CN112707388A - Graphene nano-material compound for lithium ion battery electrode - Google Patents
Graphene nano-material compound for lithium ion battery electrode Download PDFInfo
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Abstract
The invention discloses a graphene nano-material compound for a lithium ion battery electrode, and relates to the technical field of lithium ion battery materials. Firstly, carrying out a common reaction on graphene oxide and ethylenediamine to prepare modified graphene oxide, then mixing glucan and carboxymethyl chitosan, carrying out cross-linking to prepare microspheres, carrying out oxidation treatment on the microspheres by using potassium periodate, then mixing the microspheres with a modified graphene oxide dispersion solution to prepare modified microspheres, and finally mixing the modified microspheres with a tin source aqueous solution, and then putting the mixture into a carbonization furnace for carbonization to prepare the graphene nano material composite for the lithium electronic battery electrode. The graphene nano-material composite for the lithium ion battery electrode, which is prepared by the invention, has excellent electrochemical performance and still has better coulombic efficiency after repeated use.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to a graphene nano-material compound for a lithium ion battery electrode.
Background
The problems of environmental pollution, energy crisis and the like are increasingly prominent, so that the development of new energy sources and the construction of a low-carbon society which can be continuously developed become urgent. The lithium ion battery is a green, novel and high-energy battery, and is widely applied to portable electronic products, electric automobiles, energy storage equipment and the like. The performance of the lithium ion battery cathode material has a great influence on the performance of the whole battery, and the improvement of the capacity and the stability of the cathode material is of great importance to the improvement of the performance of the whole battery.
Tin dioxide, as a negative electrode material capable of providing high theoretical specific capacity, cannot be directly used for preparing a negative electrode because of large volume expansion generated in the charging and discharging processes, and is often coated with buffer materials such as carbon materials and the like on the surface to solve the problem. The development of this class of composites is influenced by two factors: (1) the uniformity of the distribution of the stannic oxide molecules directly influences the electrical property of the prepared material; (2) the safety, energy consumption, time and the like of the medicine used in the preparation process directly influence the greenness and feasibility of the material. Therefore, it is very important to find a simple, mild and environment-friendly method for uniformly dispersing the tin dioxide nanoparticles on the surface of another buffer material.
Due to the special structure of the graphene, the graphene has the characteristics of super-strong conductivity, large specific surface area, chemical and physical stability and the like, has infinite possibility in the application field of lithium ion battery materials, and can be used for loading tin dioxide nanoparticles and leveling the volume expansion of tin dioxide. However, after the negative electrode material prepared by loading tin dioxide on the surface of graphene in the traditional process is charged and discharged for many times, the rate performance of the electrode material is obviously reduced, so that a recyclable graphene nano material compound for the electrode of the lithium ion battery needs to be researched.
Disclosure of Invention
The invention aims to provide a graphene nano-material composite for a lithium ion battery electrode and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the graphene nano-material composite for the lithium ion battery electrode is characterized by mainly comprising the following raw material components in parts by weight: 10-20 parts of modified graphene oxide, 20-30 parts of carboxymethyl chitosan and 5-12 parts of tin dioxide.
The graphene nano-material composite for the lithium electronic battery electrode is characterized by further comprising the following principle components in parts by weight: 5-10 parts of oxidized dextran.
Preferably, the modified graphene oxide is prepared by the joint reaction of graphene oxide and ethylenediamine.
Preferably, the oxidized glucan is prepared by reacting glucan with potassium periodate.
As optimization, the graphene nano-material composite for the lithium electronic battery electrode mainly comprises the following raw material components in parts by weight: 15 parts of modified graphene oxide, 28 parts of carboxymethyl chitosan, 8 parts of tin dioxide and 7 parts of oxidized dextran.
As an optimization, the preparation method of the graphene nano-material composite for the lithium ion battery electrode mainly comprises the following preparation steps:
(1) mixing carboxymethyl chitosan and glucan in a hydrochloric acid solution, and adding a mixed cross-linking agent for cross-linking to prepare microspheres;
(2) dispersing graphene oxide in water, adding ammonia water and ethylenediamine, and stirring for reaction to obtain modified graphene oxide;
(3) and (2) reacting the microspheres obtained in the step (1) with potassium periodate to obtain pretreated microspheres, and mixing the pretreated microspheres with the modified graphene oxide dispersion liquid obtained in the step (2) for reaction to obtain modified microspheres.
