CN115395000A - Composite positive electrode material, preparation method thereof, positive plate and battery - Google Patents
Composite positive electrode material, preparation method thereof, positive plate and battery Download PDFInfo
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- CN115395000A CN115395000A CN202211215989.9A CN202211215989A CN115395000A CN 115395000 A CN115395000 A CN 115395000A CN 202211215989 A CN202211215989 A CN 202211215989A CN 115395000 A CN115395000 A CN 115395000A
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- 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 composite positive electrode material, a preparation method thereof, a positive plate and a battery, and relates to the technical field of batteries; the composite anode material comprises an inner core and a shell wrapped on the outer circumference of the inner core, wherein the inner core is a conjugated organic material embedded with alkali metal ions, and the shell is a fluorinated pentacene compound. On one hand, the conjugated organic material has good conductivity, can reduce the resistance of charge transfer, and leads the polarization of the battery to be smaller and the cycle performance to be more excellent; meanwhile, the embedding of the alkali metal ions can supplement the alkali metal lost in the charging and discharging process so as to improve the cycle performance, specific capacity and first-effect performance of the battery; on the other hand, the fluorinated pentacene compound has high electron mobility and electronegativity, can improve the conductivity of the material, and improve the transmission rate of alkali metal ions, so as to further improve the cycle performance, specific capacity and first-effect performance of the battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a composite positive electrode material, a preparation method thereof, a positive plate and a battery.
Background
Secondary batteries have been widely regarded by researchers as one of green chemical power sources. However, since the secondary battery is still under preliminary research, there are still many technical problems to be solved. Among them, the synthesis of new cathode materials and the study of their electrochemical properties in battery systems are one of the important directions in the study of secondary batteries.
So far, the research on the embeddable materials has been mainly focused on the positive electrode of the secondary battery, and the common positive electrode materials of the lithium ion battery are lithium iron phosphate, lithium manganate, lithium cobaltate, ternary and the like. Na of sodium ion battery, as opposed to lithium ion battery + The charge density of (a) is high and the solvation is more severe, and thus most of the positive electrode materials that can be used for lithium secondary batteries cannot be directly applied to sodium secondary batteries.
Currently, the positive electrode for sodium secondary batteries is mainly focused on studies of embeddable materials, such as transition metal oxides, prussian blue, polyanion type, and the like. And the prior sodium secondary battery is difficult to simultaneously ensure the specific capacity, the cycle performance and the first efficiency performance.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a composite positive electrode material and a preparation method thereof, and the composite positive electrode material can simultaneously improve the specific capacity, the cycle performance and the first-effect performance of a battery.
The invention also aims to provide a positive plate which comprises the composite positive electrode material. Therefore, the specific capacity, the cycle performance and the first-efficiency performance of the battery can be simultaneously improved.
The invention also aims to provide a battery, which comprises the positive plate. Therefore, the battery also has the advantages of higher specific capacity, cycle performance and first-efficiency performance.
The embodiment of the invention is realized by the following steps:
in a first aspect, the present invention provides a composite positive electrode material comprising:
the core is a conjugated organic material embedded with alkali metal ions, and the shell is a fluorinated pentacene compound.
In an alternative embodiment, the conjugated organic material is 1,2,5,6,9,10-hexabenzisohexone, formula 1,2,5,6,9,10-coronenehxone; alternatively, the conjugated organic material is a carbonyl derivative of pentacene.
In an alternative embodiment, the conjugated organic material is a carbonyl derivative of pentacene, and the carbonyl derivative of pentacene is 5,7,12,14-pentacenetetrone or 6,13-pentacenedione.
In alternative embodiments, the alkali metal ion is a lithium ion or a sodium ion; and/or the fluorinated pentacene compound is perfluorinated pentacene; and/or the mass of the shell accounts for 1-10% of the mass of the whole composite positive electrode material.
In a second aspect, the present invention provides a method of making a composite positive electrode material of any one of the preceding embodiments, comprising:
depositing alkali metal ions on the surface of the conjugated organic material to obtain an inner core;
and coating the fluorinated pentacene compound on the surface of the inner core to obtain the composite cathode material.
In an alternative embodiment, the step of depositing alkali metal ions on the surface of the conjugated organic material to obtain the core comprises:
coating the solution containing the conjugated organic material on a substrate and drying to obtain an intermediate, wherein the solution containing the conjugated organic material comprises the following components in a mass ratio of (0.5-2): (8-10): (0.5-2): (15-20) the binder, the solvent, the conductive agent, and the conjugated organic material;
connecting the intermediate with the anode of a discharge instrument as an anode, connecting the cathode of the discharge instrument with alkali metal as a cathode, extending the anode and the cathode into an organic solvent in which alkali metal salt is dissolved, and performing electrochemical deposition to deposit alkali metal ions on the surface of the conjugated organic material to obtain an inner core.
In an alternative embodiment, the step of coating the surface of the core with the fluorinated pentacene compound to obtain the composite cathode material comprises:
mixing the core and the fluorinated pentacene compound, and then sequentially carrying out tabletting, low-temperature heat treatment and crushing to obtain a composite cathode material;
the pressure of the tablet is 10-15MPa; and/or the treatment temperature of the low-temperature heat treatment is 80-100 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time after the low-temperature treatment is 10-24h.
