CN112320796A - Preparation method for simply increasing graphite layer spacing - Google Patents
Preparation method for simply increasing graphite layer spacing Download PDFInfo
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- CN112320796A CN112320796A CN202011192113.8A CN202011192113A CN112320796A CN 112320796 A CN112320796 A CN 112320796A CN 202011192113 A CN202011192113 A CN 202011192113A CN 112320796 A CN112320796 A CN 112320796A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
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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
- 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
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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 preparation method for simply increasing graphite interlayer spacing, which is characterized by comprising the following steps: (1) mixing graphite oxide serving as a raw material and a hydrazine hydrate solution according to a mass ratio of 1: 2-4, fully and uniformly mixing; (2) carrying out ultrasonic treatment on the suspension liquid in the step (1) to uniformly disperse graphite powder in a water solvent; (3) performing rapid pre-freezing treatment on the graphite suspension subjected to ultrasonic treatment in the step (2), and performing microwave treatment; (4) carrying out rapid pre-freezing treatment on the graphite mixed solution subjected to microwave treatment in the step (3), wherein intermittent ultrasonic treatment is used as assistance in the freezing process until the graphite mixed solution is completely frozen; (5) the frozen graphite suspension solid in the step (4) is frozen and dried, the preparation method can solve the technical problem that the graphite cathode material is poor in lithium ion intercalation and deintercalation in the prior art, reduce the loss of irreversible capacity and enhance the first coulombic efficiency.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method for simply increasing the spacing between graphite layers.
Background
At present, graphite is a good two-dimensional conductive carbon material, has a layered structure and a stable structure, and is a mainstream negative electrode material for lithium batteries at present, but the radius of lithium ions is greater than the interlayer spacing of graphite, so that the lithium ions are not easy to be inserted and separated, the irreversible capacity loss and the cycle performance reduction are caused, and therefore, the increase of the interlayer spacing of the graphite negative electrode is beneficial to the improvement of the negative electrode performance of the lithium ion battery and the rapid insertion and separation of the lithium ions. Graphite oxide is a graphite derivative, and is usually prepared by a Hummers method, and functional groups are grafted between graphite layers to enlarge the interlayer spacing, but the removal of oxygen-containing functional groups in graphite oxide is not complete, so that the potential safety hazard exists, and explosion is caused by the presence of oxygen-containing functional groups during battery charging test, so that it is necessary to increase the interlayer spacing and ensure the complete removal of the oxygen-containing functional groups by using graphite oxide as a raw material for increasing the graphite interlayer spacing.
In winter, a lot of plants die due to the action of low temperature, and the death is mainly caused by the fact that free water in plant bodies forms ice crystals due to the action of low temperature, and regular planes exist between the ice crystals and are easy to combine to form larger ice crystals to burst cells, so that the death of the plants is caused.
Patent document CN105720269A discloses a preparation method of a large-interlayer-distance graphite cathode material for a sodium ion battery, in the invention, graphite oxide and a carbon source substance are compounded and mixed to obtain a carbon source coated graphite oxide material, then the graphite oxide material is rapidly frozen by liquid nitrogen, and then the graphite oxide material is placed in a microwave heating device for reaction, and finally the large-interlayer-distance graphite cathode material is obtained. Oxygen-containing functional groups in the carbon source-coated graphite oxide cannot be completely removed, so that potential safety hazards exist; further, although the graphite layers are easily opened by the oxygen-containing functional groups due to the van der waals force, there is a possibility that the graphite layers are restored after the oxygen-containing functional groups are removed. Therefore, the structure of the reduced graphite oxide is fixed, and the maximum graphite interlayer spacing is kept.
Disclosure of Invention
The invention aims to provide a preparation method for simply increasing the graphite interlayer spacing, so as to solve the technical problem of poor lithium ion intercalation and deintercalation of graphite cathode materials in the prior art, reduce the loss of irreversible capacity and enhance the first coulombic efficiency.
In order to achieve the above object, the technical solution of the present invention provides a simple preparation method for increasing the graphite interlayer spacing, comprising the following steps:
(1) mixing graphite oxide serving as a raw material and a hydrazine hydrate solution according to a mass ratio of 1: 2-4, fully and uniformly mixing;
(2) carrying out ultrasonic treatment on the suspension liquid in the step (1) to uniformly disperse graphite powder in a water solvent;
(3) performing rapid pre-freezing treatment on the graphite suspension subjected to ultrasonic treatment in the step (2), and performing microwave treatment;
(4) carrying out rapid pre-freezing treatment on the graphite mixed solution subjected to microwave treatment in the step (3), wherein intermittent ultrasonic treatment is used as assistance in the freezing process until the graphite mixed solution is completely frozen;
(5) and (4) freeze-drying the frozen graphite suspension solid in the step (4).
