CN114975894A - Graphite fluoride positive electrode, preparation method thereof and battery - Google Patents
Graphite fluoride positive electrode, preparation method thereof and battery Download PDFInfo
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- CN114975894A CN114975894A CN202210680958.4A CN202210680958A CN114975894A CN 114975894 A CN114975894 A CN 114975894A CN 202210680958 A CN202210680958 A CN 202210680958A CN 114975894 A CN114975894 A CN 114975894A
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Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The application relates to the technical field of graphite fluoride batteries, in particular to a graphite fluoride positive electrode and a preparation method thereof as well as a battery. The preparation method of the graphite fluoride anode comprises the steps of carrying out ultrasonic treatment on a solution containing graphite fluoride and a conductive agent under 200-300W for 15-40min, and then drying a solid phase. The graphite fluoride anode prepared by the method has a good three-dimensional conductive network, and is beneficial to improving the electron transfer rate and the ion transmission rate. The graphite fluoride anode prepared by the method is used for preparing the battery, is beneficial to improving the specific capacity, the capacity retention rate and the platform voltage of the battery under high discharge rate, and is expected to be applied to high-capacity and high-power discharge scenes.
Description
Technical Field
The application relates to the technical field of graphite fluoride batteries, in particular to a graphite fluoride positive electrode, a preparation method thereof and a battery.
Background
Lithium/graphite fluoride batteries have been a classic primary battery for over forty years. The core component of the electrolyte is a graphite fluoride anode which receives external circuit electrons during discharging and is combined with metal ions such as lithium ions in the electrolyte, and charge transfer is realized through conversion reaction M + CFx → MF + C (M is the metal ions such as the lithium ions). Because the conversion reaction can fully utilize all electrons which can be transferred when the material undergoes redox reaction, the theoretical capacity (865mAh/g) of the graphite fluoride is far higher than that of the traditional embedded electrode material. The lithium/graphite fluoride battery also has the advantages of high platform voltage (which can reach more than 2.7V), low self-discharge (the capacity loss is less than 0.5 percent per year) and the like, and has wide application prospect in the fields of electronic products, medical appliances and the like. However, the lithium/graphite fluoride battery has problems of large capacity attenuation, discharge voltage hysteresis and the like under high-rate discharge conditions due to factors such as poor electronic conductivity of the graphite fluoride material, high insulation of metal fluorides such as lithium fluoride and the like, and the application of the graphite fluoride material in the field of high-power energy conversion devices is limited.
The key to improving the conductivity of the graphite fluoride anode is to solve the electrochemical polarization problem of primary battery devices such as lithium/graphite fluoride batteries and the like and improve the rate capability. Therefore, the design of a novel graphite fluoride anode is imperative to improve the rate performance of the primary battery on the premise of no specific capacity attenuation, discharge voltage loss, voltage hysteresis and cost increase.
Disclosure of Invention
The present application aims to provide a graphite fluoride positive electrode, a method for producing the same, and a battery, which aim to solve the technical problem of poor conductivity of the conventional graphite fluoride positive electrode.
In a first aspect, the present application provides a method for preparing a graphite fluoride positive electrode, comprising: and (3) carrying out ultrasonic treatment on the solution containing the graphite fluoride and the conductive agent at 200-300W for 15-40min, and then drying the solid phase.
Ultrasonic treatment is carried out for 15-40min under 200-300W, graphite fluoride in the solution can be uniformly dispersed into single-layer two-dimensional graphite fluoride nanosheets, the graphite fluoride is not easy to agglomerate and defluorinate, and the conductive agent can be dispersed among the two-dimensional graphite fluoride nanosheets by ultrasonic treatment. After ultrasonic treatment, the solid phase is dried, and the conductive agent positioned between the two-dimensional graphite fluoride nanosheets can be in good contact with the two-dimensional graphite fluoride nanosheets, so that the prepared graphite fluoride anode has a good three-dimensional conductive network. The three-dimensional conductive network can provide an electron rapid transmission channel, and the two-dimensional graphite fluoride nanosheet layer provides an ion rapid transmission channel, so that the electron migration rate and the ion transmission rate are improved. The graphite fluoride anode prepared by the method is used for manufacturing the battery, is beneficial to improving the specific capacity, the capacity retention rate and the platform voltage of the battery under high discharge rate, and is expected to be applied to high-capacity and high-power discharge scenes.