In a third aspect, the present invention provides a positive electrode sheet, including:
a current collector;
the positive active layer is arranged on at least one surface of the current collector; the positive active layer is obtained by coating positive active slurry on a current collector; the positive electrode active slurry includes the composite positive electrode material according to any one of the preceding embodiments, or includes the composite positive electrode material prepared by the method for preparing the composite positive electrode material according to any one of the preceding embodiments.
In an optional embodiment, the positive active slurry further comprises a conductive agent and a binder, and the mass percentages of the composite positive electrode material, the conductive agent and the binder are 50-93%, 1-25% and 5-25%, respectively.
In a fourth aspect, the present invention provides a battery comprising the positive electrode sheet of the foregoing embodiment.
The embodiment of the invention has at least the following advantages or beneficial effects:
the embodiment of the invention provides a composite cathode material and a preparation method thereof.
On one hand, the composite positive electrode material can reduce the resistance of charge transfer through the excellent conductivity of the specific conjugated organic material, so that the polarization of the battery is smaller, and the cycle performance is better; meanwhile, alkali metal ions are embedded into the conjugated organic material, so that the alkali metal lost in the charging and discharging process can be supplemented, and the cycle performance, specific capacity and first-effect performance of the battery are improved; on the other hand, the fluorinated pentacene compound has the advantages that the shell is arranged, the stability of the core structure can be improved, the conductivity of the material can be further improved by utilizing the characteristic of high electron mobility, the characteristic of high electronegativity can be utilized to assist the embedding and the releasing of alkali metal ions, the transmission rate of the alkali metal ions can be improved, and the cycle performance, the specific capacity and the first-efficiency performance of the battery can be further improved.
The embodiment of the invention also provides a positive plate which comprises the composite positive electrode material. Therefore, the specific capacity, the cycle performance and the first-efficiency performance of the battery can be simultaneously improved.
The embodiment of the invention also provides a battery, which comprises the positive plate. Therefore, the battery also has the advantages of higher specific capacity, cycle performance and first-effect performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed 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 invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a molecular structural formula of a conjugated organic material provided in an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention 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.
The features and properties of the present invention are described in further detail below with reference to examples.
The embodiment of the invention provides a composite cathode material, which is active particles forming a cathode plate, is in a core-shell structure and comprises a core and a shell wrapping the outer circumference of the core, wherein the core is a conjugated organic material embedded with alkali metal ions, and the shell is a fluorinated pentacene compound.
On one hand, the conjugated organic material has excellent conductivity, so that the resistance of charge transfer can be reduced, the polarization of the battery is smaller, and the cycle performance is better; meanwhile, alkali metal ions are embedded into the conjugated organic material, so that the alkali metal lost in the charging and discharging process can be supplemented, and the cycle performance, specific capacity and first-effect performance of the battery are improved; on the other hand, the fluorinated pentacene compound shell can further improve the conductivity of the material by utilizing the characteristic of high electron mobility, and can assist the alkali metal ions to be embedded and separated by utilizing the characteristic of high electronegativity, so that the transmission rate of the alkali metal ions can be improved, and the cycle performance, the specific capacity and the first-efficiency performance of the battery are further improved.
Alternatively, in the embodiment of the present invention, the conjugated organic material may be 1,2,5,6,9,10-hexabenzisohexone, whose molecular formula is 1,2,5,6,9,10-coronenehxone, which is commonly referred to as COHON, and the molecular formula of the COHON is shown in fig. 1. Charge transfer occurs between the COHON molecules and the active metal substrate, and a delocalized pi-bond is formed integrally. The formation of delocalized pi bonds can endow COHON molecules with better conductivity, so that the conductivity of a positive electrode is higher, the resistance of charge transfer can be reduced, the polarization of a battery is smaller, and the cycle performance of the battery is improved.
Meanwhile, oxygen atoms on each carbonyl group of COHON molecules obtain an electron during discharging, and alkali metal ions are embedded into the electron to generate enol alkali metal salt; during charging, lithium ions are extracted, carbonyl is reduced, and reversible intercalation and extraction of alkali metal ions are realized through conversion between carbonyl and enol structures. Therefore, the COHON molecules are embedded with the alkali metal ions, so that the alkali metal ions can be stored through the COHON molecules, more alkali metal ions can be stored through 6 carbonyl groups, and the alkali metal ions can be better and faster de-embedded so as to ensure the cycle performance and the specific capacity of the battery. In addition, by embedding alkali metal ions in COHON molecules, alkali metal lost in the charging and discharging process can be supplemented, so that the cycle performance, specific capacity and first-effect performance of the battery are improved.
Alternatively, in embodiments of the present invention, the conjugated organic material may also be selected to be a conjugated organic semiconductor material, for example, a carbonyl derivative of pentacene. The carbonyl derivative of pentacene can also generate charge transfer with an active metal substrate to form a delocalized pi bond. The formation of delocalized pi bonds makes the anode higher in conductivity, thereby reducing the resistance to charge transfer, and making the polarization of the battery smaller, thereby increasing the cycle performance of the battery.