(4) Mixing and reacting the modified microspheres obtained in the step (3) with a tin source aqueous solution according to a mass ratio, and then carbonizing to obtain a graphene nano material compound for a lithium ion battery electrode;
(5) and (4) carrying out index analysis on the graphene nano material composite for the lithium electronic battery electrode obtained in the step (4).
As an optimization, the preparation method of the graphene nano-material composite for the lithium ion battery electrode mainly comprises the following preparation steps:
(1) mixing carboxymethyl chitosan and glucan according to a mass ratio of 5:1, adding water which is 10-20 times of the mass of the carboxymethyl chitosan, stirring and mixing to obtain a mixed solution, dripping the mixed solution into a hydrochloric acid solution with a mass fraction of 8% at a speed of 5-8 mL/min, stirring and dispersing to obtain a microsphere blank dispersion solution, adjusting the pH value of the microsphere blank dispersion solution to be neutral, adding a mixed cross-linking agent solution which is 1-2 times of the mass of the microsphere blank dispersion solution, stirring and reacting, filtering, and drying to obtain microspheres;
(2) mixing graphene oxide and water according to a mass ratio of 1:200, performing ultrasonic dispersion to obtain a graphene oxide dispersion liquid, adjusting the pH of the graphene oxide dispersion liquid to 10 by using ammonia water with a mass fraction of 10%, adding ethylenediamine with the mass of 0.1 time that of the graphene oxide dispersion liquid, stirring for reaction, filtering, and drying to obtain modified graphene oxide;
(3) mixing the microspheres obtained in the step (1) with a sodium acetate buffer solution with the pH value of 3.6 according to a mass ratio of 1:10, adding potassium periodate with the mass of 0.2-0.3 time that of the microspheres, stirring for reaction, filtering to obtain pretreated microspheres, mixing the modified graphene oxide obtained in the step (2) with water according to a mass ratio of 1: 100, performing ultrasonic dispersion to obtain a modified graphene oxide dispersion solution, mixing the modified graphene oxide dispersion solution and the pretreated microspheres according to a mass ratio of 20: 1-30: 1, stirring for reaction, filtering, and drying to obtain modified microspheres;
(4) mixing the modified microspheres obtained in the step (3) with a tin source aqueous solution according to a mass ratio of 1:15, stirring for reaction, filtering to obtain a composite blank, mixing the composite blank with a sodium hydroxide solution with a mass fraction of 8% according to a mass ratio of 1: 8, mixing, stirring for reaction, filtering to obtain a pretreated compound blank, carbonizing the pretreated compound blank at 500-800 ℃ for 4-8 hours, and discharging to obtain the graphene nano material compound for the lithium ion battery electrode;
(5) and (4) carrying out index analysis on the graphene nano material composite for the lithium electronic battery electrode obtained in the step (4).
Optimally, the mixed cross-linking agent solution in the step (1) is prepared by mixing glutaraldehyde and formaldehyde according to the mass ratio of 1:1, adding water with the mass of 30-40 times that of the glutaraldehyde, and stirring and dispersing the mixture.
