CN214203738U - Lithium ion battery anode electrode and lithium ion battery - Google Patents
Lithium ion battery anode electrode and lithium ion battery Download PDFInfo
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Abstract
The utility model discloses a lithium ion battery anode electrode, which comprises a current collector, wherein the upper surface and the lower surface of the current collector are respectively provided with a conductive carbon layer and an active material layer; the conductive carbon layers and the active material layers are alternately arranged in a laminated manner; by arranging the conductive carbon layer in the positive electrode, the liquid retention capacity of the electrode plate and the electrolyte passing capacity are improved, so that the impedance of the electrode plate is improved, and the battery cell cycle performance is finally improved.
Description
Technical Field
The utility model belongs to the technical field of lithium ion battery, concretely relates to lithium ion battery positive electrode and lithium ion battery.
Background
The lithium ion secondary battery has excellent performances such as high energy density, long cycle life, low cost, no memory effect and the like, and is widely applied to the daily life and the industrial field. In particular, government-related departments have been increasingly concerned about environmental issues in recent years, and due to national policy guidance and improvement and upgrade of energy density and safety performance of battery packs by emerging electric vehicles, Electric Vehicles (EV), Hybrid Electric Vehicles (HEV), and the like, which are all used as replacements for gasoline vehicles, diesel vehicles, and the like, have been increasingly confident and are required for simple urban traffic of customers.
A lithium ion secondary battery used in a battery pack has a plurality of components assembled, the electrode components including: the positive electrode is prepared by uniformly coating a positive active material with good stability on an aluminum foil current collector; a negative electrode prepared by uniformly coating a negative active material having good stability on a copper foil current collector; and (3) isolation film: the isolating membrane has the characteristics of ion conduction and electron resistance and is arranged between the positive electrode and the negative electrode; electrolyte solution: the electrolyte contains main solvents such as ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate and the like, the conductive salt is lithium hexafluorophosphate, and the electrolyte is filled around the positive electrode, the negative electrode and the isolating membrane.
For a lithium ion secondary battery, the impedance of the electrode sheet and the liquid retention capacity of the electrode sheet determine the life and performance of the battery cell. The existing lithium ion battery anode electrode has a structure that ternary anode slurry is coated on a current collector, and ternary anode materials in the ternary anode slurry account for the main proportion, but the ternary anode materials have large particle size and small specific surface area, so that the liquid retention capacity and the electrolyte passing capacity are small, and the performance of a battery cell can be greatly influenced.
SUMMERY OF THE UTILITY MODEL
In order to solve the technical problem, the utility model provides a lithium ion battery anode electrode sets up the conductive carbon layer in anode electrode, improves the ability of guaranteeing liquid of electrode slice and the ability of passing through of electrolyte to improve the impedance of electrode slice, finally promote electric core circulation performance.
In order to achieve the above purpose, the utility model adopts the following technical scheme:
a positive electrode of a lithium ion battery comprises a current collector, wherein a conductive carbon layer and an active material layer are arranged on the upper surface and the lower surface of the current collector; the conductive carbon layers and the active material layers are alternately stacked. The conductive carbon layer is made of any one or more of conductive carbon materials SP, VGCF or KS-6, the particle size of the conductive carbon layer is small, the specific surface area of the conductive carbon layer is large, and compared with a lithium ion battery positive electrode containing a single active material layer, the positive electrode can improve the liquid retention capacity and the electrolyte passing capacity of the positive electrode so as to improve the impedance of an electrode slice and finally improve the cycle performance of a battery cell.
Further, the conductive carbon layer and the active material layer on the upper surface of the current collector are symmetrically arranged with the conductive carbon layer and the active material layer on the lower surface of the current collector; when the conductive carbon layer and the active material layer are coated on the current collector, the same slurry can be coated on the upper surface and the lower surface of the current collector at the same time, and the method is convenient and quick.
The conductive carbon layer and the active material layer on the upper surface and the lower surface of the current collector are respectively one layer or more than two layers.
The active material layer is a ternary active material layer and consists of a ternary active material, a conductive agent and a binder.
The conductive carbon layer is made of any one or more of SP, VGCF or KS-6.
The current collector is a metal foil, preferably an aluminum foil.