In some embodiments of the first aspect of the present application, drying the solid phase further comprises solid-liquid separating the sonicated product; the solid-liquid separation mode is suction filtration separation, centrifugal separation or filter pressing separation.
Before the solid phase is dried, the product after ultrasonic treatment is subjected to solid-liquid separation by adopting the mode, so that the contact between the conductive agent positioned between the two-dimensional graphite fluoride nanosheets and the two-dimensional graphite fluoride nanosheets in the separated solid phase is more compact, the stability of a three-dimensional conductive network in the prepared graphite fluoride anode is improved, and the transmission efficiency of electrons and ions is improved.
Optionally, the solid-liquid separation mode is suction filtration separation, the pressure of the suction filtration separation is 0.9-0.98atm, and the time of the suction filtration separation is 20-120 min.
Under the pressure and time of the suction filtration separation, the three-dimensional stable conductive network in the graphite fluoride anode can be better maintained in the solid-liquid separation process, and the transmission efficiency of electrons and ions is further improved.
In some embodiments of the first aspect of the present application, the graphite fluoride has a fluorine to carbon ratio of 0.9 to 1.0.
The fluorine-carbon ratio of the graphite fluoride is 0.9-1.0, which is beneficial to improving the specific capacity of the battery.
In some embodiments of the first aspect of the present application, the conductive agent comprises at least one of multi-walled carbon nanotubes, single-walled carbon nanotubes, and carbon nanofibers; the length of the multi-wall carbon nano tube is 5-30 mu m, and the diameter of the multi-wall carbon nano tube is 5-15 nm; the length of the single-walled carbon nanotube is 15-20 mu m, and the diameter of the single-walled carbon nanotube is 1-2 nm; the length of the carbon nanofiber is 1-15 μm, and the diameter of the carbon nanofiber is 50-200 nm.
Under the conditions, the stability of the three-dimensional conductive network in the prepared graphite fluoride anode can be improved, and the transmission efficiency of electrons and ions can be improved.
Optionally, the conductive agent is selected from single-walled carbon nanotubes.
The conductive agent adopts the single-walled carbon nanotube, so that the conductivity of the graphite fluoride anode and the capacity retention rate of the battery under high discharge rate can be further improved; and the single-walled carbon nanotube has higher tensile strength and elastic modulus, thereby being beneficial to further improving the structural stability of the three-dimensional conductive network in the prepared graphite fluoride anode.
In some embodiments of the first aspect of the present application, the mass ratio of graphite fluoride to conductive agent is (3-7): 1.
the mass ratio of the graphite fluoride to the conductive agent is (3-7): 1, the graphite fluoride positive electrode has good conductivity, and the battery has higher specific capacity.
Optionally, the mass ratio of the graphite fluoride to the conductive agent is 5: 1.
in some embodiments of the first aspect of the present disclosure, the solvent in the solution containing graphite fluoride and the conductive agent comprises at least one of ethanol, N-methylpyrrolidone, and dimethylformamide.
In some embodiments of the first aspect of the present application, the temperature of drying is 80-110 ℃ and the time of drying is 8-24 h.
Under the above-mentioned drying condition, be favorable to improving drying efficiency.
In a second aspect, the present application provides a graphite fluoride positive electrode comprising a conductive agent and graphite fluoride having a lamellar structure; part of the conductive agent is distributed among the graphite fluoride sheets and is in contact with the graphite fluoride; the thickness of the graphite fluoride sheet is 10-30 nm.