Illustratively, in embodiments of the invention, the carbonyl derivative of pentacene is 5,7,12,14-pentacenetetrone or 6,13-pentacenedione. Wherein 5,7,12,14-pentacene tetrone is commonly known as P40,6,13-pentacene dione is commonly known as P20. When P2O and P40 are discharged, an oxygen atom on each carbonyl group of the P2O and P40 obtains an electron, and an alkali metal ion is simultaneously inserted to generate lithium enol salt or sodium enol salt; during charging, alkali metal ions are removed, carbonyl is reduced, and reversible intercalation and removal of the alkali metal ions are realized through conversion between carbonyl and enol structures. Therefore, the alkali metal ions are embedded in the pentacene carbonyl derivative, the pentacene carbonyl derivative can be used for storing the alkali metal ions, more alkali metal ions can be stored through the carbonyl group, and the alkali metal ions can be better and faster de-embedded so as to ensure the cycle performance and the specific capacity of the battery. In addition, by embedding alkali metal ions in the carbonyl derivative of the pentacene, the alkali metal lost in the charging and discharging process can be supplemented, so that the cycle performance, the specific capacity and the first-effect performance of the battery are improved.
In addition, in the embodiment of the invention, the density of the perfluorinated pentacene is lower than that of the COHON molecule or P40 or P20, so that the perfluorinated pentacene can be better coated on the surface of the COHON molecule or P40 or P20, the stability of the core molecule structure is maintained, and the cycle, capacity and first-efficiency performance of the battery are further improved. Meanwhile, the fluorinated pentacene compound has high electron mobility, and the conductivity of the material can be integrally improved. And moreover, the electronegativity of the fluorine element is higher, so that the insertion and extraction of alkali metal ions in the core are facilitated, the transmission rate of the alkali metal ions is improved, the C-F bond of the fluorinated pentacene compound is a group for pulling electrons, the working potential of the material can be increased, and the cycle, capacity and first-effect performance of the battery can be further improved. Furthermore, the fluorinated pentacene compound is insoluble in an organic solvent, is a nonpolar and hydrophobic molecule, can effectively prevent the COHON molecule or P40 or P20 from being dissolved in the electrolyte, and can further improve the cycle performance of the battery.
In the examples of the present invention, the alkali metal ions are lithium ions or sodium ions. The alkali metal ions are embedded in the conjugated organic material, so that on one hand, the cycle performance and the specific capacity of the battery can be improved through de-embedding, on the other hand, lithium or sodium can be supplemented, and the alkali metal ions lost in the charging and discharging operation process of the battery can be supplemented, so that the cycle performance, the specific capacity and the first efficiency performance of the battery can be further improved. Preferably, in an embodiment of the present invention, the alkali metal ion is a sodium ion. When the alkali metal ions are sodium ions, the corresponding composite positive electrode material is a positive electrode material of a sodium ion battery.
It should be noted that, in the examples of the present invention, the fluorinated pentacene compound is perfluorinated pentacene. The perfluoro pentacene has high electron mobility, can integrally improve the conductivity of the material, and meanwhile, the electronegativity of fluorine is high, so that the embedding and the separation of alkali metal ions in the core are facilitated, the transmission rate of the alkali metal ions is improved, and the cycle performance, the specific capacity and the first efficiency performance of the battery can be further improved.
In addition, it is also noted that in the present embodiment, the mass of the casing accounts for 1 to 10% of the mass of the entire composite positive electrode material, and may be selected to be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, for example. That is, the fluorinated pentacene compound is used in a relatively small amount. The activity of the conjugated organic material embedded with alkali metal ions of the inner core can be ensured by controlling the using amount of the fluorinated pentacene compound, the cycle performance, the specific capacity and the first-efficiency performance of the battery can be ensured, and the stability of the inner core structure can be maintained by the fluorinated pentacene compound, so that the cycle performance, the specific capacity and the first-efficiency performance of the battery can be further improved.
The embodiment of the invention also provides a preparation method of the composite cathode material, which comprises the following steps:
s1: depositing alkali metal ions on the surface of the conjugated organic material to obtain an inner core;
s2: and coating the fluorinated pentacene compound on the surface of the inner core to obtain the composite cathode material.
In detail, in step S1, the deposition manner may be either electrodeposition or vapor deposition. Illustratively, it can be selected from electrodeposition, and specifically includes: s11: coating the solution containing the conjugated organic material on a base material and drying to obtain an intermediate; s12: connecting the intermediate with the anode of a discharge instrument as an anode, connecting the cathode of the discharge instrument with alkali metal as a cathode, and extending the anode and the cathode into an organic solvent dissolved with alkali metal salt to perform electrochemical deposition so as to deposit alkali metal ions on the surface of the conjugated organic material to obtain an inner core.
In step S11, the substrate may be any one of a metal plate, a metal foil, a metal rod, and a metal mesh. The solution containing the conjugated organic material comprises a binder, a conductive agent, the conjugated organic material (COHON, P40 or P20) and a solvent, wherein the mass ratio of the binder to the solvent to the conductive agent to the conjugated organic material is (0.5-2): (8-10): (0.5-2): (15-20). And, illustratively, the conductive agent may be selected as carbon black (Super-P), the binder may be selected as polyvinyl fluoride (PVDF), and the solvent may be selected as N-methylpyrrolidone (NMP). The components of the solution of the conjugated organic material are limited, so that the structural stability of the prepared core can be fully improved, the chemical performance of the core is ensured, and the service performance of the battery can be ensured. Meanwhile, in step S11, the drying temperature is higher than the room temperature, and the higher the temperature is, the shorter the drying time is, and the drying time can be adjusted as required.