Further, in an aspect of the present invention, the conductive carbon layer and the active material layer on the upper and lower surfaces of the current collector are both a layer; the active material layer is directly disposed on the upper and lower surfaces of the current collector, and the conductive carbonA layer disposed on a surface of the active material layer; the active material layer had a compacted density of 3.41g/cm3(ii) a The thickness of the conductive carbon layer is 7-9 mu m; the active material layer has an areal density of 200 to 220g/m when coated2。
In another aspect of the present invention, the conductive carbon layers on the upper and lower surfaces of the current collector are two layers, which are respectively a first conductive carbon layer and a second conductive carbon layer; the active material layer is a layer. Wherein the first conductive carbon layer is directly disposed on upper and lower surfaces of the current collector, the active material layer is disposed on a surface of the first conductive carbon layer, and the second conductive carbon layer is disposed on a surface of the active material layer; the active material layer had a compacted density of 3.41g/cm3(ii) a The total thickness of the first conductive carbon layer and the second conductive carbon layer is 14-18 μm, and preferably 16 μm; the active material layer has an areal density of 200 to 220g/m when coated2。
In another aspect of the present invention, the conductive carbon layers on the upper and lower surfaces of the current collector are both a single layer; the active material layers are two layers, namely a first active material layer and a second active material layer; the first active material layer is directly disposed on upper and lower surfaces of the current collector, the conductive carbon layer is disposed on a surface of the first active material layer, and the second active material layer is directly disposed on a surface of the conductive carbon layer. The first active material layer has an area density of M when coated1The second active material layer has an area density of M when coated2，M1+M2＝M，M＝200～220g/m2Wherein M is1: m ═ 1:3, 1:2, or 2: 3. The compacted density of the active material layer of the positive electrode of the lithium ion battery is 3.41g/cm3。
The utility model also provides a lithium ion battery who contains lithium ion battery positive electrode.
Compared with the prior art, the utility model discloses following beneficial effect has: the liquid retention capacity and the electrolyte passing capacity of the electrode plate are improved, so that the impedance of the electrode plate is improved, and the cycle performance of the battery cell is finally improved.
Drawings
FIG. 1 is a structural view of a positive electrode of a lithium ion battery in comparative example 1;
FIG. 2 is a structural view of a positive electrode of a lithium ion battery in example 1;
FIG. 3 is a structural view of a positive electrode of a lithium ion battery in example 2;
FIG. 4 is a structural view of a positive electrode of a lithium ion battery in example 3;
FIG. 5 is a graph showing a comparison of the impedance of the electrode sheet in comparative example 1 and each example;
fig. 6 is a graph comparing the liquid saturation capacity of the electrode sheets in comparative example 1 and each example;
in the figure, 1-current collector, 2-conductive carbon layer, 3-active material layer, 2-1-first conductive carbon layer, 2-2-second conductive carbon layer, 3-1-first active material layer, 3-2-second active material layer.
Detailed Description
The present invention will be described in detail with reference to examples and comparative examples.
In each of the following examples and comparative examples, a ternary positive electrode slurry and a carbon conductive agent slurry of the same composition were used.
Comparative example 1
The utility model provides a lithium ion battery positive electrode, includes aluminium foil and active material layer, all set up two-layer active material layer on the upper and lower surface of aluminium foil.
The preparation method of the lithium ion battery anode electrode comprises the following steps:
(1) dry-mixing the ternary active material ME8E and the conductive agent SP for 1h, adding the mixed material into PVDF glue solution, continuously stirring for 2h, and then carrying out defoaming treatment to obtain ternary anode slurry; the mass ratio of the ternary active material to the conductive agent SP to the PVDF glue solution is 100:2: 1.5.
(2) Uniformly coating the ternary cathode slurry on the upper and lower surfaces of an aluminum foil with the thickness of 15 mu M by using a spray coater, wherein the coating surface density of each surface is M0The pole pieces are oven dried and micro-rolled for the purpose of better coating the secondCoating a layer of ternary active material on the surface of the pole piece after micro rolling0The ternary positive electrode slurry is prepared by drying a pole piece in an oven and then rolling the dried pole piece, wherein the rolled thickness of the pole piece is M 04/compacted Density + thickness of aluminum foil, M in this example0＝100～120g/m2The target compacted density was 3.41g/cm3The thickness of the aluminum foil is 15 μ M, so in this example, the laminated thickness H of the pole piece is M0 × 4/3.41+15 μ M, where the laminated thickness H is equal to the laminated thickness in example 1, i.e., H2.
Example 1
A positive electrode of a lithium ion battery comprises a current collector, wherein a conductive carbon layer and an active material layer are arranged on the upper surface and the lower surface of the current collector; the conductive carbon layers and the active material layers are alternately arranged in a laminated manner; the conductive carbon layer and the active material layer on the upper surface of the current collector are symmetrically arranged with the conductive carbon layer and the active material layer on the lower surface of the current collector.
