CN114744156A - Positive pole piece structure and preparation method thereof - Google Patents
Positive pole piece structure and preparation method thereof Download PDFInfo
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- CN114744156A CN114744156A CN202210325991.5A CN202210325991A CN114744156A CN 114744156 A CN114744156 A CN 114744156A CN 202210325991 A CN202210325991 A CN 202210325991A CN 114744156 A CN114744156 A CN 114744156A
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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
- H01M4/139—Processes of manufacture
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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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
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
- H01M50/593—Spacers; Insulating plates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application provides a positive pole piece structure and a preparation method thereof. The preparation method of the positive pole piece structure comprises the following steps: the method comprises the steps of coating a first active material layer and a second active material layer on a current collector, coating a third active material layer and a fourth active material layer, and coating an insulating layer. First active material layer and fourth active material layer end both parallel and level, the insulating layer respectively with fourth active material layer and first active material layer juncture parallel and level, that is to say, neither overlap between first active material layer, fourth active material layer and the insulating layer three, also there is the clearance, so, not only can improve lithium ion battery's security, can also avoid positive pole piece overvoltage, assurance lithium ion battery electrical property to appear.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a positive pole piece structure and a preparation method thereof.
Background
The conventional positive plate of the current lithium ion battery is to coat an active substance on an aluminum foil, but the safety performance of the battery is more and more difficult to ensure along with the improvement of the capacity of the lithium ion battery; in order to improve the safety performance of the battery, the prior proposal 1 (application number: CN201821812658.2) proposes a new positive pole piece structure, which has two active materials and an insulating material layer, wherein the second positive active material layer is on the first active material layer, the first active material layer covers the position of the current collector, and the insulating material layer covers the position of the current collector; a gap is formed between the first active material layer and the insulating layer; although the safety performance of the battery is improved by the structure, the safety performance cannot be ensured if the first active material layer and the insulating layer are punctured by a needle due to the gap, so that the structure has defects;
the former case 2 has between first active material layer and the insulating layer to pile up each other and form overlap portion on the basis of former case 1, though this kind of structure can improve the security performance, first active material layer overlaps with the insulating layer and can increases the increase of the thickness of here to lead to the pole piece to have the risk of excessive pressure when colding pressing, and then influence electric core performance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a positive pole piece structure and a preparation method thereof, wherein the positive pole piece structure can improve the safety of a lithium ion battery, avoid overvoltage of a positive pole piece and ensure the electrical performance of the lithium ion battery.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a positive pole piece structure comprises the following steps:
coating a first active material on the surface of a current collector to obtain a first active material layer;
coating a second active material on one side of the current collector, which is far away from the first active material, so as to obtain a second active material layer;
coating a third active material on one surface, away from the current collector, of the second active material layer to obtain a third active material layer;
coating a fourth active material on one surface, away from the current collector, of the first active material layer to obtain a fourth active material layer, wherein the fourth active material layer is flush with the first active material layer, and a blank area is left on one surface, close to the fourth active material layer and the first active material layer, of the current collector;
coating an insulating layer on the blank area, wherein the insulating layer is flush with the junction of the fourth active material layer and the first active material layer respectively to obtain a precursor of the positive pole piece;
drying the precursor of the positive pole piece to obtain a positive secondary pole piece;
and carrying out rolling operation on the secondary positive pole piece to obtain the positive pole piece structure.
In one embodiment, the first active material, the second active material, the third active material, and the fourth active material are each at least one of lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, sodium iron phosphate, lithium vanadium phosphate, sodium vanadium phosphate, lithium vanadyl phosphate, sodium vanadyl phosphate, lithium vanadyl vanadate, lithium manganate, lithium nickelate, lithium nickel cobalt manganese manganate, lithium rich manganese based material, lithium nickel cobalt aluminate, and lithium titanate.
In one embodiment, the first active material, the second active material, the third active material, and the fourth active material further comprise a binder.
In one embodiment, the binder is at least one of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene, and styrene butadiene rubber.
In one embodiment, the first active material, the second active material, the third active material and the fourth active material further include a conductive agent.
In one embodiment, the conductive agent is at least one of carbon nanotubes, conductive carbon black, acetylene black, graphene, ketjen black, and carbon fibers.
In one embodiment, the insulating layer includes at least one of inorganic particles and a polymer.
In one embodiment, the inorganic particles are at least one of alumina, silica, magnesia, titania, hafnia, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconia, yttria, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate.
In one embodiment, the polymer is at least one of a homopolymer of vinylidene fluoride, a copolymer of hexafluoropropylene, polystyrene, polyphenylacetylene, sodium polyvinyl acetate, potassium polyvinyl acetate, polymethyl methacrylate, polyethylene, polypropylene, and polytetrafluoroethylene.
The application also provides a positive pole piece structure, and the positive pole piece structure is prepared by the preparation method of the positive pole piece structure in any embodiment.
Compared with the prior art, the invention has at least the following advantages:
1. according to the preparation method of the positive pole piece structure, the active material layer with the double-layer structure is adopted in the area covered by the active material layer on the positive current collector, the insulating layer is arranged in the area not covered by the active material layer, the insulating layer can avoid failure caused by internal short circuit generated when the lithium ion battery is pierced by external force, and therefore the safety of the lithium ion battery is effectively improved.