Part of the conductive agent in the graphite fluoride anode provided by the application is distributed among single-layer two-dimensional graphite fluoride nano sheets with the thickness of 10-30nm and is in contact with the graphite fluoride, so that a good three-dimensional conductive network is formed, and the electronic conductivity and the ion transmission are improved. The graphite fluoride anode prepared by the method is used for preparing the battery, and is beneficial to improving the specific capacity, the capacity retention rate and the platform voltage of the battery under high discharge rate.
In a third aspect, the present application provides a battery comprising a negative electrode and a graphite fluoride positive electrode as provided in the second aspect above; or, the graphite fluoride positive electrode comprises a negative electrode and the graphite fluoride positive electrode prepared by the method for preparing the graphite fluoride positive electrode provided by the first aspect.
The battery provided by the application can improve the electronic conductivity and the ion transmission property, and realizes the coupling of ion diffusion and rapid electronic transmission; the specific capacity, the capacity retention rate and the platform voltage of the battery under high discharge rate can be improved, and the battery has a good application prospect.
In some embodiments of the third aspect of the present application, the negative electrode comprises a lithium or magnesium plate.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 is an SEM image of a graphite fluoride positive electrode used in example 1 of the present application.
FIG. 2 is an SEM photograph of the graphite fluoride powder obtained in example 1 of the present application.
Fig. 3 is an electrochemical impedance spectrum of the graphite fluoride positive electrode prepared in example 1 of the present application before and after discharge.
Fig. 4 is a constant current discharge curve of the battery manufactured in example 1 of the present application at different rates.
Fig. 5 is a constant current discharge curve at 0.1C rate of the battery prepared in example 2 of the present application.
Fig. 6 is a constant current discharge curve at different rates of the battery manufactured in comparative example 1 of the present application.
Fig. 7 is a constant current discharge curve at different rates of the battery manufactured in comparative example 2 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In order to improve the conductivity of the graphite fluoride positive electrode, the inventors found that if the graphite fluoride and the conductive agent are directly ground and mixed to prepare the graphite fluoride positive electrode, the graphite fluoride positive electrode still has the problems of poor electrode conductivity and hindered ion migration although the conductive agent is introduced into the graphite fluoride positive electrode; the inventors have also found that if the graphite fluoride is partially defluorinated, the decrease in the fluorine content of the active material also causes a significant decrease in the discharge capacity, and thus the demand for graphite fluoride positive electrodes cannot be satisfied.
In order to improve the rate performance of the primary battery without specific capacity attenuation, discharge voltage loss, voltage hysteresis and cost increase, the application provides a preparation method of a graphite fluoride anode, which comprises the steps of carrying out ultrasonic treatment on a solution containing graphite fluoride and a conductive agent under the conditions of 200-300W for 15-40min and then drying a solid phase.
Ultrasonic treatment is carried out for 15-40min under 200-300W, graphite fluoride in the solution can be uniformly dispersed into single-layer two-dimensional graphite fluoride nanosheets, the graphite fluoride is not easy to agglomerate and defluorinate, and the conductive agent can be dispersed among the two-dimensional graphite fluoride nanosheets by ultrasonic treatment. After ultrasonic treatment, the solid phase is dried, and the conductive agent positioned between the two-dimensional graphite fluoride nanosheets can be in good contact with the two-dimensional graphite fluoride nanosheets, so that the prepared graphite fluoride anode has a good three-dimensional conductive network. The three-dimensional conductive network can provide an electron rapid transmission channel, and the two-dimensional graphite fluoride nanosheet layer provides an ion rapid transmission channel, so that the electron migration rate and the ion transmission rate are improved. The graphite fluoride anode prepared by the method is used for preparing the battery, so that the specific capacity, the capacity retention rate and the platform voltage of the battery under high discharge rate can be improved, and the battery is expected to be applied to high-capacity and high-power discharge scenes. Compared with the traditional grinding and mixing mode of graphite fluoride and a conductive agent, a stable three-dimensional conductive network which is contacted with each other can be formed between the conductive agent and the graphite fluoride without adding a bonding agent.
