CN218867198U - Battery and electric equipment - Google Patents
Battery and electric equipment Download PDFInfo
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- CN218867198U CN218867198U CN202223489032.1U CN202223489032U CN218867198U CN 218867198 U CN218867198 U CN 218867198U CN 202223489032 U CN202223489032 U CN 202223489032U CN 218867198 U CN218867198 U CN 218867198U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The embodiment of the application discloses battery and consumer, wherein the battery includes: the electrode assembly comprises a negative electrode plate, a diaphragm and a positive electrode plate which are sequentially stacked; the diaphragm comprises a ceramic composite layer, a first conducting layer and a lithium supplementing layer which are sequentially stacked, wherein the first conducting layer is arranged between the ceramic composite layer and the lithium supplementing layer, and is arranged on one surface of the ceramic composite layer. According to the application, the battery is pre-lithiated by utilizing the lithium supplement layer, and meanwhile, an electronic conductive path is formed among the lithium supplement layer, the first conductive layer and the negative pole piece or among the lithium supplement layer, the first conductive layer and the positive pole piece, so that the number of the electronic conductive paths in the battery is increased, the pre-lithiation utilization rate and the pre-lithiation efficiency of the battery are improved, the first charge-discharge efficiency of the battery is improved, the cycle life of the secondary battery is prolonged, and the multiplying power performance of the battery is finally improved.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a battery and electric equipment.
Background
With the popularization of new energy vehicles and the rapid development of consumer electronics, the demand of batteries is increasing, and the development of batteries with longer cycle life and higher energy density has also become a research focus at present.
In the first charge and discharge process of the existing battery, a negative active material consumes a lithium source in a positive active material, and a layer of Solid Electrolyte Interface (SEI) film is formed on the surface of a negative active material layer, so that irreversible battery capacity loss is caused, and the first charge and discharge efficiency of the battery is influenced; meanwhile, along with the charge and discharge cycle use of the battery, the SEI film can be gradually thickened and even repaired to be damaged, active lithium in the positive active material is further consumed, so that the capacity attenuation and cycle life reduction of the battery are caused, and the rate capability of the battery is influenced. Therefore, how to improve the rate capability of the battery becomes an urgent problem to be solved.
SUMMERY OF THE UTILITY MODEL
The embodiment of the application provides a battery and electric equipment to promote the multiplying power performance of battery.
In order to solve the above technical problem, an embodiment of the present application discloses the following technical solutions:
on one hand, the application provides a battery, which comprises an electrode assembly and electrolyte, wherein the electrode assembly comprises a negative pole piece, a diaphragm and a positive pole piece which are sequentially stacked;
the diaphragm comprises a ceramic composite layer, a first conducting layer and a lithium supplementing layer which are sequentially stacked, wherein the first conducting layer is arranged between the ceramic composite layer and the lithium supplementing layer, and is arranged on one surface of the ceramic composite layer.
In addition or alternatively to one or more of the features disclosed above, the ceramic composite layer includes a first adhesive layer, a base film, a ceramic layer, and a second adhesive layer, which are sequentially stacked;
the first conducting layer is arranged on the surface of one side, away from the base film, of the first bonding layer, so that the first conducting layer and the lithium supplementing layer face the negative pole piece; alternatively, the first and second electrodes may be,
the first conducting layer is arranged on the surface of one side, away from the base film, of the second bonding layer, so that the first conducting layer and the lithium supplementing layer face the positive pole piece.
In addition to or as an alternative to one or more of the features disclosed above, the first conductive layer has a thickness H 1 μ m, satisfying: h is not less than 5 mu m 1 ≤40μm。
In addition to or in lieu of one or more of the features disclosed above, the lithium-supplementing layer has a thickness H 2 μ m, satisfying: h is not less than 1 mu m 2 ≤20μm。
In addition to or in lieu of one or more of the features disclosed above, a width of the lithium supplement layer is less than a width of the first conductive layer.
In addition, or alternatively, to one or more features disclosed above, further comprising: at least one second conductive layer arranged on a surface of the first conductive layer on a side facing the lithium supplement layer, the second conductive layer being disposed outside the lithium supplement layer in a width direction;
the second conductive layer has a thickness of H 3 μ m, satisfying: h is not less than 1 mu m 3 ≤20μm。
In addition to or in lieu of one or more of the features disclosed above, the electrode assembly is hot pressed such that an electron conductive path is formed between the lithium supplement layer, the first conductive layer, the second conductive layer, and the negative electrode tab; or alternatively
The electrode assembly adopts a hot-pressing mode so that an electronic conducting path is formed among the lithium supplement layer, the first conducting layer, the second conducting layer and the positive pole piece.
In addition to or in lieu of one or more of the features disclosed above, the base film has a thickness H 4 μ m, satisfying: h is less than or equal to 5 mu m 4 Less than or equal to 30 mu m; and/or the presence of a gas in the atmosphere,
the thickness of the ceramic layer is H 5 μ m, satisfying: h is not less than 1 mu m 5 Less than or equal to 10 mu m; and/or the presence of a gas in the gas,
the thickness of the first adhesive layer is H 6 μ m, satisfying: h is not less than 1 mu m 6 Less than or equal to 10 mu m; and/or the presence of a gas in the gas,
the thickness of the second adhesive layer is H 7 μ m, satisfying: h is not less than 1 mu m 7 ≤10μm。
In addition or alternatively to one or more features disclosed above, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector;
the thickness of the positive current collector is H a μ m, satisfying: h is not less than 5 mu m a Less than or equal to 30 mu m; and/or
The thickness of the positive active material layer is H b μ m, satisfying: h is more than or equal to 10 mu m b ≤100μm；
The negative pole piece comprises a negative current collector and a negative active material layer arranged on the negative current collector;
the thickness of the negative current collector is H c μ m, satisfying: h is not less than 1 mu m c Less than or equal to 20 mu m; and/or
The thickness of the negative active material layer is H d μ m, satisfying: h is more than or equal to 20 mu m d ≤140μm。
In another aspect, the present application further discloses a powered device, which includes a battery as defined in any one of the above-mentioned features, in addition to or instead of one or more of the above-mentioned features, as a power supply source for the powered device.