The conductive carbon layer and the active material layer are both one layer; the active material layers are arranged on the upper surface and the lower surface of the current collector, and the conductive carbon layers are arranged on the surfaces of the active material layers; the thickness of the conductive carbon layer is 7-9 μm; the active material layer has an areal density of 200 to 220g/m when coated2。
The active material layer is a ternary active material layer, and is formed by coating, drying and rolling ternary anode slurry consisting of a ternary active material, a conductive agent SP and a binder PVDF glue solution according to a mass ratio of 100:2: 1.5. The ternary active material is any one or more of S85E, ME8E, LG811B and XC 83A.
The conductive carbon layer is formed by mixing any one of SP, VGCF or KS-6 as a conductive agent and NMP according to the mass ratio of 1:50, coating, drying and rolling.
The current collector is an aluminum foil.
The preparation method of the positive electrode of the lithium ion battery in the embodiment comprises the following steps:
(1) dry-mixing the ternary active material ME8E and the conductive agent SP for 1h, adding the mixed material into PVDF glue solution, continuously stirring for 2h, and then carrying out defoaming treatment to obtain ternary anode slurry; the mass ratio of the ternary active material to the conductive agent SP to the PVDF glue solution is 100:2: 1.5.
(2) Mixing a conductive agent VGCF and NMP according to the mass ratio of 1:50, dispersing by using high-speed stirring equipment for 3-6h, standing for 1h to observe whether the carbon conductive agent slurry is precipitated, and if so, continuing stirring or ultrasonically dispersing until the dispersion is stable;
(3) uniformly coating the ternary positive electrode slurry prepared in the step (1) on the upper surface and the lower surface of an aluminum foil with the thickness of 15 microns by using a spray coater, wherein the density of the coated surface of each surface is M, drying the pole piece in an oven, carrying out first rolling, and carrying out rolling compaction to obtain 60% of the final compacted active material layer, namely the thickness H1 of the rolled pole piece is M2/(compacted density 60%) + the thickness of the aluminum foil, wherein M is 200-220 g/M2The target compacted density was 3.41g/cm3The thickness of the aluminum foil is 15 μ M, so in this example the laminated thickness H1 ═ M × 2/(3.41 × 60%) +15 μ M; obtaining an active material layer;
(4) and (3) uniformly coating a layer of the carbon conductive agent slurry prepared in the step (2) on the surface of the active material layer, wherein the total thickness of the coated layer is 10-15um, the thickness after rolling is actually 8um, the pole piece is dried by an oven and finally rolled until the active material layer is compacted to 100% to form a conductive carbon layer, and the rolling thickness H2 is M2/3.41 +15 μ M +8 μ M.
Example 2
A positive electrode of a lithium ion battery comprises a current collector, wherein a conductive carbon layer and an active material layer are arranged on the upper surface and the lower surface of the current collector; the conductive carbon layers and the active material layers are alternately arranged in a laminated manner; the conductive carbon layer and the active material layer on the upper surface of the current collector are symmetrically arranged with the conductive carbon layer and the active material layer on the lower surface of the current collector.
The conductive carbon layers on the upper surface and the lower surface of the current collector are two layers, namely a first conductive carbon layer and a second conductive carbon layer; the active material layers on the upper and lower surfaces of the current collector are both one layer; wherein the first conductive carbon layer is directly arranged on the current collectorThe active material layer is disposed on a surface of the first conductive carbon layer, and the second conductive carbon layer is disposed on a surface of the active material layer; the total thickness of the first conductive carbon layer and the second conductive carbon layer is 14-18 μm, and preferably 16 μm; the active material layer has an areal density of 200 to 220g/m when coated2。
The active material layer is a ternary active material layer, and is formed by coating, drying and rolling ternary anode slurry consisting of a ternary active material, a conductive agent SP and a binder PVDF glue solution according to a mass ratio of 100:2: 1.5.
The ternary active material is any one or more of S85E, ME8E, LG811B and XC 83A.
The conductive carbon layer is formed by mixing any one of SP, VGCF or KS-6 as a conductive agent and NMP according to the mass ratio of 1:50, coating, drying and rolling.
The current collector is an aluminum foil.
The preparation method of the positive electrode of the lithium ion battery in the embodiment comprises the following steps:
(1) dry-mixing the ternary active material ME8E and the conductive agent SP for 1h, adding the mixed material into PVDF glue solution, continuously stirring for 2h, and then carrying out defoaming treatment to obtain ternary anode slurry; the mass ratio of the ternary active material to the conductive agent SP to the PVDF glue solution is 100:2: 1.5.
