CN112786838A - Manufacturing method of pre-lithium pole piece and battery - Google Patents
Manufacturing method of pre-lithium pole piece and battery Download PDFInfo
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- CN112786838A CN112786838A CN202110168939.9A CN202110168939A CN112786838A CN 112786838 A CN112786838 A CN 112786838A CN 202110168939 A CN202110168939 A CN 202110168939A CN 112786838 A CN112786838 A CN 112786838A
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- lithium
- plastic film
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- diaphragm
- battery
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 123
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000013589 supplement Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000002985 plastic film Substances 0.000 claims abstract description 44
- 229920006255 plastic film Polymers 0.000 claims abstract description 44
- 239000011888 foil Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 229920006267 polyester film Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 238000004804 winding Methods 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for manufacturing a pre-lithium pole piece and a battery, the method for manufacturing the pre-lithium pole piece utilizes a plastic film to cover the edge of a negative pole diaphragm and a hollow foil area, a lithium supplement material can be covered with most of the area of the negative pole diaphragm, the edge parts of two sides of the lithium supplement material can be covered on the plastic film, and the boundary line of the plastic film and the negative pole diaphragm is a straight line, when the plastic film is peeled off, the lithium supplement material covering the plastic film is peeled off together with the plastic film, and therefore, even if the edge of the lithium supplement material is not flat, most of the lithium supplement material is left on the surface of the negative electrode diaphragm, and the edge of the lithium supplement material left on the surface of the negative electrode diaphragm is straight and cannot exceed the area where the negative electrode diaphragm is located, so that the lithium supplement amount of the negative electrode pole piece can be accurately controlled, and the pre-lithium pole piece with excellent performance is obtained, therefore, the energy density of the battery is high, and the cycle life of the battery is long.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a manufacturing method of a pre-lithium pole piece and a battery.
Background
The improvement of the energy density and the cycle life of the battery is a main target of battery development, the iron phosphate lithium battery is highly emphasized due to high safety performance and excellent cycle performance, however, the energy density of a battery cell hardly reaches 200Wh/kg, but the requirement of high energy density can be met through the optimized design of the battery cell, and the premise is that the technical barrier of rapid attenuation of the capacity of a thick electrode must be overcome.
At present, the most easily realized technology of 200Wh/kg target is a pre-lithiation technology of lithium-coated metal lithium foil, two layers of 2-6 μm ultrathin lithium foils with an A/B surface are generally coated on a negative electrode diaphragm of a negative electrode, active lithium consumed by SEI film formation is compensated, and therefore long-service life cycle and high energy density are realized, however, a phenomenon of irregular transverse width is formed by extrusion deformation of a calender in a regular incoming lithium belt, so that a part of the lithium belt in a lamination stage is attached to a current collector outside the negative electrode diaphragm, and the amount of lithium supplement cannot be accurately controlled, and the performance of a battery is influenced.
Disclosure of Invention
The invention aims to provide a manufacturing method of a pre-lithium pole piece and a battery, which can prevent lithium metal from being attached to a negative current collector, realize accurate control on lithium supplement amount and enable the battery to have higher energy density and longer cycle life.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the method for manufacturing the pre-lithium pole piece comprises the following steps:
s1, providing a negative pole piece and a plastic film, wherein the negative pole piece comprises a negative pole current collector and a negative pole diaphragm coated on the surface of the negative pole current collector, the area of the negative pole current collector, which is not covered by the negative pole diaphragm, is a hollow foil area, and the hollow foil areas are positioned on two sides of the negative pole diaphragm;
s2, enabling the plastic film to completely cover the empty foil area through a rolling process, enabling the plastic film to cover the edges of two sides of the negative electrode diaphragm, and enabling a boundary of the plastic film and the negative electrode diaphragm to be a straight line;
s3, providing a lithium supplement material, and enabling the lithium supplement material to be combined with the negative electrode membrane through a combination process, wherein two sides of the lithium supplement material at least cover the edge of the plastic membrane;
and S4, peeling the plastic film to obtain the pre-lithium electrode sheet.
In a preferred embodiment of the present invention, the width of the plastic film covering one side of the negative electrode film piece is 0.1mm to 5 mm.
In a preferred embodiment of the present invention, the lithium supplement material is lithium powder or a lithium ribbon.
In a preferred embodiment of the present invention, the negative electrode sheet is dried before step S2.
On the other hand, a battery is provided, which comprises a positive pole piece and the pre-lithium pole piece manufactured by the manufacturing method of the pre-lithium pole piece in any technical scheme.