In step S12, the type of the alkali metal negative electrode is determined according to the battery type, and the negative electrode of the lithium secondary battery is lithium metal and the negative electrode of the sodium secondary battery is sodium metal. And after the electrodeposition is finished, taking out the anode, drying, and taking down the surface coating layer from the base material to obtain the inner shell. The core prepared by electrodeposition has a stable structure, and can fully ensure the cycle performance, specific capacity and first-effect performance of the battery.
In detail, in step S2, the step of coating the surface of the core with the fluorinated pentacene compound to obtain the composite positive electrode material includes: and mixing the core and the fluorinated pentacene compound, and then sequentially carrying out tabletting, low-temperature heat treatment and crushing to obtain the composite cathode material. Wherein the pressure of the tablet is 10-15MPa; the treatment temperature of the low-temperature heat treatment is 80-100 ℃, the temperature rising speed is 5-10 ℃/min, and the heat preservation time after the low-temperature heat treatment is 10-24h. The water on the organic matters can be removed through low-temperature heat treatment, and the organic matters are favorably compounded to form a stable material structure. Namely, the shell can be quickly wrapped on the core by the preparation method, so that the stability of the core structure is further improved, and the cycle performance, the specific capacity and the first-efficiency performance of the battery are further improved.
Embodiments of the present invention also provide a positive electrode sheet including a current collector and a positive active layer. The selection of the current collector is related to the polarity, the current collector of the positive plate is generally an aluminum foil, and the current collector of the negative plate is generally a copper foil. Of course, the current collector may also be a composite current collector, and the embodiment of the present invention is not described in detail. The positive active layer is obtained by coating positive active slurry on a current collector; the positive active slurry is obtained by dispersing a composite positive material, a conductive agent and a binder in a solvent. Illustratively, the conductive agent may be selected as carbon black (Super-P), the binder may be selected as polyvinyl fluoride (PVDF), and the solvent may be selected as N-methylpyrrolidone (NMP).
As an optional scheme, the mass percentages of the composite positive electrode material, the conductive agent and the binder are respectively 50-93%, 1-25% and 5-25%. The cycle performance, specific capacity and first-effect performance of the battery prepared from the composite anode material can be further ensured by controlling the use amounts of the composite anode material, the conductive agent and the binder.
The embodiment of the invention also provides a battery, which comprises the positive plate, a shell, a negative plate, a diaphragm and electrolyte. The positive plate, the diaphragm and the negative plate are sequentially placed, the pole core is formed in a winding or laminating mode, and finally the pole core is arranged in the shell and then electrolyte is injected to obtain the battery. Because the battery comprises the positive plate, the battery also has the advantages of higher cycle performance, specific capacity and first-efficiency performance.
In the embodiment of the present invention, the negative electrode sheet of the lithium ion battery may be selected as ground metallic lithium, and the negative electrode sheet of the sodium ion battery may be selected as ground metallic sodium. In addition, the negative plate can also be a composite structure of a current collector and a negative active layer, the current collector is selected from copper foil, the negative active layer is obtained by coating negative active slurry on the current collector, the negative active slurry can be obtained by dispersing a negative active material, a conductive agent and a binder in a solvent, and the negative active material can be selected from graphite, graphene and the like. The mass percentages of the negative active material, the conductive agent and the binder are respectively 50-93%, 1-25% and 5-25%; the conductive agent can be selected from carbon black, and the binder can be selected from styrene butadiene rubber emulsion (SBR).
It should be noted that the separator may be made of PP, PE, or a composite material of PP and PE. Illustratively, the separator is selected to be Celgard 3000.
In addition, it is to be noted that the electrolyte of the lithium secondary battery is a lithium hexafluorophosphate electrolyte or a THF electrolyte, and the electrolyte of the sodium secondary battery is a sodium hexafluorophosphate electrolyte or a THF electrolyte.
Of course, in the embodiment of the present invention, the conductive agent in each preparation process may also be selected to be the carbon nanotube, and the binder may also be mixed with a dispersant or a thickener, such as carboxymethyl cellulose (CMC), and the embodiment of the present invention is not limited.
