CN113594404B - Preparation method of integrated carbon fluoride anode - Google Patents
Preparation method of integrated carbon fluoride anode Download PDFInfo
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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
- H01M4/5835—Comprising fluorine or fluoride salts
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Abstract
The application discloses a preparation method of an integrated carbon fluoride anode in the technical field of preparation of battery electrodes, which comprises the following steps: sieving the carbon nano tube and the graphene in an ethanol solution for dispersion to obtain a graphene/carbon nano tube suspension; filtering the graphene/carbon nanotube suspension in vacuum through a microporous filter membrane, drying, and then removing the filter membrane to obtain a graphene/carbon nanotube current collector; carrying out fluorination reaction on a graphene/carbon nano tube current collector and mixed reaction gas consisting of a gas fluorine source and diluent gas at the temperature of 600-800 ℃ to obtain the novel integrated carbon fluoride anode. This application is through three-dimensional graphite alkene of high temperature fluorination/carbon nanotube mass flow body, forms the integration carbon fluoride positive pole of compatible graphite alkene of fluorinating and carbon fluoride nanotube, graphite alkene, carbon nanotube, can wholly improve carbon fluoride material electric conductivity, improves specific energy and increase power output ability, synthesizes promotion carbon fluoride combined material multiplying power performance and energy density.
Description
Technical Field
The invention relates to the technical field of preparation of battery electrodes, in particular to a preparation method of an integrated carbon fluoride anode.
Background
In a lithium carbon fluoride (Li-CFx) cell, carbon fluoride (CFx) cathode performance is a critical factor in determining performance of a lithium carbon fluoride cell. The performance of the carbon fluoride anode is closely related to the composition of the carbon fluoride material and the electrode components and the preparation process flow.
In order to improve the comprehensive performance of the carbon fluoride anode, from the perspective of carbon fluoride materials, novel carbon materials, such as carbon nanotubes, carbon nanofibers, mesoporous carbon materials, fullerenes, graphene and the like, are adopted as precursors for fluorination. These nano-CFx materials generally have a large specific surface area and a small particle size, thereby improving electrochemical reaction activity, rapid diffusion of Li +, and reduction of reaction resistance, and can improve rate characteristics of lithium fluorocarbon batteries to some extent, compared to conventional graphite fluoride. However, as the fluorination degree of the nano carbon material is increased, the electrical conductivity is reduced, so that the nano material has the problem of difficult dispersion in the process of preparing the slurry, and the nano CFx material still has no commercial application condition.
In addition, in order to improve electrode conductivity, a metal current collector such as copper foil, aluminum foil, etc. is generally used as a current collector and carbon nanotubes, graphene, acetylene black, etc. are used as a conductive agent to be connected to a carbon fluoride material through a binder to form a carbon fluoride positive electrode. The inert binder is adopted in the preparation process of the electrode, so that the inactive substance proportion in the electrode is increased, and the exertion of the energy density of the lithium fluorocarbon battery is limited to a great extent. Meanwhile, the dispersion of the conductive agent and the contact effect of the carbon fluoride active substance with the conductive agent and the current collector also influence the conductivity of the carbon fluoride anode, thereby influencing the rate performance of the battery. Therefore, it is highly desirable to develop a method for preparing a highly conductive fluorocarbon positive electrode without an inert binder and a current collector.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a novel integrated carbon fluoride anode which does not need an inert binder, is easy to disperse and is compatible with the energy density and the power performance of a battery.
One of the purposes of the invention is to provide a preparation method of an integrated carbon fluoride anode, which comprises the following steps:
s1, dispersing: sieving the carbon nano tube and the graphene, placing the sieved carbon nano tube and the graphene in a dispersing agent, and dispersing to obtain a graphene/carbon nano tube suspension;
s2, suction filtration: transferring the graphene/carbon nanotube suspension prepared in the step S1 to a filter provided with a microporous filter membrane for vacuum filtration, transferring the microporous filter membrane loaded with a filtration product to a vacuum oven for drying, and removing the microporous filter membrane after drying to obtain a graphene/carbon nanotube current collector;
s3, fluorination: and (3) placing the graphene/carbon nano tube current collector obtained in the step (S2) in a reaction container, and carrying out fluorination reaction on the graphene/carbon nano tube current collector and reaction gas consisting of a gas fluorine source and diluent gas at the temperature of 600-800 ℃ to obtain the novel integrated carbon fluoride anode.
