CN113206221A - Lithium battery, lithium battery pole piece and preparation method thereof - Google Patents
Lithium battery, lithium battery pole piece and preparation method thereof Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
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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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- 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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- 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
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- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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 application provides a lithium battery, a lithium battery pole piece and a preparation method thereof. The preparation method of the lithium battery pole piece comprises the steps of coating first lithium cobaltate coating slurry containing small-particle lithium cobaltate on an aluminum foil to prepare a primary pole piece, coating second lithium cobaltate coating slurry containing conventional spherical lithium cobaltate, namely unbroken spherical lithium cobaltate on the primary pole piece to prepare a secondary pole piece, and rolling the secondary pole piece to obtain the lithium battery pole piece. The specific surface area of the small-particle lithium cobaltate is large, so that uniform distribution of PVDF glue solution and a conductive agent is facilitated, and meanwhile, the particle size of the small-particle lithium cobaltate is small, so that damage to a pole piece aluminum foil during rolling is small, and large-particle lithium cobaltate can be buffered, namely extrusion of conventional spherical lithium cobaltate on an aluminum foil is facilitated, so that the compaction density and flexibility of a lithium battery pole piece are improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium battery, a lithium battery pole piece and a preparation method thereof.
Background
The lithium ion battery has the advantages of high discharge voltage, high energy density, high power density, long cycle life, no memory effect and the like, and is widely applied to the fields of small chargeable and dischargeable batteries such as consumer electronics, electric tools, medical electronics and the like; the method is gradually popularized in the traffic fields of electric bicycles, pure electric vehicles, hybrid electric vehicles, rail traffic, aerospace, ships and naval vessels and the like; the method has good application prospect in energy fields such as large-scale renewable energy access, power grid peak regulation and frequency modulation, distributed power, microgrid off-grid, household power, data center standby power supply, communication base stations, energy recovery, green buildings and the like, and emerging technical fields such as wearable electronics, transparent electronics and robots. In the process of market development, the demand for energy density of batteries is also higher and higher. The lithium ion battery is composed of components such as a positive electrode, a negative electrode, a diaphragm, electrolyte and the like, and the battery core is manufactured through the process flows of homogenizing, coating, rolling, slitting, winding, injecting, assembling, forming and the like. The improvement of the cell energy density can be solved through the angles of gram capacity, thickness and the like of each component material. In the aspect of the positive electrode, the energy density can be required by introducing a high-gram-capacity positive electrode material, improving the surface density of the positive electrode and improving the compaction of the positive electrode.
However, with the increase of the surface density and the compacted density, the flexibility of the positive plate is reduced and the positive plate becomes brittle under the existing rolling process, so that the pole plate is seriously wrinkled during winding, the roundness of the wound battery cell is influenced, and the positive plate is possibly broken; meanwhile, active substances are peeled off from the surface of the current collector at the serious position of the wrinkle, so that capacity exertion and electric core circulation performance at the later stage are influenced.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a lithium battery, a lithium battery pole piece and a preparation method thereof, wherein the lithium battery and the lithium battery pole piece have high compaction density and good flexibility.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a lithium battery pole piece comprises the following steps:
crushing the spherical lithium cobaltate to obtain small-particle lithium cobaltate;
mixing the first PVDF glue solution, the first conductive agent and the small-particle lithium cobalt oxide to obtain first lithium cobalt oxide coating slurry;
coating the first lithium cobaltate coating slurry on an aluminum foil to obtain a first lithium cobaltate coating;
carrying out primary drying operation on the aluminum foil coated with the first lithium cobaltate coating slurry to obtain a primary electrode sheet;
mixing the second PVDF glue solution, the second conductive agent and conventional particle lithium cobaltate to obtain second lithium cobaltate coating slurry;
coating the second lithium cobaltate coating slurry on the primary electrode sheet to obtain a second lithium cobaltate coating;
performing secondary drying operation on the primary pole piece coated with the second lithium cobaltate coating slurry to obtain a secondary pole piece;
carrying out primary rolling operation on the secondary pole piece;
and performing secondary rolling operation on the secondary pole piece after the primary rolling operation is completed to obtain the lithium battery pole piece.
In one embodiment, the small-particle lithium cobaltate has a D50 ≦ 17 μm and a BET > 0.2m2/g。
In one embodiment, the first conductive agent and the second conductive agent are both at least one of carbon black, carbon nanotubes, graphene, and ketjen black.
In one embodiment, the first rolling operation is a hot pressing operation.
In one embodiment, the second rolling operation is a cold pressing operation.
In one embodiment, after the step of performing the second drying operation on the primary sheet coated with the second lithium cobaltate coating slurry to obtain a secondary sheet, before the step of performing the first rolling operation on the secondary sheet, the method further comprises the following steps:
and carrying out limiting operation on the rolling gap.
A lithium battery pole piece is prepared by the preparation method of the lithium battery pole piece according to any one of the embodiments.
In one embodiment, the lithium battery pole piece comprises a lithium cobaltate coating and an aluminum foil, wherein the lithium cobaltate coating is respectively coated on the surfaces of two sides of the aluminum foil.