2. In the preparation method of the positive pole piece structure, the first active material layer and the fourth active material layer are flush with each other, and the insulating layer is flush with the junction of the fourth active material layer and the first active material layer respectively, namely, the first active material layer, the fourth active material layer and the insulating layer are not overlapped and have no gap, so that the problem that the pole piece has overvoltage risk during cold pressing due to the fact that the thickness of the pole piece is increased due to the fact that the first active material layer, the fourth active material layer and the insulating layer are overlapped can be solved, and the performance of a lithium ion battery cell is improved; on the other hand, the problem of short circuit caused by needling the position due to the gap between the first active material layer and the insulating layer can be avoided, and the safety of the lithium ion battery is further improved.
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 flow chart of a method for manufacturing a positive electrode sheet structure according to an embodiment;
FIG. 2 is a schematic structural diagram of the positive electrode tab shown in FIG. 1;
fig. 3 is a schematic view of another structure of the positive electrode tab shown in fig. 1.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not represent the only embodiments.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The application provides a preparation method of a positive pole piece structure. The preparation method of the positive pole piece structure comprises the following steps: coating a first active material on the surface of a current collector to obtain a first active material layer; coating a second active material on one side of the current collector, which is far away from the first active material, so as to obtain a second active material layer; coating a third active material on one surface, which faces away from the current collector, of the second active material layer to obtain a third active material layer; coating a fourth active material on one surface, away from the current collector, of the first active material layer to obtain a fourth active material layer, wherein the fourth active material layer is flush with the first active material layer, and a blank area is left on one surface, close to the fourth active material layer and the first active material layer, of the current collector; coating an insulating layer on the blank area, wherein the insulating layer is flush with the junction of the fourth active material layer and the first active material layer respectively to obtain a precursor of the positive pole piece; drying the precursor of the positive pole piece to obtain a positive secondary pole piece; and carrying out rolling operation on the secondary positive pole piece to obtain the positive pole piece structure.
According to the preparation method of the positive pole piece structure, the active material layer with the double-layer structure is adopted in the area covered by the active material layer on the positive current collector, the insulating layer is arranged in the area not covered by the active material layer, the insulating layer can avoid failure caused by internal short circuit generated when the lithium ion battery is pierced by external force, and therefore the safety of the lithium ion battery is effectively improved. Furthermore, the first active material layer and the fourth active material layer are parallel and level, and the insulating layer is respectively parallel and level with the junction of the fourth active material layer and the first active material layer, namely, the first active material layer, the fourth active material layer and the insulating layer are not overlapped and have no gap, so that the problem that the pole piece has an overvoltage risk during cold pressing due to the fact that the thickness of the pole piece is increased due to the overlapping of the first active material layer, the fourth active material layer and the insulating layer can be solved, and the performance of the lithium ion battery cell is improved; on the other hand, the problem of short circuit caused by needling the position due to the gap between the first active material layer and the insulating layer can be avoided, and the safety of the lithium ion battery is further improved.
In order to better understand the preparation method of the positive electrode sheet structure of the present invention, the following further explains the preparation method of the positive electrode sheet structure of the present invention, as shown in fig. 1, the preparation method of the positive electrode sheet structure of an embodiment includes part or all of the following steps:
and S100, coating a first active material on the surface of the current collector to obtain a first active material layer.
In the present embodiment, the current collector is a positive electrode current collector, i.e., an aluminum foil. The first active material layer is formed by preparing a first active material into a positive electrode slurry and then coating the positive electrode slurry on an aluminum foil. Further, the first active material layer covers part of the surface of the positive current collector to leave a blank area on the surface of the positive current collector.
And S200, coating a second active material on one surface of the current collector, which is far away from the first active material, to obtain a second active material layer.
In the present embodiment, the current collector is a positive electrode current collector, i.e., an aluminum foil. The second active material layer is formed by preparing a second active material into a positive electrode slurry and then coating the positive electrode slurry on an aluminum foil.
And S300, coating a third active material on one surface of the second active material layer, which is far away from the current collector, to obtain a third active material layer.
In this embodiment, prepare into positive pole thick liquids with the third active material, then coat the one side that deviates from the mass flow body with above-mentioned thick liquids in the second active material layer, make third active material layer range upon range of in the same one side of the anodal mass flow body with the second active material layer, and third active material layer and second active material layer can overlap completely, both ends parallel and level to improve the planarization of positive pole piece effectively.
S400, coating a fourth active material on one surface of the first active material layer, which is away from the current collector, to obtain a fourth active material layer, wherein the fourth active material layer is flush with the first active material layer, and a blank area is left on one surface of the current collector, which is close to the fourth active material layer and the first active material layer.
In this embodiment, the first active material layer and the fourth active material layer are aligned, a blank space is left on one side of the current collector close to the fourth active material layer and the first active material layer, and the blank space is used for coating an insulating layer, so that the insulating layer is aligned with the junction of the fourth active material layer and the first active material layer respectively, that is, the first active material layer, the fourth active material layer and the insulating layer are not overlapped and have no gap, so that on one hand, the problem that the pole piece has an overvoltage risk during cold pressing due to the fact that the thickness of the pole piece is increased due to the overlapping of the first active material layer, the fourth active material layer and the insulating layer can be solved, and the performance of the lithium ion battery cell is further improved; on the other hand, the problem of short circuit caused by needling the position due to the gap between the first active material layer and the insulating layer can be avoided, and the safety of the lithium ion battery is further improved.
