CN112952051A - Negative pole piece, preparation method of negative pole piece, lithium ion hard-package battery cell, lithium ion battery package and application of lithium ion hard-package battery cell - Google Patents
Negative pole piece, preparation method of negative pole piece, lithium ion hard-package battery cell, lithium ion battery package and application of lithium ion hard-package battery cell Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative 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
- 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
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Abstract
The invention provides a negative pole piece which comprises a negative pole current collector and a negative pole coating coated on the surface of the negative pole current collector, wherein the negative pole coating comprises a negative pole inner coating coated on the surface of the negative pole current collector and a negative pole outer safety coating coated on the surface of the negative pole inner coating, and the negative pole outer safety coating is a high lithium intercalation potential active material layer with the potential of Li +/Li being more than 0.5V. The invention also provides a preparation method of the negative pole piece, a lithium ion hard-package battery core, a lithium ion battery package and application thereof, which can inhibit lithium precipitation in the electrochemical reaction process on one hand, and can separate lithium dendrite generated by coating chromatographic lithium in the negative pole from the diaphragm on the other hand, so as to effectively avoid the situation that the lithium dendrite directly contacts with the diaphragm and pierces the diaphragm to cause short circuit, and remarkably improve the safety of the battery.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a negative pole piece, a preparation method of the negative pole piece, a lithium ion hard-package battery cell, a lithium ion battery package and application of the lithium ion hard-package battery cell.
Background
The lithium ion battery has the advantages of high energy density, high power density, long service life, small self-discharge rate, no memory effect, environmental protection and the like, so the lithium ion battery is obviously superior to other traditional secondary batteries in cost performance and is applied to more and more industries; in recent years, lithium ion batteries have gradually entered the fields of electric bicycles, electric motorcycles, and new energy vehicles, and particularly, with the rapid development of the new energy vehicle industry, higher and higher requirements are put forward on various performances of lithium ion batteries, particularly in terms of battery safety.
In the circulation process of the lithium ion battery, along with the continuous reaction of the electrolyte on the surface of the negative electrode, an SEI (solid electrolyte interface) film on the surface of the negative electrode is gradually thickened, the internal resistance of the battery is gradually increased, the internal polarization is increasingly large, lithium is easily separated from the surface of the negative electrode, the separated lithium slowly grows to form lithium dendrites, and the lithium dendrites can cause short circuit in the battery when penetrating through a diaphragm to cause thermal runaway.
In order to improve the safety of lithium ion batteries, various studies have been conducted to suppress the occurrence and destruction of lithium dendrites in the negative electrode as much as possible. For example, a ceramic layer is coated on the surface of the polymer diaphragm, and the specific method is that a layer of inorganic ceramic material (such as aluminum oxide) is coated on the surface of the polyolefin diaphragm, so that the method can improve the thermal shrinkage temperature and the mechanical strength of the diaphragm to a certain extent, and can greatly improve the safety of the lithium ion battery; however, the ceramic layer has poor adhesion on the surface of the separator, and when the battery core is laminated or wound, the problems of powder falling or roller sticking and the like are easily caused, so that the practical application effect is poor, and the consistency of the battery is also reduced.
Disclosure of Invention
In view of this, a negative electrode plate with a reasonably designed electrode plate structure and material to improve the safety performance of a lithium ion battery, a preparation method of the negative electrode plate, a lithium ion hard-package battery cell, a lithium ion battery package and applications thereof are provided.
The invention provides a negative pole piece which comprises a negative pole current collector and a negative pole coating coated on the surface of the negative pole current collector, wherein the negative pole coating comprises a negative pole inner coating coated on the surface of the negative pole current collector and a negative pole outer safety coating coated on the surface of the negative pole inner coating, and the negative pole outer safety coating is a high lithium intercalation potential active material layer with the potential of Li +/Li being more than 0.5V.
In one embodiment, the negative electrode outer safety coating comprises a mixture of a negative electrode active material, a binder and a conductive agent, and the negative electrode active material of the negative electrode outer safety coating comprises LTO and TiO2、Nb2O5、LiVO2、Li3VO4One or two of them.