In one embodiment, the lithium cobaltate coating comprises a first lithium cobaltate coating and a second lithium cobaltate coating, the number of layers of the first lithium cobaltate coating is two, the number of layers of the second lithium cobaltate coating is two, the two first lithium cobaltate coatings are respectively coated on the surfaces of the two side faces of the aluminum foil, and the two second lithium cobaltate coatings are respectively coated on the two side faces, away from the aluminum foil, of the first lithium cobaltate coating.
A lithium battery comprising a lithium battery pole piece as described in the previous embodiment.
Compared with the prior art, the invention has at least the following advantages:
1. the preparation method of the lithium battery pole piece comprises the steps of coating first lithium cobaltate coating slurry containing small-particle lithium cobaltate on an aluminum foil to prepare a primary pole piece, coating second lithium cobaltate coating slurry containing conventional spherical lithium cobaltate, namely unbroken spherical lithium cobaltate on the primary pole piece to prepare a secondary pole piece, and rolling the secondary pole piece to obtain the lithium battery pole piece. The specific surface area of the small-particle lithium cobaltate is large, so that uniform distribution of PVDF glue solution and a conductive agent is facilitated, and meanwhile, the particle size of the small-particle lithium cobaltate is small, so that damage to a pole piece aluminum foil during rolling is small, and large-particle lithium cobaltate can be buffered, namely extrusion of conventional spherical lithium cobaltate on an aluminum foil is facilitated, so that the compaction density and flexibility of a lithium battery pole piece are improved.
2. In the preparation method of the lithium battery pole piece, the secondary pole piece which is coated and dried is rolled twice, wherein the first rolling is hot pressing, and the second rolling is cold pressing. Because the first rolling operation is a hot pressing operation, the rebound rate of the pole piece material can be effectively controlled, and the compaction density of the pole piece is improved; after hot pressing operation is completed, cold pressing operation is performed on the pole piece, and shaping and surface flatness of the pole piece can be better controlled, so that flexibility of the pole piece is guaranteed while compaction density of the pole piece is 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 lithium battery electrode tab in one embodiment;
fig. 2 is a process flow chart of the first rolling operation and the second rolling operation in the preparation method of the lithium battery pole piece 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 lithium battery pole piece. The preparation method of the lithium battery pole piece comprises the following steps: crushing the spherical lithium cobaltate to obtain small-particle lithium cobaltate; mixing the first PVDF glue solution, the first conductive agent and the small-particle lithium cobalt oxide to obtain first lithium cobalt oxide coating slurry; coating the first lithium cobaltate coating slurry on an aluminum foil to obtain a first lithium cobaltate coating; carrying out primary drying operation on the aluminum foil coated with the first lithium cobaltate coating slurry to obtain a primary electrode sheet; mixing the second PVDF glue solution, the second conductive agent and conventional particle lithium cobaltate to obtain second lithium cobaltate coating slurry; coating the second lithium cobaltate coating slurry on the primary electrode sheet to obtain a second lithium cobaltate coating; performing secondary drying operation on the primary pole piece coated with the second lithium cobaltate coating slurry to obtain a secondary pole piece; carrying out primary rolling operation on the secondary pole piece; and performing secondary rolling operation on the secondary pole piece after the primary rolling operation is completed to obtain the lithium battery pole piece.
The preparation method of the lithium battery pole piece comprises the steps of firstly coating first lithium cobaltate coating slurry containing small-particle lithium cobaltate on an aluminum foil to prepare a primary pole piece, then coating second lithium cobaltate coating slurry containing conventional spherical lithium cobaltate, namely unbroken spherical lithium cobaltate, on the primary pole piece to prepare a secondary pole piece, and then rolling the secondary pole piece to obtain the lithium battery pole piece. The specific surface area of the small-particle lithium cobaltate is large, so that uniform distribution of PVDF glue solution and a conductive agent is facilitated, and meanwhile, the particle size of the small-particle lithium cobaltate is small, so that damage to a pole piece aluminum foil during rolling is small, and large-particle lithium cobaltate can be buffered, namely extrusion of conventional spherical lithium cobaltate on an aluminum foil is facilitated, so that the compaction density and flexibility of a lithium battery pole piece are improved. Further, this application carries out twice rolling operation totally to accomplishing the inferior pole piece of coating drying operation, and wherein the operation of rolling for the first time is hot pressing operation, and the operation of rolling for the second time is cold pressing operation. Because the first rolling operation is a hot pressing operation, the rebound rate of the pole piece material can be effectively controlled, and the compaction density of the pole piece is improved; after hot pressing operation is completed, cold pressing operation is performed on the pole piece, and shaping and surface flatness of the pole piece can be better controlled, so that flexibility of the pole piece is guaranteed while compaction density of the pole piece is improved.
In order to better understand the method for manufacturing a lithium battery pole piece of the present invention, the following further explains the method for manufacturing a lithium battery pole piece of the present invention, and as shown in fig. 1, the method for manufacturing a lithium battery pole piece of an embodiment includes some or all of the following steps:
s100, crushing the spherical lithium cobaltate to obtain small-particle lithium cobaltate.