Further, the mass ratio of the carbon nanotubes to the graphene in the step S1 is 1: 10-10: 1.
Further, the carbon nanotube is one of a single-walled carbon nanotube and a multi-walled carbon nanotube, and the graphene is one of single-layered graphene and multi-layered graphene.
Further, the dispersing agent in the step S1 is an ethanol solution, and a cell wall breaking machine is used for dispersing, wherein the dispersing power is 500-1500W, and the dispersing time is 5-30 min, so that the graphene/carbon nanotube suspension with the concentration of 1-10 mg/ml is finally formed.
Further, the dispersing agent is methanol, ethanol, diesel oil, N-methyl pyrrolidone (NMP) or tetrahydrofuran, and in order to maintain the stability of the suspension after dispersion, 25-30% of N, N-dimethylformamide solution is added.
Further, in step S2, the diameter of the microporous membrane is 5-10 μm.
Dispersing the carbon nano tube and the graphene by a cell wall breaking machine to obtain a graphene/carbon nano tube suspension, and filtering the graphene/carbon nano tube suspension on a micron filter membrane to form a film by vacuum filtration to obtain the three-dimensional graphene/carbon nano tube current collector. The three-dimensional space structure formed by stacking the graphene and the carbon nano tube can effectively increase the specific surface area of the material and shorten the ion diffusion path, and the space structure and the thickness of the graphene/carbon nano tube current collector can be regulated and controlled by the ratio and the concentration of the graphene/carbon nano tube in the graphene/carbon nano tube suspension.
Further, the reaction in the step S3 is carried out in a nitrogen or inert gas environment, the internal pressure of the reactor reaches 0.05MPa to 0.3MPa, the pressure is maintained for 12 to 15 hours, then the temperature is slowly raised to 600 ℃ to 800 ℃, and then the reaction gas is continuously filled into the reactor for 4 to 8 hours; wherein the inert gas is one of helium or argon.
Furthermore, the volume fraction of the fluorine source in the reaction gas is 6-10%, and the flow rate of the gas flow rate is 0.08-0.20 ml/min.
Further, in step S3, the gas fluorine source is one of fluorine gas and nitrogen trifluoride.
Further, the diluent gas in step S3 is one of nitrogen or argon.
In the S3 fluorination stage, the fluorination degree is controlled by the reaction rate and time of fluorine source gas, a novel integrated fluorinated carbon anode compatible with fluorinated graphene, fluorinated carbon nanotubes and graphene and carbon nanotubes is formed, and in the novel integrated fluorinated carbon anode, the proportion of fluorinated current collector is regulated and controlled by the fluorine source and the fluorination time.
The invention also aims to provide the novel integrated carbon fluoride anode prepared by any one of the methods.
The working principle and the beneficial effects of the invention are as follows: the invention disperses the carbon nano tube and the graphene through a cell wall breaking machine, obtains the graphene/carbon nano tube suspension through vacuum filtration, the preparation method comprises the steps of filtering a micron filter membrane to form a membrane, obtaining a three-dimensional graphene/carbon nanotube current collector, and performing high-temperature fluorination to form a novel integrated carbon fluoride anode compatible with the fluorinated graphene and the carbon fluoride nanotube, the graphene and the carbon nanotube, and solves the problems that the dispersion of the fluorinated graphene or the carbon fluoride nanotube in the electrode preparation process is difficult, the conductivity of the carbon fluoride anode is poor, an inert binder limits the load capacity of active substances in the carbon fluoride anode, and the energy density and the power performance of a carbon fluoride battery are difficult to be compatible.
Because the integrated carbon fluoride anode contains the high-conductivity graphene and the carbon nano tube three-dimensional current collector as the conductive framework, the composite material has better conductivity and larger specific surface area, and can increase active reaction sites. The method can effectively reduce the weight of the inert adhesive of the carbon fluoride anode, and in addition, the three-dimensional electrode structure formed by the flaky graphene and the linear carbon nano tubes can effectively improve the electrode conductivity and the electrolyte wettability and shorten the lithium ion migration path, so that the energy density and the high-rate output characteristic of the carbon fluoride battery are effectively improved, the loading capacity of an active substance is improved from 40% to 80%, the specific energy of the carbon fluoride battery is improved by 20%, the problem of high-rate output voltage hysteresis and the like is obviously improved.