One of the above technical solutions has the following advantages or beneficial effects: this application is through setting up the benefit lithium layer in the diaphragm, in order to utilize and mend the lithium layer and carry out lithiation in advance to the battery, and simultaneously, this application still sets up first conducting layer in the diaphragm, so that mend the lithium layer, perhaps mend the lithium layer between first conducting layer and the negative pole piece, form electron conduction path between first conducting layer and the positive pole piece, in order to increase the quantity of electron conduction path in the battery, thereby avoid between benefit lithium layer and the negative pole piece or mend the electron conduction path between lithium layer and the positive pole piece when weakening battery lithiation in advance insufficient, improve battery lithium utilization ratio in advance and lithiation efficiency in advance, improve the first charge-discharge efficiency of battery, promote secondary battery's cycle life, finally promote the multiplying power performance of battery.
Drawings
The technical solution and other advantages of the present application will become apparent from the detailed description of the embodiments of the present application with reference to the accompanying drawings.
Fig. 1 is a schematic structural diagram of a battery according to an embodiment of the present application;
FIG. 2 is a schematic diagram of a diaphragm according to an embodiment of the present application;
FIG. 3 is a schematic diagram of an electrical conduction path of a battery according to one embodiment of the present application;
FIG. 4 is a schematic diagram of a battery according to a second embodiment of the present application;
FIG. 5 is a schematic diagram of a diaphragm according to a second embodiment of the present application;
fig. 6 is a schematic diagram of an electronic conduction path of a battery according to a second embodiment of the present application.
Detailed Description
In order to make the purpose, technical solution and advantages of the present application more clearly understood, the present application is further described in detail below with reference to the accompanying drawings and the detailed description. It should be understood that the detailed description and specific examples, while indicating the present application, are given by way of illustration only and not by way of limitation.
In the description of the present application, it is to be understood that the terms "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the present application and for simplicity in description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed in a particular orientation, and be operated in a particular manner, and are not to be construed as limiting the present application. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", may explicitly or implicitly include one or more of the described features. In the description of the present application, "plurality" means two or more unless specifically limited otherwise.
In the description of the present application, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; they may be mechanically coupled, directly coupled, or indirectly coupled through intervening agents, both internally and/or in any other manner known to those skilled in the art. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
In this application, unless expressly stated or limited otherwise, the first feature "on" or "under" the second feature may comprise direct contact of the first and second features, or may comprise contact of the first and second features not directly but through another feature in between. Also, the first feature being "on," "above" and "over" the second feature includes the first feature being directly on and obliquely above the second feature, or merely indicating that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature includes the first feature being directly above and obliquely above the second feature, or simply meaning that the first feature is at a lesser level than the second feature.
At present, in order to improve the first charge-discharge efficiency, energy density and cycle life of the battery, a prelithiation technology is adopted to supplement a lithium source consumed in the first charge-discharge and cycle use of a positive electrode active material. Currently mainstream lithium supplementation schemes can be divided into two major categories: (1) the lithium is supplemented to the positive pole piece, mainly some lithium-containing oxide additives, and the lithium supplementing mode has limited lithium supplementing quantity; (2) and (3) lithium supplement of the negative pole piece: generally, lithium powder or a lithium tape is directly combined with a negative electrode plate, but the lithium powder is not dispersed in a non-aqueous polar organic solvent such as N-methyl pyridine, so that the lithium powder cannot be mixed with positive and negative electrode slurry using the non-aqueous polar organic solvent, and the lithium tape can cause negative electrode extension or reverse stripping of the lithium tape from the negative electrode. The lithium supplement technologies have certain defects, and the defects are more beneficial to the battery.
In order to improve the problem, the application provides a diaphragm with a lithium supplement layer and a conducting layer, so that the diaphragm is arranged in a battery product with high energy density, the battery is subjected to pre-lithiation by utilizing the lithium supplement layer, and meanwhile, the number of electronic conducting paths in the battery is increased, so that the problem that the pre-lithiation of the battery is insufficient when the electronic conducting paths between the lithium supplement layer and a negative pole piece or between the lithium supplement layer and a positive pole piece are weakened is avoided, the pre-lithiation utilization rate and the pre-lithiation efficiency of the battery are improved, the first charge and discharge efficiency of the battery is improved, the cycle life of the secondary battery is prolonged, and the multiplying power performance of the battery is finally improved.
In an embodiment of the present application, as shown in fig. 1 to 6, the present application provides a battery 100, which includes an electrode assembly and an electrolyte, the electrode assembly includes a negative electrode tab 110, a separator 120, and a positive electrode tab 130, the negative electrode tab 110, the separator 120, and the positive electrode tab 130 are stacked.
I. Diaphragm
As shown in fig. 2 and 5, one feature of the battery 100 in the present application is that the separator 120 may include a ceramic composite layer 121, a first conductive layer 122 and a lithium supplement layer 123, which are sequentially stacked, the first conductive layer 122 is disposed between the ceramic composite layer 121 and the lithium supplement layer 123, and the first conductive layer 122 is disposed on one surface of the ceramic composite layer 121.
Here, the "first" of the first conductive layers 122 is only for distinguishing different conductive layers provided on the diaphragm 120, and is not intended to limit the number or order of the conductive layers.
The lamination means that the ceramic composite layer 121, the first conductive layer 122, and the lithium supplement layer 123 form a sandwich structure, and the first conductive layer 122 is a "core" in the sandwich structure.