In the application, the power of ultrasonic treatment is 200-300W, so that 500 nm-thick graphite fluoride is peeled into 10-30 nm-thick single-layer two-dimensional graphite fluoride nanosheets, and the conductive agent is contained between the single-layer two-dimensional graphite fluoride nanosheets. If the ultrasonic power is too high, the defluorination phenomenon of the graphite fluoride can be generated, and the specific capacity of the battery is reduced; if the ultrasonic power is too low, the graphite fluoride can not be effectively dispersed into single-layer two-dimensional graphite fluoride nano-sheets, which is not beneficial to forming a good three-dimensional conductive network.
Illustratively, the power of the sonication may be 200W, 220W, 250W, 260W, 280 or 300W, etc.; the time of ultrasonic treatment is 15min, 20min, 25min, 30min or 40min, etc.
Furthermore, the power of ultrasonic treatment is 260W, the time of ultrasonic treatment is 30min, and the specific capacity and the capacity retention rate of the battery under high discharge rate can be further improved.
As an example, the sonication may be performed in an ultrasonic washer or a cell disruptor.
In the embodiment of the application, the fluorine-carbon ratio of the graphite fluoride is 0.9-1.0, which is beneficial to improving the specific capacity of the battery. Illustratively, the fluorocarbon ratio of the graphite fluoride may be 0.9, 0.92, 0.95, or 1.0, and so forth.
The conductive agent comprises at least one of multi-wall carbon nanotubes, single-wall carbon nanotubes and carbon nanofibers, and the conductive agent has better conductivity.
Furthermore, when the conductive agent is a multi-walled carbon nanotube, the length of the multi-walled carbon nanotube is 5-30 μm, and the diameter of the multi-walled carbon nanotube is 5-15 nm; when the conductive agent is single-walled carbon nanotubes, the length of the single-walled carbon nanotubes is 15-20 mu m, and the diameter of the single-walled carbon nanotubes is 1-2 nm; when the conductive agent is carbon nanofiber, the length of the carbon nanofiber is 1-15 μm, and the diameter of the carbon nanofiber is 50-200 nm. Under the condition of the particle size, the stability of a three-dimensional conductive network in the prepared graphite fluoride anode can be improved, and the transmission efficiency of electrons and ions can be improved.
In the embodiment of the application, the conductive agent is a single-walled carbon nanotube, so that the conductivity of the graphite fluoride anode and the capacity retention rate of the battery under high discharge rate can be further improved; and the single-walled carbon nanotube has higher tensile strength and elastic modulus, thereby being beneficial to further improving the structural stability of the three-dimensional conductive network in the prepared graphite fluoride anode.
The mass ratio of the graphite fluoride to the conductive agent is (3-7): 1, the graphite fluoride positive electrode has good conductivity, and the battery has higher specific capacity. If the content of the graphite fluoride is too high, the conductivity of the graphite fluoride anode is obviously reduced; if the content of the conductive agent is too high, the discharge capacity of the battery is significantly deteriorated, and thus the battery cannot be effectively used.
As an example, the mass ratio of the graphite fluoride to the conductive agent may be 3: 1. 4: 1. 5: 1 or 7: 1, etc.
Further, the mass ratio of the graphite fluoride to the conductive agent is 5: 1, the battery can further have good conductivity and higher specific capacity.
The solvent in the solution containing graphite fluoride and the conductive agent is an organic solvent; the organic solvent comprises at least one of ethanol, N-methyl pyrrolidone and dimethylformamide. In the examples of the present application, N-methylpyrrolidone is used as the organic solvent. It should be noted that in other possible embodiments, the organic solvent may be other substances, such as N, N-dimethylformamide, N or N-dimethylacetamide, and the like.