The above preparation process is described in detail below with reference to specific examples and comparative examples:
example 1
This example provides a battery prepared by the following method:
s1: preparing a composite cathode material:
the step S1 specifically includes:
s11: the preparation method comprises the following steps of (1) mixing a binder, a solvent, a conductive agent and a conjugated organic material according to a mass ratio of 0.5:8:0.5:15, and illustratively, the conjugated organic material is 1,2,5,6,9,10-coronene hexone, the conductive agent is selected to be carbon black (Super-P), the binder is selected to be polyvinyl fluoride (PVDF), and the solvent is selected to be N-methylpyrrolidone (NMP); coating the mixed slurry on a metal plate and drying to obtain an intermediate; connecting the intermediate with the anode of a discharge instrument as an anode, connecting the cathode of the discharge instrument with metal lithium as a cathode, extending the anode and the cathode into an organic solvent in which lithium metal salt is dissolved to carry out electrochemical deposition, and depositing alkali metal ions on the surface of the conjugated organic material to obtain an inner core;
s12: performing tabletting, low-temperature heat treatment and crushing on the perfluorinated pentacene and the inner core to obtain a composite anode material; the perfluorinated pentacene accounts for 5% of the composite positive electrode material by mass, and the pressure of tabletting is 10MPa; the treatment temperature of the low-temperature heat treatment is 80 ℃, the heating rate is 5 ℃/min, and the heat preservation time after the low-temperature treatment is 24h;
s2: preparing a positive plate:
step S2 specifically comprises dispersing 50%, 25% and 25% of composite anode material, conductive agent and binder in a solvent to obtain anode active slurry; coating the positive active slurry on an aluminum foil and performing vacuum drying; wherein the conductive agent is carbon black, the binder is polyvinyl fluoride, and the solvent is N-methyl pyrrolidone; the positive electrode load was 21mg/cm 2 ；
S3: preparing a battery:
step S3 specifically comprises the steps of winding the positive plate, the diaphragm and the negative plate to obtain a pole core, and filling the pole core into the shell and injecting electrolyte to obtain the lithium secondary battery; wherein the negative plate is polished metal lithium, the diaphragm is Celgard 3000, and the electrolyte is 0.25M LiPF 6 。
Example 2
This example provides a battery prepared by the following method:
s1: preparing a composite cathode material:
the step S1 specifically includes:
s11: the preparation method comprises the following steps of (1): 9:1:18 to form a mixed slurry, and illustratively, the conjugated organic material is 1,2,5,6,9,10-coronene hexone, the conductive agent is selected from carbon black (Super-P), the binder is selected from polyvinyl fluoride (PVDF), and the solvent is selected from N-methyl pyrrolidone (NMP); coating the mixed slurry on a metal plate and drying to obtain an intermediate; connecting the intermediate with the anode of a discharge instrument as an anode, connecting the cathode of the discharge instrument with metal sodium as a cathode, extending the anode and the cathode into an organic solvent in which lithium metal salt is dissolved to carry out electrochemical deposition, and depositing alkali metal ions on the surface of the conjugated organic material to obtain an inner core;
s12: performing tabletting, low-temperature heat treatment and crushing on the perfluorinated pentacene and the inner core to obtain a composite anode material; the perfluoro pentacene accounts for 10% of the composite anode material by mass, and the pressure of the tablet is 12MPa; the treatment temperature of the low-temperature heat treatment is 90 ℃, the heating rate is 7 ℃/min, and the heat preservation time after the low-temperature treatment is 20h;
s2: preparing a positive plate:
step S2 specifically comprises dispersing 70%, 20% and 10% of composite anode material, conductive agent and binder in a solvent to obtain anode active slurry; coating the positive active slurry on an aluminum foil and performing vacuum drying; wherein the conductive agent is carbon black, the binder is polyvinyl fluoride, and the solvent is N-methyl pyrrolidone; the positive electrode load was 21mg/cm 2 ；
S3: preparing a battery:
step S3 specifically comprises the steps of winding the positive plate, the diaphragm and the negative plate to obtain a pole core, and filling the pole core into the shell and injecting electrolyte to obtain the lithium secondary battery; wherein the negative plate is polished sodium metal, the diaphragm is Celgard 3000, and the electrolyte is 0.25M LiPF 6 。
Example 3
The present example provides a battery, which is prepared by the following method:
s1: preparing a composite cathode material:
the step S1 specifically includes:
s11: the preparation method comprises the following steps of (1): 9:1:18 to form a mixed slurry, and illustratively, the conjugated organic material is 1,2,5,6,9,10-coronenehexanone, the conductive agent is carbon black (Super-P), the binder is polyvinyl fluoride (PVDF), and the solvent is N-methylpyrrolidone (NMP); coating the mixed slurry on a metal plate and drying to obtain an intermediate; connecting the intermediate with the anode of a discharge instrument as an anode, connecting the cathode of the discharge instrument with metal lithium as a cathode, extending the anode and the cathode into an organic solvent in which lithium metal salt is dissolved to carry out electrochemical deposition, and depositing alkali metal ions on the surface of the conjugated organic material to obtain an inner core;
s12: performing tabletting, low-temperature heat treatment and crushing on the perfluorinated pentacene and the inner core to obtain a composite anode material; the perfluorinated pentacene accounts for 5% of the composite positive electrode material by mass, and the pressure of tabletting is 14MPa; the treatment temperature of the low-temperature heat treatment is 95 ℃, the heating rate is 9 ℃/min, and the heat preservation time after the low-temperature treatment is 18h;