The ceramic composite layer 121 has a surface facing the negative electrode tab 110 and a surface facing away from the negative electrode tab 110, and the first conductive layer 122 is disposed on one of the surfaces of the ceramic composite layer 121, which means that the first conductive layer 122 may be disposed on the surface of the ceramic composite layer 121 facing the negative electrode tab 110, such that the first conductive layer 122 and the lithium supplement layer 123 face the negative electrode tab 110; the first conductive layer 122 can be disposed on a surface of the ceramic composite layer 121 facing away from the negative electrode tab 110 such that the first conductive layer 122 and the lithium supplement layer 123 face the positive electrode tab 130.
It can be understood that, this application is through setting up lithium supplement layer 123 in diaphragm 120, in order to utilize lithium supplement layer 123 to carry out lithiation in advance to the battery, simultaneously, this application still sets up first conducting layer 122 in diaphragm 120, so that form electron conducting path between lithium supplement layer 123, first conducting layer 122 and the negative pole piece 110 or between lithium supplement layer 123, first conducting layer 122 and positive pole piece 130, in order to increase the quantity of electron conducting path in the battery, thereby avoid supplementing the battery and pre-lithiating inadequately when the electron conducting path between lithium supplement layer 123 and negative pole piece 110 or between lithium supplement layer 123 and positive pole piece 130 weakens, improve battery lithium utilization ratio in advance and pre-lithiation efficiency, improve the first charge-discharge efficiency of battery, promote secondary battery's cycle life, finally promote the multiplying power performance of battery.
In the embodiment of the present application, as shown in fig. 2 and 5, the ceramic composite layer 121 includes a first adhesive layer 1211, a base film 1212, a ceramic layer 1213, and a second adhesive layer 1214, which are sequentially stacked;
the first and second adhesive layers 1211 and 1214 are only used to distinguish different adhesive layers disposed in the ceramic composite layer 121, and are not limited to the number or sequence of the adhesive layers.
The lamination means that the first adhesive layer 1211, the base film 1212, the ceramic layer 1213 and the second adhesive layer 1214 form a sandwich structure, and the base film 1212 and the ceramic layer 1213 form a "core" of the sandwich structure.
Further, in the first embodiment of the present application, as shown in fig. 1 and fig. 2, the first conductive layer 122 is disposed on a surface of the first adhesive layer 1211 facing away from the base film 1212, so that the first conductive layer 122 and the lithium supplement layer 123 face the negative electrode plate 110, and thus an electronic conductive path can be formed between the conductive layer 122 and the lithium supplement layer 123 and the negative electrode plate 110, thereby increasing the number of electronic conductive paths in the battery.
In the second embodiment of the present application, as shown in fig. 4 and fig. 5, the first conductive layer 122 is disposed on the surface of the second adhesive layer 1214 away from the base film 1212, so that the first conductive layer 122 and the lithium supplement layer 123 face the positive electrode plate 130, and thus an electronic conductive path can be formed between the conductive layer 122 and the lithium supplement layer 123 and the positive electrode plate 130, thereby increasing the number of electronic conductive paths in the battery.
In the embodiment of the present application, the thickness of the first conductive layer 122 is H 1 μ m, satisfying: h is not less than 5 mu m 1 Less than or equal to 40 mu m. I.e., the thickness H of the first conductive layer 122 1 Can be controlled within the range of 5-40 μm. For example, the thickness H of the first conductive layer 122 1 May be in the range of 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, or any two thereof. It is worth to say that the thickness H 1 The above specific numerical values of (a) are given by way of example only, as long as any value within the range of 5 to 40 μm is within the scope of the present application. By varying the thickness H of the first conductive layer 122 in this application 1 The thickness is controlled within the range of 5-40 μm to ensure the electronic conduction effect of the first conductive layer 122, and further ensure the pre-lithiation effect of the battery, so as to improve the pre-lithiation utilization rate and pre-lithiation efficiency of the battery, and finally improve the multiplying power performance of the battery.
Further, the first conductive layer 122 includes, but is not limited to, carbon black, carbon fiber, carbon nanotube, graphene, acetylene black, and the like. The above-mentioned conductive materials may be used alone or in any combination.
In the embodiment of the present application, the thickness of the lithium supplement layer 123 is H 2 μ m, satisfying: h is not less than 1 mu m 2 Less than or equal to 20 mu m. I.e. thickness H of lithium supplement layer 123 2 Can be controlled within the range of 1 to 20 μm. For example, the thickness H of the lithium supplement layer 123 2 The thickness may be in the range of 1 μm, 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, or 20 μm, or any two thereof. It is worth to say that the thickness H 2 The above specific numerical values of (a) are given by way of example only, as long as any value within the range of 1 to 20 μm is within the scope of the present application. By adding lithium layer 123 of thickness H in this application 2 The thickness of the diaphragm 120 is controlled within the range of 1-20 μm, so that the lithium supplement layer 123 has a good lithium supplement effect and an electronic conduction effect while the thickness of the diaphragm 120 in the application is ensured, and further the pre-lithiation effect of the battery is ensured, so that the pre-lithiation utilization rate and the pre-lithiation efficiency of the battery are improved, and the multiplying power performance of the battery is finally improved.
In the embodiment of the present application, the width of the lithium supplement layer 123 is smaller than that of the first conductive layer 122, so as to facilitate the subsequent arrangement of the second conductive layer, thereby further increasing the electron conduction path in the battery.
Further, the lithium supplement layer 123 includes, but is not limited to, elemental lithium, lithium silicon alloy, lithium nickel lithium rich, lithium iron lithium rich, lithium aluminum alloy, lithium oxide, lithium vanadyl salt, lithium magnesium alloy, lithium zinc alloy, lithium copper alloy, and the like. The lithium-supplementing materials can be used singly or in any combination.
Preferably, the lithium supplement material may form the lithium supplement layer 123 on the first conductive layer 122 by an atomic layer deposition technique or a coating technique.