In the application, the solid-liquid separation of the product after ultrasonic treatment is carried out before the solid phase is dried, and the solid-liquid separation mode is suction filtration separation, centrifugal separation or filter pressing separation. Before the solid phase is dried, the product after ultrasonic treatment is subjected to solid-liquid separation by adopting the mode, so that the contact between the conductive agent positioned between the two-dimensional graphite fluoride nanosheets and the two-dimensional graphite fluoride nanosheets in the separated solid phase is more compact, the stability of a three-dimensional conductive network in the prepared graphite fluoride anode is improved, and the transmission efficiency of electrons and ions is improved.
In the embodiment of the application, the solid-liquid separation mode adopts suction filtration separation, the suction filtration separation can enable the separated solid phase to form a composite film, the composite film can be directly used as a graphite fluoride anode after being dried, the forming treatment is not needed, and the operation is simple and efficient.
Further, the pressure of the suction filtration separation is 0.9-0.98atm, and the time of the suction filtration separation is 20-120 min. Under the pressure and time of the suction filtration separation, the three-dimensional stable conductive network in the graphite fluoride anode can be better maintained in the solid-liquid separation process, and the transmission efficiency of electrons and ions is further improved.
Illustratively, the pressure of the suction filtration separation may be 0.9atm, 0.95atm, or 0.98atm, or the like; the time for the suction filtration separation can be 20min, 30min, 60min, 90min or 120min and the like.
In other practical embodiments, the solid-liquid separation method may be a method such as normal pressure filtration, as long as the solid-phase substances in the product after the ultrasonic treatment can be separated.
In the embodiment of the application, the temperature for drying the solid phase is 80-110 ℃, and the time for drying the solid phase is 8-24h, which is beneficial to improving the drying efficiency. By way of example, the temperature of the dried solid phase may be 80 ℃, 85 ℃, 90 ℃, 100 ℃, or 110 ℃ or the like; the time for drying the solid phase is 8h, 10h, 12h, 15h, 20h or 24h, and the like.
It should be noted that in other possible embodiments, the dried solid phase may be dried at room temperature.
The application provides a graphite fluoride anode which is prepared by adopting the preparation method of the graphite fluoride anode.
The graphite fluoride anode prepared by the preparation method of the graphite fluoride anode has a good three-dimensional conductive network, and is beneficial to improving the electronic conductivity and the ion transmission property. The graphite fluoride anode prepared by the method is used for preparing the battery, and is beneficial to improving the specific capacity and the capacity retention rate of the battery under high discharge rate.
The application also provides a graphite fluoride anode, which comprises a conductive agent and graphite fluoride with a lamellar structure, wherein part of the conductive agent is distributed among the lamellae of the graphite fluoride and is in contact with the graphite fluoride; the thickness of the graphite fluoride sheet is 10-30 nm.
Part of the conductive agent in the graphite fluoride anode provided by the application is distributed among single-layer two-dimensional graphite fluoride nano sheets with the thickness of 10-30nm and is in contact with the graphite fluoride, so that a good three-dimensional conductive network is formed, and the electronic conductivity and the ion transmission are improved. The graphite fluoride anode prepared by the method is used for preparing the battery, and is beneficial to improving the specific capacity, the capacity retention rate and the platform voltage of the battery under high discharge rate.
The application provides a battery, which comprises a negative electrode and the graphite fluoride positive electrode.
The battery provided by the application can improve the electronic conductivity and the ion transmission performance, and realizes the coupling of ion diffusion and rapid electron transmission; the specific capacity, the capacity retention rate and the platform voltage of the battery under high discharge rate can be improved, and the battery has a good application prospect.
In some embodiments of the present application, the negative electrode comprises a magnesium or lithium sheet. When the magnesium sheet is selected as the negative electrode to prepare the magnesium/graphite fluoride primary battery, the voltage platform is above 1.65V under the discharge condition of 0.1C, and the discharge specific capacity is above 830mAh/g (cut-off voltage is 0.5V); when the electrode is made of lithium sheets to prepare the lithium/graphite fluoride primary battery, the voltage platform is above 2.0V under the 2C discharge condition, the discharge specific capacity is above 640mAh/g, the specific capacity is above 760mAh/g under the 0.1C discharge condition, the cut-off voltage is 1.5V, and the problem of initial discharge voltage hysteresis is solved.