And S500, coating an insulating layer on the blank area, wherein the insulating layer is flush with the junction of the fourth active material layer and the first active material layer respectively, and thus obtaining the precursor of the positive pole piece.
It can be understood that, in the prior two electrode plate structures, one electrode plate structure has two active materials and one insulating material in common, wherein the second positive active material layer is on the first active material layer, the first active material layer covers the position of the current collector, and the insulating material is coated on the position of the current collector; a gap is formed between the first active material layer and the insulating layer; although the safety performance of the battery is improved by the structure, the safety performance cannot be ensured if the first active material layer and the insulating layer are punctured by a needle due to the gap, so that the structure has defects; the other structure is that on the basis of the pole piece structure, the first active material layer and the insulating layer are mutually stacked to form an overlapping part, although the structure can improve the safety performance, the overlapping can increase the thickness of the position, and the pole piece has the risk of overvoltage during cold pressing, so that the performance of the battery core is influenced. In this embodiment, the blank area is coated with the insulating layer, and the insulating layer is flush with the junction of the fourth active material layer and the first active material layer, so that the first active material layer, the fourth active material layer and the insulating layer are not overlapped, and a gap does not exist.
S600, drying the precursor of the positive pole piece to obtain a positive secondary pole piece.
In this embodiment, a drying device is used to dry the precursor of the positive electrode sheet, i.e., the aluminum foil coated with the positive active material coating slurry, so as to volatilize water in the positive active material coating slurry, so that the positive active material coating and the insulating layer are cured on the aluminum foil, thereby forming a positive secondary electrode sheet, i.e., a positive electrode sheet formed further.
S700, performing rolling operation on the positive secondary pole piece to obtain a positive pole piece structure.
In this embodiment, the first pair of roller devices, i.e. the two roller shafts are used to perform the first rolling operation on the secondary pole piece, and the battery pole piece is also pulled between the rotating pair of rollers, so that the battery pole piece is deformed under pressure. In the embodiment, the secondary pole piece is rolled twice, and the first rolling operation can effectively improve the compaction density of the secondary pole piece, so that the discharge capacity of the battery is increased, the internal resistance is reduced, the polarization loss is reduced, the cycle life of the battery is prolonged, and the utilization rate of the lithium ion battery is improved. In addition, the secondary pole piece is rolled twice, so that the problems of reduced flexibility, fragile pole piece, serious pole piece wrinkle in winding and the like caused by one-time rolling can be prevented.
In one embodiment, the first active material, the second active material, the third active material and the fourth active material are at least one of lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, sodium iron phosphate, lithium vanadium phosphate, sodium vanadium phosphate, lithium vanadyl phosphate, sodium vanadyl phosphate, lithium vanadate, lithium manganate, lithium nickelate, lithium nickel cobalt manganese manganate, a lithium rich manganese based material, lithium nickel cobalt aluminate and lithium titanate. In the embodiment, the application of lithium cobaltate to the positive pole piece structure has the following advantages of 1. inhibiting battery polarization, reducing heat effect and improving rate performance; 2. the internal resistance of the battery is reduced, and the dynamic internal resistance amplification in the circulation process is obviously reduced; 3. the consistency is improved, and the cycle life of the battery is prolonged; 4. the adhesive force of the active substance and the current collector is improved, and the manufacturing cost of the pole piece is reduced; 5. protecting the current collector from being corroded by the electrolyte; 6. the processing performance of lithium iron phosphate and lithium titanate materials is improved. In another embodiment, the negative active material is at least one of artificial graphite, natural graphite, mesocarbon microbeads, soft carbon, hard carbon, silicon oxy-compound, silicon-carbon composite, tin alloy, niobium titanate, and lithium titanate.
In one embodiment, the first active material, the second active material, the third active material and the fourth active material further comprise a binder. In this example, the binder is a polymer compound that adheres the active material to the current collector in the fabrication of the electrode. The electrode plate has the main functions of bonding and keeping active substances, enhancing the contact between the active materials and the conductive agent and between the active materials and the current collector, and simultaneously stabilizing the structure of the electrode plate. Further, since the conventional water-soluble binder SBR contains unsaturated double bonds and can be oxidized by a voltage of 4V or more theoretically, the rebound of SBR is relatively large in the processing of the pole piece. Secondly, water can cause damage to almost all cathode materials, lithium iron phosphate is minor, but for high nickel, lithium is eluted too much, which can result in increased slurry PH and decreased capacity. Third, aqueous systems are difficult to dry and residual moisture can have an impact on capacity recycling. Fourth, the density of the existing anode materials such as lithium cobaltate, ternary materials and the like is large, the mass of substances in unit volume is also large, water is used as a solvent when an SBR + CMC bonding system is adopted, but the deposition of materials in slurry is easily caused in the batching process of the anode materials with large density, and the slurry cannot be fully dispersed at all. Once the agitation stopped, the slurry settled down sharply. And PVDF oil-soluble material is used as a binder, and is dissolved by an organic solvent, wherein the organic solvent is N-methyl pyrrolidone (NMP), so that the problems can be effectively solved, the structure of the pole piece is stabilized, and the protection effect on the pole piece is improved.