In addition, the preparation method is simple, and the aim of preparing the carbon fluoride anode integrating the conductive, current collecting and fluorinated active substances can be fulfilled only by simple dispersion, suction filtration and fluorination.
Drawings
FIG. 1 is a flow diagram of a method for preparing a novel integrated fluorocarbon anode of the present invention;
FIG. 2 is a graph showing the discharge rate of the novel integrated fluorocarbon positive electrode of example 1 of the present invention at the same rate as that of the conventional commercial fluorocarbon material.
Detailed Description
The following is further detailed by way of specific embodiments:
example 1: a preparation method of a novel integrated carbon fluoride anode is shown in figure 1 and specifically comprises the following steps:
s1, dispersing: sieving a multi-wall carbon nanotube and 4-5 layers of multi-layer graphene, putting the multi-wall carbon nanotube and the multi-layer graphene into a beaker filled with 200ml (volume ratio of 2: 1) of ethanol + N, N-Dimethylformamide (DMF) mixed dispersion solvent according to a mass ratio of 1:10, and dispersing by using a cell wall breaking machine with a dispersion power of 1500W for 5min to form a graphene/carbon nanotube suspension with a concentration of 10 mg/ml.
S2, suction filtration: and transferring the graphene/carbon nanotube suspension prepared in the step S1 to a filter provided with a microporous filter membrane for vacuum filtration, wherein the diameter of a pore of the microporous filter membrane is 10 microns, transferring the microporous filter membrane loaded with the filtration product to a vacuum oven for drying, and removing the microporous filter membrane after drying to obtain the graphene/carbon nanotube current collector.
S3, fluorination: and (3) placing the graphene/carbon nano tube current collector prepared in the step (S2) in a reaction container, introducing nitrogen into the reactor to enable the internal pressure to reach 0.3MPa, keeping the pressure for 15 hours, slowly heating to 600 ℃, continuously introducing reaction gas into the reactor for 4 hours, wherein the reaction gas is mixed gas consisting of fluorine gas and nitrogen, the volume fraction of a fluorine source in the reaction gas is 10%, the flow rate of the fluorine gas is 0.08 ml/min, cooling to room temperature, and taking out to obtain the novel integrated carbon fluoride anode.
Example 2: a preparation method of a novel integrated carbon fluoride anode specifically comprises the following steps:
s1, dispersing: sieving a multi-wall carbon nano tube and multi-layer graphene, putting the multi-wall carbon nano tube and the multi-layer graphene into a beaker filled with 500ml (volume ratio of 2: 1) of methanol + N, N-Dimethylformamide (DMF) mixed dispersion solvent according to a mass ratio of 10:1, and dispersing by using a cell wall breaking machine with a dispersion power of 500W for 30min to form a graphene/carbon nano tube suspension with a concentration of 1 mg/ml.
S2, suction filtration: and transferring the graphene/carbon nano tube suspension prepared in the step S1 to a filter provided with a microporous filter membrane for vacuum filtration, wherein the diameter of a pore of the microporous filter membrane is 5 microns, transferring the microporous filter membrane loaded with the filtration product to a vacuum oven for drying, and removing the microporous filter membrane after drying to obtain the graphene/carbon nano tube current collector.
S3, fluorination: and (3) placing the graphene/carbon nano tube current collector prepared in the step (S2) into a reaction container, introducing helium into the reactor to enable the internal pressure to reach 0.05MPa, keeping the pressure for 12 hours, slowly heating to 800 ℃, continuously introducing reaction gas into the reactor for 8 hours, wherein the reaction gas is mixed gas consisting of fluorine gas and argon gas, the fluorine source volume fraction in the reaction gas is 6%, the fluorine gas flow rate is 0.20 ml/min, cooling to room temperature, and taking out to obtain the novel integrated carbon fluoride anode.
