CN217239504U - Lithium ion battery positive pole piece and lithium ion battery - Google Patents
Lithium ion battery positive pole piece and lithium ion battery Download PDFInfo
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- CN217239504U CN217239504U CN202122314905.4U CN202122314905U CN217239504U CN 217239504 U CN217239504 U CN 217239504U CN 202122314905 U CN202122314905 U CN 202122314905U CN 217239504 U CN217239504 U CN 217239504U
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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 utility model relates to a lithium ion power battery technical field discloses a lithium ion battery positive pole piece and lithium ion battery. The lithium ion positive pole piece comprises a positive current collector and a composite layer arranged on the surface of the positive current collector; the composite layer comprises an inner lithium supplement layer and at least one lithium supplement active layer stacked on the inner lithium supplement layer, and the lithium supplement active layer comprises a positive electrode material layer and an outer lithium supplement layer stacked on the positive electrode material layer. Through the composite coating process, the inner lithium supplement layer and the outer lithium supplement layer are arranged, so that the content of active lithium of the positive electrode can be improved, the capacity of the battery is improved, the capacity attenuation is reduced, and the service life of the battery is greatly prolonged.
Description
Technical Field
The utility model relates to a lithium ion power battery technical field specifically, relates to a lithium ion battery positive pole piece and lithium ion battery.
Background
The driving mileage and the cycle life of the automobile are very key indexes of the electric automobile, are important factors for limiting the development of the electric automobile at present, are also factors considered by consumers firstly, and are the direction of research of most battery manufacturers on how to improve the electric quantity and the cycle life of a battery pack. In long circulation, the battery core reaches the later circulation stage, due to serious polarization and increased internal resistance, reversible active lithium ions in the battery core are reduced, the capacity of the battery can be quickly attenuated, and even the risk of water jump exists. The lithium ion battery anode with high capacity, low internal resistance and high cycle stability and the lithium ion battery with long service life are urgently needed to be provided.
Therefore, in order to improve the single capacity of the battery, the coating thickness of the pole piece needs to be increased, and the lithium content of the material is increased, so that the lithium supplementing technology is adopted in the technology, the lithium content is effectively increased, and meanwhile, the coating thickness is increased by the composite coating technology, and the battery capacity is greatly increased.
Disclosure of Invention
The utility model aims at overcoming the problem that lithium ion battery that exists hinders height, capacity low, cyclic life is poor among the prior art, providing a lithium ion battery positive pole piece and lithium ion battery. The lithium ion battery has the advantages that the active lithium content of the positive electrode is high, the battery capacity is improved, the capacity attenuation is reduced, and the battery service life is prolonged.
In order to achieve the above object, the present invention provides a positive electrode plate of a lithium ion battery, including a positive current collector 1, wherein the positive current collector further includes a composite layer 2; wherein the content of the first and second substances,
the composite layer 2 is arranged on the surface of the positive current collector 1;
the composite layer 2 comprises an inner lithium supplement layer 3 formed on the surface of the positive electrode current collector 1, and at least one lithium supplement active layer stacked on the inner lithium supplement layer 3;
the lithium supplement active layer comprises a positive electrode material layer 4 and an external lithium supplement layer 5 which is arranged on the positive electrode material layer 4 in a laminated mode;
the inner lithium supplement layer and the outer lithium supplement layer have the same composition.
In some embodiments, the positive electrode current collector 1 has opposite a-side surface and B-side surface, and the composite layer 2 is disposed on the a-side surface and/or the B-side surface.
In some embodiments, the composite layer 2 is disposed on the a-side surface and the B-side surface.
In some embodiments, the number of layers of the lithium supplement active layer contained in the composite layer 2 disposed on the a-side surface is M a The number of layers of the lithium-supplement active layer contained in the composite layer 2 arranged on the surface on the side of the B-side is M b ，M a And M b Are all more than or equal to 1 and are different or the same.
In some embodiments, said M a And M b Is 1 to 4; the total thickness of the positive pole piece is not more than 135 μm.
In some embodiments, the total thickness of the positive electrode material layer is 90 to 96 μm;
preferably, the ratio of the thickness of the positive electrode material layer to the total thickness of the inner lithium supplement layer and the outer lithium supplement layer is 1-3: 1.
In some embodiments, the inner lithium supplement layer and the outer lithium supplement layer comprise a lithium supplement material and a conductive material; the lithium-supplementing material is selected from Li 3 N，LiN 3 ，Li 2 O，Li 2 S，Li 2 O 2 At least one of; the conductive material is graphene.