Further, the binder may be at least one selected from the group consisting of a vinylidene fluoride-hexafluoropropylene copolymer, a polyamide, a polyacrylonitrile, a polyacrylate, a polyacrylic acid, a polyacrylate, a sodium carboxymethylcellulose, a polyvinylpyrrolidone, a polyvinyl ether, a polymethyl methacrylate, a polytetrafluoroethylene, a polyhexafluoropropylene, and a styrene-butadiene rubber. In this example, the use of polyacrylonitrile as the binder has the following advantages: 1. swelling hardly occurs in an electrolyte carbonate solvent, and the electrode plate structure is stable in the charging and discharging processes; 2. the carboxyl content in the structure is higher than that of sodium carboxymethyl cellulose, and the structure can form stronger hydrogen bond action with an active substance material containing hydroxyl and other groups on the surface, so that more uniform coating is formed on the surface of an electrode than the sodium carboxymethyl cellulose; 3. a compact film can be formed in the electrode plate, and the electric contact between the active substance and the current collector is increased; 4. excellent tensile mechanical strength and is beneficial to mechanical processing. The polytetrafluoroethylene also has excellent chemical stability, electrical insulation, self-lubricating property, non-flammability, atmospheric aging resistance and high and low temperature adaptability, has high mechanical strength, and is beneficial to improving the stability of the pole piece structure.
In one embodiment, the first active material, the second active material, the third active material and the fourth active material further include a conductive agent. It can be understood that the normal charge and discharge process of the lithium battery requires the participation of lithium ions and electrons, which requires that the electrodes of the lithium ion battery must be mixed conductors of ions and electrons, and the electrode reaction can only occur at the junctions of the electrolyte, the conductive agent and the active material. Secondly, most of the positive active materials are transition metal oxides or transition metal phosphates, which are semiconductors or insulators and have poor conductivity, and a conductive agent must be added to improve the conductivity. In this embodiment, by adding the conductive agent to the first active material, the second active material, the third active material, and the fourth active material, the conductive contact between the active materials can be increased, and the electron conductivity can be improved, that is, micro-current can be collected between the active materials and the current collector, so as to reduce the contact resistance of the electrodes and accelerate the movement speed of electrons.
Further, the conductive agent is at least one of carbon nanotubes, conductive carbon black, acetylene black, graphene, ketjen black, and carbon fibers. In this embodiment, the conductive agent can form an electronic conduction network cooperating with the active material of the positive plate, so that the electrode active particles can be electrically connected well, and the carbon nanotube conductive agent can be more easily and fully mixed in the above glue solution compared with other conductive agents, thereby reducing the stirring time, improving the gram specific capacity of the positive electrode of the battery, indirectly improving the internal space of the battery core, and improving the energy density of the battery core. The conductive graphite also has better conductivity, the particles of the conductive graphite are closer to the particle size of active substance particles, and the particles are in point contact with each other, so that a conductive network structure with a certain scale can be formed, and the conductive rate is improved, and the capacity of the negative electrode can be improved when the conductive graphite is used for the negative electrode. The conductive carbon fiber has a linear structure, and a good conductive network is easily formed in the electrode to show better conductivity, so that the polarization of the electrode is reduced, the internal resistance of the battery is reduced, and the performance of the battery is improved. In the battery using carbon fiber as the conductive agent, the contact form of the active substance and the conductive agent is point-line contact, and compared with the point-point contact form of conductive carbon black and conductive graphite, the contact form is not only beneficial to improving the conductivity of the electrode, but also capable of reducing the consumption of the conductive agent and improving the capacity of the battery. Graphene is used as a novel conductive agent, and due to the unique sheet structure (two-dimensional structure), the contact with an active substance is in a point-surface contact mode instead of a conventional point contact mode, so that the effects of the conductive agent and the like can be maximized, the using amount of the conductive agent is reduced, the active substance can be used more, and the capacity of a lithium battery is improved.
In one embodiment, the insulating layer includes at least one of inorganic particles and a polymer. It can be understood that, through at blank area coating insulating layer, and the insulating layer respectively with fourth active material layer and first active material layer juncture parallel and level for neither overlapping between first active material layer, fourth active material layer and the insulating layer three, also there is the clearance, so, not only can improve the security performance of battery, can also guarantee that positive pole piece is not excessive pressure, guarantees the electrical property of battery. In order to further improve the insulating effect and the structural stability of the pole piece of the insulating layer, in the present embodiment, the insulating layer includes at least one of inorganic particles and polymers. The inorganic insulating particles have better insulating property, and the inorganic insulating particles are mutually combined to form the inorganic insulating layer, so that the flatness of the insulating layer is improved, and the flatness and the stability of the pole piece structure are further improved.
Further, the inorganic particles are at least one of alumina, silica, magnesia, titania, hafnia, tin oxide, ceria, nickel oxide, zinc oxide, calcium oxide, zirconia, yttria, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate. In this embodiment, the silicon dioxide has better insulation, and the resistivity of the silicon dioxide film grown by thermal oxidation is about 1015-1016Ohm-meter, and the silicon dioxide has higher dielectric strength and higher breakdown voltage. The aluminum hydroxide used as the inorganic particles of the insulating layer has a good insulating effect, has good flame retardance, and can achieve a corrosion-resistant effect, so that the safety and stability of the pole piece structure are effectively improved.