In the embodiment of the present application, as shown in fig. 2 and 5, the diaphragm 120 further includes: at least one second conductive layer 124, the second conductive layer 124 is arranged on the surface of the first conductive layer 122 on the side facing the lithium supplement layer 123, and the second conductive layer 124 is disposed on the outer side of the lithium supplement layer 123 in the width direction;
as can be understood, in the present application, the second conductive layer 124 is disposed in the separator, so that an electron conductive path is formed between the lithium supplement layer 123, the first conductive layer 122, the second conductive layer 124 and the negative electrode tab 110 or between the lithium supplement layer 123, the first conductive layer 122, the second conductive layer 124 and the positive electrode tab 130, so as to further increase the number of electron conductive paths in the battery, further improve the pre-lithium utilization rate and the pre-lithiation efficiency of the battery, and finally improve the rate capability of the battery.
Further, the thickness of the second conductive layer 124 is H 3 μ m, satisfying: h is not less than 1 mu m 3 Less than or equal to 20 mu m. I.e., the thickness H of the second conductive layer 124 3 Can be controlled within the range of 1 to 20 μm. For example, the thickness H of the second conductive layer 124 3 The thickness may be in the range of 1 μm, 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, or 20 μm, or any two thereof. It is worth noting that the thickness H 3 The above specific numerical values of (a) are given by way of example only, as long as any value within the range of 1 to 20 μm is within the scope of the present application. By varying the thickness H of the second conductive layer 124 in this application 3 The thickness is controlled within the range of 1-20 μm to ensure the electronic conduction effect of the second conductive layer 124, and further ensure the pre-lithiation effect of the battery, so as to improve the pre-lithiation utilization rate and pre-lithiation efficiency of the battery, and finally improve the multiplying power performance of the battery.
In a preferred embodiment of the present application, the second conductive layer 124 and the lithium supplement layer 123 have an overlapping region therebetween, and the width of the overlapping region is not greater than 0.5mm.
Further, the second conductive layer 124 includes, but is not limited to, carbon black, carbon fiber, carbon nanotube, graphene, acetylene black, and the like. The above-mentioned conductive materials may be used alone or in any combination.
In the first embodiment of the present application, the electrode assembly is hot-pressed to make the lithium supplement layer 123, the first conductive layer 122, the second conductive layer 124 and the negative electrode tab 110 closely contact with each other, so that an electronic conduction path is formed between the lithium supplement layer 123, the first conductive layer 122, the second conductive layer 124 and the negative electrode tab 110;
specifically, as shown in fig. 3, in the present application, an electronic conduction path is formed between the lithium supplement layer 123 and the negative electrode plate 110, an electronic conduction path is formed between the lithium supplement layer 123, the first conduction layer 122, the second conduction layer 124 and the negative electrode plate 110, and an electronic conduction path is formed between the lithium supplement layer 123, the second conduction layer 124 and the negative electrode plate 110, so as to ensure that the battery of the present application has an adequate electronic conduction path during the pre-chemical process, ensure the pre-lithiation of the battery, improve the pre-lithiation utilization rate and the pre-lithiation efficiency of the battery, and finally improve the rate capability of the battery.
In the second embodiment of the present application, the electrode assembly is hot-pressed, so that the lithium supplement layer 123, the first conductive layer 122, the second conductive layer 124 and the positive electrode tab 130 are in close contact with each other, and an electronic conduction path is formed between the lithium supplement layer 123, the first conductive layer 122, the second conductive layer 124 and the positive electrode tab 130.
Specifically, as shown in fig. 6, in the present application, an electronic conduction path is formed between the lithium supplement layer 123 and the positive electrode plate 130, an electronic conduction path is formed between the lithium supplement layer 123, the first conduction layer 122, the second conduction layer 124 and the positive electrode plate 130, and an electronic conduction path is formed between the lithium supplement layer 123, the second conduction layer 124 and the positive electrode plate 130, so as to ensure that the battery of the present application has a sufficient electronic conduction path when it is pre-chemical, ensure that the pre-lithiation of the battery is performed, improve the pre-lithiation utilization rate and the pre-lithiation efficiency of the battery, improve the first charge-discharge efficiency of the battery, and finally improve the rate capability of the battery.
In the embodiment of the present application, the thickness of the base film 1212 is H 4 μ m, satisfying: h is not less than 5 mu m 4 Less than or equal to 30 mu m. I.e., thickness H of base film 1212 4 Can be controlled within the range of 5-30 μm. For example, thickness H of base film 1212 4 May be in the range of 5 μm, 7.5 μm, 10 μm, 12.5 μm, 15 μm, 17.5 μm, 20 μm, 22.5 μm, 25 μm, 27.5 μm, 30 μm or any two thereof. It is worth noting that the thickness H 4 The above specific numerical values of (a) are given only by way of example, as long as any value within the range of 5 to 30 μm is within the scope of protection of the present application.
Further, the base film 1212 includes, but is not limited to, PP film, PE film, and the like. The material of the base film 1212 may be used alone or in any combination.
In the embodiment of the present application, the ceramic layer 1213 has a thickness H 5 μ m, satisfying: h is less than or equal to 1 mu m 5 Less than or equal to 10 mu m. I.e., the thickness H of the ceramic layer 1213 5 Can be controlled within the range of 1-10 μm. For example, the thickness H of the ceramic layer 1213 5 The thickness may be in the range of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or any two thereof. It is worth to say that the thickness H 5 The above specific numerical values of (a) are given by way of example only, as long as any value within the range of 1 to 10 μm is within the scope of the present application.