In the step (1), the graphite oxide is prepared by a conventional or modified Hummers method, and is one or more of a high-purity graphite type material after demagnetization, which is in a shape of sphere, sheet and spheroidal block; the hydrazine hydrate solution content is 40-80% hydrazine hydrate aqueous solution.
As one preferable scheme, the ultrasonic treatment in the step (2) has the ultrasonic frequency of 500-1200Hz and the ultrasonic time of 10-60 min.
Preferably, the rapid pre-freezing treatment in the step (3) is at least one of an ultra-low temperature refrigerator freezing method, a liquid nitrogen freezing method and a cold trap freezing method.
As one preferable scheme, the microwave treatment in the step (3) has the power of 500- & lt 1000 & gt W and the treatment time of 10-180 s.
As one preferable scheme, in the step (4), the ultrasonic treatment is performed discontinuously, the ultrasonic frequency is 500-1200Hz, and the ultrasonic time is 10-20 s.
In a preferable scheme, in the step (5), the freeze drying is carried out, the temperature of a cold trap is-60 to-80 ℃, the pressure is close to a vacuum state, and the drying time is 12 to 36 hours.
In summary, the technical scheme of the preparation method for simply increasing the graphite interlayer spacing has at least the following beneficial effects: the preparation method comprises the steps of fully and uniformly mixing the graphite oxide serving as the raw material with a hydrazine hydrate aqueous solution; then quickly freezing, then quickly reducing the mixed solid substance by microwaves, and increasing the graphite interlayer spacing and removing oxygen-containing functional groups by a microwave reduction method; the preparation method comprises the steps of carrying out freeze drying treatment on the reduced graphite mixed liquid again, keeping the graphite structure by means of quick freezing, enabling the formed ice crystals to expand the interlayer spacing again, removing hydrazine hydrate aqueous solution substances outside the graphite by vacuum sublimation, combining the ice crystals formed by a freezing method to be beneficial to increasing the originally larger interlayer spacing, completely removing oxygen-containing functional groups of the graphite oxide by a microwave reduction method and increasing the interlayer spacing, and finally keeping the interlayer spacing by means of freeze drying without damaging other structures of the graphite.
The preparation method provided by the invention adopts the graphite oxide material with original holes and the hydrazine hydrate aqueous solution as raw materials, and in addition, the invention can effectively stabilize and increase the graphite layer spacing by freeze drying treatment after increasing the graphite layer spacing, can meet the national standard of lithium battery production, has safe and environment-friendly preparation process, does not need to increase a large number of process flows on the original basis, and is suitable for industrial large-area popularization and use.
In order to make the present invention and other objects, advantages, features and functions more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a Scanning Electron Microscope (SEM) picture of the graphite material prepared by the method of example 1 of the present invention.
Fig. 2 is an XRD chart of the graphite materials prepared by the methods of example 1 and comparative example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Example 1
This example 1 provides a simple preparation method for increasing the distance between graphite layers, including the following steps: mixing spherical graphite oxide and 60% hydrazine hydrate aqueous solution according to the mass ratio of 1: 4, fully and uniformly mixing, then carrying out ultrasonic treatment with ultrasonic frequency of 1200Hz and ultrasonic time of 30min to uniformly disperse graphite powder in a water solvent, quickly freezing the graphite oxide suspension subjected to ultrasonic treatment by using liquid nitrogen, then placing the graphite oxide suspension in a microwave device with reaction power of 1000W and reaction time of 180s, then carrying out quick pre-freezing treatment on the graphite mixed solution subjected to microwave reduction treatment by using liquid nitrogen, wherein the freezing process is assisted by intermittent ultrasonic treatment, the ultrasonic frequency is 1200Hz and the ultrasonic time is 20s until the graphite is completely frozen, and finally placing the frozen graphite suspension solid in a freeze dryer for freeze drying, wherein the temperature of a cold trap is-72 ℃, the pressure is close to a vacuum state, and the drying time is 36 h.