In one embodiment, the polymer is at least one of a homopolymer of vinylidene fluoride, a copolymer of hexafluoropropylene, polystyrene, polyphenylacetylene, sodium polyvinyl acetate, potassium polyvinyl acetate, polymethyl methacrylate, polyethylene, polypropylene, and polytetrafluoroethylene. It can be understood that the polymer insulating layer has the advantages of good insulating property, light weight and good rolling smoothness, so that the structural stability and the smoothness of the pole piece structure can be effectively improved. In order to further improve the stability of the polymer insulation layer, in this embodiment, the polymer is at least one of homopolymer of vinylidene fluoride, copolymer of hexafluoropropylene, polystyrene, polyphenylacetylene, sodium polyvinyl acid, potassium polyvinyl acid, polymethyl methacrylate, polyethylene, polypropylene and polytetrafluoroethylene. The vinylidene fluoride homopolymer has good insulativity and good chemical corrosion resistance, so that the stability of the pole piece structure can be effectively improved.
In one embodiment, a fourth active material is coated on one surface of the first active material layer, which is away from the current collector, to obtain a fourth active material layer, wherein the fourth active material layer is flush with the first active material layer, after the step of leaving a blank space on one surface of the current collector, which is close to the fourth active material layer and the first active material layer, and after the step of coating an insulating layer on the blank space, and the insulating layer is flush with the junction of the fourth active material layer and the first active material layer, respectively, before the step of obtaining the positive electrode plate precursor, the method for preparing the positive electrode plate structure further includes the following steps: the first active material layer and the fourth active material layer are subjected to a prebaking operation. It can be understood that, because be the thick liquids state after first active material and the coating of fourth active material, still have certain mobility, if form the direct insulating layer that coats in blank area of fourth active material layer at the coating, insulating layer coating takes place to dissolve mutually with first active material and fourth active material easily to cause the problem that first active material layer and fourth active material layer and insulating layer overlap, and then lead to the pole piece to have the risk of excessive pressure when colding pressing, and then influence electric core performance. In order to prevent the insulating layer coating from overlapping with the first active material layer and the fourth active material layer, in this embodiment, after the coating of the first active material layer and the fourth active material layer is completed, the first active material layer and the fourth active material layer are pre-dried, so that the solvent in the first active material layer and the fourth active material layer is volatilized and dissipated, and the first active material layer and the fourth active material layer are primarily cured, thereby preventing the insulating layer coating from overlapping with the first active material layer and the fourth active material layer during coating, and further ensuring the leveling property of the junction of the insulating layer with the fourth active material layer and the first active material layer.
Further, after the step of pre-drying the first active material layer and the fourth active material layer, and before the step of coating the insulating layer on the blank area, wherein the insulating layer is flush with the junction of the fourth active material layer and the first active material layer, respectively, to obtain the precursor of the positive electrode plate, the method for preparing the positive electrode plate structure further comprises the following steps: and coating a longitudinal insulating layer on the sides of the fourth active material layer and the first active material layer close to the blank area, wherein the height of the longitudinal insulating layer is equal to the sum of the heights of the fourth active material layer and the first active material layer. It can be understood that, because first active material layer and fourth active material layer carry out the stoving operation in advance, have obtained preliminary cure for one side that first active material layer and insulating layer contacted, and one side that fourth active material layer and insulating layer contacted all have the surface smoother, the relatively poor problem of adsorptivity, thereby make the insulating layer and the juncture of first active material layer and fourth active material layer produce the space easily, if this position of acupuncture, the security performance can't be guaranteed. In order to improve the tightness of the junction between the insulating layer and the first active material layer and the junction between the insulating layer and the fourth active material layer, in this embodiment, after the step of performing the pre-drying operation on the first active material layer and the fourth active material layer, and before the step of coating the insulating layer on the blank area, and the insulating layer is flush with the junction between the fourth active material layer and the first active material layer, respectively, to obtain the precursor of the positive electrode plate, the method for preparing the positive electrode plate structure further includes the following steps: one side that is close to the blank region at fourth active material layer and first active material layer coats one deck vertical insulating layer, and the height sum of fourth active material layer and first active material layer such as vertical insulating layer, vertical insulating layer can play the effect of infiltrating above-mentioned juncture, and keeps away from according to similar compatible, has better adsorptivity between vertical insulating layer and the insulating layer of follow-up coating to improve the compactness of the juncture of insulating layer and first active material layer and fourth active material layer, improve the security of positive pole piece structure.
Furthermore, after the step of coating a longitudinal insulating layer on the side of the fourth active material layer and the first active material layer close to the blank area, and before the step of coating an insulating layer on the blank area, wherein the insulating layer is flush with the junction of the fourth active material layer and the first active material layer respectively, so as to obtain the precursor of the positive pole piece, the preparation method of the positive pole piece structure further comprises the following steps: and spraying inorganic particles on the surfaces of the longitudinal insulating layer and the blank area. It can be understood that, since the fourth active material layer and the first active material layer have been preliminarily cured, the longitudinal insulating layer has better fluidity and the vacant area has poor adsorbability, so that the coating operation of the insulating layer is not easily controlled, and the problem of poor leveling property is easily caused. In order to improve the leveling property of the insulating layer, in this embodiment, after the step of coating a longitudinal insulating layer on the sides of the fourth active material layer and the first active material layer close to the blank area, and before the step of coating an insulating layer on the blank area, and the insulating layer is respectively leveled with the junction of the fourth active material layer and the first active material layer, the method for preparing the positive electrode sheet structure further includes the following steps: the operation of spraying inorganic particles is carried out on the surfaces of the longitudinal insulating layer and the blank area, so that the inorganic particles are adhered to the surfaces of the longitudinal insulating layer and the blank area, the adsorbability of the surfaces of the longitudinal insulating layer and the blank area is enhanced, the material of the insulating layer is easier to coat and shape, and the improvement of the evenness of the insulating layer is facilitated. In addition, the inorganic particles are the main material of the insulating layer coating, have better insulativity and better intermiscibility with the insulating layer, so that the contact surface of the insulating layer, the longitudinal insulating layer and the blank area can be more compact, and the stability of the structure of the positive pole piece is improved.