In the embodiment of the present application, the thickness of the first adhesive layer 1211 is H 6 μ m, satisfying: h is not less than 1 mu m 6 Less than or equal to 10 mu m. I.e., the thickness H of the first adhesive layer 1211 6 Can be controlled within the range of 1-10 μm. For example, the thickness H of the first adhesive layer 1211 6 The thickness may be in the range of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or any two thereof. It is worth noting that the thickness H 6 The above specific numerical values of (a) are given by way of example only, as long as any value within the range of 1 to 10 μm is within the scope of the present application.
Further, the first adhesive layer 1211 includes, but is not limited to, polyvinylidene fluoride resin, polymethyl methacrylate, styrene butadiene rubber, and silica sol. The above-mentioned adhesive materials may be used alone or in any combination.
In the embodiment of the present application, the thickness of the second adhesive layer 1214 is H 7 μ m, satisfying: h is less than or equal to 1 mu m 7 Less than or equal to 10 mu m. I.e., the thickness H of the second adhesive layer 1214 7 Can be controlled within the range of 1-10 μm. For example, the thickness H of the second adhesive layer 1214 7 The thickness may be in the range of 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, or any two thereof. It is worth to say that the thickness H 7 The above specific numerical values of (a) are given by way of example only, as long as any value within the range of 1 to 10 μm is within the scope of the present application.
Further, the second adhesive layer 1214 includes, but is not limited to, polyvinylidene fluoride resin, polymethyl methacrylate, styrene-butadiene rubber, silica sol. The above-mentioned adhesive materials may be used alone or in any combination.
II. Positive pole piece
In an embodiment of the present application, a positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector.
1. Positive current collector
The kind of the positive electrode current collector is not particularly limited, and it may be any material known to be suitable for use as a positive electrode current collector, as long as the effects of the present application are not impaired.
In the embodiments of the present application, the positive electrode current collector includes, but is not limited to, aluminum foil, aluminum alloy foil, nickel alloy foil, titanium alloy foil. The materials of the positive electrode collector described above may be used alone or in any combination. In one embodiment, the positive current collector is an aluminum foil.
In the examples of the present application, the positive electrode current collector has a thickness of H a μ m, satisfying: h is less than or equal to 5 mu m a Less than or equal to 30 mu m. I.e. the thickness H of the positive current collector a Can be controlled within the range of 5-30 μm. For example, the thickness H of the positive electrode current collector a May be in the range of 5 μm, 7.5 μm, 10 μm, 12.5 μm, 15 μm, 17.5 μm, 20 μm, 22.5 μm, 25 μm, 27.5 μm, 30 μm or any two thereof. It is worth noting that the thickness H a The above specific numerical values of (a) are given only by way of example, as long as any value within the range of 5 to 30 μm is within the scope of protection of the present application.
2. Positive electrode active material layer
The positive electrode active material layer may be provided in one layer or multiple layers, and each of the multiple layers of positive electrode active material may contain the same or different positive electrode active materials. The positive electrode active material is any substance capable of reversibly inserting and extracting metal ions such as lithium ions.
Positive electrode active material
The positive electrode active material layer includes, but is not limited to, a positive electrode active material including, but not limited to, lithium manganate, lithium cobaltate, lithium iron phosphate, lithium manganese iron phosphate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate. The above-mentioned positive electrode active materials may be used alone or in any combination.
Positive electrode conductive agent
The kind of the positive electrode conductive agent in the present application is not limited, and any known conductive material may be used as long as the effects of the present application are not impaired.
In embodiments of the present application, the positive electrode conductive agent may include, but is not limited to, carbon black, carbon fiber, carbon nanotube, graphene, acetylene black. The above-mentioned positive electrode conductive materials may be used alone or in any combination.
Positive electrode binder
The type of the positive electrode binder used in the production of the positive electrode active material layer is not particularly limited as long as the effects of the present application are not impaired.
In embodiments of the present application, the positive electrode binder includes, but is not limited to, polyvinylidene fluoride, polyacrylonitrile, polyamide, vinylidene fluoride-hexafluoropropylene, polyester, polyamideimide, polycarbonate, polytetrafluoroethylene. The positive electrode binder may be used alone or in any combination thereof.
In the examples of the present application, the thickness of the positive electrode active material layer was H b μ m, satisfying: h is more than or equal to 10 mu m b Less than or equal to 100 mu m. I.e., the thickness H of the positive electrode active material layer b Can be controlled within the range of 10 to 100 μm. For example, the thickness H of the positive electrode active material layer b The thickness may be in the range of 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, or any two thereof. It is worth to say that the thickness H b The above specific numerical values of (a) are given by way of example only, as long as any value within the range of 10 to 100 μm is within the scope of the present application.
III, negative pole piece
In an embodiment of the present application, a negative electrode tab includes a negative electrode current collector and a negative active material layer disposed on the negative electrode current collector;
1. negative current collector
The kind of the negative electrode current collector is not particularly limited, and it may be any material known to be suitable for use as a negative electrode current collector, as long as the effects of the present application are not impaired.
In embodiments of the present application, the negative electrode current collector includes, but is not limited to, a copper foil, a stainless steel foil, a nickel foil, a carbon foil, a conductive resin film, a carbon fiber film, a carbon nanotube film, a graphene film. The above-mentioned negative electrode current collector materials may be used alone or in any combination. In one embodiment, the negative current collector is a copper foil. As used herein, the term "copper foil" includes copper alloy foils.
In the examples of the present application, the thickness of the negative electrode current collector is H c μ m, satisfying: h is not less than 1 mu m c Less than or equal to 20 mu m. I.e. the thickness H of the negative current collector c Can be controlled within the range of 1 to 20 μm. For example, the thickness H of the negative electrode current collector c The thickness may be in the range of 1 μm, 2 μm, 4 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, or 20 μm, or any two thereof. It is worth noting that the thickness H c The above specific numerical values of (a) are given by way of example only, as long as any value within the range of 1 to 20 μm is within the scope of the present application.