Example 2
This example 2 provides a simple preparation method for increasing the distance between graphite layers, including the following steps: mixing spherical graphite oxide and 60% hydrazine hydrate aqueous solution according to the mass ratio of 1: 4, fully and uniformly mixing, then carrying out ultrasonic treatment with ultrasonic frequency of 1200Hz and ultrasonic time of 30min to uniformly disperse graphite powder in a hydrosolvent, quickly freezing the graphite oxide suspension after ultrasonic treatment by using liquid nitrogen, then placing the graphite oxide suspension in a microwave device with reaction power of 500W and reaction time of 60s, then carrying out quick pre-freezing treatment on the graphite mixed solution after microwave reduction treatment by using liquid nitrogen, wherein intermittent ultrasonic treatment is used as assistance in the freezing process, the ultrasonic frequency is 1200Hz and the ultrasonic time is 20s until complete freezing is carried out, and finally placing the frozen graphite suspension solid in a freeze dryer for freeze drying, wherein the temperature of a cold trap is-72 ℃, the pressure is close to a vacuum state, and the drying time is 36 h.
Example 3
This example 3 provides a simple preparation method for increasing the distance between graphite layers, including the following steps: mixing spherical graphite oxide and 60% hydrazine hydrate aqueous solution according to the mass ratio of 1: 4, fully and uniformly mixing, then carrying out ultrasonic treatment with ultrasonic frequency of 1200Hz and ultrasonic time of 30min to uniformly disperse graphite powder in a hydrosolvent, quickly freezing the graphite oxide suspension after ultrasonic treatment by using liquid nitrogen, then placing the graphite oxide suspension in a microwave device with reaction power of 800W and reaction time of 60s, then carrying out quick pre-freezing treatment on the graphite mixed solution after microwave reduction treatment by using liquid nitrogen, wherein intermittent ultrasonic treatment is used as assistance in the freezing process, the ultrasonic frequency is 1200Hz and the ultrasonic time is 20s until complete freezing is carried out, and finally placing the frozen graphite suspension solid in a freeze dryer for freeze drying, wherein the temperature of a cold trap is-72 ℃, the pressure is close to a vacuum state, and the drying time is 36 h.
Comparative example 1
The experimental procedure of comparative example 1 was identical to that of example 1 except that the freeze-dried part was removed and the microwave reduced product was directly dried.
Comparative example 2
The experimental procedure of comparative example 2 was identical to that of example 2 except that the freeze-dried portion was removed and the microwave reduced product was directly dried.
Comparative example 3
The experimental procedure of comparative example 3 was identical to that of example 3 except that the freeze-dried portion was removed and the microwave reduced product was directly dried.
Application example
In the preparation of all pole pieces, carbon black (SP) is used as a conductive agent, sodium carboxymethyl cellulose (CMC) is used as a binder, and the mass ratio of the conductive agent to the synthesized active material is 1: 1: 8, mixing and dissolving the mixture in deionized water and a small amount of alcohol, and magnetically stirring for more than 8 hours to prepare uniformly dispersed battery slurry for later use. And (3) uniformly coating the battery slurry on the surface of an electrode (the cut foam copper or copper foil), carrying out vacuum drying at 85 ℃ for 12h, tabletting and weighing for later use. The electrochemical performance of the electrodes was tested by assembling a button-type half cell (CR 2025) using a glove box (model Mbraun) from Labstar, Germany. The button half cell assembly completely adopts a lithium sheet as a counter electrode, a foam nickel sheet as a buffer gasket, and the water oxygen content of the manufacturing environment is respectively as follows: water concentration < 2 ppm, oxygen concentration < 2 ppm. The electrolyte used was 1M LiPF6 dissolved in EC and DMC organic solvents. Cell cycle formation was tested on novice devices.
The following methods were used to compare the effects of examples 1 to 3 and comparative examples 1 to 3.
The electron microscope image described in the invention adopts American Saimer Feishell Phonom Generation 5 to test the morphology.
The physical phase analysis detection is carried out by using XRD-D2 PHASER of Bruker company.
The oxygen content was analyzed and determined using ELEMENTRAC ON-p from Elter, Germany.
Ultrastructural observations were performed using TECNAIG2F20 from philips, the netherlands.