Example 3: a preparation method of a novel integrated carbon fluoride anode specifically comprises the following steps:
s1, dispersing: sieving a multi-wall carbon nano tube and multi-layer graphene, putting the multi-wall carbon nano tube and the multi-layer graphene into a beaker filled with 300 ml of N-methyl pyrrolidone + N, N-dimethyl formamide (DMF) mixed dispersion solvent with the volume ratio of 4:1 according to the mass ratio of 1:1, and dispersing by a cell wall breaking machine with the dispersion power of 1000W for 20 min to form graphene/carbon nano tube suspension with the concentration of 5 mg/ml.
S2, suction filtration: and transferring the graphene/carbon nanotube suspension prepared in the step S1 to a filter provided with a microporous filter membrane for vacuum filtration, wherein the diameter of a pore of the microporous filter membrane is 8 microns, transferring the microporous filter membrane loaded with the filtration product to a vacuum oven for drying, and removing the microporous filter membrane after drying to obtain the graphene/carbon nanotube current collector.
S3, fluorination: and (3) placing the graphene/carbon nano tube current collector prepared in the step (S2) into a reaction container, introducing argon into the reactor, keeping the pressure for 14 hours, slowly heating to 700 ℃, continuously introducing reaction gas into the reactor for 6 hours, wherein the reaction gas is mixed gas consisting of nitrogen trifluoride and argon, the volume fraction of a fluorine source in the reaction gas is 8%, the flow rate of fluorine gas is 0.10 ml/min, cooling to room temperature, and taking out to obtain the novel integrated carbon fluoride anode.
The novel integrated fluorocarbon anode prepared in example 1 was compared with the existing commercial fluorocarbon material in an experiment, and the specific experimental procedures were as follows: the novel integrated fluorocarbon anode prepared in example 1 was directly used as an anode after drying at 100 ℃, and a group of lithium fluorocarbon batteries were assembled in a 1% dry room with metal lithium as a cathode. And then, adopting a commercial carbon fluoride material (Shandong) as a positive electrode material, SP and CNTS as conductive agents, and CMC + SBR as a binder, wherein the weight ratio of the positive electrode material: conductive agent: the binder =80:10:10, and the mixture was mixed uniformly to form a positive electrode slurry, which was coated on an aluminum foil, and dried at 100 ℃ to form a fluorocarbon positive electrode, and the rest was completely the same as in example 1, and another group of lithium fluorocarbon batteries having the same weight was assembled. The two groups of lithium fluorocarbon batteries are subjected to discharge test under the conditions of normal temperature of 25 ℃ and 0.5C multiplying power at the same time, and the comparison of multiplying power performance and low-pressure hysteresis performance is shown in figure 2. As is apparent from FIG. 2, the cell made of the commercial carbon fluoride material (Shandong) has a clear voltage hysteresis peak at a rate of 0.5C, a low-wave voltage as low as 2.21V, a discharge plateau voltage of 2.34V, a working cell window of 3.58V-1.50V, a cell capacity of 0.97Ah and a specific energy of 439.92 Wh/kg. As can be seen from fig. 2, the discharge plateau voltage of the battery manufactured by using the novel integrated fluorocarbon anode in example 1 can be increased to 2.50V, the battery capacity is 1.09Ah, no voltage hysteresis occurs, and the corresponding specific energy of the battery can reach 545 Wh/kg. Therefore, under the same battery preparation condition, the voltage platform of the battery made of the novel integrated carbon fluoride anode is improved to 2.50V from 2.34V without obvious voltage hysteresis, the specific energy increasing rate reaches 23.89%, the novel integrated carbon fluoride anode has good conductivity and higher working voltage, and the novel integrated carbon fluoride anode has a larger application prospect in light battery design.