(2) Mixing a conductive agent VGCF and NMP according to the mass ratio of 1:50, dispersing by using high-speed stirring equipment for 3-6h, standing for 1h to observe whether the carbon conductive agent slurry is precipitated, and if so, continuing stirring or ultrasonically dispersing until the dispersion is stable;
(3) uniformly coating the carbon conductive agent slurry prepared in the step (2) on the upper surface and the lower surface of an aluminum foil with the thickness of 15 micrometers by using a spray coater, wherein the total thickness of the coating is 10-15 micrometers, drying the pole piece, and then carrying out micro rolling on the pole piece to form a first conductive carbon layer, wherein the total thickness of the first conductive carbon layer after the micro rolling is 10 micrometers;
(4) then uniformly coating a layer prepared in the step (1) on the surface of the first conductive carbon layerThe coating surface density of the ternary positive electrode slurry is M, the pole piece is dried and then is subjected to first rolling compaction to obtain 60% of the final compacted active material layer, namely the thickness H3 of the rolled pole piece is M2/(compaction density 60%) + the thickness of the aluminum foil + the thickness of the first conductive carbon layer, wherein M is 200-220 g/M2The target compacted density was 3.41g/cm3The thickness of the aluminum foil is 15 μ M, therefore H3 ═ M2/(3.41 × 60%) +15 μ M +10 μ M; obtaining an active material layer;
(5) and (3) uniformly coating a layer of the carbon conductive agent slurry prepared in the step (2) on the surface of the active material layer, wherein the coating thickness is 10-15 microns, drying the pole piece in an oven, and finally rolling the pole piece until the compacted active material layer is 100%, so as to form a second conductive carbon layer, wherein the total thickness of the second conductive carbon layer and the first conductive layer is 16 microns, and the thickness of the rolled pole piece H4 is M2/compacted density + the thickness of the aluminum foil + the total thickness of the first conductive carbon layer and the second conductive carbon layer is M2/3.41 +15 microns +16 microns.
Example 3
A positive electrode of a lithium ion battery comprises a current collector, wherein a conductive carbon layer and an active material layer are arranged on the upper surface and the lower surface of the current collector; the conductive carbon layers and the active material layers are alternately arranged in a laminated manner; the conductive carbon layer and the active material layer on the upper surface of the current collector are symmetrically arranged with the conductive carbon layer and the active material layer on the lower surface of the current collector.
The conductive carbon layers on the upper surface and the lower surface of the current collector are both one layer; the active material layers on the upper surface and the lower surface of the current collector are two layers, namely a first active material layer and a second active material layer; the first active material layer is disposed directly on upper and lower surfaces of the current collector. The thickness of the conductive carbon layer is 7-9 μm, and preferably 8 μm; the first active material layer has an area density of M when coated1The second active material layer has an area density of M when coated2，M1+M2＝M，M＝200～220g/m2Wherein M is1: m ═ 1:3, 1:2, or 2: 3.
The active material layer is a ternary active material layer, and is formed by coating, drying and rolling ternary anode slurry consisting of a ternary active material, a conductive agent SP and a binder PVDF glue solution according to a mass ratio of 100:2: 1.5.
The ternary active material is any one or more of S85E, ME8E, LG811B and XC 83A.
The conductive carbon layer is formed by mixing any one of SP, VGCF or KS-6 as a conductive agent and NMP according to the mass ratio of 1:50, coating, drying and rolling.
The current collector is an aluminum foil.
The preparation method of the positive electrode of the lithium ion battery in the embodiment comprises the following steps:
(1) dry-mixing the ternary active material ME8E and the conductive agent SP for 1h, adding the mixed material into PVDF glue solution, continuously stirring for 2h, and then carrying out defoaming treatment to obtain ternary anode slurry; the mass ratio of the ternary active material to the conductive agent SP to the PVDF glue solution is 100:2: 1.5.
(2) Mixing a conductive agent VGCF and NMP according to the mass ratio of 1:50, dispersing by using high-speed stirring equipment for 3-6h, standing for 1h to observe whether the carbon conductive agent slurry is precipitated, and if so, continuing stirring or ultrasonically dispersing until the dispersion is stable;
(3) uniformly coating the ternary cathode slurry prepared in the step (1) on the upper surface and the lower surface of an aluminum foil with the thickness of 15 mu M by using a spray coater, wherein the coating surface density of each surface is M1Drying the pole piece by an oven and carrying out primary rolling compaction to 60% of the final compaction of the active material layer, namely the thickness H5 of the rolled pole piece is M 12/(compacted density 60%) + thickness of aluminium foil, target compacted density in this example was 3.41g/cm3The thickness of the aluminum foil is 15 μ M, so that the thickness H5 after lamination of the pole piece is M in this example12/(3.41 × 60%) +15 μm; obtaining a first active material layer;
(4) then uniformly coating a layer of the carbon conductive agent slurry prepared in the step (2) on the surface of the active material layer, wherein the coating thickness is 10-15 mu m, and after drying the pole piece, carrying out micro rolling on the pole piece to form a conductive carbon layer;
(5) then the surface of the conductive carbon layer is uniformCoating a layer of the ternary cathode slurry prepared in the step (1), wherein the coated surface density is M2Wherein M is1+M2＝M，M＝200～220g/m2，M1: m is 1: 2; and drying the pole piece by an oven, and finally rolling until the active material layer is compacted to 100% to form a second active material layer, wherein the thickness of the conductive carbon layer is 8 mu M, and the rolled thickness H6 after final rolling is M2/3.41 +15 mu M +8 mu M.