TABLE 1
| Oxygen content (%) | First cycle efficiency (%) | Interlayer spacing (nm) | |
| Example 1 | 0 | 95.4 | 0.52 |
| Example 2 | 0.001 | 92.7 | 0.49 |
| Example 3 | 0 | 94.8 | 0.51 |
| Comparative example 1 | 0 | 91.5 | 0.47 |
| Comparative example 2 | 0.001 | 88.1 | 0.45 |
| Comparative example 3 | 0 | 89.6 | 0.45 |
As can be seen from the above table, the graphite oxide raw material can remove oxygen-containing functional groups to different degrees after being subjected to hydrothermal reduction treatment, wherein examples 1 and 3 and comparative examples 1 and 3 completely remove the oxygen-containing functional groups, which indicates that the experimental conditions have reached the standard for removing the oxygen-containing functional groups; and the larger the interlayer distance obtained from the above table, the better the first cycle efficiency, and the larger the interlayer distances of the examples are than those of the comparative examples, indicating that the freeze-drying method can stabilize the reduced interlayer distance.
According to the preparation method for simply increasing the graphite interlayer spacing, the original material graphite oxide and the hydrazine hydrate aqueous solution are fully and uniformly mixed; then quickly freezing, then quickly reducing the mixed solid substance by microwaves, and increasing the graphite interlayer spacing and removing oxygen-containing functional groups by a microwave reduction method; the preparation method comprises the steps of carrying out freeze drying treatment on the reduced graphite mixed liquid again, keeping the graphite structure by means of quick freezing, enabling the formed ice crystals to expand the interlayer spacing again, removing hydrazine hydrate aqueous solution substances outside the graphite by vacuum sublimation, combining the ice crystals formed by a freezing method to be beneficial to increasing the originally larger interlayer spacing, completely removing oxygen-containing functional groups of the graphite oxide by a microwave reduction method and increasing the interlayer spacing, and finally keeping the interlayer spacing by means of freeze drying without damaging other structures of the graphite.
The preparation method provided by the embodiment of the invention adopts the graphite oxide material with original holes and the hydrazine hydrate aqueous solution as raw materials, and in addition, the invention can effectively stabilize and increase the graphite interlayer spacing by freeze drying treatment after increasing the graphite interlayer spacing, can meet the national standard of lithium battery production, has safe and environment-friendly preparation process, does not need to increase a large number of process flows on the original basis, and is suitable for industrialized large-area popularization and use.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (7)
1. A simple preparation method for increasing the graphite interlayer spacing is characterized by comprising the following steps:
(1) mixing graphite oxide serving as a raw material and a hydrazine hydrate solution according to a mass ratio of 1: 2-4, fully and uniformly mixing;
(2) carrying out ultrasonic treatment on the suspension liquid in the step (1) to uniformly disperse graphite powder in a water solvent;
(3) performing rapid pre-freezing treatment on the graphite suspension subjected to ultrasonic treatment in the step (2), and performing microwave treatment;
(4) carrying out rapid pre-freezing treatment on the graphite mixed solution subjected to microwave treatment in the step (3), wherein intermittent ultrasonic treatment is used as assistance in the freezing process until the graphite mixed solution is completely frozen;
(5) and (4) freeze-drying the frozen graphite suspension solid in the step (4).
2. The method for preparing graphite with simple and easy increased interlamellar spacing according to claim 1, wherein in the step (1), the graphite oxide is prepared by a conventional or modified Hummers method, and is one or more of a spherical shape, a sheet shape and a spheroidal block shape of the demagnetized high-purity graphite type material; the hydrazine hydrate solution content is 40-80% hydrazine hydrate aqueous solution.
3. The method as claimed in claim 1, wherein the step (2) is performed with ultrasonic frequency of 500-1200Hz and ultrasonic time of 10-60 min.
4. The method for preparing graphite with increased interlamellar spacing according to claim 1, wherein the rapid pre-freezing treatment in step (3) is at least one of ultra-low temperature refrigerator freezing, liquid nitrogen freezing and cold trap freezing.
5. The method as claimed in claim 1, wherein the microwave treatment in step (3) has a power of 500- "1000W" and a treatment time of 10-180 s.
6. The method as claimed in claim 1, wherein the step (4) is performed by intermittent ultrasound, the ultrasound frequency is 500-1200Hz, and the ultrasound time is 10-20 s.
7. The simple preparation method for increasing the graphite interlayer spacing according to claim 1, wherein in the step (5), the graphite is freeze-dried, the temperature of a cold trap is-60 to-80 ℃, the pressure is close to a vacuum state, and the drying time is 12 to 36 hours.
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| CN114824213A (en) * | 2022-04-25 | 2022-07-29 | 惠州锂威新能源科技有限公司 | Composite graphite, preparation method thereof, negative plate and secondary battery |
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