Preferably, the lithium supplement material is lithium nitride.
The utility model discloses the second aspect provides a lithium ion battery, wherein, lithium ion battery includes foretell positive pole piece.
Through the technical scheme, the utility model discloses the beneficial technological effect who gains as follows:
1) through interior lithium layer of mending direct and the laminating of anodal mass flow body, have stronger adhesion, increase the peeling strength of whole anodal coating.
2) The thinner internal lithium supplement layer can reduce the contact internal resistance and reduce the DCR; the thicker external lithium supplement layer can increase the battery capacity and optimize the cycle performance.
3) The technical method is simple, and can reduce the cost of materials and batteries and increase the benefit.
Other features and advantages of the present invention will be described in detail in the detailed description which follows.
Drawings
FIG. 1 is a view showing a positive electrode plate (M) according to the present invention a ＝1，M b Schematic structural section of 1);
FIG. 2 is a view showing a positive electrode plate (M) according to the present invention a ＝2，M b 1) in cross section.
Description of the reference numerals
1 positive current collector 2 composite layer 3 internal lithium supplement layer
4 positive electrode material layer 5 external lithium-supplementing layer
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The utility model provides a lithium ion battery anode piece, which comprises an anode current collector 1 and a composite layer 2; wherein the content of the first and second substances,
the composite layer 2 is arranged on the surface of the positive current collector 1;
the composite layer 2 comprises an inner lithium supplement layer 3 formed on the surface of the positive electrode current collector 1, and at least one lithium supplement active layer stacked on the inner lithium supplement layer 3;
the lithium supplement active layer comprises a positive electrode material layer 4 and an external lithium supplement layer 5 which is arranged on the positive electrode material layer 4 in a laminated mode;
the inner lithium supplement layer and the outer lithium supplement layer have the same composition.
In the prior art, a single active layer is generally coated on a positive current collector of a lithium ion battery, but the adhesion of the single-layer coated active layer is poor, and stripping and falling of materials are easily generated after long circulation. The utility model discloses an inventor discovers through the research, mixes through adopting conducting material and benefit lithium material, for example, adopts lithium nitride and graphite alkene to make into inside and outside benefit lithium layer, and wherein inside benefit lithium layer can strengthen the peeling strength of bulk material coating, reduces the contact internal resistance, and simultaneously, outside benefit lithium layer can obviously promote the battery first effect, promotes battery capacity simultaneously, reduces the internal resistance, increases battery cycle performance.
It can be understood by those skilled in the art that the materials used for the inner lithium supplement layer and the outer lithium supplement layer are the same, but the composition is not limited thereto as long as the corresponding lithium supplement function is provided.
According to the utility model discloses, anodal mass flow body 1 has A side surface and B side surface that back to back, be provided with on A side surface and/or the B side surface composite bed 2.
Preferably, the composite layer 2 is provided on the a-side surface and the B-side surface.
According to the utility model discloses, set up on the A side surface the composite bed 2 contains mend the number of piles of lithium active layer and be M a The number of layers of the lithium-supplement active layer contained in the composite layer 2 arranged on the surface on the side of the B-side is M b ，M a And M b Are all more than or equal to 1 and are different or the same.
In the present invention, the surface of the positive current collector a is the same as the surface of the positive current collector B, and is distinguished only as the description of the two side surfaces. The composite layer can be arranged on a single side surface of the positive current collector, or the composite layer can be arranged on two side surfaces of the positive current collector, and meanwhile, the number of layers of the lithium supplement active layers on the surface of the A side and the surface of the B side of the positive current collector can be the same or different. For example, the composite layer is provided on both the a-side surface and the B-side surface of the positive electrode current collector, M a And M b When all are 1, the structural section of the positive pole piece is as shown in figure 1: and the two surfaces of the positive current collector are sequentially stacked with an inner lithium supplement layer 3, a positive material layer 4 and an outer lithium supplement layer 5. When M is a ＝2，M b 1, positive pole piece structure sectionAs shown in fig. 2, the side surface of the positive electrode current collector a is sequentially stacked with an inner lithium supplement layer 3, a positive electrode material layer 4, an outer lithium supplement layer 5, a positive electrode material layer 4 and an outer lithium supplement layer 5, and the side surface B is sequentially stacked with an inner lithium supplement layer 3, a positive electrode material layer 4 and an outer lithium supplement layer 5. The technical personnel in the field can understand, under the condition of controlling certain pole piece thickness and the condition of layer thickness proportional relation, the utility model discloses in mend lithium active layer can carry out repeated range upon range of, guarantee to mend the lithium layer setting outward can, do not have the specific requirement to the individual layer thickness value of interior lithium layer, anodal material layer and outer lithium layer of meneing.