2. Negative electrode active material layer
The anode active material layer may be one or more layers, and each of the plurality of layers may contain the same or different anode active materials. In the examples of the present application, the chargeable capacity of the negative electrode active material is greater than the discharge capacity of the positive electrode active material to prevent lithium metal from being precipitated on the negative electrode sheet during charging.
Negative electrode active material
In embodiments of the present application, the negative active material layer includes, but is not limited to, a negative active material including, but not limited to, artificial graphite, natural graphite, mesocarbon microbeads, hard carbon, soft carbon, a silicon-based composite, a tin-based composite. The above-described anode active materials may be used alone or in any combination.
Negative electrode conductive agent
The kind of the anode conductive agent used in the production of the anode active material layer in the present application is not limited, and any known conductive material may be used as long as the effect of the present application is not impaired.
In an embodiment of the present application, the negative electrode active material layer includes, but is not limited to, a negative electrode conductive agent. The negative electrode conductive agent may include, but is not limited to, carbon black, carbon fiber, carbon nanotube, graphene, acetylene black, and the like. The above negative electrode conductive materials may be used alone or in any combination.
Negative electrode binder
The kind of the anode binder used in the production of the anode active material layer is not particularly limited as long as the effect of the present application is not impaired.
In an embodiment of the present application, the negative electrode active material layer includes, but is not limited to, a negative electrode binder. Negative binders include, but are not limited to, polyvinylidene fluoride, polyacrylonitrile, polyamide, vinylidene fluoride-hexafluoropropylene, polyester, polyamideimide, polycarbonate, polytetrafluoroethylene. The above-mentioned negative electrode binder may be used alone or in any combination.
In the examples of the present application, the thickness of the anode active material layer was H d μ m, satisfying: h is more than or equal to 20 mu m d Less than or equal to 140 mu m. I.e., the thickness H of the anode active material layer d Can be controlled within the range of 20-140 μm. For example, the thickness H of the anode active material layer d May be in the range of 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm or any two thereof. It is worth to say that the thickness H d The above specific numerical values of (a) are given by way of example only, as long as any value within the range of 20 to 140 μm is within the scope of the present application.
IV, electrolyte
The electrolyte used in the battery of the present application includes an electrolyte and a solvent dissolving the electrolyte.
The electrolyte is not particularly limited in the present application, and any known electrolyte may be used as long as the effects of the present application are not impaired. In the case of batteries, lithium salts are generally used. In embodiments of the present application, the electrolyte includes, but is not limited to, liPF 6 。
Meanwhile, the electrolyte content is not particularly limited in the present application as long as the effects of the present application are not impaired. For example, the concentration of the organic solvent may be 0.8mol/L to 2.2mol/L.
The solvent is not particularly limited in the present application, and any known solvent can be used as long as the effect of the present application is not impaired.
In the embodiments of the present application, the solvent includes, but is not limited to, ethylene Carbonate (EC), propylene Carbonate (PC), diethyl carbonate (DEC), ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), butylene Carbonate (BC), and Methyl Ethylene Carbonate (MEC). The above solvents may be used alone or in any combination thereof.
In the first embodiment of the present application, after the electrolyte is injected into the battery, the electrolyte provides an ion path for diffusion and migration of lithium ions. Under the action of an electronic conducting path, an ion path, a negative electrode pole piece and a lithium potential difference in the battery, lithium and electrolyte in the lithium supplementing layer are subjected to pre-lithiation reaction to form an SEI (solid electrolyte interphase) film layer on the surface of the negative electrode active material layer, so that the loss of positive electrode active lithium in the first charging and discharging process of the battery is compensated by the lithium supplementing layer, the first charging and discharging efficiency of the battery is improved, and the multiplying power performance of the battery is finally improved.
In the second embodiment of the present application, after the electrolyte is injected into the battery, the electrolyte provides an ion path for diffusion and migration of lithium ions. When the battery is charged and discharged for the first time, lithium ions in the lithium supplementing layer are diffused to the negative electrode of the battery through the ion passage, electrons in the lithium supplementing layer are transmitted to one side of the negative electrode of the battery through the electron conducting passage and the external circuit to generate a pre-lithiation reaction to form an SEI film layer on the surface of the negative electrode active material layer, so that the loss of positive active lithium in the first charging and discharging process of the battery is compensated by the lithium supplementing layer, the first charging and discharging efficiency of the battery is improved, and the multiplying power performance of the battery is finally improved.
On the other hand, the application also provides electric equipment, which comprises the battery as the power supply source of the electric equipment.
Specifically, the electric equipment can be an electric vehicle, an energy storage battery and the like.
Taking a lithium ion battery as an example and describing the preparation of the lithium ion battery with reference to specific examples, those skilled in the art will understand that the preparation method described in the present application is only an example, and any other suitable preparation method is within the scope of the present application.
The following describes performance evaluation according to examples and comparative examples of lithium ion batteries of the present application.
Example 1
1. Preparation of lithium ion battery
1. Preparation of positive pole piece
Mixing a positive electrode active material lithium iron phosphate, a conductive agent carbon black and a binding agent polyvinylidene fluoride according to a mass ratio of 96.5; and (3) uniformly coating the two sides of the positive electrode slurry on a carbon-coated aluminum foil of a positive electrode current collector, then transferring the positive electrode slurry to a 120 ℃ oven for drying, and then rolling, slitting and cutting into pieces to obtain the positive electrode piece.
2. Preparation of negative pole piece
Taking artificial graphite as a negative electrode active material, carbon black as a conductive agent, and polyvinylidene fluoride as a binder according to a mass ratio of 96:1:3, mixing, adding deionized water serving as a solvent, mixing, and stirring for a certain time to obtain uniform cathode slurry with certain fluidity; and uniformly coating the two sides of the negative electrode slurry on a negative electrode current collector copper foil, transferring the negative electrode slurry to a 110 ℃ oven for drying, and then rolling, slitting and cutting to obtain a negative electrode plate.