By way of example, the battery prepared by using the graphite fluoride positive electrode provided by the application can be one of a button battery, a detachable two-electrode measuring device or an aluminum plastic film soft package battery shell group.
The characteristics and properties of the graphite fluoride positive electrode and the battery of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides a graphite fluoride positive electrode and a battery, which are prepared by the following steps:
(1) preparing a graphite fluoride positive electrode:
adding 15mg of graphite fluoride powder and 3mg of single-walled carbon nanotubes into 100ml of N-methylpyrrolidone, and carrying out ultrasonic treatment at the power of 260W for 30 minutes to form uniformly dispersed suspension. And (3) filtering the suspension through a filter membrane with the diameter of 4.7cm and the pore diameter of 0.45 micrometer for 30min under the pressure of 0.98atm to obtain a composite film, and placing the composite film in a vacuum drying oven at the temperature of 80 ℃ for 12 hours to obtain the graphite fluoride anode. Wherein, the fluorine-carbon ratio of the graphite fluoride is 0.9; the average length of the single-walled carbon nanotubes was 20 μm, and the average diameter of the single-walled carbon nanotubes was 2 nm.
(2) Preparing a battery:
and (2) assembling a lithium/graphite fluoride battery by using a lithium sheet as a negative electrode and the graphite fluoride positive electrode obtained in the step (1). Wherein the housing adopts CR2032 type stainless steel battery case, the diaphragm adopts celgard-2325 series diaphragm, and the electrolyte adopts 1M LiPF 6 And the mass ratio of Ethylene Carbonate (EC) to dimethyl carbonate (DMC) in the electrolyte is 1: 1.
Example 2
This example provides a graphite fluoride positive electrode and a battery, and differs from example 1 in that: the negative electrode in the battery is a magnesium sheet.
Example 3
This example provides a graphite fluoride positive electrode and a battery, and differs from example 1 in that: the filtration was replaced by atmospheric filtration.
Example 4
This example provides a graphite fluoride positive electrode and a battery, and differs from example 1 in that: the power of the sonication was 200W.
Example 5
This example provides a graphite fluoride positive electrode and a battery, and differs from example 1 in that: the mass of the graphite fluoride powder was 13.5mg, and the mass of the single-walled carbon nanotube was 4.5 mg.
Comparative example 1
The present comparative example provides a graphite fluoride positive electrode and a battery, and differs from example 1 in that: the power of the sonication was 390W.
Comparative example 2
The present comparative example provides a graphite fluoride positive electrode and a battery, and differs from example 1 in that: the preparation steps of the graphite fluoride anode are different. The preparation steps of the graphite fluoride anode are as follows:
15mg of graphite fluoride powder, 3mg of single-walled carbon nanotubes and 2mg of polyvinylidene fluoride were added to 100ml of N-methylpyrrolidone and ground in a mortar for 30 minutes to form a uniformly dispersed slurry. The slurry was uniformly spread on an aluminum foil 16 μm thick and placed in a vacuum oven at 80 ℃ for 12 hours. Wherein, the fluorine-carbon ratio of the graphite fluoride is 0.9; the average length of the single-walled carbon nanotubes was 20 μm, and the average diameter of the single-walled carbon nanotubes was 2 nm.
Experimental example 1
SEM characterization was performed on the graphite fluoride positive electrode prepared in example 1 and the graphite fluoride powder used in example 1, and the characterization results are shown in fig. 1 and 2, respectively. The electrochemical impedance test before and after discharge was performed on the battery manufactured in example 1, and the test results are shown in fig. 3.