It can be understood that lithium cobaltate has a high tap density, which contributes to an increase in the volumetric specific capacity of the battery. The lithium cobaltate is used as a pole piece material, so that the adhesion of active substances and a current collector can be improved, and the manufacturing cost of the pole piece is reduced. In this embodiment, a crushing operation is performed on the spherical lithium cobaltate by using a jet mill to obtain small lithium cobaltate particles, so as to reduce the particle size of the lithium cobaltate particles and increase the specific surface area of the lithium cobaltate particles, thereby facilitating the rolling operation after the lithium cobaltate is coated.
S200, mixing the first PVDF glue solution, the first conductive agent and the small-particle lithium cobaltate to obtain first lithium cobaltate coating slurry.
It can be understood that PVDF, which is known as poly (vinylidene fluoride) in english, has small atomic radius, strong electronegativity, strong electron-withdrawing effect, and strong bonding capability. In this example, the first PVDF glue solution, the first conductive agent, and the small-particle lithium cobaltate were mixed in a ratio of 1.0: 1.5: 97.5, and stirring and mixing, so that the viscosity and the fluidity of the lithium cobaltate coating slurry can be effectively improved, and the obtained first lithium cobaltate coating slurry is used for coating on an aluminum foil. In addition, the small lithium cobaltate particles have smaller particle size and larger specific surface area, so that the small lithium cobaltate particles can be more uniformly dispersed in the first PVDF glue solution, the uniform distribution of the PVDF glue solution and the conductive agent is facilitated, and the bonding effect of the pole piece active material on the aluminum foil can be effectively improved.
S300, coating the first lithium cobaltate coating slurry on the aluminum foil to obtain a first lithium cobaltate coating.
In this example, the first lithium cobaltate coating slurry was coated on an aluminum foil to form a first lithium cobaltate coating on the surface of the aluminum foil. Because the first lithium cobaltate coating contains small-particle lithium cobaltate, the damage to the aluminum foil can be reduced when the pole piece is rolled.
S400, carrying out primary drying operation on the aluminum foil coated with the first lithium cobaltate coating slurry to obtain a primary electrode plate.
In this embodiment, the aluminum foil coated with the first lithium cobalt oxide coating slurry is subjected to a first drying operation by a drying device to volatilize moisture of the first lithium cobalt oxide coating slurry, so that the first lithium cobalt oxide coating is cured on the aluminum foil to form a primary electrode sheet, i.e., an electrode sheet having a primary prototype.
And S500, mixing the second PVDF glue solution, the second conductive agent and the conventional particle lithium cobaltate to obtain second lithium cobaltate coating slurry.
In this example, the second PVDF glue solution, the second conductive agent, and the conventional particle lithium cobaltate were mixed in a ratio of 1.0: 1.5: 97.5, and stirring and mixing, so that the viscosity and the fluidity of the lithium cobaltate coating slurry can be effectively improved, and the obtained second lithium cobaltate coating slurry is used for coating the primary electrode sheet. The specific surface area of the small-particle lithium cobaltate is large, so that uniform distribution of PVDF glue solution and a conductive agent is facilitated, and meanwhile, the particle size of the small-particle lithium cobaltate is small, so that damage to a pole piece aluminum foil during rolling is small, and large-particle lithium cobaltate can be buffered, namely extrusion of conventional spherical lithium cobaltate on an aluminum foil is facilitated, so that the compaction density and flexibility of a lithium battery pole piece are improved.
S600, coating the second lithium cobaltate coating slurry on the primary electrode sheet to obtain a second lithium cobaltate coating.
In this example, the second lithium cobaltate coating slurry was coated on an aluminum foil to form a second lithium cobaltate coating on the surface of the primary sheet. It should be noted that lithium cobaltate belongs to an α -NaFeO2 type structure, and has a two-dimensional layered structure, which is suitable for the deintercalation of lithium ions. The second lithium cobaltate coating slurry contains conventional spherical lithium cobaltate, and is coated on the primary pole piece, so that a structure more suitable for lithium ion deintercalation is formed on the pole piece, and the electric capacity and the cyclicity of the lithium battery positive pole piece are further improved. In addition, the granularity of the small-particle lithium cobaltate is smaller, so that the large-particle lithium cobaltate can be buffered, namely the extrusion of the conventional spherical lithium cobaltate on an aluminum foil is realized, and the compaction density and the flexibility of a lithium battery pole piece are improved.
And S700, carrying out secondary drying operation on the primary pole piece coated with the second lithium cobaltate coating slurry to obtain a secondary pole piece.
In this embodiment, the aluminum foil coated with the second lithium cobaltate coating slurry is subjected to a second drying operation by a drying device to volatilize moisture in the second lithium cobaltate coating slurry, so that the second lithium cobaltate coating is cured on the aluminum foil to form a secondary electrode sheet, i.e. a further formed electrode sheet.
And S800, carrying out primary rolling operation on the secondary pole piece.
As shown in fig. 2, in this embodiment, the first pair of roller devices 100 performs a first rolling operation on the secondary pole piece by using two roller shafts, and also pulls the battery pole piece between the rotating pair of rollers, so that the battery pole piece is deformed under pressure. In the application, the secondary pole piece 200 is rolled twice, and the compaction density of the secondary pole piece 200 can be effectively improved through the primary rolling operation, 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, by performing rolling operation on the secondary pole piece 200 twice, the problems of reduced flexibility, brittle pole piece, serious pole piece wrinkle during winding and the like caused by one-time rolling can be prevented.