In one embodiment, the negative electrode inner coating comprises a mixture of a negative electrode active material, a binder, and a conductive agent, and the negative electrode active material of the negative electrode inner coating comprises at least one of graphite, soft carbon, hard carbon, mesocarbon microbeads, and a silicon-based material.
In one embodiment, the negative electrode inner coating and the negative electrode outer safety coating each include a mixture of a negative electrode active material, a binder and a conductive agent, the binder includes at least one of CMC, SBR, PVDF, PI, PAA, and the conductive agent of the negative electrode inner coating and the negative electrode outer safety coating includes at least one of carbon black, carbon nanotubes, VGCF, graphene.
In one embodiment, the stripping force of the negative electrode plate is 12-16N/m.
In one embodiment, the resistivity of the negative electrode plate is 1 to 2 Ω when the resistivity is 0.02 to 0.04 Ω · m.
The invention also provides a preparation method of the negative pole piece, which comprises the following steps:
providing a foil for serving as a negative electrode current collector;
providing a negative electrode inner coating material and a negative electrode outer safety coating material;
coating the slurry prepared by the negative electrode inner coating material on the surface of the foil to form a negative electrode inner coating;
after the negative electrode inner coating is dried, coating slurry made of a negative electrode outer safety coating material on the surface of the negative electrode inner coating to form a negative electrode outer safety coating;
and after the negative electrode outer safety coating is dried, rolling and flaking the foil to obtain the negative electrode piece.
In one embodiment, the negative electrode inner coating material and the negative electrode outer safety coating material comprise a mixture of a negative electrode active material, a binder and a conductive agent, and when the negative electrode inner coating material and the negative electrode outer safety coating material are prepared, the negative electrode active material, the binder and the conductive agent are added into a solvent according to a specific ratio and uniformly mixed to obtain a negative electrode slurry.
In one embodiment, the negative active material in the negative outer safety coating material comprises LTO and TiO2、Nb2O5、LiVO2、Li3VO4The negative electrode active material in the negative electrode inner coating material comprises at least one of graphite, soft carbon, hard carbon, mesocarbon microbeads and a negative electrode active material in a silicon-based material.
In one embodiment, the negative electrode outer safety coating is a high intercalation potential active material layer with Li +/Li potential greater than 0.5V.
In one embodiment, the binders of the negative electrode inner coating material and the negative electrode outer safety coating material include at least one of CMC, SBR, PVDF, PI, and PAA, and the conductive agents of the negative electrode inner coating material and the negative electrode outer safety coating material include at least one of carbon black, carbon nanotube, VGCF, and graphene.
In one embodiment, the negative electrode inner coating layer and the negative electrode outer safety coating layer are prepared by a squeeze coating method or a slit extrusion coating method.
The invention also provides a lithium ion hard-coated battery cell which comprises a positive pole piece, the battery negative pole piece and a diaphragm arranged between the positive pole piece and the battery negative pole piece, wherein the positive pole piece, the negative pole piece and the diaphragm are manufactured into a naked battery cell, and the naked battery cell is sealed in a hard shell.
The invention provides a lithium ion battery pack which comprises the lithium ion hard pack battery core.
The lithium ion battery pack described above is applied to an automobile, a motorcycle, or a bicycle.
According to the invention, the negative electrode inner coating (active material layer) of the negative electrode current collector is coated with the negative electrode outer safety coating, and the negative electrode outer safety coating is the high lithium intercalation potential active material layer with the Li +/Li potential of more than 0.5V and even as high as 1.8V, so that lithium precipitation in the electrochemical reaction process can be inhibited, and lithium dendrite generated by lithium intercalation potential in the negative electrode can be separated from the diaphragm, so that the situation that the lithium dendrite is directly contacted with the diaphragm to pierce the diaphragm to cause short circuit is effectively avoided, and the battery safety is remarkably improved.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understandable, the following specific preferred embodiments are described in detail.