Preferably, the tin source aqueous solution in the step (4) is a tin dichloride aqueous solution with the mass fraction of 12% or a tin tetrachloride aqueous solution with the mass fraction of 10%.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method, when the graphene nano material composite for the lithium electronic battery electrode is prepared, ethylene diamine is used for modifying graphene oxide, and potassium periodate is used for oxidizing glucan; firstly, after the ethylene diamine modifies the graphene oxide, amino can be grafted on the surface of the graphene oxide, so that after the ethylene diamine is mixed with the oxidized dextran, the amino can generate a cross-linking reaction with aldehyde groups on the oxidized dextran, the oxidized graphene is adsorbed on the surface of a microsphere formed by the dextran and the carboxymethyl chitosan to form a core-shell structure, and because the carboxymethyl chitosan and the schiff base structure formed by the dextran and the carboxymethyl chitosan have a strong adsorption and fixation effect on metal ions, tin ions can be uniformly adsorbed on the surface of the microsphere after the microsphere is mixed with a tin source aqueous solution, and simultaneously tin dioxide can be uniformly fixed on the surface of the graphene oxide after carbonization, the tin dioxide can be prevented from falling off due to volume expansion in the use process of the composite, so that the product has good electrochemical performance, and secondly, because the microsphere volume shrinks in the carbonization process, but because the existence of the graphite oxide that the microballon top layer covered, graphite oxide can prevent the microballon excessive shrinkage to make microballon inside form certain hollow structure, and then further improved the electrochemical properties of product, moreover, the microballon after the carbonization can be with firm being fixed in graphite oxide surface of tin dioxide, prevents dropping and the reunion of tin dioxide, can reduce graphite oxide into graphite alkene simultaneously, consequently can further improve the electrochemical properties of product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe the method for testing each index of the graphene nanomaterial composite for lithium ion battery electrode manufactured in the following examples as follows:
and (3) electrochemical performance testing: the graphene nano-material composite for the lithium-ion battery electrode and the comparative product obtained in each example are respectively mixed with a conductive agent and a binder according to the mass ratio of 8:1:1, added into an agate mortar, subjected to dry grinding for a few minutes, and then added with N-methyl pyrrolidone dropwise to be continuously ground until the slurry in the mortar becomes uniform paste. And uniformly coating the slurry on a copper foil by using a scraping machine, then drying the copper foil in an oven at the temperature of 80 ℃ for 6 hours, taking the pole piece out of the oven, and cutting the pole piece into a circular pole piece with a certain diameter by using a tablet press. And then putting the circular pole piece into a vacuum drying oven with the temperature of 120 ℃ for drying for 12 hours, and taking out the circular pole piece. A metal lithium sheet is used as a counter electrode, the prepared round pole piece is used as a working electrode, the Celgard2500 type diaphragm is adopted to separate the two pole pieces, electrolyte is added dropwise, and the 2430 type button cell is assembled in a high-purity argon glove box (the humidity and the oxygen content are less than 1.0 ppm); the button cells produced from the examples and comparative examples were tested at a current density of 1000mA g-1And 2000mA · g-1Discharge capacity at that time, and current density of 1000mA · g-1The reversible capacity after 300 times of charge and discharge under the conditions (1).
Example 1
The graphene nano-material composite for the lithium ion battery electrode mainly comprises the following components in parts by weight: 15 parts of modified graphene oxide, 28 parts of carboxymethyl chitosan, 8 parts of tin dioxide and 7 parts of oxidized dextran.
A preparation method of a graphene nano-material composite for a lithium ion battery electrode mainly comprises the following preparation steps:
(1) mixing carboxymethyl chitosan and glucan in a mass ratio of 5:1 in a beaker, adding water with the mass of 20 times that of the carboxymethyl chitosan into the beaker, stirring and mixing for 30min at the temperature of 30 ℃ and the rotating speed of 380r/min, obtaining mixed liquor, dripping the mixed liquor into 8 percent hydrochloric acid solution at the speed of 8mL/min, stirring and dispersing for 60min under the condition that the rotating speed is 280r/min, obtaining microsphere blank dispersion liquid, adjusting the pH of the microsphere blank dispersion liquid to be neutral by ammonia water with the mass fraction of 5%, adding a mixed cross-linking agent solution with the mass 1 time that of the microsphere blank dispersion solution into the microsphere blank dispersion solution, stirring and reacting for 4 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a filter cake, and drying the filter cake for 2 hours at the temperature of 65 ℃ to obtain microspheres;
(2) mixing graphene oxide and water according to a mass ratio of 1:200, performing ultrasonic dispersion for 30min under the condition of a frequency of 55kHz to obtain a graphene oxide dispersion liquid, adjusting the pH of the graphene oxide dispersion liquid to 10 by using ammonia water with a mass fraction of 10%, adding ethylenediamine with the mass of 0.1 time of that of the graphene oxide dispersion liquid into the graphene oxide dispersion liquid, stirring and reacting for 6h under the conditions of a temperature of 45 ℃ and a rotating speed of 320r/min, filtering to obtain a modified graphene oxide blank, and drying the modified graphene oxide blank for 2h under the condition of a temperature of 80 ℃ to obtain modified graphene oxide;