And S900, performing secondary rolling operation on the secondary pole piece after the primary rolling operation is completed to obtain the lithium battery pole piece.
As shown in fig. 2, an arrow a represents a rolling direction of the secondary pole piece, in this embodiment, the secondary pole piece 200 that has completed the first rolling operation is subjected to a second rolling operation by the second pair of roller devices 300, the compacted density of the secondary pole piece 200 that has undergone the first rolling operation is greatly increased, and then the secondary pole piece 200 that has completed the first rolling operation is subjected to a second rolling operation, so that the compacted density of the secondary pole piece 200 can be further increased, thereby further increasing the discharge capacity of the battery, reducing the internal resistance, reducing the polarization loss, prolonging the cycle life of the battery, and increasing the utilization rate of the lithium ion battery. In addition, the secondary pole piece 200 which finishes the primary rolling operation is rolled for the second time, so that the secondary pole piece 200 can be further shaped, and the stability of the pole piece structure is improved.
In one embodiment, the small-particle lithium cobaltate has a D50 ≦ 17 μm and a BET > 0.2m2(ii) in terms of/g. It is understood that D50 refers to the corresponding particle size when the cumulative percentage of particle size distribution of the small lithium cobaltate particles reaches 50%. Its physical meaning is that the particle size is greater than 50% of its particles and less than 50% of its particles, D50 also being referred to as the median or median particle size. The BET is a BET specific surface area test method which is widely applied to particle surface adsorption performance research and data processing of related detection instruments, a BET formula is the method which is most widely applied in the industry at present and has the strongest reliability of test results, and almost all relevant standards at home and abroad are established according to a BET equation. In this example, the small-particle lithium cobaltate has a D50 ≦ 17 μm and a BET > 0.2m2(iv)/g, wherein D50 represents the particle size of the small lithium cobaltate particles and BET represents the surface area of the small lithium cobaltate particles. When the D50 of the small-particle lithium cobaltate is less than or equal to 17 mu m and the BET is more than 0.2m2And in the process of/g, the PVDF glue solution and the conductive agent can be uniformly distributed, the damage to the pole piece aluminum foil is smaller during rolling, and large-particle lithium cobalt oxide can be buffered, namely the extrusion of the conventional spherical lithium cobalt oxide on the aluminum foil is facilitated, so that the compaction density and the flexibility of the lithium battery pole piece are improved. The D50 of the conventional spherical lithium cobaltate is 30-34 μm, and BET < 0.2m2/g。
In one embodiment, the first conductive agent and the second conductive agent are both at least one of carbon black, carbon nanotubes, graphene, and ketjen black. It can be understood that, with the commercialization of lithium batteries becoming more and more widespread, the battery of lithium batteries is in the charge-discharge process on the surface of the positive electrode material when the battery discharges, the lithium ions in the holes enter the positive electrode active material, if the current increases, the polarization increases, the discharge is difficult, the conductivity between electrons is poor, the conductivity is far from insufficient by the active material, in order to ensure that the electrode has good charge-discharge performance, a certain amount of conductive agent is usually added during the manufacture of the pole piece, and the function of collecting micro-current between the active material and the current collector is achieved. In this embodiment, the first conductive agent and the second conductive agent in the lithium battery electrode sheet are both at least one of carbon black, carbon nanotubes, graphene, and acetylene black. Carbon black has better ionic and electronic conductivity, and is favorable for adsorption of electrolyte to improve ionic conductivity because carbon black has larger specific surface area. In addition, the carbon black particles are agglomerated to form a branched chain structure, and can form a chain type conductive structure with the active material, which is beneficial to improving the electronic conductivity of the material. The carbon nano tube can serve as a lead in a conductive network, has an electric double layer effect, exerts the high rate characteristic of the super capacitor, has good heat conduction performance, is beneficial to heat dissipation of the battery during charging and discharging, reduces polarization of the battery, improves high and low temperature performance of the battery, and prolongs the service life of the battery. The graphene conductive agent has excellent dispersibility and conductivity, and the rate performance and the cycling stability of the lithium battery can be effectively improved by adding a small amount of the conductive agent. The graphene is dispersed in the electrode material, so that the diffusion and the electronic conduction of lithium ions are facilitated, and the performance of the battery is better improved. Ketjen black has a unique branched morphology compared to other conductive carbon blacks used in batteries. The advantage of this form is that the conductor has many conductive contacts and the branches form many conductive paths, so that very high conductivity can be achieved with only a small amount of addition.