3. Preparation of the electrolyte
Ethylene Carbonate (EC), ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) were mixed in a volume ratio of 1 6 Mixing uniformly to prepare the electrolyte.
4. Preparation of the separator
Preparing the molten polyethylene resin into a crystalline film by using a film blowing process by adopting a dry process, and forming a base film with a slit-shaped porous structure by using biaxial stretching; then, sequentially coating a ceramic layer of Al2O3 and a first adhesive layer of polyvinylidene fluoride on one side of the base film, and only coating the first adhesive layer of polyvinylidene fluoride on the other side of the base film; then coating a first conductive layer on the first adhesive layer by using a coating technology; forming a lithium supplementing layer on the first conductive layer by depositing metal lithium by an atomic layer; and coating a second conductive layer on the first conductive layer and on two sides of the lithium supplement layer to form the diaphragm.
5. Preparation of lithium ion battery
Drying the negative pole piece and the positive pole piece prepared in the steps, assembling the negative pole piece, the diaphragm, the positive pole piece, the diaphragm and the negative pole piece into a battery cell together with the diaphragm by a lamination process according to the circulation sequence of the negative pole piece, the diaphragm, the positive pole piece, the diaphragm and the negative pole piece, carrying out hot pressing on the battery cell for 30s by adopting the hot pressing temperature of 95 ℃ and the hot pressing pressure of 550kgf, welding a positive pole aluminum tab and a negative pole copper nickel-plated tab on the hot-pressed battery cell, and putting the welded battery cell into a punched aluminum-plastic film for packaging; the lithium ion battery is prepared by pouring electrolyte and forming constant volume.
Wherein the thickness H of the first conductive layer 122 1 3 μm, thickness H of lithium supplement layer 123 2 Is 3 μm, the thickness H of the second conductive layer 124 3 3 μm, thickness H of base film 1212 4 A thickness H of the ceramic layer 1213 of 9 μm 5 Thickness H of the first adhesive layer 1211 of 3 μm 6 1 μm, thickness H of the second adhesive layer 1214 7 1 μm, thickness H of the positive electrode current collector a 12 μm, thickness H of the positive electrode active material layer b 75 μm, thickness H of the negative electrode collector c 6 μm, thickness H of the negative electrode active material layer d It was 79 μm.
2. Test method
1. Method for testing first charge performance of lithium ion battery
After the lithium ion battery is precharged, the lithium ion battery is stood for 30min at 25 ℃, then constant-current and constant-voltage charging is carried out until the voltage reaches 3.65V and the constant-voltage charging cutoff current reaches 0.05C, the first charging capacity (including the precharging capacity) is obtained, the lithium ion battery is stood for 10min, then constant-current discharging is carried out until the voltage reaches 2.0V, the first discharging capacity is obtained, and the first charging and discharging efficiency is calculated.
2. Method for testing cycle performance of lithium ion battery
And (2) standing the lithium ion battery for 30min at 25 ℃, then carrying out constant current discharge at a rate of 1C, standing for 10min, then carrying out constant current and constant voltage charge at a rate of 1C, standing for 10min, then carrying out full charge-full discharge cycle test, respectively recording the first charge-discharge capacity and the discharge capacity after 2000 cycles, and calculating the capacity retention rate =2000 cycle discharge capacity/the first discharge capacity multiplied by 100%.
Example 2
A lithium ion battery was prepared according to the method of example 1, while the lithium ion battery was tested according to the test method of example 1, except that:
thickness H of first conductive layer 122 1 4 μm, thickness H of the lithium supplement layer 123 2 Is 4 μm, and the thickness H of the second conductive layer 124 3 And was 4 μm.
Example 3
A lithium ion battery was prepared according to the method of example 1, while the lithium ion battery was tested according to the test method of example 1, except that:
thickness H of first conductive layer 122 1 5 μm, thickness H of the lithium-supplement layer 123 2 Is 5 μm, and the thickness H of the second conductive layer 124 3 Is 5 μm.
Example 4
A lithium ion battery was prepared according to the method of example 1, while the lithium ion battery was tested according to the test method of example 1, except that:
thickness H of first conductive layer 122 1 6 μm, thickness H of the lithium supplement layer 123 2 6 μm, thickness H of the second conductive layer 124 3 Is 6 μm.
Comparative example 1
A lithium ion battery was prepared according to the method of example 1, while testing the lithium ion battery according to the test method of example 1, except that:
the lithium supplement layer 123, the first conductive layer 122, and the second conductive layer 124 are not provided in the separator.
Comparative example 2
A lithium ion battery was prepared according to the method of example 1, while the lithium ion battery was tested according to the test method of example 1, except that:
the first conductive layer 122 and the second conductive layer 124 are not provided in the separator, and the thickness H of the lithium supplement layer 123 is set 2 Is 3 μm.
Comparative example 3
A lithium ion battery was prepared according to the method of example 1, while the lithium ion battery was tested according to the test method of example 1, except that:
the first conductive layer 122 and the second conductive layer 124 are not provided in the separator, and the thickness H of the lithium supplement layer 123 is set 2 And was 4 μm.
Comparative example 4
A lithium ion battery was prepared according to the method of example 1, while the lithium ion battery was tested according to the test method of example 1, except that:
the first conductive layer 122 and the second conductive layer 124 are not provided in the separator, and the thickness H of the lithium supplement layer 123 is set 2 Is 5 μm.
Comparative example 5
A lithium ion battery was prepared according to the method of example 1, while the lithium ion battery was tested according to the test method of example 1, except that:
the first conductive layer 122 and the second conductive layer 124 are not provided in the separator, and the thickness H of the lithium supplement layer 123 is set 2 And 6 μm.