(3) mixing the microspheres obtained in the step (1) and a sodium acetate buffer solution with the pH value of 3.6 in a mass ratio of 1:10 in a flask, adding potassium periodate with the mass of 0.2 time that of the microspheres into the flask, stirring and reacting for 3 hours at the temperature of 45 ℃ and the rotating speed of 400r/min, filtering to obtain pretreated microspheres, mixing the modified graphene oxide obtained in the step (2) and water in a mass ratio of 1: 100, performing ultrasonic dispersion for 30min under the condition of the frequency of 45kHz to obtain modified graphene oxide dispersion liquid, mixing the modified graphene oxide dispersion liquid and the pretreated microspheres according to the mass ratio of 20:1, stirring and reacting for 180min under the conditions of the temperature of 50 ℃ and the rotating speed of 300r/min, filtering to obtain pre-modified microsphere blanks, and drying the pre-modified microsphere blanks for 2h under the condition of the temperature of 80 ℃ to obtain modified microspheres;
(4) mixing the modified microspheres obtained in the step (3) with a tin source aqueous solution according to a mass ratio of 1:15, stirring and reacting for 100min at a temperature of 30 ℃ and a rotating speed of 420r/min, filtering to obtain a composite blank, and mixing the composite blank with a sodium hydroxide solution with a mass fraction of 8% according to a mass ratio of 1: 8, mixing, stirring and reacting for 3 hours at the temperature of 40 ℃, filtering to obtain a pretreated compound blank, carbonizing the pretreated compound blank for 6 hours at the temperature of 600 ℃, and discharging to obtain the graphene nano material compound for the lithium ion battery electrode;
(5) and (4) carrying out index analysis on the graphene nano material composite for the lithium electronic battery electrode obtained in the step (4).
Optimally, the mixed cross-linking agent solution in the step (1) is prepared by mixing glutaraldehyde and formaldehyde according to the mass ratio of 1:1, adding water 36 times of the mass of the glutaraldehyde, and stirring and dispersing the mixture.
Preferably, the tin source aqueous solution in the step (4) is a tin dichloride aqueous solution with the mass fraction of 12% or a tin tetrachloride aqueous solution with the mass fraction of 10%.
Example 2
The graphene nano-material composite for the lithium ion battery electrode mainly comprises the following components in parts by weight: 15 parts of graphene oxide, 28 parts of carboxymethyl chitosan, 8 parts of tin dioxide and 7 parts of oxidized dextran.
A preparation method of a graphene nano-material composite for a lithium ion battery electrode mainly comprises the following preparation steps:
(1) mixing carboxymethyl chitosan and glucan in a mass ratio of 5:1 in a beaker, adding water with the mass of 20 times that of the carboxymethyl chitosan into the beaker, stirring and mixing for 30min at the temperature of 30 ℃ and the rotating speed of 380r/min, obtaining mixed liquor, dripping the mixed liquor into 8 percent hydrochloric acid solution at the speed of 8mL/min, stirring and dispersing for 60min under the condition that the rotating speed is 280r/min, obtaining microsphere blank dispersion liquid, adjusting the pH of the microsphere blank dispersion liquid to be neutral by ammonia water with the mass fraction of 5%, adding a mixed cross-linking agent solution with the mass 1 time that of the microsphere blank dispersion solution into the microsphere blank dispersion solution, stirring and reacting for 4 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a filter cake, and drying the filter cake for 2 hours at the temperature of 65 ℃ to obtain microspheres;
(2) mixing the microspheres obtained in the step (1) and a sodium acetate buffer solution with the pH value of 3.6 in a mass ratio of 1:10 in a flask, adding potassium periodate with the mass of 0.2 time that of the microspheres into the flask, stirring and reacting for 3 hours at the temperature of 45 ℃ and the rotating speed of 400r/min, filtering to obtain pretreated microspheres, mixing graphene oxide and water in a mass ratio of 1: 100, performing ultrasonic dispersion for 30min under the condition of the frequency of 45kHz to obtain graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid and the pretreated microspheres according to the mass ratio of 20:1, stirring and reacting for 180min under the conditions of the temperature of 50 ℃ and the rotating speed of 300r/min, filtering to obtain a pre-modified microsphere blank, and drying the pre-modified microsphere blank for 2h under the condition of the temperature of 80 ℃ to obtain modified microspheres;
(3) mixing the modified microspheres obtained in the step (2) with a tin source aqueous solution according to a mass ratio of 1:15, stirring and reacting for 100min at a temperature of 30 ℃ and a rotating speed of 420r/min, filtering to obtain a composite blank, and mixing the composite blank with a sodium hydroxide solution with a mass fraction of 8% according to a mass ratio of 1: 8, mixing, stirring and reacting for 3 hours at the temperature of 40 ℃, filtering to obtain a pretreated compound blank, carbonizing the pretreated compound blank for 6 hours at the temperature of 600 ℃, and discharging to obtain the graphene nano material compound for the lithium ion battery electrode;
(4) and (4) carrying out index analysis on the graphene nano material composite for the lithium electronic battery electrode obtained in the step (3).