s2: preparing a positive plate:
step S2 specifically comprises the steps of dispersing 80%, 10% and 10% of composite anode material, conductive agent and binder in a solvent to obtain anode active slurry; coating the positive active slurry on an aluminum foil and performing vacuum drying; wherein the conductive agent is carbon black, the binder is polyvinyl fluoride, and the solvent is N-methylpyrrolidone; the positive electrode loading capacity is 21mg/cm 2 ；
S3: preparing a negative plate:
step S3 specifically comprises dispersing 80%, 10% and 10% by mass of the negative electrode active material, the conductive agent and the binder in a solvent to obtain negative electrode active slurry; coating the negative active slurry on a copper foil and performing vacuum drying; wherein the negative active material is graphite, the conductive agent is carbon black, the binder is styrene butadiene rubber emulsion, and the solvent is N-methyl pyrrolidone; negative electrode load 21mg/cm 2 ；
S4: preparing a battery:
step S4 specifically comprises the steps of winding the positive plate, the diaphragm and the negative plate to obtain a pole core, and filling the pole core into the shell and injecting electrolyte to obtain the lithium secondary battery; wherein the negative plate is polished metal lithium, the diaphragm is Celgard 3000, and the electrolyte is 0.25M LiPF 6 。
Example 4
This example provides a battery prepared by the following method:
s1: preparing a composite cathode material:
the step S1 specifically includes:
s11: the preparation method comprises the following steps of (1) mixing a binder, a solvent, a conductive agent and a conjugated organic material according to a mass ratio of 2:10:2:20, and illustratively, the conjugated organic material is 1,2,5,6,9,10-coronene hexone, the conductive agent is selected to be carbon black (Super-P), the binder is selected to be polyvinyl fluoride (PVDF), and the solvent is selected to be N-methylpyrrolidone (NMP); coating the mixed slurry on a metal plate and drying to obtain an intermediate; connecting the intermediate with the anode of a discharge instrument as an anode, connecting the cathode of the discharge instrument with metal sodium as a cathode, extending the anode and the cathode into an organic solvent in which lithium metal salt is dissolved to carry out electrochemical deposition, and depositing alkali metal ions on the surface of the conjugated organic material to obtain an inner core;
s12: performing tabletting, low-temperature heat treatment and crushing on the perfluorinated pentacene and the inner core to obtain a composite anode material; the pressure of the pressed tablet is 15MPa; the perfluoro pentacene accounts for 5% of the composite anode material by mass, the treatment temperature of low-temperature heat treatment is 100 ℃, the heating rate is 10 ℃/min, and the heat preservation time after the low-temperature treatment is 10h;
s2: preparing a positive plate:
step S2 specifically comprises the steps of dispersing the composite anode material, the conductive agent and the binder which are respectively 94%, 1% and 5% in mass percentage in a solvent to obtain anode active slurry; coating the positive active slurry on an aluminum foil and performing vacuum drying; wherein the conductive agent is carbon black, the binder is polyvinyl fluoride, and the solvent is N-methylpyrrolidone; the positive electrode load was 21mg/cm 2 ；
S3: preparing a negative plate:
step S3 specifically comprises dispersing 94%, 1% and 5% by mass of a negative electrode active material, a conductive agent and a binder in a solvent to obtain a negative electrode active slurry; coating the negative active slurry on a copper foil and performing vacuum drying; wherein the negative active material is graphite, the conductive agent is carbon black, the binder is styrene butadiene rubber emulsion, and the solvent is N-methyl pyrrolidone; negative electrode load amount 21mg/cm 2 ；
S4: preparing a battery:
step S4 specifically comprises the steps of winding the positive plate, the diaphragm and the negative plate to obtain a pole core, and filling the pole core into the shell and injecting electrolyte to obtain the lithium secondary battery; wherein the negative plate is polished metal lithium, the diaphragm is Celgard 3000, and the electrolyte is 0.25M THF.
Example 5
This example provides a battery whose manufacturing method is different from that of example 1 in that, in step S11, a binder, a solvent, a conductive agent, and a conjugated organic material are mixed in a mass ratio of 1:9:1:18 and the conjugated organic material is 5,7,12,14-pentacenetetraone.
Example 6
This example provides a battery prepared by a method different from that of example 5 in that, in step S11, the conjugated organic material is 6,13-pentacenedione.
Comparative example 1
Comparative example 1 provides a battery, which is manufactured by a method different from that of example 1 in that, in step S11, the positive electrode material used in comparative example 1 is a conjugated polymer, and specifically poly-p-phenylene vinylene, and an outer clad layer arrangement without a fluorinated pentacene compound is provided.
Comparative example 2
Comparative example 2 provides a battery, which is manufactured by a method different from that of example 1 in that, in step S11, the positive electrode material used in comparative example 2 is a COHON molecule, but does not have an outer clad layer arrangement of a fluorinated pentacene compound.
Comparative example 3
Comparative example 3 provides a battery, which is manufactured by a method different from that of example 2 in that, in step S11, the positive electrode material used in comparative example 3 is a conjugated polymer, and specifically, poly-p-phenylene vinylene, and an outer clad layer provided with a fluorinated pentacene compound is provided.
Comparative example 4
Comparative example 4 provides a battery, which is manufactured by a method different from that of example 2 in that, in step S11, the positive electrode material used in comparative example 4 is a COHON molecule, but does not have an outer clad layer arrangement of a fluorinated pentacene compound.