Example 1
Coating a first active material on the surface of a current collector to obtain a first active material layer; coating a second active material on one side of the current collector, which is far away from the first active material, so as to obtain a second active material layer; coating a third active material on one surface of the second active material layer, which is far away from the current collector, so as to obtain a third active material layer; coating a fourth active material on one surface of the first active material layer, which is far away from the current collector, to obtain a fourth active material layer, wherein the fourth active material layer is flush with the first active material layer, and a blank space is reserved on one surface of the current collector, which is close to the fourth active material layer and the first active material layer; coating an insulating layer on the blank area, wherein the insulating layer is flush with the junction of the fourth active material layer and the first active material layer respectively to obtain a precursor of the positive pole piece; placing the precursor of the positive pole piece in a thermostat at 82 ℃ for 3 minutes to carry out drying operation to obtain a positive secondary pole piece; and carrying out rolling operation on the positive secondary pole piece to obtain a positive pole piece structure, wherein the rolling linear speed is set to be 5 m/min.
Example 2
Coating a first active material on the surface of a current collector to obtain a first active material layer; coating a second active material on one surface of the current collector, which is far away from the first active material, so as to obtain a second active material layer; coating a third active material on one surface of the second active material layer, which is far away from the current collector, so as to obtain a third active material layer; coating a fourth active material on one surface of the first active material layer, which is far away from the current collector, to obtain a fourth active material layer, wherein the fourth active material layer is flush with the first active material layer, and a blank space is reserved on one surface of the current collector, which is close to the fourth active material layer and the first active material layer; coating an insulating layer on the blank area, wherein the insulating layer is flush with the junction of the fourth active material layer and the first active material layer respectively to obtain a precursor of the positive pole piece; placing the precursor of the positive pole piece in a thermostat at 85 ℃ for 4 minutes to carry out drying operation to obtain a positive secondary pole piece; and carrying out rolling operation on the positive secondary pole piece to obtain a positive pole piece structure, wherein the rolling linear speed is set to be 7 m/min.
Example 3
Coating a first active material on the surface of a current collector to obtain a first active material layer; coating a second active material on one side of the current collector, which is far away from the first active material, so as to obtain a second active material layer; coating a third active material on one surface of the second active material layer, which is far away from the current collector, so as to obtain a third active material layer; coating a fourth active material on one surface of the first active material layer, which is far away from the current collector, to obtain a fourth active material layer, wherein the fourth active material layer is flush with the first active material layer, and a blank space is reserved on one surface of the current collector, which is close to the fourth active material layer and the first active material layer; coating an insulating layer on the blank area, wherein the insulating layer is flush with the junction of the fourth active material layer and the first active material layer respectively to obtain a precursor of the positive pole piece; placing the precursor of the positive pole piece in a thermostat at 90 ℃ for 5 minutes to carry out drying operation to obtain a positive secondary pole piece; and carrying out rolling operation on the positive secondary pole piece to obtain a positive pole piece structure, wherein the rolling linear speed is set to be 10 m/min.
The application also provides a positive pole piece structure, and the positive pole piece structure is prepared by the preparation method of the positive pole piece structure in any embodiment.
As shown in fig. 2, in one embodiment, the positive electrode tab structure 10 includes a tab current collector 100, an active material layer 200, and an insulating layer 300. The pole piece current collector 100 is provided with a first coating area and a second coating area, and the first coating area and the second coating area are respectively positioned on two opposite surfaces of the pole piece current collector 100; the active material layer 200 comprises a first active material layer 210, a second active material layer 220, a third active material layer 230 and a fourth active material layer 240, the first active material layer 210 is attached to the first coating area, the second active material layer 220 is attached to the second coating area, the third active material layer 230 is attached to one side, away from the pole piece current collector 100, of the second active material layer 220, the fourth active material layer 240 is attached to one side, away from the pole piece current collector 100, of the first active material layer 210, the fourth active material layer 240 is flush with the first active material layer 210, and a blank area is left on one side, close to the fourth active material layer 240 and the first active material layer 210, of the current collector; the insulating layer 300 is attached to the blank area, and the insulating layer 300 is flush with the interface between the fourth active material layer 240 and the first active material layer 210.