Optimally, the mixed cross-linking agent solution in the step (1) is prepared by mixing glutaraldehyde and formaldehyde according to the mass ratio of 1:1, adding water 36 times of the mass of the glutaraldehyde, and stirring and dispersing the mixture.
Preferably, the tin source aqueous solution in the step (3) is a tin dichloride aqueous solution with the mass fraction of 12% or a tin tetrachloride aqueous solution with the mass fraction of 10%.
Example 3
The graphene nano-material composite for the lithium ion battery electrode mainly comprises the following components in parts by weight: 15 parts of modified graphene oxide, 28 parts of carboxymethyl chitosan, 8 parts of tin dioxide and 7 parts of glucan.
A preparation method of a graphene nano-material composite for a lithium ion battery electrode mainly comprises the following preparation steps:
(1) mixing carboxymethyl chitosan and glucan in a mass ratio of 5:1 in a beaker, adding water with the mass of 20 times that of the carboxymethyl chitosan into the beaker, stirring and mixing for 30min at the temperature of 30 ℃ and the rotating speed of 380r/min, obtaining mixed liquor, dripping the mixed liquor into 8 percent hydrochloric acid solution at the speed of 8mL/min, stirring and dispersing for 60min under the condition that the rotating speed is 280r/min, obtaining microsphere blank dispersion liquid, adjusting the pH of the microsphere blank dispersion liquid to be neutral by ammonia water with the mass fraction of 5%, adding a mixed cross-linking agent solution with the mass 1 time that of the microsphere blank dispersion solution into the microsphere blank dispersion solution, stirring and reacting for 4 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a filter cake, and drying the filter cake for 2 hours at the temperature of 65 ℃ to obtain microspheres;
(2) mixing graphene oxide and water according to a mass ratio of 1:200, performing ultrasonic dispersion for 30min under the condition of a frequency of 55kHz to obtain a graphene oxide dispersion liquid, adjusting the pH of the graphene oxide dispersion liquid to 10 by using ammonia water with a mass fraction of 10%, adding ethylenediamine with the mass of 0.1 time of that of the graphene oxide dispersion liquid into the graphene oxide dispersion liquid, stirring and reacting for 6h under the conditions of a temperature of 45 ℃ and a rotating speed of 320r/min, filtering to obtain a modified graphene oxide blank, and drying the modified graphene oxide blank for 2h under the condition of a temperature of 80 ℃ to obtain modified graphene oxide;
(3) mixing the modified graphene oxide obtained in the step (2) with water according to a mass ratio of 1: 100, performing ultrasonic dispersion for 30min under the condition of the frequency of 45kHz to obtain modified graphene oxide dispersion liquid, mixing the modified graphene oxide dispersion liquid and microspheres according to the mass ratio of 20:1, stirring and reacting for 180min under the conditions of the temperature of 50 ℃ and the rotating speed of 300r/min, filtering to obtain pre-modified microsphere blank, and drying the pre-modified microsphere blank for 2h under the condition of the temperature of 80 ℃ to obtain modified microspheres;
(4) mixing the modified microspheres obtained in the step (3) with a tin source aqueous solution according to a mass ratio of 1:15, stirring and reacting for 100min at a temperature of 30 ℃ and a rotating speed of 420r/min, filtering to obtain a composite blank, and mixing the composite blank with a sodium hydroxide solution with a mass fraction of 8% according to a mass ratio of 1: 8, mixing, stirring and reacting for 3 hours at the temperature of 40 ℃, filtering to obtain a pretreated compound blank, carbonizing the pretreated compound blank for 6 hours at the temperature of 600 ℃, and discharging to obtain the graphene nano material compound for the lithium ion battery electrode;
(5) and (4) carrying out index analysis on the graphene nano material composite for the lithium electronic battery electrode obtained in the step (4).