Drawings
Fig. 1 is a schematic structural diagram of a negative electrode sheet formed by coating a negative electrode coating on a surface of a negative electrode current collector according to the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the present invention is described in detail below with reference to the preferred embodiments.
As shown in fig. 1, the present invention provides a negative electrode tab, which includes a negative electrode current collector 10 and a negative electrode coating 20 coated on a surface of the negative electrode current collector 10.
In the present invention, the negative electrode coating 20 includes a negative electrode inner coating 21 coated on the surface of the negative electrode current collector 10 and a negative electrode outer safety coating 22 coated on the surface of the negative electrode inner coating 21.
Since the negative electrode inner coating 21 is a conventional negative electrode material layer that can provide a lithium storage space, and the negative electrode outer safety coating 22 (the negative electrode outer safety coating 22 can also provide some lithium intercalation capacity, but the contribution is not significant, and is negligible here)) bonded to the negative electrode inner coating 21 is a high lithium intercalation potential active material layer with a high voltage, which is active material layer with a high lithium intercalation potential for Li+The potential of Li (to the lithium potential) is more than 0.5V, meanwhile, the negative pole outer safety coating 22 is used as a safety functional coating, on one hand, a mechanical layer with high mechanical strength can be added between the negative pole coating 20 and a diaphragm arranged between a positive pole piece and a negative pole piece, so that the safety is improved, on the other hand, when the lithium ion battery is overcharged, the negative pole outer safety coating 22 is provided with a voltage platform to inhibit lithium precipitation in the electrochemical reaction process, the situation that lithium precipitation occurs due to overcharge is avoided, simple substance lithium precipitated from the negative pole inner coating 21 is present between the negative pole inner coating 21 and the negative pole outer safety coating 22 and is not directly present between the negative pole outer safety coating 22 and the diaphragm, and the situation that lithium dendrite is contacted with the diaphragm to puncture the diaphragm, so that an inner short circuit is caused can be effectively avoided; and further the cathode outer safety coating 22 has the effect of reducing the impedance of the safety coating, and can compensate the capacity loss of the battery to a certain extent, so as to effectively improve the safety of the lithium ion-containing battery.
Specifically, the anode inner coating 21 and the anode outer safety coating 22 provided by the present invention are made by mixing an anode active material, a binder, and a conductive agent.
In detail, the negative active material of the negative outer safety coating 22 includes LTO (lithium titanate, Li)2TiO3)、TiO2(titanium dioxide) and Nb2O5Niobium pentoxide and LiVO2、Li3VO4One or two of them, it is understood that the anode active material of the anode outer safety coating 22, which is any one of the above substances alone or any two of them mixed, can achieve a potential of more than 0.5V to Li +/Li, even as high as 1.8V. In a preferred embodiment, when LTO is used alone, the intercalation potential of LTO to Li +/Li, i.e., LTO (the potential for intercalating lithium ions into LTO) can reach 1.5V, so that the LTO can be used aloneThe negative pole piece can not separate lithium even under the condition of overcharging, and the safety of the battery can be obviously improved.
In practical application, the invention can select voltage cathode materials with different voltage requirements as the cathode outer safety coating 22 according to the requirements of battery design, and the thickness and the formula of the cathode outer safety coating 22 can be adjusted according to the requirements.
Further, the negative electrode active material in the negative electrode undercoating 21 provided by the present invention is a low lithium intercalation material having a lower lithium intercalation potential relative to the positive electrode material; specifically, in general, the positive electrode has a higher potential, so that the lithium ion battery has a higher working voltage, and therefore, the closer the potential of the negative electrode material after lithium intercalation is to the potential of metal lithium, the higher the working voltage of the lithium ion battery is, generally, the potential of the carbon-based negative electrode material after lithium intercalation is close to 0.1V (vs.li +/Li) or even lower, while the silicon-based negative electrode material is about 0.1 to 0.2V, and some negative electrode materials have a higher potential after lithium intercalation, such as lithium titanate, and the potential is as high as 1.55V. Therefore, the low lithium intercalation material provided by the invention is at least one of common graphite, soft carbon, hard carbon, mesocarbon microbeads and silicon-based materials.