In order to improve the stability of the pole piece after being compacted, in one embodiment, after the step of mixing the first PVDF glue solution, the first conductive agent and the small-particle lithium cobaltate to obtain the first lithium cobaltate coating slurry, before the step of coating the first lithium cobaltate coating slurry on the aluminum foil to obtain the first lithium cobaltate coating: the first lithium cobaltate coating slurry was subjected to a heating stirring operation. It can be understood that, because the PVDF glue solution has a higher viscosity, the conductive agent and the small-particle lithium cobalt oxide are difficult to be uniformly dispersed in the PVDF glue solution, and if the first PVDF glue solution, the first conductive agent and the small-particle lithium cobalt oxide are not uniformly mixed, the problem of dusting of the pole piece is easily caused. And the PVDF glue solution has higher viscosity, which can cause resistance to stirring operation and influence stirring efficiency. In this embodiment, the first lithium cobaltate coating slurry, that is, the slurry obtained by mixing the first PVDF glue solution, the first conductive agent, and the small-particle lithium cobaltate, is heated and stirred, so that the temperature of the first PVDF glue solution is increased and the viscosity of the first PVDF glue solution is reduced through the heating operation, which is beneficial to stirring the first lithium cobaltate coating slurry, so that the first PVDF glue solution, the first conductive agent, and the small-particle lithium cobaltate are mixed more uniformly, thereby preventing the pole piece from falling off powder in a subsequent rolling process, and further improving the stability of the pole piece. In this embodiment, the heating temperature is 40 ℃ to 45 ℃, so that the viscosity of the first PVDF glue solution is low, the first PVDF glue solution is easy to stir and mix, and the viscosity of the first PVDF glue solution is not damaged. Similarly, after the step of mixing the second PVDF glue solution, the second conductive agent and the small-particle lithium cobalt oxide to obtain the second lithium cobalt oxide coating slurry, the step of coating the second lithium cobalt oxide coating slurry on the primary electrode sheet to obtain the second lithium cobalt oxide coating is preceded by: and heating and stirring the second lithium cobaltate coating slurry.
In one embodiment, the first drying operation of the aluminum foil coated with the first lithium cobaltate coating slurry specifically comprises the following steps: firstly, the aluminum foil coated with the first lithium cobaltate coating slurry is subjected to hot air blowing operation, and then the first lithium cobaltate coating is subjected to cold air blowing operation. It can be understood that, the aluminum foil coated with the first lithium cobalt oxide coating slurry is subjected to a first drying operation by the drying device, so that moisture in the first lithium cobalt oxide coating slurry can be volatilized, the first lithium cobalt oxide coating is solidified on the aluminum foil, and a primary electrode plate, namely, the electrode plate with the primary prototype, is formed. However, after the first lithium cobalt oxide coating slurry is coated, the first lithium cobalt oxide coating may have irregularities such as pores and wrinkles, and the uneven thickness of the slurry coating may also cause uneven drying, which may easily affect the compacting effect of the pole piece. In this embodiment, during the first drying operation of the aluminum foil coated with the first lithium cobaltate coating slurry, the hot air blowing operation is performed on the aluminum foil coated with the first lithium cobaltate coating slurry, and then the cold air blowing operation is performed on the first lithium cobaltate coating. By performing hot air blowing operation on the first lithium cobaltate coating slurry, on one hand, moisture in the first lithium cobaltate coating slurry can be volatilized quickly, and the drying efficiency is improved effectively; on the other hand, the hot air can blow the wrinkles and the depressions on the surface of the first lithium cobaltate coating slurry evenly in the drying process, so that the surface of the first lithium cobaltate coating slurry is smooth and uniform in thickness, and the compaction density of the pole piece is improved. Further, after the hot air blowing operation is completed, the cold air blowing operation is performed on the first lithium cobalt oxide coating, so that the first lithium cobalt oxide coating is better shaped, the structural stability of the first lithium cobalt oxide coating is improved, deformation is avoided when the first lithium cobalt oxide coating slurry is coated on the first lithium cobalt oxide coating, and the structural stability of the pole piece is further improved.
In one embodiment, the first rolling operation is a hot pressing operation. It can be understood that the battery pole piece is pressed and deformed by a double-roller device, namely, a first rolling operation is carried out on the secondary pole piece by using two roller shafts, and the battery pole piece is pulled into the space between the rotating double rollers. The compaction density of the high pole piece can be effectively improved through the primary rolling operation, 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 this embodiment, the first rolling operation is a hot pressing operation, and the hot pressing has an effect of softening the pole piece, so that the pole piece is more easily compacted. It should be noted that, in this application, carry out twice rolling operation to inferior pole piece altogether, the first rolling operation, hot pressing operation is incomplete rolling promptly, when the compaction pole piece, can also guarantee the pliability of pole piece.
Further, the hot pressing temperature in the hot pressing operation is 90 ℃ to 120 ℃. It can be understood that the secondary pole piece is subjected to hot pressing operation, so that the effect of softening the pole piece can be achieved, and the pole piece is easier to compact. However, if the hot pressing temperature is too high, coking is easily caused to the secondary pole piece; if the hot pressing temperature is too low, the secondary pole piece cannot be softened well. In the embodiment, the hot pressing temperature in the hot pressing operation is 100 ℃, so that the secondary pole piece achieves a better softening effect, is easier to compact, and is beneficial to improving the compact density of the pole piece.