Optimally, the mixed cross-linking agent solution in the step (1) is prepared by mixing glutaraldehyde and formaldehyde according to the mass ratio of 1:1, adding water 36 times of the mass of the glutaraldehyde, and stirring and dispersing the mixture.
Preferably, the tin source aqueous solution in the step (4) is a tin dichloride aqueous solution with the mass fraction of 12% or a tin tetrachloride aqueous solution with the mass fraction of 10%.
Comparative example
The graphene nano-material composite for the lithium ion battery electrode mainly comprises the following components in parts by weight: 15 parts of graphene oxide, 28 parts of carboxymethyl chitosan, 8 parts of tin dioxide and 7 parts of glucan.
A preparation method of a graphene nano-material composite for a lithium ion battery electrode mainly comprises the following preparation steps:
(1) mixing carboxymethyl chitosan and glucan in a mass ratio of 5:1 in a beaker, adding water with the mass of 20 times that of the carboxymethyl chitosan into the beaker, stirring and mixing for 30min at the temperature of 30 ℃ and the rotating speed of 380r/min, obtaining mixed liquor, dripping the mixed liquor into 8 percent hydrochloric acid solution at the speed of 8mL/min, stirring and dispersing for 60min under the condition that the rotating speed is 280r/min, obtaining microsphere blank dispersion liquid, adjusting the pH of the microsphere blank dispersion liquid to be neutral by ammonia water with the mass fraction of 5%, adding a mixed cross-linking agent solution with the mass 1 time that of the microsphere blank dispersion solution into the microsphere blank dispersion solution, stirring and reacting for 4 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a filter cake, and drying the filter cake for 2 hours at the temperature of 65 ℃ to obtain microspheres;
(2) mixing graphene oxide and water according to a mass ratio of 1: 100, performing ultrasonic dispersion for 30min under the condition of the frequency of 45kHz to obtain graphene oxide dispersion liquid, mixing the graphene oxide dispersion liquid and microspheres according to the mass ratio of 20:1, stirring and reacting for 180min under the conditions of the temperature of 50 ℃ and the rotating speed of 300r/min, filtering to obtain pre-modified microsphere blanks, and drying the pre-modified microsphere blanks for 2h under the condition of the temperature of 80 ℃ to obtain modified microspheres;
(3) mixing the modified microspheres obtained in the step (2) with a tin source aqueous solution according to a mass ratio of 1:15, stirring and reacting for 100min at a temperature of 30 ℃ and a rotating speed of 420r/min, filtering to obtain a composite blank, and mixing the composite blank with a sodium hydroxide solution with a mass fraction of 8% according to a mass ratio of 1: 8, mixing, stirring and reacting for 3 hours at the temperature of 40 ℃, filtering to obtain a pretreated compound blank, carbonizing the pretreated compound blank for 6 hours at the temperature of 600 ℃, and discharging to obtain the graphene nano material compound for the lithium ion battery electrode;
(4) and (4) carrying out index analysis on the graphene nano material composite for the lithium electronic battery electrode obtained in the step (3).
Optimally, the mixed cross-linking agent solution in the step (1) is prepared by mixing glutaraldehyde and formaldehyde according to the mass ratio of 1:1, adding water 36 times of the mass of the glutaraldehyde, and stirring and dispersing the mixture.