As can be seen from FIGS. 1 and 2, the flake thickness of the raw material graphite fluoride powder used in example 1 was 400-500 nm; and after the graphite fluoride powder is subjected to ultrasonic treatment for 30 minutes under the power of 260W, the graphite fluoride is peeled into single-layer two-dimensional graphite fluoride nano sheets with the thickness of 10-30nm, and the single-walled carbon nano tube is positioned between the single-layer two-dimensional graphite fluoride nano sheets, which shows that the graphite fluoride and the single-walled carbon nano tube can jointly form a good three-dimensional conductive network after the ultrasonic treatment for 30 minutes under the power of 260W.
As can be seen from fig. 3, the impedance spectrum shape of the battery before and after discharge of the graphite fluoride positive electrode prepared in example 1 is not changed much, and only the impedance spectrum shape is different in the region corresponding to the bulk resistance, which illustrates that the three-dimensional conductive network and the layered structure formed in the graphite fluoride positive electrode prepared in example 1 play a crucial role in the whole discharge process, and simultaneously, the electron conductivity and the ion transport property are improved, and the coupling of the ion diffusion and the rapid electron transport is realized.
Experimental example 2
The batteries manufactured in examples 1-2 and comparative examples 1-2 were subjected to constant current discharge tests, and the test results are shown in fig. 4 to 7, respectively.
As can be seen from fig. 4, the specific capacity of the battery prepared in example 1 under the 2C rate (high rate) discharge condition can reach 644mAh/g, and the platform voltage is maintained above 2.0V; meanwhile, the specific capacity of the battery under the discharge condition of 0.1C multiplying power (low multiplying power) reaches 760mAh/g, which is close to the theoretical capacity of 830mAh/g, and the situation that the fluoridized graphite in the battery prepared in the embodiment 1 does not have an obvious defluorination phenomenon is shown. And the capacity retention rate of the battery prepared in example 1 under the 2C rate discharge condition is 84% at 0.1C, which shows that the rate performance of the graphite fluoride positive electrode prepared in example 1 can be improved. In addition, no significant initial voltage hysteresis was observed under the 0.1C, 0.5C, 1C, and 2C rate discharge conditions.
As can be seen from fig. 5, the specific capacity of the battery prepared in example 2 under the 0.1C rate (low rate) discharge condition reaches 830mAh/g (higher than that of example 1), which is equivalent to the theoretical capacity of graphite fluoride, and the plateau voltage is maintained at 1.65V or more. Because the two-electron reaction has a slower charge transfer rate compared with the single-electron reaction, the electrochemical polarization in the magnesium ion battery is generally more obvious, and the specific capacity is lost; while the test results in fig. 5 show that: the graphite fluoride anode with the three-dimensional conductive network can effectively improve the conductivity of graphite fluoride, reduce electrochemical polarization and play an obvious role in a magnesium ion battery.
As can be seen from fig. 6, the specific capacity of the battery prepared in comparative example 1 under 0.1C-rate (low-rate) discharge conditions was only 450mAh/g, which was much smaller than 760mAh/g in example 1; the specific capacity of the battery under the 2C rate (high rate) discharge condition is only 345mAh/g and is also far less than 644mAh/g in the embodiment 1; the ultrasonic power is 390W, which can cause defluorination phenomenon of the graphite fluoride, and the specific capacity of the battery is reduced.
As can be seen from fig. 7, the specific capacities of the batteries prepared in comparative example 2 under the 1C and 2C rate discharge conditions were only 375mAh/g and 357mAh/g, respectively, the plateau voltage was below 1.9V, and the capacity retention rate under 2C rate discharge was only 43%, both of which were much lower than those of example 1. And the battery prepared in comparative example 2 had an initial voltage hysteresis, indicating that the conductivity at the start of discharge of comparative example 2 was insufficient. As can be seen from comparison of comparative example 2 and example 1, a three-dimensional conductive network cannot be formed in the graphite fluoride positive electrode prepared by the hybrid milling method.