In some embodiments, a composite layer may be disposed only on the side of the positive current collector a, and the positive current collector a and the positive current collector B are stacked in the same manner as described above, in which case there is no specific requirement on the composition of the side of the positive current collector B, and the positive current collector B may be disposed for a conventional process, for example, the composite layer is disposed on the side of the positive current collector a, and the conventional single-layer positive electrode material layer is disposed on the side of the positive current collector B. It will be appreciated by those skilled in the art that the composite layers may be flexibly arranged in actual cell assembly, depending on the different cell structures and target properties.
In the utility model, M a And M b Is 1 to 4; the total thickness of the positive pole piece is not more than 135 μm.
In the present invention, the total thickness of the positive electrode material layer is 90 to 96 μm.
The utility model discloses in, interior benefit lithium layer thickness is less than outer benefit lithium layer thickness: interior benefit lithium layer is direct paste with the foil, and thinner interior benefit lithium layer just can have stronger adhesion, is difficult for droing, increases the peeling strength of bulk material coating, and thinner interior benefit lithium layer simultaneously can reduce the contact internal resistance, reduces DCR, and thicker outer benefit lithium layer can contain more lithium sources, increases active lithium ion's content, increases battery capacity, and simultaneously in the cycle process of battery, in time supplyes lithium ion, and the battery performance is more excellent. If the thickness of the inner lithium supplement layer is larger than that of the outer lithium supplement layer, the internal resistance of the battery can be increased, and meanwhile, the adhesion force of materials and the foil can be caused, and the risk of material falling is caused.
Preferably, the ratio of the thickness of the positive electrode material layer to the total thickness of the inner lithium supplement layer and the outer lithium supplement layer is 1-3: 1. The thickness of the composite layer 2 is preferably controlled within the above range, and in the assembly of the battery, the ratio of the total thickness of the inner lithium supplement layer and the outer lithium supplement layer to the thickness of the positive electrode material layer is more than 3:1, which affects the wetting effect of the electrolyte and causes insufficient wetting, and the ratio of the thickness is less than 1:1, which provides less active material and results in insufficient lithium supply.
The utility model discloses in, interior benefit lithium layer, positive material layer and benefit lithium layer outward and adopt the mode range upon range of successive layer coating. Specifically, according to the utility model provides a pair of M a ＝1，M b The anodal pole piece that 1, can be earlier mended the lithium thick liquids after mixing, even spraying is on anodal mass flow body A side surface, carry out the pole piece and dry, again with anodal material thick liquids, even coating is mended the upper strata on lithium layer in, dry the piece, will mend lithium layer thick liquids evenly spraying at the upper strata on anodal material layer outward at last, dry the piece, anodal mass flow body A side surface technology is the same with the aforesaid, roll and cross cutting after the stoving, obtain the positive plate. Preferably, the drying temperature is 80-95 ℃, and the rolling strength is 20-30 t.
According to the utility model, the inner lithium supplement layer and the outer lithium supplement layer comprise lithium supplement materials and conductive materials; preferably, the lithium source of the lithium-supplementing layer may be selected from Li 3 N，LiN 3 ，Li 2 O，Li 2 S，Li 2 O 2 The lithium nitride is a fast ion conductor, has higher electric conductivity than other inorganic lithium salts, has higher decomposition voltage, lower electronic conductivity, higher ionic conductivity and better chemical stability, is matched with a conductive material for supplementing lithium to the positive electrode, can increase the electric conductivity and reduce the internal resistance of the battery, and can provide a large amount of active lithium and greatly increase the capacity of the battery.
For example, in the preparation of the internal and external lithium supplement layer slurry, 60 to 75 mass% of lithium nitride powder, 20 to 30 mass% of graphene powder, 5 to 10 mass% of binder PVDF, and NMP solvent are uniformly mixed to obtain the lithium supplement layer slurry. Wherein the binder is selected from at least one of polyvinylidene fluoride, copolymer of polyhexafluoropropylene-polyvinylidene fluoride, polyvinyl acetate, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, alkylated polyethylene oxide, polyvinyl ether, polymethyl methacrylate, polyethyl acrylate, polytetrafluoroethylene, polyvinyl chloride, polyacrylonitrile, polyvinyl pyridine, styrene butadiene rubber and acrylonitrile-butadiene rubber; the solvent is at least one selected from N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, N-dimethylaminopropylamine, ethylene oxide and tetrahydrofuran.