Preferably, the tin source aqueous solution in the step (3) is a tin dichloride aqueous solution with the mass fraction of 12% or a tin tetrachloride aqueous solution with the mass fraction of 10%.
Examples of effects
Table 1 below shows the results of performance analysis of the graphene nanomaterial composites for lithium ion battery electrodes using examples 1 to 3 of the present invention and a comparative example.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example | |
| 1000mA·g-1Discharge capacity (mAh. g)-1） | 608 | 569 | 512 | 415 |
| 2000mA·g-1Discharge capacity (mAh. g)-1） | 583 | 564 | 496 | 403 |
| Reversible capacity (mAh. g)-1） | 542 | 457 | 432 | 360 |
From the comparison of experimental data of example 1 and a comparative example in table 1, it can be found that the use of the modified graphene oxide and the dextran oxide in the preparation of the graphene nanomaterial composite for the lithium-ion battery electrode can effectively improve the discharge capacity of the graphene nanomaterial composite for the lithium-ion battery electrode, and the composite can maintain good reversible capacity after being used for many times and has higher coulombic efficiency; from the comparison of the experimental data of the embodiment 1 and the embodiment 2, it can be found that when the modified graphene oxide is not used in the preparation of the graphene nanomaterial composite for the lithium electronic battery electrode, the graphene oxide cannot be adsorbed on the surface of the microsphere, so that the tin dioxide cannot be fixed on the surface of the graphene in the subsequent process, and the tin dioxide expands and falls off in the use process, thereby affecting the electrochemical performance of the product; from the comparison of the experimental data of example 1 and example 3, it can be found that when the graphene nanomaterial composite for the electrode of the lithium-ion battery is prepared, no glucan is oxidized, tin ions cannot be effectively adsorbed on the surface of the microsphere, so that the nano tin dioxide on the surface of the graphene is reduced at a later stage, and the electrochemical performance of the product is affected.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (1)
1. The utility model provides a graphite alkene nano-material complex for lithium ion battery electrode which characterized in that: the material mainly comprises the following raw material components in parts by weight: 15 parts of modified graphene oxide, 28 parts of carboxymethyl chitosan, 8 parts of tin dioxide and 7 parts of oxidized glucan;
the preparation method of the graphene nano-material composite for the lithium electronic battery electrode mainly comprises the following preparation steps:
(1) mixing carboxymethyl chitosan and glucan in a mass ratio of 5:1 in a beaker, adding water with the mass of 20 times that of the carboxymethyl chitosan into the beaker, stirring and mixing for 30min at the temperature of 30 ℃ and the rotating speed of 380r/min, obtaining mixed liquor, dripping the mixed liquor into 8 percent hydrochloric acid solution at the speed of 8mL/min, stirring and dispersing for 60min under the condition that the rotating speed is 280r/min, obtaining microsphere blank dispersion liquid, adjusting the pH of the microsphere blank dispersion liquid to be neutral by ammonia water with the mass fraction of 5%, adding a mixed cross-linking agent solution with the mass 1 time that of the microsphere blank dispersion solution into the microsphere blank dispersion solution, stirring and reacting for 4 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a filter cake, and drying the filter cake for 2 hours at the temperature of 65 ℃ to obtain microspheres;
(2) mixing graphene oxide and water according to a mass ratio of 1:200, performing ultrasonic dispersion for 30min under the condition of a frequency of 55kHz to obtain a graphene oxide dispersion liquid, adjusting the pH of the graphene oxide dispersion liquid to 10 by using ammonia water with a mass fraction of 10%, adding ethylenediamine with the mass of 0.1 time of that of the graphene oxide dispersion liquid into the graphene oxide dispersion liquid, stirring and reacting for 6h under the conditions of a temperature of 45 ℃ and a rotating speed of 320r/min, filtering to obtain a modified graphene oxide blank, and drying the modified graphene oxide blank for 2h under the condition of a temperature of 80 ℃ to obtain modified graphene oxide;