The foregoing is merely an example of the present invention and common general knowledge of known specific structures and features of the embodiments is not described herein in any greater detail. It should be noted that, for those skilled in the art, without departing from the structure of the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (6)
1. The preparation method of the integrated carbon fluoride anode is characterized by comprising the following steps of:
s1, dispersing: sieving the carbon nano tube and the graphene, placing the carbon nano tube and the graphene in a dispersing agent, and dispersing to obtain a graphene/carbon nano tube suspension; the dispersing agent is an ethanol solution, and is dispersed by a cell wall breaking machine, the dispersing power is 500-1500W, the dispersing time is 5-30 min, and finally graphene/carbon nano tube suspension with the concentration of 1-10 mg/ml is formed;
s2, suction filtration: transferring the graphene/carbon nanotube suspension prepared in the step S1 to a filter provided with a microporous filter membrane for vacuum filtration, transferring the microporous filter membrane loaded with a filtration product to a vacuum oven for drying, and removing the microporous filter membrane after drying to obtain a graphene/carbon nanotube current collector;
s3, fluorination: placing the graphene/carbon nano tube current collector obtained in the step S2 in a reaction container, and carrying out a fluorination reaction with reaction gas consisting of a gas fluorine source and diluent gas at the temperature of 600-800 ℃ to obtain a novel integrated carbon fluoride anode; reacting in a nitrogen or inert gas environment, keeping the internal pressure of the reactor to be 0.05-0.3 MPa, maintaining the pressure for 12-15 hours, slowly heating to 600-800 ℃, and continuously filling reaction gas into the reactor for 4-8 hours; the inert gas is helium or argon; the volume fraction of the gas fluorine source in the reaction gas is 6-10%, and the flow rate of the gas fluorine source is 0.08-0.20 ml/min; the gas fluorine source is one of fluorine gas or nitrogen trifluoride.
2. The method of preparing an integrated fluorinated carbon cathode according to claim 1, wherein: in the step S1, the mass ratio of the carbon nanotubes to the graphene is 1: 10-10: 1.
3. The method of preparing an integrated fluorinated carbon cathode according to claim 2, wherein: the carbon nano tube is one of a single-walled carbon nano tube or a multi-walled carbon nano tube, and the graphene is one of single-layer graphene or multi-layer graphene.
4. The method of preparing an integrated fluorinated carbon cathode according to claim 3, wherein: in step S2, the diameter of the microporous membrane is 5-10 μm.
5. The method of preparing an integrated fluorinated carbon cathode according to claim 4, wherein: the diluent gas in step S3 is one of nitrogen or argon.
6. An integrated fluorocarbon positive electrode prepared by the method of any one of claims 1 to 5.
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| CN114975894B (en) * | 2022-06-15 | 2024-02-20 | 松山湖材料实验室 | Graphite fluoride anode, preparation method thereof and battery |
| CN115084539B (en) * | 2022-06-21 | 2023-03-14 | 贵州梅岭电源有限公司 | Carbon fluoride electrode and preparation method thereof |
| CN114975956A (en) * | 2022-06-21 | 2022-08-30 | 贵州梅岭电源有限公司 | Fluorinated graphene/fluorinated graphite composite positive electrode material and preparation method thereof |
| CN115465857A (en) * | 2022-09-15 | 2022-12-13 | 贵州梅岭电源有限公司 | Conductive fluorinated graphene nanoribbon material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361084A (en) * | 2011-10-10 | 2012-02-22 | 中国电子科技集团公司第十八研究所 | Carbon fluoride for lithium battery anode material |
| WO2012088697A1 (en) * | 2010-12-30 | 2012-07-05 | 海洋王照明科技股份有限公司 | Graphene ramification-carbon nanotube composite material and preparation method thereof |
| CN103456520A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Manufacturing method and application for graphene/carbon nano-tube composite film |
| CN109216698A (en) * | 2018-09-11 | 2019-01-15 | 山东理工大学 | A kind of preparation method of lithium fluorocarbon cell positive electrode material fluorinated nano graphite |
| CN109666915A (en) * | 2019-01-30 | 2019-04-23 | 中南大学 | A kind of preparation method of complex metal layer coating carbon nanotubes/graphene composite material |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012088697A1 (en) * | 2010-12-30 | 2012-07-05 | 海洋王照明科技股份有限公司 | Graphene ramification-carbon nanotube composite material and preparation method thereof |
| CN102361084A (en) * | 2011-10-10 | 2012-02-22 | 中国电子科技集团公司第十八研究所 | Carbon fluoride for lithium battery anode material |
| CN103456520A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Manufacturing method and application for graphene/carbon nano-tube composite film |
| CN109216698A (en) * | 2018-09-11 | 2019-01-15 | 山东理工大学 | A kind of preparation method of lithium fluorocarbon cell positive electrode material fluorinated nano graphite |
| CN109666915A (en) * | 2019-01-30 | 2019-04-23 | 中南大学 | A kind of preparation method of complex metal layer coating carbon nanotubes/graphene composite material |
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