 1.
Example 4
The difference between this example and example 1 is that the temperature of the secondary annealing treatment in step (4) of this example is 800 ℃, the remaining steps and parameters are the same as those in example 1, and a hard carbon anode material is obtained, the process flow diagram of which is shown in fig. 1 and labeled as CRN800, and a cathode is prepared from the hard carbon anode material CRN800, and the steps and parameters are the same as those in example 1.
Experimental examples electrochemical testing and characterization
The cells were assembled using the materials CRN500, CRN600, CRN700, and CRN800 obtained in experimental examples 1 to 4, and after standing for 24 hours, the cells were subjected to Electrochemical Impedance (EIS) and cyclic voltammetry tests using a CH660E electrochemical workstation. The frequency of the alternating current impedance is 10mHz to 10KHz, the scanning rate of the cyclic voltammetry is 0.1mV/s, and the voltage range is 0.01 to 3.0V. The CT2001A LANHE charging and discharging instrument performs charging and discharging circulation and multiplying power performance tests on the battery. The charging and discharging voltage range is 0.01-3.0V, and the charging and discharging current density is 50 mAh/g-500 mAh/g.
Observing the appearance of the biomass-based hard carbon negative electrode material by using an S-3400N scanning electron microscope (F-SEM) produced by Hitachi, Japan; performing phase characterization on the material by using an X-ray diffractometer (XRD); performing structural representation on the material by using a laser Raman spectrometer DXR; the particle size distribution range of the material was measured by an LS13320 laser diffraction particle size analyzer manufactured by Beckmann Coulter, USA.
Test one
The microscopic morphology of the sample was analyzed by SEM, and the microscopic morphology of the surface of the sample was observed and analyzed, as shown in fig. 2, wherein (a) is the SEM image of CRN500 of example 1, (b) is the SEM image of CRN600 of example 2, (c) is the SEM image of CRN700 of example 3, and (d) is the SEM image of CRN800 of example 4, it can be seen that the morphologies at different temperatures are irregular, the particle size is non-uniform, the average particle size is 8 μm, and many small particles are attached to the surface of large particles.
Test two
The sample was subjected to phase analysis using an X-ray diffractometer (XRD) and a laser micro-raman spectrometer. As shown in fig. 3 and fig. 4, fig. 3 shows that a broad peak and a weaker bread peak appear around 22 ° and 44 ° of 2 θ, which are characteristic diffraction peaks of crystal faces of (002) and (110) of hard carbon materials, and the diffraction peak at 22 ° is gradually sharpened with the increase of temperature, which indicates that the graphitization degree of the material is increased and the order degree is increased. While the characteristic diffraction peak corresponding to (110) is considered to be a honeycomb structure formed by sp2 hybridization. In addition, no sharp peak is obvious on the two diffraction peaks, which indicates that the sample carbon material shows a disordered structure.
Raman analysis was used to investigate the effect of temperature on graphitization of CRN materials, and as shown in FIG. 4, two peaks appeared at 1350cm-1 and 1590cm-1, correlating with the characteristic D and G bands, D representing defects in the carbon layer structure and carbon material, and G representing the vibration of sp2 hybridized carbon atoms in the graphite sheet structure. Generally, the intensity ratio (ID/IG) of the D peak and the G peak is used to indicate the degree of graphitization of the carbon material and the average size of sp2 domains. The ID/IG ratios of CRN500, CRN600, CRN700 and CRN800 are 0.684, 0.689, 0.932 and 0.943 respectively, and it is obvious that the peak strength ratios increase with the increase of the carbonization temperature, which indicates that the graphitization degree of the material is increased, and the graphite carbon represented by the G peak with higher strength is dominant.
Test three
FIG. 5 shows that CRN500, CRN600, CRN700 and CRN800 at a current rate of 100mAhg-1The initial high specific capacity is 590, 1014, 827 and 665mAhg respectively-1The difference of the coulomb efficiency of the first circle is not large and is stabilized at 50%. The coulombic efficiency is improved to more than 90% from the second circle, the CRN600 is particularly outstanding in the aspects of capacity retention rate and first circle discharge specific capacity, and the reversible capacity is gradually increased after 70 circles of circulation.
The irreversible capacity is degraded mainly because the SEI film formed on the surface of lithium metal is fragile and unstable, the SEI film is broken and regenerated during the process of lithium ion deintercalation, and most of Li is consumed+And electrolytes, resulting in low initial coulombic efficiency. As the cycling continues, the coulombic efficiencies are essentially the same, indicating that a stable SEI film is formed and the carbon electrode material is in a stable state.