The composition of the positive electrode material layer is not limited, and common positive electrode materials can be used for preparing positive electrode material layer slurry, such as one or more of nickel cobalt lithium manganate, lithium cobaltate and lithium iron phosphate. When the nickel cobalt lithium manganate is adopted as the positive electrode material, the requirement of high energy density can be met, and meanwhile, the nickel cobalt lithium manganate is matched with lithium nitride and graphene, so that a better lithium supplementing effect can be achieved. For example, 96.7 to 97.6 wt% of the mixed positive electrode material, 0.5 to 0.7 wt% of the carbon nanotube, 0.9 to 1.1 wt% of the conductive agent SP, 1 to 1.5 wt% of the binder PVDF polymer, and the solvent NMP may be mixed and stirred uniformly to obtain the positive electrode material layer slurry. The above substances are all known chemicals, and any combination thereof is also easily available.
A second aspect of the present invention provides a lithium ion battery, wherein the lithium ion battery includes the above-mentioned positive electrode. The cathode can be selected from one or more of common cathode materials, such as graphite materials, silicon carbon materials and silicon oxygen materials. Preferably, the electrolyte adopts a long-circulation electrolyte, so that the cycle life of the lithium ion battery can be further prolonged. Preferably, the lithium salt in the long-circulating electrolyte may be selected from LiPF 6 、LiBF 4 One or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and vinylene carbonate, and the additive is selected from vinylene carbonate VC, vinylene carbonate VEC, fluoroethylene carbonate FEC and sulfurOne or more of vinyl acetate DTD. The above substances are all known chemicals, and any combination thereof is also easily available.
According to the utility model provides a lithium ion battery of anodal assembly can obviously promote the battery first effect, promotes battery capacity simultaneously, reduces the internal resistance, increases battery cycle performance, mends the lithium layer outward and passes through the diaphragm, keeps apart with the negative pole, and a large amount of lithium ions can freely shuttle around, promote battery capacity, mend the lithium layer in the while and can reduce the internal resistance, increase battery cycle performance, extension battery life.
The present invention will be described in detail by way of examples.
Example 1
The preparation method of the anode comprises the following steps:
1. preparation of positive electrode slurry
Step one, adding 65 wt% of lithium nitride powder, 25 wt% of graphene powder, 10 wt% of binder PVDF and NMP solvent, adding the solvent (NMP) according to the solid content of the lithium supplement slurry of 40%, mixing according to the revolution speed of 25 rpm/rotation speed of 3000rpm, uniformly stirring in a stirring pot after mixing to obtain the lithium supplement slurry, and controlling the viscosity of the lithium supplement slurry to be 3000 +/-1000 cp.
And step two, mixing 97 wt% of 811 type nickel cobalt lithium manganate material, 0.5 wt% of carbon nano tube, 1 wt% of conductive agent SP, 1.5 wt% of binder PVDF polymer and solvent NMP, and uniformly stirring in a stirring pot to obtain the anode material layer slurry.
2. Spraying of positive plate
Firstly, uniformly spraying 1Kg of mixed lithium supplementing slurry on the side surface of a foil material foil A, drying a pole piece to obtain an inner lithium supplementing layer, uniformly spraying 9Kg of anode material layer slurry on the upper layer of the inner lithium supplementing layer, drying the pole piece, and finally, uniformly spraying 2Kg of lithium supplementing slurry on the upper layer of the anode material layer, drying the pole piece, wherein the process of the side surface of the foil material B is the same as that of the side surface of the foil material foil A, and rolling and die cutting are carried out after drying to obtain the anode piece.
The drying temperature is 80-95 ℃, and the rolling strength is 20-30 t.
The schematic structural cross-sectional view of the positive electrode plate in example 1 is shown in fig. 1 and is characterized by SEM test, wherein the total thickness of the positive electrode is 130 μm, the total thickness of the composite layer is 120 μm, the total thickness of the internal lithium supplement layer is 10 μm, the total thickness of the positive electrode material layer is 90 μm, and the total thickness of the external lithium supplement layer is 20 μm.