Because the negative electrode inner coating 21 provided by the invention adopts the lithium ion battery negative electrode material coating formed by the low-embedded lithium material, compared with the traditional inert safe material coating, the negative electrode inner coating has smaller influence on the internal resistance of the lithium ion battery, has lower impedance, and can compensate the capacity loss of the battery to a certain extent, thereby improving the safety and ensuring the electrochemical performance of the battery as much as possible.
The binder of the inner and outer cathode safety coatings 21 and 22 provided by the invention comprises at least one of CMC (carboxyl Methyl Cellulose-phenoxy Methyl Cellulose), SBR (Styrene Butadiene Rubber), PVDF (polyvinylidene fluoride), PI (Polyimide-Polyimide), PAA (polyacrylic acid-polyacrylic acid), and the conductive agent of the inner and outer cathode safety coatings 21 and 22 comprises at least one of carbon black, carbon nanotube, VGCF (Vapor-growth carbon fiber-Vapor phase-growth carbon fiber), and graphene.
According to the invention, the negative electrode outer safety coating 22 is coated on the surface of the negative electrode inner coating 21 and is rolled together with the whole pole piece, so that the binding power and the mechanical strength of the negative electrode outer safety coating 22 and the negative electrode inner coating 21 as well as the negative electrode inner coating 21 and the negative electrode current collector 10 can be greatly improved, the safety of the battery is effectively improved, and the functions of impedance and battery capacity compensation are realized. In the present invention, the roll forming process refers to a process of forming various complex parts by using the principle of rolling extrusion depending on the plastic movement property of the material, and related equipment and specific processes refer to the prior art and are not described herein in detail.
Specifically, the invention also provides a preparation method of the negative pole piece, which comprises the following steps:
providing a foil for use as a negative current collector 10;
providing a negative electrode inner coating material and a negative electrode outer safety coating material;
coating slurry made of the negative electrode inner coating material on the surface of the foil to form a negative electrode inner coating 21;
after the negative electrode inner coating 21 is dried, coating slurry made of a negative electrode outer safety coating material on the surface of the negative electrode inner coating 21 to form a negative electrode outer safety coating 22;
and after the negative electrode outer safety coating 22 is dried, rolling and flaking the foil to obtain a negative electrode plate.
According to the invention, the negative electrode inner coating material is coated on the foil of the negative electrode current collector 10, the negative electrode outer safety coating 22 is coated on the surface of the negative electrode inner coating 21, and then the negative electrode inner coating and the whole pole piece are manufactured into the battery negative electrode pole piece through a rolling process, so that the adhesive force between the negative electrode active layers 20 and the foil of the negative electrode current collector 10 is greatly improved, the reliability of the battery negative electrode pole piece is greatly improved, meanwhile, the mechanical strength of the safety coating is also improved in the rolling process, the safety coating is difficult to puncture by burrs or lithium dendrites generated by overcharging, the safety of the battery is improved, the production and processing equipment is changed, the construction can be carried out only by.
In detail, the negative electrode inner coating material and the negative electrode outer safety coating material provided by the invention comprise a mixture of a negative electrode active material, a binder and a conductive agent, and when the negative electrode inner coating material and the negative electrode outer safety coating material are prepared, the negative electrode active material, the binder and the conductive agent are added into solvent-deionized water (NMP solvent is used under the condition of an oily system) according to a specific proportion and uniformly mixed to obtain negative electrode slurry. In a preferred embodiment, the ratio of the negative electrode active material, the binder and the conductive agent is 80-95: 1-10: 1 to 10, for example: 80:10:10, 81:10:9, 82:9:9, 83: 8:9, 84:8:8, 85:8:7, 86:7:7, 87:6:7, 88:6:6, 89:5:6, 90:5:5, 91:4:5, 92:4:4, 93:4:3, 94:3:3, 95:2:3, which can be specifically adjusted as required.