(3) mixing the microspheres obtained in the step (1) and a sodium acetate buffer solution with the pH value of 3.6 in a mass ratio of 1:10 in a flask, adding potassium periodate with the mass of 0.2 time that of the microspheres into the flask, stirring and reacting for 3 hours at the temperature of 45 ℃ and the rotating speed of 400r/min, filtering to obtain pretreated microspheres, mixing the modified graphene oxide obtained in the step (2) and water in a mass ratio of 1: 100, performing ultrasonic dispersion for 30min under the condition of the frequency of 45kHz to obtain modified graphene oxide dispersion liquid, mixing the modified graphene oxide dispersion liquid and the pretreated microspheres according to the mass ratio of 20:1, stirring and reacting for 180min under the conditions of the temperature of 50 ℃ and the rotating speed of 300r/min, filtering to obtain pre-modified microsphere blanks, and drying the pre-modified microsphere blanks for 2h under the condition of the temperature of 80 ℃ to obtain modified microspheres;
(4) mixing the modified microspheres obtained in the step (3) with a tin source aqueous solution according to a mass ratio of 1:15, stirring and reacting for 100min at a temperature of 30 ℃ and a rotating speed of 420r/min, filtering to obtain a composite blank, and mixing the composite blank with a sodium hydroxide solution with a mass fraction of 8% according to a mass ratio of 1: 8, mixing, stirring and reacting for 3 hours at the temperature of 40 ℃, filtering to obtain a pretreated compound blank, carbonizing the pretreated compound blank for 6 hours at the temperature of 600 ℃, and discharging to obtain the graphene nano material compound for the lithium ion battery electrode;
(5) performing index analysis on the graphene nano material composite for the lithium electronic battery electrode obtained in the step (4);
the mixed cross-linking agent solution in the step (1) is prepared by mixing glutaraldehyde and formaldehyde according to the mass ratio of 1:1, adding water 36 times of the mass of the glutaraldehyde, and stirring and dispersing to obtain a mixed cross-linking agent solution;
and (4) the tin source aqueous solution in the step (4) is a tin dichloride aqueous solution with the mass fraction of 12% or a tin tetrachloride aqueous solution with the mass fraction of 10%.
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| CN113430713A (en) * | 2021-05-21 | 2021-09-24 | 徐恩淼 | Composite board with electromagnetic shielding performance and preparation method thereof |
| CN116072438A (en) * | 2023-04-06 | 2023-05-05 | 今朝时代(青岛)新能源科技有限公司 | Three-dimensional graphene composite material for super capacitor and preparation method thereof |
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| CN115559110B (en) * | 2022-12-02 | 2023-04-07 | 杭州德海艾科能源科技有限公司 | Carbon nano composite material modified graphite felt for vanadium battery and preparation method thereof |
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| CN103985847B (en) * | 2014-05-14 | 2016-08-24 | 武汉理工大学 | Oligochitosan self assembly auxiliary prepares the method for tin ash/Graphene composite lithium ion battery cathode material |
| CN105131349A (en) * | 2015-08-22 | 2015-12-09 | 苏州正业昌智能科技有限公司 | Preparation method of graphene oxide-chitosan composite material |
| CN105355891B (en) * | 2015-12-02 | 2018-03-06 | 中国科学技术大学 | Tin oxide-based composite material and preparation method thereof |
| CN106299309A (en) * | 2016-09-30 | 2017-01-04 | 上海交通大学 | Graphene half cladding tin oxide nano particles cluster composite material and preparation method thereof |
| CN107629076B (en) * | 2017-09-13 | 2019-06-18 | 华南理工大学 | A kind of ordered big hole metal organic frame monocrystalline and preparation method thereof |
| CN109273675B (en) * | 2018-08-03 | 2020-10-23 | 深圳市山木新能源科技股份有限公司 | Graphene composite material, preparation method thereof and lithium ion battery cathode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113430713A (en) * | 2021-05-21 | 2021-09-24 | 徐恩淼 | Composite board with electromagnetic shielding performance and preparation method thereof |
| CN116072438A (en) * | 2023-04-06 | 2023-05-05 | 今朝时代(青岛)新能源科技有限公司 | Three-dimensional graphene composite material for super capacitor and preparation method thereof |
| CN116072438B (en) * | 2023-04-06 | 2023-08-22 | 今朝时代(青岛)新能源科技有限公司 | Three-dimensional graphene composite material for super capacitor and preparation method thereof |
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