Comparative example 1
The same as example 1, except that only the positive electrode material layer slurry was sprayed on the a/B side of the foil.
Test example 1
The positive electrode in example 1 was assembled into a pouch battery and subjected to a performance test, wherein the pouch battery was prepared as follows:
step one, mixing artificial graphite, a binding agent CMC, a conductive agent SP and SBR according to a mass ratio of 96: 1.2: 1: and 1.8, mixing the mixture in deionized water, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on a copper foil, rolling the coated copper foil, and cutting after rolling to obtain the negative electrode sheet.
Step two, adopting long-circulating electrolyte as the electrolyte, wherein the electrolyte contains 1.2mol/L lithium salt LiPF 6 The solvent is ethylene carbonate, and the additive is VC/FEC.
Step three, performing Z-shaped lamination on the obtained positive plate, the obtained negative plate and the diaphragm to obtain a bare cell, packaging by adopting an aluminum plastic film, injecting liquid to obtain a battery (taking 58AH as an example), performing chemical composition and capacity grading, testing ACR of the battery at normal temperature of 25 ℃, fully charging 1C to 100% SOC, standing for 30min, placing 1C to 0% SOC, respectively placing at 25 ℃ and 45 ℃ according to the flow, and performing electrical property testing in a circulating process step, wherein the test result is shown in Table 1.
Test example 2
The positive electrode of comparative example 1 was assembled into a pouch cell according to the method of test example 1, and performance tests were performed, the results of which are shown in table 1.
TABLE 1
Practical experimental data show that the technology can obviously improve the battery capacity and the first effect, and simultaneously can obviously reduce the internal resistance and increase the cycle performance.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. In the technical concept scope of the present invention, it can be right to perform multiple simple modifications to the technical solution of the present invention, including each technical feature combined in any other suitable manner, these simple modifications and combinations should be considered as the disclosed content of the present invention, all belonging to the protection scope of the present invention.
Claims (8)
1. A lithium ion battery positive pole piece comprises a positive current collector (1) and is characterized by also comprising a composite layer (2); wherein the content of the first and second substances,
the composite layer (2) is arranged on the surface of the positive current collector (1);
the composite layer (2) comprises an inner lithium supplement layer (3) formed on the surface of the positive electrode current collector (1), and at least one lithium supplement active layer stacked on the inner lithium supplement layer (3);
the lithium supplement active layer comprises a positive electrode material layer (4) and an external lithium supplement layer (5) which is stacked on the positive electrode material layer (4);
the inner lithium supplement layer and the outer lithium supplement layer have the same composition.
2. The positive electrode sheet according to claim 1, wherein the positive electrode current collector (1) has opposite a-side surface and B-side surface, and the composite layer (2) is disposed on the a-side surface and/or the B-side surface.
3. The positive electrode sheet according to claim 2, wherein the composite layer (2) is provided on the a-side surface and the B-side surface.
4. The positive electrode sheet according to claim 3, wherein the number of the lithium-supplementing active layers contained in the composite layer (2) provided on the surface of the side A is M a And, andthe number of layers of the lithium-supplementing active layer contained in the composite layer (2) arranged on the surface of the side B is M b ，M a And M b Are all more than or equal to 1 and are different or the same.
5. The positive electrode sheet according to claim 4, wherein M is a And M b Is 1 to 4;
and/or the total thickness of the positive pole piece is not more than 135 μm.
6. The positive electrode sheet according to claim 5, wherein the total thickness of the positive electrode material layer is 90 to 96 μm;
and/or the ratio of the thickness of the positive electrode material layer to the total thickness of the inner lithium supplement layer and the outer lithium supplement layer is 1-3: 1.
7. The positive electrode plate as claimed in claim 6, wherein the ratio of the total thickness of the external lithium supplement layer to the total thickness of the internal lithium supplement layer is 1.5-2: 1.
8. A lithium ion battery, characterized in that the lithium ion battery comprises the positive electrode sheet according to any one of claims 1 to 7.
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| CN117558873A (en) * | 2024-01-09 | 2024-02-13 | 上海瑞浦青创新能源有限公司 | Lithium supplementing negative electrode sheet, preparation method thereof and lithium ion battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117558873A (en) * | 2024-01-09 | 2024-02-13 | 上海瑞浦青创新能源有限公司 | Lithium supplementing negative electrode sheet, preparation method thereof and lithium ion battery |
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