3. Test results
Table 1 shows the thickness H of the first conductive layer 122 1 Thickness H of lithium-supplement layer 123 2 Thickness H of the second conductive layer 124 3 Thickness H of base film 1212 4 Thickness H of ceramic layer 1213 5 Thickness H of first adhesive layer 1211 6 Thickness H of second adhesive layer 1214 7 Thickness H of positive current collector a Thickness H of positive electrode active material layer b Thickness H of negative current collector c Thickness H of the negative electrode active material layer d Influence on the first charge-discharge performance and cycle performance of the lithium ion battery.
TABLE 1
The result shows that when the lithium supplement layer is arranged in the diaphragm, the first charge-discharge efficiency of the battery can be obviously improved, and when the lithium supplement layer, the first conductive layer and the second conductive layer are arranged in the diaphragm, the first charge-discharge efficiency of the battery can be further improved.
When the thickness H of the first conductive layer 122 is larger 1 The thickness H of the lithium supplement layer 123 is controlled within the range of 5-40 μm 2 The thickness H of the second conductive layer 124 is controlled within the range of 1 to 20 μm 3 The thickness H of the base film 1212 is controlled within the range of 1-20 μm 4 The thickness H of the ceramic layer 1213 is controlled within the range of 5 to 30 μm 5 The thickness H of the first adhesive layer 1211 is controlled within a range of 1 to 10 μm 6 The thickness H of the negative second adhesive layer 1214 is controlled within the range of 1-10 μm 7 The thickness H of the positive current collector is controlled within the range of 1-10 mu m a The thickness H of the positive electrode active material layer is controlled within the range of 5-30 μm b The thickness H of the negative current collector is controlled within the range of 10-100 mu m c The thickness H of the negative electrode active material layer is controlled within the range of 1-20 μm d When the thickness can be controlled within the range of 20-140 mu m, the first charge-discharge efficiency and the cycle performance of the battery can be further remarkably improved.
The above steps are provided only to help understand the method, structure and core idea of the present application. It will be apparent to those skilled in the art that various changes and modifications can be made herein without departing from the principles of the disclosure, and these changes and modifications also fall within the scope of the claims of the disclosure.
Claims (10)
1. A battery, comprising: the electrode assembly comprises a negative electrode plate, a diaphragm and a positive electrode plate which are sequentially stacked;
the diaphragm comprises a ceramic composite layer, a first conducting layer and a lithium supplementing layer which are sequentially stacked, wherein the first conducting layer is arranged between the ceramic composite layer and the lithium supplementing layer, and is arranged on one surface of the ceramic composite layer.
2. The battery according to claim 1, wherein the ceramic composite layer comprises a first adhesive layer, a base film, a ceramic layer, and a second adhesive layer, which are sequentially stacked;
the first conducting layer is arranged on the surface of one side, away from the base film, of the first bonding layer, so that the first conducting layer and the lithium supplementing layer face the negative pole piece; alternatively, the first and second electrodes may be,
the first conducting layer is arranged on the surface of one side, departing from the base film, of the second bonding layer, so that the first conducting layer and the lithium supplementing layer face the positive pole piece.
3. The battery of any of claims 1-2, wherein the first conductive layer has a thickness H 1 μ m, satisfying: h is not less than 5 mu m 1 ≤40μm。
4. The battery of any of claims 1-2, wherein the lithium-supplementing layer has a thickness H 2 μ m, satisfying: h is not less than 1 mu m 2 ≤20μm。
5. The battery of any of claims 1-2, wherein the width of the lithium supplement layer is less than the width of the first conductive layer.
6. The battery of any one of claims 1-2, further comprising: at least one second conductive layer arranged on a surface of the first conductive layer on a side facing the lithium supplement layer, the second conductive layer being disposed outside the lithium supplement layer in a width direction;
the second conductive layer has a thickness of H 3 μ m, satisfying: h is not less than 1 mu m 3 ≤20μm。
7. The battery of claim 6, wherein the electrode assembly is hot pressed such that an electron conduction path is formed between the lithium supplement layer, the first conductive layer, the second conductive layer, and the negative electrode tab; or alternatively
The electrode assembly adopts a hot-pressing mode so that an electronic conducting path is formed among the lithium supplement layer, the first conducting layer, the second conducting layer and the positive pole piece.
8. The battery of claim 2, wherein the base film has a thickness H 4 μ m, satisfying: h is not less than 5 mu m 4 Less than or equal to 30 mu m; and/or the presence of a gas in the gas,
the thickness of the ceramic layer is H 5 μ m, satisfying: h is not less than 1 mu m 5 Less than or equal to 10 mu m; and/or the presence of a gas in the gas,
the thickness of the first adhesive layer is H 6 μ m, satisfying: h is not less than 1 mu m 6 Less than or equal to 10 mu m; and/or the presence of a gas in the gas,
the thickness of the second adhesive layer is H 7 μ m, satisfying: h is not less than 1 mu m 7 ≤10μm。
9. The battery of claim 1, wherein the positive pole piece comprises a positive current collector and a positive active material layer disposed on the positive current collector;
the thickness of the positive current collector is H a μ m, satisfying: h is not less than 5 mu m a Less than or equal to 30 mu m; and/or
The thickness of the positive active material layer is H b μ m, satisfying: h is more than or equal to 10 mu m b ≤100μm；
The negative pole piece comprises a negative current collector and a negative active material layer arranged on the negative current collector;
the thickness of the negative current collector is H c μ m, satisfying: h is not less than 1 mu m c Less than or equal to 20 mu m; and/or
The thickness of the negative active material layer is H d μ m, satisfying: h is more than or equal to 20 mu m d ≤140μm。
10. An electric device comprising the battery according to any one of claims 1 to 9 as a power supply source for the electric device.
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| CN116230944B (en) * | 2023-05-05 | 2023-09-01 | 四川新能源汽车创新中心有限公司 | Thermal-insulation pre-lithiation functional layer and lithium ion battery thereof |
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