Correspondingly, the negative electrode active material in the negative electrode inner coating material is a lithium intercalation potential active material for intercalating lithium ions, and the lithium intercalation potential active material comprises at least one of graphite, soft carbon, hard carbon, mesocarbon microbeads and silicon-based materials. The binder of the negative electrode inner coating material and the negative electrode outer safety coating material comprises CMC, SBR, PVDF, PI and PAA; the conductive agent of the negative electrode inner coating material and the negative electrode outer safety coating material comprises at least one of carbon black, carbon nano tubes, VGCF and graphene.
Further, the negative electrode inner coating 21 and the negative electrode outer safety coating 22 are prepared by a transfer coating method or a slit extrusion coating method, and specifically, which method can be selected according to needs, for example, when the thickness of the negative electrode outer safety coating 22 is thick, extrusion coating with double extrusion slit-slit extrusion coating can be adopted, two electrode sheet layers are coated at one time, and the whole electrode sheet coated on the negative electrode current collector 10 with the negative electrode inner coating 21 and the negative electrode outer safety coating 22 is dried.
The method for preparing the negative electrode inner coating 21 and the negative electrode outer safety coating 22 by using the extrusion coating method comprises the following steps:
supplying negative coating slurry by using a negative slurry tank and a conveying pipeline;
pumping the slurry in the negative slurry tank to a negative coating head by using a pump;
coating the negative current collector 10 by using a negative coating head;
after the coating is finished, the negative current collector 10 coated with the negative coating slurry is conveyed to a drying rack of a heater through a conveying roller to be dried, and the negative current collector 10 with the negative coating 20 is formed.
For other details regarding the extrusion coating method, reference may be made to the prior art, and details thereof are not repeated herein.
By implementing the negative pole piece and the preparation method of the negative pole piece, the safety design in the battery core can be effectively improved, the safety of the battery is obviously improved, and meanwhile, the influence on the electrochemical performance of the battery is small, so that the negative pole piece and the preparation method of the negative pole piece have good application prospects.
Further, a peel strength test experiment and a four-probe test experiment are performed on the negative electrode plate (including a high intercalation potential active material layer with a Li +/Li potential greater than 0.5V) and the conventional negative electrode plate (including a conventional lithium potential active material layer, and other experimental conditions are consistent), so as to obtain the peel force (the maximum force required for peeling the contact surface of the negative electrode plate in unit width), the sample resistivity and the square sample resistance value of the negative electrode plate and the conventional negative electrode plate, which is specifically shown in the following table:
| peeling force | Resistivity of sample | Resistance value of square sample | |
| The invention negative pole piece | 12～16N/m | 0.02～0.04Ω·m | 1～2Ω |
| Traditional negative pole piece | 7～10N/m | 0.03～0.05Ω·m | 1～3Ω |
Table one: experimental data of stripping force, resistivity value and square resistance value of the negative pole piece sample piece and the traditional negative pole piece
According to the experimental test data measured in table one, it can be known that: the negative pole piece sample provided by the invention has larger stripping force, and compared with the sample resistivity and the square sample resistance value of the traditional negative pole piece, the negative pole piece sample provided by the invention has smaller square resistance value and smaller resistivity, so that the negative pole piece provided by the invention has good conductivity, and can not influence other performances of the battery cell while ensuring the safety of the battery cell.
Because the cathode outer safety coating 22 in the invention is a high lithium intercalation potential active material layer with higher voltage for Li +/Li potential greater than 0.5V, and the cathode active material in the high lithium intercalation potential active material layer comprises LTO and TiO with higher voltage2、Nb2O5、LiVO2、Li3VO4One or both of them, to avoid overcharge of the cathode outer safety coating 22; according to the four-probe test experiment, the potential of the negative outer safety coating 22 in the negative pole piece is high, so that lithium cannot be separated out (lithium metal cannot be separated out) even under the condition of overcharge, the safety design of the interior of a lithium ion hard-coated battery core made of the negative pole piece is guaranteed, the safety of the battery is obviously improved, the electrochemical performance of the battery is slightly influenced, and the negative outer safety coating 22 has a good application prospect.