In a preferred embodiment of the present invention, the positive electrode sheet includes a positive electrode current collector and a positive electrode film coated on the surface of the positive electrode current collector, and the capacity of the negative electrode film per unit area/the capacity of the positive electrode film per unit area is 1.16 to 2.16, (the capacity of the negative electrode film per unit area-the lithium coating mass per unit area × 3861.3mAh/g × 80%)/the capacity of the positive electrode film per unit area is not less than 1.06.
In a preferable embodiment of the present invention, the lithium supplement amount is 0.5 to 8% of the mass of the positive electrode membrane.
As a preferable solution of the present invention, the second snap-gauge includes a first segment and a second segment that are arranged at an interval, and the buckle is arranged in the middle of the first snap-gauge and located between the first segment and the second segment.
As a preferable scheme of the present invention, the battery further includes a separator, and the positive electrode sheet, the pre-lithium electrode sheet, and the separator are wound by a winding machine into a winding core.
As a preferable aspect of the present invention, the battery further includes a case, and the winding core is disposed in the case.
The invention has the beneficial effects that:
the method for manufacturing the pre-lithium pole piece comprises the steps of covering the edge of a negative pole diaphragm and a blank foil area by using a plastic film, covering a lithium supplement material with most of the area of the negative pole diaphragm, covering the edge parts of two sides of the lithium supplement material on the plastic film, wherein the boundary between the plastic film and the negative pole diaphragm is a straight line, and peeling the plastic film, wherein the lithium supplement material covered on the plastic film is peeled along with the plastic film, so that even if the edge of the lithium supplement material is not flat, most of the lithium supplement material is remained on the surface of the negative pole diaphragm, and the edge of the lithium supplement material remained on the surface of the negative pole diaphragm is flat and cannot exceed the area where the negative pole diaphragm is located, so that the lithium supplement amount of the negative pole piece can be accurately controlled, the pre-lithium pole piece with excellent performance is obtained, and the energy density of a battery is high, and the cycle life.
Drawings
FIG. 1 is a schematic structural view of a pre-lithium electrode sheet according to an embodiment of the present invention before peeling a plastic film;
fig. 2 is a top view of fig. 1.
In the figure:
1. a negative pole piece; 11. a negative current collector; 12. a negative electrode diaphragm; 2. a plastic film; 3. and (5) supplementing lithium materials.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In the present invention, unless otherwise expressly stated or limited, "above" or "below" a first feature means that the first and second features are in direct contact, or that the first and second features are not in direct contact but are in contact with each other via another feature therebetween. Also, the word "over" a first feature or feature in a second feature may include the word "over" or "over" the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature "under" a second feature may include a first feature that is directly under and obliquely under the second feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
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, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
As shown in fig. 1 and fig. 2, the method for manufacturing a pre-lithium electrode sheet of the present embodiment includes the following steps:
s1, providing a negative pole piece 1 and a plastic film 2, wherein the negative pole piece 1 comprises a negative pole current collector 11 and a negative pole diaphragm 12 coated on the surface of the negative pole current collector 11, the area of the negative pole current collector 11 which is not covered by the negative pole diaphragm 12 is a hollow foil area, and the hollow foil area is positioned on two sides of the negative pole diaphragm 12;
s2, enabling the plastic film 2 to completely cover the empty foil area through a rolling process, enabling the plastic film 2 to cover the edges of two sides of the negative electrode diaphragm 12, and enabling a boundary of the plastic film 2 and the negative electrode diaphragm 12 to be a straight line;
s3, providing a lithium supplement material 3, and enabling the lithium supplement material 3 to be combined with the negative electrode membrane 12 through a combination process, wherein two sides of the lithium supplement material 3 at least cover the edge of the plastic film 2;
and S4, peeling the plastic film 2 to obtain the pre-lithium electrode plate.
In the method for manufacturing the pre-lithium pole piece, the plastic film 2 is covered on the edge of the negative pole membrane 12 and the empty foil area, the lithium supplement material 3 is covered with most of the area of the negative pole membrane 12, the edge parts of two sides of the lithium supplement material 3 are covered on the plastic film 2, and the boundary line between the plastic film 2 and the negative pole membrane 12 is a straight line, and after the plastic film 2 is peeled, the lithium supplement material 3 covered on the plastic film 2 is peeled along with the plastic film 2, so that even if the edge of the lithium supplement material 3 is not flat, most of the lithium supplement material 3 is left on the surface of the negative pole membrane 12, and the edge of the lithium supplement material 3 left on the surface of the negative pole membrane 12 is flat and does not exceed the area of the negative pole membrane 12, so that the lithium supplement amount of the negative pole piece 1 can be accurately controlled, and the pre-lithium pole piece with excellent performance is obtained.