Experimental example 3
The cells of examples 1-5 were each subjected to a constant current discharge test, and the test results are shown in table 1.
TABLE 1
As can be seen from table 1: the specific capacities of the batteries manufactured in examples 3 and 5 under 2C and 0.1C rate discharge conditions were lower than the specific capacities of the batteries manufactured in example 1 under 2C and 0.1C rate discharge conditions, the specific capacities of the batteries manufactured in example 4 under 2C rate discharge conditions were lower than the specific capacities of the batteries manufactured in example 1 under 2C rate discharge conditions, and the capacity retention rate of the batteries prepared in examples 3-5 under 2C rate discharge is also lower than that of the batteries prepared in example 1 under 2C rate discharge, which indicates that the specific capacity and the capacity retention rate of the prepared batteries can be affected by the solid-liquid separation mode (i.e. the filtration pressure and time) after ultrasonic treatment, the power of ultrasonic treatment and the proportion of the graphite fluoride and the single-walled carbon nanotube (i.e. the conductive agent). Compared with the examples 3-5, the ultrasonic power, the suction filtration pressure and time and the raw material ratio of the graphite fluoride and the conductive agent in the example 1 can further improve the discharge rate performance and the specific capacity.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A method for preparing a graphite fluoride positive electrode is characterized by comprising the following steps: and (3) carrying out ultrasonic treatment on the solution containing the graphite fluoride and the conductive agent at 200-300W for 15-40min, and then drying the solid phase.
2. The method for preparing a graphite fluoride positive electrode according to claim 1, further comprising performing solid-liquid separation on the product after the ultrasonic treatment before the drying of the solid phase; the solid-liquid separation mode is suction filtration separation, centrifugal separation or filter pressing separation;
optionally, the solid-liquid separation mode is suction filtration separation, the pressure of the suction filtration separation is 0.9-0.98atm, and the time of the suction filtration separation is 20-120 min.
3. The method for producing a graphite fluoride positive electrode according to claim 1, wherein the graphite fluoride has a fluorine-carbon ratio of 0.9 to 1.0.
4. The method for producing a graphite fluoride positive electrode according to claim 1, wherein the conductive agent comprises at least one of a multiwall carbon nanotube, a single wall carbon nanotube, and a carbon nanofiber; the length of the multi-wall carbon nano tube is 5-30 mu m, and the diameter of the multi-wall carbon nano tube is 5-15 nm; the length of the single-walled carbon nanotube is 15-20 mu m, and the diameter of the single-walled carbon nanotube is 1-2 nm; the length of the carbon nanofiber is 1-15 mu m, and the diameter of the carbon nanofiber is 50-200 nm;
optionally, the conductive agent is selected from single-walled carbon nanotubes.
5. The method for producing a graphite fluoride positive electrode according to claim 1, wherein the mass ratio of the graphite fluoride to the conductive agent is (3-7): 1;
optionally, the mass ratio of the graphite fluoride to the conductive agent is 5: 1.
6. the method for producing a graphite fluoride positive electrode according to claim 1, wherein the solvent in the solution containing graphite fluoride and the conductive agent includes at least one of ethanol, N-methylpyrrolidone, and dimethylformamide.
7. The method for preparing a graphite fluoride positive electrode according to claim 1, wherein the drying temperature is 80-110 ℃ and the drying time is 8-24 h.
8. A graphite fluoride positive electrode is characterized by comprising a conductive agent and graphite fluoride with a lamellar structure; part of the conductive agent is distributed between the sheets of the graphite fluoride and is in contact with the graphite fluoride; the thickness of the graphite fluoride sheet layer is 10-30 nm.
9. A battery comprising a negative electrode and a positive electrode of graphite fluoride according to claim 8; or, comprising a negative electrode and a graphite fluoride positive electrode produced by the method for producing a graphite fluoride positive electrode according to any one of claims 1 to 7.
10. The battery of claim 9, wherein the negative electrode comprises a lithium or magnesium sheet.
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