Test four
FIG. 6 shows current rates at 50, 100, 200 and 500mAg-1After charging and discharging, the material recovers to 50mAg-1When the method is used, the specific capacity is basically recovered to the initial value, and good cycle reversible performance is exerted.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a hard carbon negative electrode material is characterized by comprising the following steps:
and carrying out thermal decomposition by using the red willow branches as a carbon source to obtain the hard carbon cathode material.
2. The method of claim 1, comprising the steps of:
and sequentially carrying out primary annealing treatment, crushing and screening treatment and secondary annealing treatment on the red willow branches, and then carrying out acid soaking treatment and deacidification treatment to obtain the hard carbon negative electrode material.
3. The preparation method according to claim 2, wherein the rate of temperature rise in the primary annealing treatment is 1 to 3 ℃/min;
preferably, the temperature of the primary annealing treatment is 350-450 ℃;
preferably, the temperature of the primary annealing treatment is 350-450 ℃;
preferably, the time for heat preservation of the primary annealing treatment is 1-3 hours.
4. The preparation method according to claim 2, wherein the rate of temperature rise in the secondary annealing treatment is 1 to 3 ℃/min;
preferably, the temperature of the secondary annealing treatment is 500-800 ℃;
preferably, the temperature of the secondary annealing treatment is 500-800 ℃;
preferably, the time for heat preservation of the secondary annealing treatment is 1-3 hours.
5. The preparation method according to claim 2, wherein the temperature of the acid soaking treatment is 60-80 ℃;
preferably, the time of the acid soaking treatment is more than 5 hours;
preferably, the concentration of the acid liquor for the acid soaking treatment is 0.08-0.1mol/L, preferably 0.1 mol/L;
preferably, the acid solution for the acid soaking treatment includes at least one of hydrochloric acid and hydrofluoric acid.
6. The production method according to any one of claims 1 to 5, characterized by comprising the steps of:
(a) cleaning, namely ultrasonically cleaning the red willow branches with the length less than 10cm for several times by using polar liquid, and drying to obtain the cleaned red willow branches;
(b) performing primary annealing treatment, namely heating the cleaned red willow branches obtained in the step (a) to 350-450 ℃ at a heating rate of 1-3 ℃/min in an inert gas atmosphere, and preserving heat at 350-450 ℃ for 1-3h to obtain the red willow branches subjected to primary annealing treatment;
(c) crushing and screening, namely mixing the primarily annealed salix purpurea hassk branches obtained in the step (b) with ball-milled beads according to the mass ratio of 1: 7-15 to obtain a mixture, adding an organic solvent to cover the surface of the mixture, crushing at the rotation speed of 200-400 rpm for more than 70h, and screening to obtain carbonized salix purpurea hassk branch powder;
(d) performing secondary annealing treatment, namely putting the carbonized red willow branch powder obtained in the step (c) in an inert gas atmosphere, heating to 500-800 ℃ at the heating rate of 1-3 ℃/min, and preserving heat at 500-800 ℃ for 1-3h to obtain the carbonized red willow branch powder subjected to secondary annealing treatment;
(e) acid soaking, namely soaking the carbonized red willow branch powder obtained in the step (d) after the secondary annealing treatment into 0.1mol/L hydrochloric acid solution, and stirring for more than 5 hours at the temperature of 60-80 ℃ to obtain the carbonized red willow branch powder after acid soaking;
(f) and (e) acid removal treatment, namely ultrasonically cleaning the carbonized red willow branch powder obtained in the step (e) after acid soaking by using ethanol and/or water to remove acid, then centrifugally removing acid, wherein the acid removal treatment is performed for more than 4 times to ensure that the pH value is more than 6, and finally, drying is performed for more than 8 hours to obtain the hard carbon cathode material.
7. A hard carbon anode material prepared by the preparation method of any one of claims 1 to 6.
8. A negative electrode comprising the hard carbon negative electrode material according to claim 7.
9. A method for producing the anode according to claim 8, comprising the steps of:
mixing the hard carbon negative electrode material of claim 7 with a conductive agent and a binder, adding a solvent dropwise, grinding the mixture into a pasty liquid, coating the pasty liquid on a wafer, drying and tabletting to obtain a negative electrode;
preferably, the mass ratio of the hard carbon negative electrode material to the mixture of the conductive agent and the binder is 8:1: 1;
preferably, the solvent comprises N-methylpyrrolidone;
preferably, the conductive agent includes Super P;
preferably, the binder comprises PVDF.
10. A lithium ion battery comprising the negative electrode according to claim 8.
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