In one embodiment, the second rolling operation is a cold pressing operation. It can be understood that, after the first rolling operation is carried out on the secondary pole piece, the secondary pole piece which finishes the first rolling operation is subjected to the second rolling operation through the roller pair device, the compacted density of the secondary pole piece which passes through the first rolling operation is greatly improved, and then the secondary pole piece which finishes the first rolling operation is subjected to the second rolling operation, so that the compacted density of the secondary pole piece can be further improved, the discharge capacity of the battery is further 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 this embodiment, the second rolling operation is a cold pressing operation, the secondary pole piece has already completed partial compaction after the first rolling operation, and the secondary pole piece is subjected to the cold pressing operation again, so that the secondary pole piece can be further compacted on the one hand, the compaction density of the pole piece is further improved, and meanwhile, the phenomenon that the flexibility of the pole piece is reduced due to one-time hot pressing or one-time cold pressing and the pole piece becomes brittle is avoided. On the other hand, the secondary pole piece is subjected to hot pressing and then cold pressing, so that the shape setting of the pole piece can be facilitated, and the stability and the flexibility of the compacted pole piece are improved.
In one embodiment, after the step of subjecting the secondary pole piece to the hot pressing operation and before the step of subjecting the secondary pole piece to the cold pressing operation, the method further comprises the following steps: and carrying out cold air blowing operation on the surface of the secondary pole piece after the hot pressing operation is finished. It will be appreciated that hot pressing has the effect of softening the pole pieces, making them easier to compact. In this application, carry out twice rolling operation to inferior pole piece altogether, the operation is rolled for the first time, and hot pressing operation is for not rolling completely promptly, in the compaction pole piece, can also guarantee the pliability of pole piece. However, since the pole piece is in a softened state after hot pressing, the surface of the pole piece is likely to be uneven after rolling. And the softened pole piece structure is easy to have an unstable problem. In this embodiment, a cold air blowing operation is performed on the surface of the secondary pole piece after the hot pressing operation is completed, specifically, a cold air blowing device is arranged at an outlet of the hot pressing double-roller device, an included angle between the cold air blowing device and the surface of the pole piece is greater than 0 degree and smaller than 90 degrees, and cold air is blown to the pole piece after the hot pressing is completed by the cold air blowing device, so that on one hand, a flattening and shaping effect can be achieved on the pole piece, thereby facilitating the cold pressing operation of the pole piece again, further improving the compaction density of the pole piece, and simultaneously ensuring the flexibility of the pole piece; on the other hand, cold air blowing can reduce the temperature of the surface of the pole piece after hot pressing, so that the phenomenon that the pole piece is cracked or broken due to quenching when cold pressing is directly carried out is avoided, and the flexibility of the pole piece is further improved.
In one embodiment, after the step of performing the second drying operation on the primary sheet coated with the second lithium cobaltate coating slurry to obtain the secondary sheet, before the step of performing the first rolling operation on the secondary sheet, the method further comprises the following steps: and carrying out limiting operation on the rolling gap. It will be appreciated that the lamination operation can be carried out on the pole pieces by a double roll arrangement, i.e. using two rotating rolls. However, the gap between the pair of rollers has a direct influence on the compaction density of the pole piece, and if the gap between the pair of rollers is too large, the preset compaction density cannot be achieved at one time, and the adjustment cannot be performed in the rolling process; if the gap between the pair of rollers is too small, the flexibility of the rolled pole piece is easily reduced, the pole piece becomes brittle, the pole piece is seriously wrinkled during winding, and even the situation of pole piece breakage can be caused. In this embodiment, the rolling gap is adjusted and limited by the limiting valve, and the flexibility and consistency of the pole piece can be better by limiting rolling, which is beneficial to improving the compaction density.
In one embodiment, the rolling speed in the first rolling operation and the rolling speed in the second rolling operation are both 7 m/min-11 m/min. The rolling speed of the positive plate to be rolled is 7-11 m/min, so that the rolling thickness rebound of the positive plate is avoided, and the coating density and porosity of the positive plate are improved. Experiments prove that the rolling speed of the positive plate to be rolled for two times is 7-11 m/min, so that the rebound quantity of the rolled thickness of the positive plate is small.
Example 1
Crushing the spherical lithium cobaltate by a jet mill to obtain the product with D50 being less than or equal to 17 mu m and BET being more than 0.2m2Per gram of small particle lithium cobaltate. Mixing a first PVDF glue solution, a first conductive agent and small-particle lithium cobaltate according to the weight ratio of 1.0: 1.5: 97.5 a mixing operation was carried out to prepare a first lithium cobaltate coating slurry. And coating the first lithium cobaltate coating slurry on two sides of the aluminum foil according to the preset surface density, and drying to obtain a primary electrode plate. And mixing the second PVDF glue solution, the second conductive agent and the conventional particle lithium cobaltate according to the weight ratio of 1.0: 1.5: 97.5 a mixing operation was performed to prepare a second lithium cobaltate coating slurry. And coating the second lithium cobaltate coating slurry on two sides of the primary pole piece according to the preset surface density, and drying to obtain the secondary pole piece. And carrying out hot rolling on the secondary pole piece according to a preset compaction density, and then carrying out cold pressing to obtain the lithium battery pole piece, wherein the temperature of the hot rolling is 90 ℃, and the rolling speed is 7 m/min.