Comparative example 5
Comparative example 5 provides a battery, which is manufactured by a method different from that of example 5 in that comparative example 5 employs a cathode material of 5,7,12,14-pentacenetetrone without an outer coating layer of a fluorinated pentacene compound in step S11.
Comparative example 6
Comparative example 5 provides a battery, which is manufactured by a method different from that of example 6 in that comparative example 5 employs a cathode material of 6,13-pentacenedione without an outer clad layer of a fluorinated pentacene compound in step S11.
Experimental example 1
The positive electrode sheets prepared in examples 1 to 6 and comparative examples 1 to 6 were tested for positive electrode conductivity under the following test conditions: the conductivity of the surface of the positive electrode material was measured using a Hua-test high temperature four-probe tester HEST-800, and the results are shown in Table 1.
TABLE 1 results of conductivity measurements
| Number of | Positive electrode conductivity (S/cm) |
| Example 1 (lithium, negative lithium, COHON) | 2.3×10 -5 |
| Example 2 (sodium, negative sodium, COHON) | 2.1×10 -5 |
| Example 3 (lithium, negative electrode graphite, COHON) | 2.2×10 -5 |
| Example 4 (sodium, negative electrode graphite, COHON) | 2.0×10 -5 |
| Example 5 (lithium, negative electrode lithium, P40) | 1.8×10 -5 |
| Example 6 (lithium, negative electrode lithium, P20) | 1.6×10 -5 |
| Comparative example 1 (lithium, conventional organic electrode, uncoated) | 1.8×10 -6 |
| Comparative example 2 (lithium, COHON, uncoated) | 3.2×10 -6 |
| Comparative example 3 (sodium, conventional organic electrode, with coating) | 2.0×10 -6 |
| Comparative example 4 (sodium, COHON, uncoated) | 3.0×10 -6 |
| COMPARATIVE EXAMPLE 5 (lithium, P40, uncoated) | 2.2×10 -6 |
| COMPARATIVE EXAMPLE 6 (lithium, P20, uncoated) | 1.9×10 -6 |
As can be seen from the data shown in table 1, examples 1 to 6 of the present invention provide positive electrode sheets having higher conductivity of the positive electrode, and thus can reduce the resistance to charge transfer, resulting in smaller polarization of the battery, thereby increasing the cycle performance of the battery. Meanwhile, since the electrical conductivities of comparative examples 2, 4, 5 and 6 are superior to those of comparative examples 1 and 3, it is demonstrated that the COHON molecule, P40 or P20 can effectively improve the positive electrode conductivity, and the effect of the COHON molecule is superior to that of P40 or P20. However, since comparative examples 2, 4, 5 and 6 only used a COHON molecule, and P40 or P20 was not coated with a fluorinated pentacene compound shell, the conductivity was inferior to examples 1 to 6 of the present invention. In addition, as can be seen from comparison of the data of comparative example 1 and comparative example 3, when the conventional organic electrode is used, the fluorinated pentacene compound coated outside the electrode can also improve the conductivity to some extent, but the effect is inferior to that of the COHON molecule, P40 or P20.
Experimental example 2
The cycle performance of the batteries prepared in examples 1 to 4 and comparative examples 1 to 4 was tested. The test conditions are that after the battery is assembled, a LAND blue battery test system is used for carrying out cycle performance test under the conditions of 1C/1C charge-discharge current and 0.1V-2.8V charge-discharge voltage, and the test results are shown in Table 2.
TABLE 2 test results of cycle performance
As can be seen from the data shown in tables 1 and 2, since the positive electrode sheets provided in examples 1 to 6 of the present invention have higher conductivity of the positive electrode, resistance to charge transfer can be reduced, resulting in less polarization of the battery, and thus, the cycle performance of the battery can be increased. Meanwhile, the comparative examples 2, 4, 5 and 6 have better cycle performance than the comparative examples 1 and 3, which shows that the COHON molecule, P40 or P20 can effectively improve cycle performance, and the effect of the COHON molecule is better than that of P40 or P20. However, comparative examples 2, 4, 5 and 6 are inferior to examples 1 to 6 of the present invention in cycle performance since only COHON molecules are used and P40 or P20 is not coated with a fluorinated pentacene compound shell. In addition, as can be seen from comparison of the data of comparative example 1 and comparative example 3, when the conventional organic electrode was used, the fluorinated pentacene compound coated outside the electrode also improved the cycle performance to some extent, but the effect was inferior to that of the COHON molecule, P40 or P20.
Experimental example 3
The initial specific capacities of the batteries prepared in examples 1 to 4 and comparative examples 1 to 4 were tested. The test results are shown in table 3.
TABLE 3 initial specific capacity test results
As can be seen from the data in table 3, the initial specific capacities of the batteries provided in examples 1 to 6 of the present invention are relatively high, which indicates that the composite cathode material provided in the examples of the present invention can effectively increase the initial specific capacity of the batteries. Meanwhile, since the initial specific capacities of comparative examples 2, 4, 5 and 6 are superior to those of comparative examples 1 and 3, it is demonstrated that the COHON molecule, P40 or P20 can effectively increase the initial specific capacity and the effect of the COHON molecule is superior to that of P40 or P20. However, since comparative examples 1,2, 4, 5 and 6 use only a COHON molecule, and P40 or P20 is not coated with a fluorinated pentacene compound shell, the initial specific capacity is higher than that of examples 1 to 6 of the present invention, but the initial specific capacity of examples 1 to 6 is much better than that of comparative example 3.