It should be noted that the thicknesses of the components in fig. 1 do not represent the real thickness ratios, but are schematic diagrams for clearly showing the structure of the pre-lithium electrode sheet.
In fig. 2, it should be noted that, in order to show the negative electrode diaphragm 12 for understanding the structure of the pre-lithium pole piece, the area of the lithium supplement material 3 is reduced appropriately, and actually, the negative electrode diaphragm 12 cannot be observed in the top view of fig. 1.
Preferably, the plastic film 2 has a width of 0.1mm to 5mm on the side covering the negative electrode film 12. The plastic film 2 covered on the surface of the negative electrode diaphragm 12 can reduce the area of the lithium-replenishing area of the negative electrode diaphragm 12, so the plastic film 2 is not suitable for covering too many negative electrode diaphragms 12, and the covering width of 0.1 mm-5 mm can ensure that the negative electrode diaphragm 12 with enough area can be covered by the lithium-replenishing material 3.
On the pre-lithium pole piece, the final form of the lithium supplement material 3 is an ultrathin lithium foil with the thickness of 2-6 mu m, and the initial form of the lithium supplement material 3 can be a lithium belt or lithium powder.
When the lithium supplement material 3 is a lithium belt, the lithium belt is manufactured into an ultrathin lithium foil through a calendar and is attached to the film to form a lithium-carrying transfer film, and the lithium-carrying transfer film and the negative pole piece 1 are combined through a combining mechanism to enable the lithium foil to be combined with the negative pole diaphragm 12. In addition, also can fully extend the lithium area that the supplied materials is thicker for more even tiling on the surface of negative pole diaphragm 12 after the thinner lithium piece, then cold-press through the pair roller and make the lithium piece adhere to the surface of negative pole diaphragm 12 and form one deck lithium metal, the actual thickness of lithium piece can be controlled after the lithium area that the supplied materials is thicker fully extends, and then control the lithium quality of mending comparatively accurately.
When the lithium supplement material 3 is in the initial form of lithium powder, the lithium powder can be uniformly distributed on the surface of the negative electrode diaphragm 12 by a vibration method, and then the lithium powder is adhered to the surface of the negative electrode diaphragm 12 by cold pressing with a pair of rollers to form a layer of lithium metal. In addition, the lithium can be supplemented by directly depositing the lithium powder by an electric field, so that the danger caused by flying of the lithium powder is avoided.
Preferably, the plastic film 2 is one or a combination of two or more of a polyethylene film, a polyvinyl chloride film, a polystyrene film, a polyester film, nylon, or a polypropylene film. The plastic film 2 may be adjusted according to the composition of the negative electrode film 12 so that the form of the negative electrode film 12 is not damaged when it is peeled off.
Preferably, before step S2, the negative electrode sheet 1 is dried, so that the moisture content of the negative electrode diaphragm 12 is adjusted to a specific range, and the negative electrode diaphragm 12 can maintain stable form during subsequent processing, and is also convenient for being combined with the lithium supplement material 3.
The embodiment of the invention also provides a battery, which comprises a positive pole piece and the pre-lithium pole piece manufactured by adopting the manufacturing method of the pre-lithium pole piece of any one embodiment, wherein the pre-lithium pole piece enables an SEI film formed by the battery to be more uniform, and the battery has high energy density and long cycle life.
Preferably, the positive electrode sheet comprises a positive electrode current collector and a positive electrode membrane coated on the surface of the positive electrode current collector, and the capacity of the negative electrode membrane per unit area/the capacity of the positive electrode membrane per unit area is 1.16-2.16, (the capacity of the negative electrode membrane per unit area-the lithium coating mass per unit area x 3861.3mAh/g x 80%)/the capacity of the positive electrode membrane per unit area is more than or equal to 1.06. Wherein 3861.3mAh/g is the theoretical gram capacity of lithium metal.