Example 2
Crushing the spherical lithium cobaltate by a jet mill to obtain the product with D50 being less than or equal to 17 mu m and BET being more than 0.2m2Per gram of small particle lithium cobaltate. Mixing a first PVDF glue solution, a first conductive agent and small-particle lithium cobaltate according to the weight ratio of 1.0: 1.5: 97.5 a mixing operation was carried out to prepare a first lithium cobaltate coating slurry. And coating the first lithium cobaltate coating slurry on two sides of the aluminum foil according to the preset surface density, and drying to obtain a primary electrode plate. And mixing the second PVDF glue solution, the second conductive agent and the conventional particle lithium cobaltate according to the weight ratio of 1.0: 1.5: 97.5 a mixing operation was performed to prepare a second lithium cobaltate coating slurry. According to a predetermined areal densityAnd coating the second lithium cobaltate coating slurry on two sides of the primary pole piece, and drying to obtain the secondary pole piece. And carrying out hot rolling on the secondary pole piece according to a preset compaction density, and then carrying out cold pressing to obtain the lithium battery pole piece, wherein the temperature of the hot rolling is 120 ℃, and the rolling speed is 11 m/min.
Example 3
Crushing the spherical lithium cobaltate by a jet mill to obtain the product with D50 being less than or equal to 17 mu m and BET being more than 0.2m2Per gram of small particle lithium cobaltate. Mixing a first PVDF glue solution, a first conductive agent and small-particle lithium cobaltate according to the weight ratio of 1.0: 1.5: 97.5 a mixing operation was carried out to prepare a first lithium cobaltate coating slurry. And coating the first lithium cobaltate coating slurry on two sides of the aluminum foil according to the preset surface density, and drying to obtain a primary electrode plate. And mixing the second PVDF glue solution, the second conductive agent and the conventional particle lithium cobaltate according to the weight ratio of 1.0: 1.5: 97.5 a mixing operation was performed to prepare a second lithium cobaltate coating slurry. And coating the second lithium cobaltate coating slurry on two sides of the primary pole piece according to the preset surface density, and drying to obtain the secondary pole piece. And carrying out hot rolling on the secondary pole piece according to a preset compaction density, and then carrying out cold pressing to obtain the lithium battery pole piece, wherein the hot rolling temperature is 100 ℃, and the rolling speed is 8 m/min.
The application also provides a lithium battery pole piece, which is prepared by the preparation method of the lithium battery pole piece in any embodiment.
In one embodiment, the lithium battery pole piece comprises a lithium cobaltate coating and an aluminum foil, wherein the lithium cobaltate coating is respectively coated on the surfaces of two sides of the aluminum foil. It can be understood that lithium cobaltate has a high tap density, which contributes to an increase in the volumetric specific capacity of the battery. The lithium cobaltate is used as a pole piece material, so that the adhesion of active substances and a current collector can be improved, and the manufacturing cost of the pole piece is reduced. In this embodiment, the lithium battery electrode plate includes a lithium cobaltate coating and an aluminum foil, and the lithium cobaltate coating is respectively coated on the surfaces of the two side surfaces of the aluminum foil, so that the lithium cobaltate can be completely coated on the aluminum foil, which is helpful for improving the volumetric capacity of the battery. In addition, the binding force among lithium cobaltate particles is strong, and the lithium cobaltate particles are not easy to fall off when the pole piece is rolled, so that the problem of powder falling of the pole piece is effectively reduced or avoided.
Further, the lithium cobaltate coating comprises a first lithium cobaltate coating and a second lithium cobaltate coating, the number of layers of the first lithium cobaltate coating is two, the number of layers of the second lithium cobaltate coating is two, the two first lithium cobaltate coatings are respectively coated on the surfaces of the two side faces of the aluminum foil, and the two second lithium cobaltate coatings are respectively coated on one side, away from the aluminum foil, of the first lithium cobaltate coating. The first lithium cobaltate coating contains small-particle lithium cobaltate, a PVDF glue molecular chain and a conductive agent, and the second lithium cobaltate coating contains conventional particles, a PVDF glue molecular chain and a conductive agent. In this embodiment, the lithium cobaltate coating includes two first lithium cobaltate coatings and two second lithium cobaltate coatings, the two first lithium cobaltate coatings are respectively coated on the surfaces of the two side surfaces of the aluminum foil, and the two second lithium cobaltate coatings are respectively coated on the surface of the first lithium cobaltate coating away from the aluminum foil. When the lithium battery pole piece is compacted, the second lithium cobaltate coating on the outer side can generate extrusion force on the first lithium cobaltate coating on the inner side and the aluminum foil, and the first lithium cobaltate coating containing small lithium cobaltate is adhered to the surfaces of the two side surfaces of the aluminum foil, so that the aluminum foil can be effectively reduced by lithium cobaltate particles. And because the two second lithium cobaltate coatings are respectively coated on one surface of the first lithium cobaltate coating, which is far away from the aluminum foil, large-particle lithium cobaltate can be effectively buffered, namely the conventional lithium cobaltate particles extrude the aluminum foil, so that the compaction density and the flexibility of the lithium battery pole piece are effectively improved.