In the positive electrode sheet structure 10, the first active material layer 210 is attached to the first coating area, the second active material layer 220 is attached to the second coating area, the third active material layer 230 is attached to the surface of the second active material layer 220 departing from the electrode sheet current collector 100, the fourth active material layer 240 is attached to the surface of the first active material layer 210 departing from the electrode sheet current collector 100, the fourth active material layer 240 is flush with the first active material layer 210, a blank area is left on the surface of the current collector close to the fourth active material layer 240 and the first active material layer 210, the insulating layer 300 is attached to the blank area, and the insulating layer 300 is flush with the junction of the fourth active material layer 240 and the first active material layer 210 respectively. That is, the first active material layer 210, the fourth active material layer 240 and the insulating layer 300 are not overlapped, and there is no gap between them, and the first active material layer 210, the fourth active material layer 240 and the insulating layer 300 form a mutually flush structure, so that the pole piece structure can effectively prevent the short circuit problem caused by needle punching, and improve the safety of the lithium ion battery; in addition, above-mentioned pole piece structure makes the pole piece prevent the acupuncture and causes the short circuit in, can also be favorable to improving the planarization and the stability of pole piece roll-in, avoids the pole piece to have the risk of excessive pressure when colding pressing, and then guarantees lithium ion battery's performance.
In one embodiment, the first coating region completely coincides with the second coating region, and the first active material layer 210 completely covers the first coating region and the second active material layer 220 completely covers the second coating region. In this embodiment, the first coating region is a contact area between the first active material layer 210 and the pole piece current collector 100, i.e. a first contact area; the second coating area is a contact area between the second active material layer 220 and the pole piece current collector 100, i.e., a second contact area. Because first active material layer 210 covers first coating region completely, second active material layer 220 covers the second completely and coats the district, and first coating region is identical with the second coating region completely again, consequently first area of contact equals second area of contact to improve the pressure uniformity between pole piece mass collector 100 and first active material layer 210 and second active material layer 220 in the roll-in process, and then improve the uniformity and the stability of pole piece structure.
Further, the third active material layer 230 completely covers the second active material layer 220, and the fourth active material layer 240 completely covers the first active material layer 210. In the present embodiment, the third active material layer 230 completely covers the second active material layer 220, i.e., the contact area between the third active material layer 230 and the second active material layer 220 is equal to the second contact area; fourth active material layer 240 completely covers first active material layer 210, i.e., the contact area between fourth active material layer 240 and first active material layer 210 is equal to the first contact area. That is to say, first active material layer 210, second active material layer 220, third active material layer 230 and fourth active material layer 240 have better flatness and uniformity therebetween, so as to improve the pressure uniformity between electrode sheet current collector 100 and first active material layer 210, second active material layer 220, third active material layer 230 and fourth active material layer 240 during the rolling process, thereby improving the uniformity and stability of the electrode sheet structure.
In one embodiment, the thickness of first active material layer 210 is equal to the thickness of second active material layer 220. In this embodiment, the first active material layer 210 is attached to the first coating region, and the second active material layer 220 is attached to the second coating region, that is, the first active material layer 210 and the second active material layer 220 are respectively located on two opposite surfaces of the pole piece current collector 100. In the rolling process, because the thickness of the first active material layer 210 is equal to that of the second active material layer 220, the pressures applied to the two sides of the pole piece current collector 100 are consistent, and the pole piece structure has good symmetry, thereby improving the consistency and stability of the pole piece structure.
Further, the thickness of the third active material layer 230 is equal to that of the fourth active material layer 240. In this embodiment, third active material layer 230 completely covers second active material layer 220, and fourth active material layer 240 completely covers first active material layer 210, that is, first active material layer 210 and second active material layer 220 are respectively located on two opposite surfaces of pole piece current collector 100. In the rolling process, since the thickness of the third active material layer 230 is equal to the thickness of the fourth active material layer 240, the pressures applied to the two sides of the pole piece current collector 100 are the same, and the pole piece structure has better symmetry, thereby improving the consistency and stability of the pole piece structure. In addition, two opposite surfaces of the pole piece current collector 100 are both provided with the double active material layers 200, so that the stability and the electrical property of the pole piece structure can be effectively improved, and the protection of the active material layers 200 to the pole piece structure is improved.
In one embodiment, the thickness of the insulating layer 300 is greater than the thickness of the first active material layer 210. It can be understood that, if the thickness of the insulating layer 300 is less than or equal to the thickness of the first active material layer 210, when the second active material layer 220 is coated, since the insulating layer 300 is flush with the interface between the fourth active material layer 240 and the first active material layer 210, the second active material layer 220 is easily overlapped with the insulating layer 300, although this structure can improve the safety performance, the overlapping can increase the thickness at this position, thereby causing the risk of overvoltage when the pole piece is cold-pressed, and further affecting the performance of the battery cell. In order to avoid the risk of overvoltage when the pole piece is cold-pressed, in this embodiment, the thickness of the insulating layer 300 is greater than that of the first active material layer 210, so that the second active material layer 220 can be effectively overlapped with the insulating layer 300, the risk of overvoltage when the pole piece is cold-pressed is avoided, and the performance stability of the lithium ion battery cell is ensured.
In one embodiment, one end of the first active material layer 210 is flush with one end of the second active material layer 220, the other end of the first active material layer 210 abuts against the insulating layer 300, and the sum of the lengths of the first active material layer 210 and the insulating layer 300 is equal to the length of the second active material layer 220. It can be understood that the first active material layer 210 and the second active material layer 220 are respectively located on two sides of the pole piece current collector 100, and the insulating layer 300 is respectively flush with the interface between the fourth active material layer 240 and the first active material layer 210. In order to further improve the leveling property of the pole piece structure, in this embodiment, one end of the first active material layer 210 is leveled with one end of the second active material layer 220, the other end of the first active material layer 210 is abutted to the insulating layer 300, and the sum of the lengths of the first active material layer 210 and the insulating layer 300 is equal to the length of the second active material layer 220, so that the leveling property among the first active material layer 210, the second active material layer 220 and the insulating layer 300 can be effectively improved, and the leveling property of the pole piece structure is further improved.