Experimental example 4
The full initial efficiency of the batteries prepared in examples 1 to 4 and comparative examples 1 to 4 was tested. The test results are shown in table 4.
TABLE 4 full electric first effect test results
As can be seen from the data in table 4, the first-efficiency performance of the batteries provided in examples 1 to 6 of the present invention is relatively high, which indicates that the first-efficiency performance of the batteries can be effectively improved by the composite cathode material provided in the examples of the present invention. Meanwhile, the first-effect performance of the cycle performance of comparative examples 2, 4, 5 and 6 is superior to that of comparative examples 1 and 3, so that the COHON molecule, P40 or P20 can effectively improve the cycle performance and can effectively improve the first-effect performance. However, since comparative examples 2, 4, 5 and 6 only use a COHON molecule, and P40 or P20 is not coated with a fluorinated pentacene compound shell, the first effect performance is lower than that of examples 1 to 6 of the present invention. In addition, as can be seen from comparison of data of comparative example 1 and comparative example 3, when the conventional organic electrode is used, the fluorinated pentacene compound coated outside the electrode can also improve the first effect to some extent, but the effect is inferior to that of the COHON molecule, P40 or P20.
In summary, the composite cathode material provided by the embodiment of the invention can effectively improve the cycle performance, specific capacity and first-efficiency performance of the battery.
The present invention has been described in terms of the preferred embodiment, and it is not intended to be limited to the embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A composite positive electrode material, comprising:
the core is a conjugated organic material embedded with alkali metal ions, and the shell is a fluorinated pentacene compound.
2. The composite positive electrode material according to claim 1, characterized in that:
the conjugated organic material is 1,2,5,6,9,10-hexabenzisohexone, and the molecular formula is 1,2,5,6,9,10-coronene hexone;
alternatively, the first and second electrodes may be,
the conjugated organic material is a carbonyl derivative of pentacene.
3. The composite positive electrode material according to claim 2, characterized in that:
the conjugated organic material is a carbonyl derivative of pentacene, and the carbonyl derivative of pentacene is 5,7,12,14-pentacenetetrone or 6,13-pentacenedione.
4. The composite positive electrode material according to claim 1, characterized in that:
the alkali metal ions are lithium ions or sodium ions;
and/or the presence of a gas in the gas,
the fluorinated pentacene compound is perfluorinated pentacene;
and/or the presence of a gas in the gas,
the mass of the shell accounts for 1-10% of the mass of the whole composite positive electrode material.
5. A method for producing the composite positive electrode material according to any one of claims 1 to 4, characterized by comprising:
depositing the alkali metal ions on the surface of the conjugated organic material to obtain the inner core;
and coating the fluorinated pentacene compound on the surface of the inner core to obtain the composite cathode material.
6. The method for preparing the composite positive electrode material according to claim 5, wherein the step of depositing the alkali metal ions on the surface of the conjugated organic material to obtain the core comprises:
coating the solution containing the conjugated organic material on a substrate and drying to obtain an intermediate, wherein the solution containing the conjugated organic material comprises the following components in a mass ratio of (0.5-2): (8-10): (0.5-2): (15-20) the binder, the solvent, the conductive agent, and the conjugated organic material;
and connecting the intermediate with the anode of a discharge instrument as an anode, connecting the cathode of the discharge instrument with alkali metal as a cathode, and extending the anode and the cathode into an organic solvent in which alkali metal salt is dissolved to carry out electrochemical deposition so that alkali metal ions are deposited on the surface of the conjugated organic material to obtain the inner core.
7. The method for producing the composite positive electrode material according to claim 5, wherein the step of coating the fluorinated pentacene compound on the surface of the core to obtain the composite positive electrode material comprises:
mixing the inner core and the fluorinated pentacene compound, and then sequentially carrying out tabletting, low-temperature heat treatment and crushing to obtain the composite cathode material;
the pressure of the tablet is 10-15MPa; and/or the treatment temperature of the low-temperature heat treatment is 80-100 ℃, the heating rate is 5-10 ℃/min, and the heat preservation time after the low-temperature treatment is 10-24h.
8. A positive electrode sheet, comprising:
a current collector;
the positive active layer is arranged on at least one surface of the current collector; the positive electrode active layer is obtained by coating positive electrode active slurry on the current collector, wherein the positive electrode active slurry comprises the composite positive electrode material in any one of claims 1 to 4, or comprises the composite positive electrode material prepared by the preparation method of the composite positive electrode material in any one of claims 5 to 7.
9. The positive electrode sheet according to claim 8, wherein:
the positive active slurry also comprises a conductive agent and a binder, and the composite positive material, the conductive agent and the binder are respectively 50-93%, 1-25% and 5-25% in mass percent.
10. A battery comprising the positive electrode sheet according to claim 8 or 9.
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| CN115863656B (en) * | 2023-03-01 | 2023-05-05 | 江门市科恒实业股份有限公司 | High-temperature-resistant ternary lithium ion battery positive electrode material and preparation method thereof |
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