The positive electrode pieces of the lithium ion batteries prepared in the comparative example 1 and the examples 1 to 3 were subjected to impedance and liquid retention tests.
Impedance test mode: the four-probe test is performed at 20 points uniformly tested on the area of the pole piece, the recorded data is averaged, and the result is shown in fig. 5, it can be seen from fig. 5 that the impedance of the pole piece of the comparative example is the largest, the average value is 6.14 Ω, the impedance of the example 1 and the example 2 after rolling is 4.15 Ω and is reduced by about 33% because the conductive carbon layer is coated on the surface, the conductive carbon layer is coated between the active materials in the example 3, the impedance of the active material after rolling is 5.44 Ω and is between the impedance of the comparative example 1 and the impedance of the examples 1 and 2, which shows that the impedance of the positive pole piece can be effectively reduced by coating the conductive carbon layer on the surface of the active material, and thus the resistance of the cell can be predicted to be reduced without changing the negative electrode material, the diaphragm and the electrolyte of the cell.
Liquid retention test mode: the electrode plate was cut into a square of about 20 × 20mm, immersed in the electrolyte, wiped off the electrolyte on the surface of the electrode plate with a dust-free cloth at different time points, and then weighed, and the amount of absorbed liquid of the battery cell at different time points was recorded, and as shown in fig. 6, it can be seen from fig. 6 that the amount of fine liquid of the positive electrode of the lithium ion battery of each example was significantly higher than that of the positive electrode of the comparative example 1.
The above detailed description of the positive electrode of the lithium ion battery and the lithium ion battery with reference to the embodiments is illustrative and not restrictive, and several embodiments can be enumerated without departing from the scope of the present invention, so that changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (8)
1. The positive electrode of the lithium ion battery comprises a current collector and is characterized in that a conductive carbon layer and an active material layer are arranged on the upper surface and the lower surface of the current collector; the conductive carbon layers and the active material layers are alternately arranged in a laminated manner;
the conductive carbon layers on the upper surface and the lower surface of the current collector are both one layer, and the active material layers are both more than two layers; or, the conductive carbon layers on the upper surface and the lower surface of the current collector are more than two layers, and the active material layer is one layer.
2. The positive electrode for a lithium ion battery according to claim 1, wherein the conductive carbon layer and the active material layer on the upper surface of the current collector are symmetrically arranged with the conductive carbon layer and the active material layer on the lower surface of the current collector.
3. The positive electrode of the lithium ion battery according to claim 1 or 2, wherein the conductive carbon layers on the upper and lower surfaces of the current collector are two layers, namely a first conductive carbon layer and a second conductive carbon layer; the active material layers are all one layer.
4. The positive electrode of the lithium ion battery according to claim 1 or 2, wherein the conductive carbon layers on the upper and lower surfaces of the current collector are both a layer; the active material layers are two layers, namely a first active material layer and a second active material layer.
5. The positive electrode for a lithium ion battery according to claim 1 or 2, wherein the active material layer has a compacted density of 3.41g/cm3(ii) a The thickness of the conductive carbon layer is 7-18 mu m.
6. The positive electrode for a lithium ion battery according to claim 4, wherein the active material layer has a compacted density of 3.41g/cm3(ii) a The thickness of the conductive carbon layer is 7-9 μm.
7. The positive electrode for lithium ion battery according to claim 4, wherein the positive electrode comprises a positive electrode material comprising a metal oxide, and a metal oxideThe first active material layer has an area density of M when coated1The second active material layer has an area density of M when coated2，M1+ M2=M，M=200~220g/m2Wherein M is1: m =1:3, 1:2 or 2: 3.
8. A lithium ion battery comprising the positive electrode for a lithium ion battery according to any one of claims 1 to 7.
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| CN114725312A (en) * | 2022-04-29 | 2022-07-08 | 三一技术装备有限公司 | Dry-process pole piece and preparation method thereof |
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