The application further provides a lithium battery, which comprises the lithium battery pole piece in the embodiment.
Compared with the prior art, the invention has at least the following advantages:
1. the preparation method of the lithium battery pole piece comprises the steps of coating first lithium cobaltate coating slurry containing small-particle lithium cobaltate on an aluminum foil to prepare a primary pole piece, coating second lithium cobaltate coating slurry containing conventional spherical lithium cobaltate, namely unbroken spherical lithium cobaltate on the primary pole piece to prepare a secondary pole piece, and rolling the secondary pole piece to obtain the lithium battery pole piece. The specific surface area of the small-particle lithium cobaltate is large, so that uniform distribution of PVDF glue solution and a conductive agent is facilitated, and meanwhile, the particle size of the small-particle lithium cobaltate is small, so that damage to a pole piece aluminum foil during rolling is small, and large-particle lithium cobaltate can be buffered, namely extrusion of conventional spherical lithium cobaltate on an aluminum foil is facilitated, so that the compaction density and flexibility of a lithium battery pole piece are improved.
2. In the preparation method of the lithium battery pole piece, the secondary pole piece which is coated and dried is rolled twice, wherein the first rolling is hot pressing, and the second rolling is cold pressing. Because the first rolling operation is a hot pressing operation, the rebound rate of the pole piece material can be effectively controlled, and the compaction density of the pole piece is improved; after hot pressing operation is completed, cold pressing operation is performed on the pole piece, and shaping and surface flatness of the pole piece can be better controlled, so that flexibility of the pole piece is guaranteed while compaction density of the pole piece is 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, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a lithium battery pole piece is characterized by comprising the following steps:
crushing the spherical lithium cobaltate to obtain small-particle lithium cobaltate;
mixing the first PVDF glue solution, the first conductive agent and the small-particle lithium cobalt oxide to obtain first lithium cobalt oxide coating slurry;
coating the first lithium cobaltate coating slurry on an aluminum foil to obtain a first lithium cobaltate coating;
carrying out primary drying operation on the aluminum foil coated with the first lithium cobaltate coating slurry to obtain a primary electrode sheet;
mixing the second PVDF glue solution, the second conductive agent and conventional particle lithium cobaltate to obtain second lithium cobaltate coating slurry;
coating the second lithium cobaltate coating slurry on the primary electrode sheet to obtain a second lithium cobaltate coating;
performing secondary drying operation on the primary pole piece coated with the second lithium cobaltate coating slurry to obtain a secondary pole piece;
carrying out primary rolling operation on the secondary pole piece;
and performing secondary rolling operation on the secondary pole piece after the primary rolling operation is completed to obtain the lithium battery pole piece.
2. The method for preparing the lithium battery pole piece as claimed in claim 1, wherein the D50 of the small-particle lithium cobaltate is not more than 17 μm, and BET is more than 0.2m2/g。
3. The method for preparing the lithium battery pole piece according to claim 1, wherein the first conductive agent and the second conductive agent are both at least one of carbon black, carbon nanotubes, graphene and ketjen black.
4. The method for preparing the lithium battery pole piece as claimed in claim 1, wherein the first rolling operation is a hot pressing operation.
5. The method for preparing the lithium battery pole piece as recited in claim 1, wherein the second rolling operation is a cold pressing operation.
6. The method for preparing the lithium battery pole piece according to claim 1, wherein after the step of performing the second drying operation on the primary pole piece coated with the second lithium cobaltate coating slurry to obtain a secondary pole piece, before the step of performing the first rolling operation on the secondary pole piece, the method further comprises the following steps:
and carrying out limiting operation on the rolling gap.
7. A lithium battery pole piece is characterized in that the lithium battery pole piece is prepared by the preparation method of the lithium battery pole piece as claimed in any one of claims 1 to 6.
8. The lithium battery pole piece according to claim 7, wherein the lithium battery pole piece comprises a lithium cobaltate coating and an aluminum foil, and the lithium cobaltate coating is respectively coated on the surfaces of two side surfaces of the aluminum foil.
9. The lithium battery pole piece of claim 8, wherein the lithium cobaltate coating comprises a first lithium cobaltate coating and a second lithium cobaltate coating, the number of layers of the first lithium cobaltate coating is two, the number of layers of the second lithium cobaltate coating is two, the two first lithium cobaltate coatings are respectively coated on the surfaces of the two side faces of the aluminum foil, and the two second lithium cobaltate coatings are respectively coated on the two side faces of the first lithium cobaltate coating, which are far away from the aluminum foil.
10. A lithium battery comprising a lithium battery pole piece according to any one of claims 7 to 8.
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| CN114420888A (en) * | 2022-01-20 | 2022-04-29 | 厦门海辰新能源科技有限公司 | Pole piece and preparation method and application thereof |
| CN114535295A (en) * | 2021-12-22 | 2022-05-27 | 捷威动力工业嘉兴有限公司 | Rolling equipment and rolling process for positive and negative electrode plates |
| CN115360325A (en) * | 2022-09-16 | 2022-11-18 | 楚能新能源股份有限公司 | Pole piece and preparation method thereof |
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Application publication date: 20210803 |