The negative electrode diaphragm 12 needs to have enough vacant sites to receive lithium ions coming out of the positive electrode diaphragm, so that the capacity of the negative electrode diaphragm per unit area needs to be larger than that of the positive electrode diaphragm per unit area, thereby effectively reducing the capacity loss of the battery and ensuring the cycle life and storage life of the battery. Because partial vacancy on the negative electrode membrane 12 after lithium supplement is occupied by the lithium supplement material 3, the vacancy is reduced, the vacancy which is inserted by the lithium supplement material 3 needs to be subtracted to serve as the total available vacancy, but the capacity of lithium metal in the lithium supplement material 3 is difficult to be fully exerted, when the battery is designed, different positive and negative electrode capacities are designed according to 80% of the capacity of the lithium metal in the lithium supplement material 3, the battery with better cycle life and storage life can be obtained, and the energy density can be improved by more than 8%.
The capacity of the negative electrode film per unit area is defined as the negative electrode coating mass × the negative electrode active material mass percentage (i.e., the mass percentage of the negative electrode active material in the negative electrode film 12) × the gram capacity of the negative electrode active material per unit area; the capacity of the positive electrode sheet per unit area is defined as the positive electrode coating mass × the positive electrode active material mass percentage (i.e., the mass percentage of the positive electrode active material in the positive electrode sheet) × the gram capacity of the positive electrode active material.
The lithium coating quality per unit area can be obtained according to the formula, and the total lithium coating quality is preferably 0.5-8% of the mass of the positive electrode membrane.
Preferably, the battery also comprises a diaphragm, and the positive pole piece, the pre-lithium pole piece and the diaphragm are wound into a winding core through a winding machine, so that the production efficiency is higher.
Further, the battery also comprises a shell, and the winding core is arranged in the shell. The shape of the shell can be cylindrical or square, and the manufactured battery can be a button battery, a cylindrical battery or a square battery.
Reference throughout this specification to the description of the terms "preferred," "further," or the like, as used in describing preferred embodiments of the present invention, means that a particular feature, structure, material, or characteristic described in connection with the example or illustration is included in at least one example or illustration of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above examples are only intended to illustrate the details of the invention, which is not limited to the above details, i.e. it is not intended that the invention must be implemented in such detail. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A manufacturing method of a pre-lithium pole piece is characterized by comprising the following steps:
s1, providing a negative pole piece and a plastic film, wherein the negative pole piece comprises a negative pole current collector and a negative pole diaphragm coated on the surface of the negative pole current collector, the area of the negative pole current collector, which is not covered by the negative pole diaphragm, is a hollow foil area, and the hollow foil areas are positioned on two sides of the negative pole diaphragm;
s2, enabling the plastic film to completely cover the empty foil area through a rolling process, enabling the plastic film to cover the edges of two sides of the negative electrode diaphragm, and enabling a boundary of the plastic film and the negative electrode diaphragm to be a straight line;
s3, providing a lithium supplement material, and enabling the lithium supplement material to be combined with the negative electrode membrane through a combination process, wherein two sides of the lithium supplement material at least cover the edge of the plastic membrane;
and S4, peeling the plastic film to obtain the pre-lithium electrode sheet.
2. The method for manufacturing the pre-lithium pole piece according to claim 1, wherein the width of one side of the plastic film covering the negative electrode diaphragm is 0.1-5 mm.
3. The method for manufacturing the pre-lithium pole piece according to claim 1, wherein the lithium supplement material is lithium powder or a lithium tape.
4. The method for manufacturing the pre-lithium pole piece according to claim 1, wherein the plastic film is one or a combination of more than two of a polyethylene film, a polyvinyl chloride film, a polystyrene film, a polyester film, nylon or a polypropylene film.
5. The method for manufacturing the pre-lithium pole piece according to claim 1, wherein the negative pole piece is dried before step S2.
6. A battery, characterized by comprising a positive electrode plate and a pre-lithium electrode plate manufactured by the manufacturing method of the pre-lithium electrode plate according to any one of claims 1 to 5.
7. The battery according to claim 6, wherein the positive electrode sheet comprises a positive electrode current collector and a positive electrode membrane coated on the surface of the positive electrode current collector, and the capacity of the negative electrode membrane per unit area/the capacity of the positive electrode membrane per unit area is 1.16-2.16, (the capacity of the negative electrode membrane per unit area-the lithium coating mass per unit area x 3861.3mAh/g x 80%)/the capacity of the positive electrode membrane per unit area is not less than 1.06.
8. The battery of claim 7, wherein the mass of lithium supplement is 0.5-8% of the mass of the positive electrode membrane.
9. The battery of claim 6, further comprising a separator, wherein the positive electrode sheet, the pre-lithium electrode sheet, and the separator are wound into a roll core by a winder.
10. The battery of claim 9, further comprising a housing, the jellyroll being disposed within the housing.
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