The invention provides a lithium ion battery pack, which comprises a battery module, a circuit board, a shell and the like, wherein the battery module, the circuit board and the like are assembled in the shell to form the lithium ion battery pack, the lithium ion battery pack has various specifications, can be adjusted and designed according to needs, and is not limited in the process, and the assembly mode of the lithium ion battery pack in the prior art can be applied to the invention.
The battery module is composed of a plurality of lithium ion battery cells connected in series and in parallel, and similarly, the battery module has various specifications and can be adjusted and designed according to needs. The lithium ion battery cell is divided into a lithium ion soft package battery cell and a lithium ion hard package battery cell.
The lithium ion hard-coated battery cell provided by the invention comprises a positive pole piece, the battery negative pole piece and a diaphragm arranged between the positive pole piece and the battery negative pole piece, wherein the positive pole piece, the negative pole piece and the diaphragm are made into a bare cell, and the bare cell is sealed in a hard shell.
Specifically, the preparation of the lithium ion hard-coated battery cell comprises the following steps:
the isolation film is arranged between the negative plate and the positive plate, the square naked battery cell is prepared in a winding mode, the battery cell shell is made of aluminum materials or steel materials, the naked battery cell is arranged in the battery cell shell, a dry battery cell is obtained after packaging, and the dry battery cell is subjected to procedures of baking, dewatering, liquid injection, sealing, standing, formation, degassing packaging, capacity grading and the like to obtain the lithium ion hard-package battery cell.
It should be noted that, in this embodiment, a square bare cell is prepared by winding, and certainly, in other embodiments, the bare cell may also be prepared by lamination, and the bare cell may also be prepared into other shapes, such as a cylinder or an ellipse, that is, the conventional method for preparing a lithium ion hard-coated cell may be applied to the present invention, and is not limited herein.
In more detail, the lithium ion battery pack provided by the invention can be applied to an automobile, a motorcycle or a bicycle to provide power for the automobile, the motorcycle or the bicycle.
In conclusion, the negative electrode inner coating (active material layer) of the negative electrode current collector is coated with the negative electrode outer safety coating, and the negative electrode outer safety coating is the high lithium intercalation potential active material layer with the Li +/Li potential of more than 0.5V and even as high as 1.8V, so that lithium precipitation in the electrochemical reaction process can be inhibited, lithium dendrites generated by lithium intercalation potential in the negative electrode can be separated from the diaphragm, the situation that the lithium dendrites are directly contacted with the diaphragm to pierce the diaphragm to cause short circuit is effectively avoided, and the safety of the battery is obviously improved; meanwhile, the binding force and the mechanical strength between the anode coating and the cathode inner coating and between the anode inner coating and the cathode current collector are enhanced through a rolling process, so that the functions of impedance and battery capacity compensation are realized while the safety of the battery is effectively improved.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (15)
1. The utility model provides a negative pole piece, includes negative pole mass flow body (10) and coating negative coating (20) on negative pole mass flow body (10) surface, its characterized in that: the negative electrode coating (20) comprises a negative electrode inner coating (21) coated on the surface of the negative electrode current collector (10) and a negative electrode outer safety coating (22) coated on the surface of the negative electrode inner coating (21), and the negative electrode outer safety coating (22) is a high lithium intercalation potential active material layer with the Li +/Li potential being more than 0.5V.
2. The negative electrode tab of claim 1, wherein: the negative electrode outer safety coating (22) comprises a mixture of a negative electrode active material, a binder and a conductive agent, and the negative electrode active material of the negative electrode outer safety coating (22) comprises LTO and TiO2、Nb2O5、LiVO2、Li3VO4One or two of them.
3. The negative electrode tab of claim 1, wherein: the negative electrode inner coating (21) comprises a mixture of a negative electrode active material, a binder and a conductive agent, and the negative electrode active material of the negative electrode inner coating (21) comprises at least one of graphite, soft carbon, hard carbon, mesocarbon microbeads and a silicon-based material.