As shown in fig. 3, in one embodiment, a fourth active material layer 240 covers the surface of the first active material layer 210. It can be understood that the fourth active material layer 240 is attached to the surface of the first active material layer 210 away from the pole piece current collector 100, the fourth active material layer 240 is flush with the first active material layer 210, a blank area is left on the surface of the current collector close to the fourth active material layer 240 and the first active material layer 210, the insulating layer 300 is attached to the blank area, and the insulating layer 300 is flush with the junction of the fourth active material layer 240 and the first active material layer 210 respectively. In this embodiment, the fourth active material layer 240 covers the surface of the first active material layer 210, so that the insulating layer 300 can be effectively prevented from overlapping with the first active material layer 210 or the second active material layer 220, the risk of overvoltage when the pole piece is cold-pressed is better avoided, and the performance stability of the lithium ion battery cell is ensured.
Compared with the prior art, the invention has at least the following advantages:
1. according to the preparation method of the positive pole piece structure, the active substance layer with the double-layer structure is adopted in the area covered by the active substance layer on the positive pole current collector, the insulating layer is arranged in the area not covered by the active substance layer, the insulating layer can avoid failure caused by internal short circuit generated when the lithium ion battery is pierced by external force, and therefore the safety of the lithium ion battery is effectively improved.
2. In the preparation method of the positive pole piece structure, the first active material layer and the fourth active material layer are flush with each other, and the insulating layer is flush with the junction of the fourth active material layer and the first active material layer respectively, namely, the first active material layer, the fourth active material layer and the insulating layer are not overlapped and have no gap, so that the problem that the pole piece has overvoltage risk during cold pressing due to the fact that the thickness of the pole piece is increased due to the fact that the first active material layer, the fourth active material layer and the insulating layer are overlapped can be solved, and the performance of a lithium ion battery cell is improved; on the other hand, the problem of short circuit caused by needling the position due to the gap between the first active material layer and the insulating layer can be avoided, and the safety of the lithium ion battery is further improved.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a positive pole piece structure is characterized by comprising the following steps:
coating a first active material on the surface of a current collector to obtain a first active material layer;
coating a second active material on one side, away from the first active material, of the current collector to obtain a second active material layer;
coating a third active material on one surface, away from the current collector, of the second active material layer to obtain a third active material layer;
coating a fourth active material on one surface of the first active material layer, which is far away from the current collector, so as to obtain a fourth active material layer, wherein the fourth active material layer is flush with the first active material layer, and a blank space is left on one surface, close to the fourth active material layer and the first active material layer, of the current collector;
coating an insulating layer on the blank area, wherein the insulating layer is flush with the junction of a fourth active material layer and the first active material layer respectively to obtain a positive pole piece precursor;
drying the precursor of the positive pole piece to obtain a positive secondary pole piece;
and carrying out rolling operation on the secondary positive pole piece to obtain the positive pole piece structure.
2. The method of claim 1, wherein the first active material, the second active material, the third active material, and the fourth active material are at least one of lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, sodium iron phosphate, lithium vanadium phosphate, sodium vanadium phosphate, lithium vanadyl phosphate, sodium vanadyl phosphate, lithium vanadyl vanadate, lithium manganate, lithium nickelate, lithium nickel manganese cobalt, lithium manganese rich-based material, lithium nickel cobalt aluminate, and lithium titanate.
3. The method for manufacturing a positive electrode sheet structure according to claim 2, wherein the first active material, the second active material, the third active material, and the fourth active material each further include a binder.
4. The method for preparing the positive electrode plate structure of claim 3, wherein the binder is at least one of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyvinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, polyhexafluoropropylene and styrene butadiene rubber.
5. The method for manufacturing a positive electrode sheet structure according to claim 2, wherein the first active material, the second active material, the third active material, and the fourth active material each further include a conductive agent.
6. The method for preparing the positive electrode plate structure according to claim 5, wherein the conductive agent is at least one of carbon nanotubes, conductive carbon black, acetylene black, graphene, Ketjen black and carbon fibers.
7. The method of claim 1, wherein the insulating layer comprises at least one of inorganic particles and polymers.
8. The method for preparing a positive electrode sheet structure according to claim 7, wherein the inorganic particles are at least one of aluminum oxide, silicon dioxide, magnesium oxide, titanium oxide, hafnium oxide, tin oxide, cerium oxide, nickel oxide, zinc oxide, calcium oxide, zirconium dioxide, yttrium oxide, silicon carbide, boehmite, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and barium sulfate.
9. The method for preparing the positive electrode plate structure according to claim 7, wherein the polymer is at least one of a homopolymer of vinylidene fluoride, a copolymer of hexafluoropropylene, polystyrene, polyphenylacetylene, sodium polyvinyl, potassium polyvinyl, polymethyl methacrylate, polyethylene, polypropylene and polytetrafluoroethylene.
10. A positive pole piece structure, which is characterized by being prepared by the preparation method of the positive pole piece structure as claimed in any one of claims 1 to 9.
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