4. The negative electrode tab of claim 1, wherein: the negative electrode inner coating (21) and the negative electrode outer safety coating (22) each comprise a mixture of a negative electrode active material, a binder and a conductive agent, the binder comprising at least one of CMC, SBR, PVDF, PI, PAA, the conductive agent comprising at least one of carbon black, carbon nanotubes, VGCF, graphene.
5. The negative electrode tab of claim 1, wherein: the stripping force of the negative pole piece is 12-16N/m.
6. The negative electrode tab of claim 1, wherein: when the resistivity of the negative pole piece is 0.02-0.04 omega.m, the corresponding resistance value is 1-2 omega.
7. A preparation method of a negative pole piece is characterized by comprising the following steps:
providing a foil for use as a negative current collector (10);
providing a negative electrode inner coating material and a negative electrode outer safety coating material;
coating the slurry prepared by the negative electrode inner coating material on the surface of the foil to form a negative electrode inner coating (21);
after the negative electrode inner coating (21) is dried, coating slurry made of a negative electrode outer safety coating material on the surface of the negative electrode inner coating (21) to form a negative electrode outer safety coating (22);
and after the negative electrode outer safety coating (22) is dried, rolling and flaking the foil to obtain the negative electrode pole piece.
8. The preparation method of the negative pole piece according to claim 7, characterized in that: the negative electrode inner coating material and the negative electrode outer safety coating material comprise a mixture of a negative electrode active material, a binder and a conductive agent, and when the negative electrode inner coating material and the negative electrode outer safety coating material are prepared, the negative electrode active material, the binder and the conductive agent are added into a solvent according to a specific proportion and are uniformly mixed to obtain negative electrode slurry.
9. The preparation method of the negative pole piece according to claim 8, characterized in that: the negative active material in the negative outer safety coating material comprises LTO and TiO2、Nb2O5、LiVO2、Li3VO4The negative electrode active material in the negative electrode inner coating material comprises at least one of graphite, soft carbon, hard carbon, mesocarbon microbeads and silicon-based materials.
10. The preparation method of the negative pole piece according to claim 8, characterized in that: the cathode outer safety coating (22) is a high lithium intercalation potential active material layer with a potential of more than 0.5V for Li +/Li.
11. The preparation method of the negative pole piece according to claim 8, characterized in that: the binder in the negative electrode inner coating material and the negative electrode outer safety coating material comprises at least one of CMC, SBR, PVDF, PI and PAA, and the conductive agent in the negative electrode inner coating material and the negative electrode outer safety coating material comprises at least one of carbon black, carbon nano tubes, VGCF and graphene.
12. The method for preparing the negative pole piece according to claim 11, characterized in that: the negative electrode inner coating material and the negative electrode outer safety coating material are coated by a squeeze coating method or a slit extrusion coating method.
13. A lithium ion hard-coated battery cell, which is characterized by comprising a positive electrode plate, a battery negative electrode plate prepared by the preparation method of any one of claims 7 to 12, and a diaphragm arranged between the positive electrode plate and the battery negative electrode plate, wherein the positive electrode plate, the negative electrode plate and the diaphragm are prepared into a bare cell, and the bare cell is sealed in a hard shell.
14. A lithium ion battery pack comprising the lithium ion hard pack cell of claim 13.
15. Applying the lithium ion battery pack of claim 14 to an automobile, motorcycle, or bicycle.
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Effective date of registration: 20211227 Address after: 511400 No.36 Longying Road, Shilou Town, Panyu District, Guangzhou City, Guangdong Province Applicant after: GAC AION New Energy Vehicle Co.,Ltd. Address before: 510030 23 building, Cheng Yue mansion 448-458, Dongfeng Middle Road, Yuexiu District, Guangzhou, Guangdong. Applicant before: GUANGZHOU AUTOMOBILE GROUP Co.,Ltd. |
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