CN119812196A - Electrode assembly, preparation method, and battery - Google Patents
Electrode assembly, preparation method, and battery Download PDFInfo
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- CN119812196A CN119812196A CN202411862765.6A CN202411862765A CN119812196A CN 119812196 A CN119812196 A CN 119812196A CN 202411862765 A CN202411862765 A CN 202411862765A CN 119812196 A CN119812196 A CN 119812196A
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
本发明提供了一种电极组件及制备方法、电池，包括正极片、负极片和隔膜，正极片包括正极集流体和正极活性物质层，正极活性物质层包括第一区域和第二区域，第一区域位于正极片的卷绕内圈，第二区域位于正极片的卷绕外圈；正极活性物质层的第一区域设置有多条刻蚀线；正极片的第二区域设置有多个压花；本发明在第一区域进行刻蚀，刻蚀线的槽位可以增加保液量，同时可增加卷芯N/P值和圆弧区的CB值，避免极片析锂；在第二区域进行压花，压花可以有效改善正极片的正极活性物质层的厚度与密度，压花可以改善大面密度下的正极克容量发挥，压花可以储存更多的电解液，增加更多的接触面积和脱锂通道，有效提升倍放能力和动力学性能，改善电池首效。
The present invention provides an electrode assembly and a preparation method, and a battery, including a positive electrode sheet, a negative electrode sheet and a separator. The positive electrode sheet includes a positive electrode collector and a positive electrode active material layer. The positive electrode active material layer includes a first area and a second area. The first area is located at the inner winding circle of the positive electrode sheet, and the second area is located at the outer winding circle of the positive electrode sheet. The first area of the positive electrode active material layer is provided with multiple etching lines; the second area of the positive electrode sheet is provided with multiple embossings. The present invention etches in the first area, and the grooves of the etching lines can increase the liquid retention amount, and at the same time increase the N/P value of the winding core and the CB value of the arc area to avoid lithium precipitation of the electrode sheet; embossing is performed in the second area, and the embossing can effectively improve the thickness and density of the positive electrode active material layer of the positive electrode sheet, and the embossing can improve the positive electrode specific capacity under large surface density. The embossing can store more electrolyte, increase more contact area and lithium desorption channels, effectively improve the discharge capacity and dynamic performance, and improve the first effect of the battery.
Description
Technical Field
The invention relates to the technical field of high-energy-density batteries, in particular to an electrode assembly, a preparation method and a battery.
Background
As the energy density demand of the consumer market increases. The silicon-carbon material is the main stream development material at present, but the design development of high energy density requires higher silicon doping amount and higher positive electrode coating surface density. The higher surface density means thicker electrode plates, the thicker electrode plates can increase lithium ion charge transfer resistance, a lithium ion transmission path is increased, system dynamics is obviously deteriorated, when a quick charge test is carried out, local potential unbalance and lithium enrichment can be caused by quick charge, and lithium precipitation is caused, so that the polarization effect of a high-energy-density battery cell in a quick charge mode needs to be reduced, improvement on the dynamics of a positive electrode plate is needed, meanwhile, the liquid retention capacity of the positive electrode plate is always low aiming at a high-energy-density system, long cycle period is caused, water jump is easy, and the liquid retention performance of the battery cell needs to be improved. Therefore, how to overcome the above-mentioned technical problems and drawbacks becomes an important problem to be solved.
Disclosure of Invention
Aiming at the problems of lithium ion charge transfer resistance increase, obvious system dynamics deterioration and low lithium precipitation and liquid retention capacity caused by local potential imbalance in a positive plate of a current high-energy-density battery, the invention provides an electrode assembly, a preparation method and a battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
The first aspect of the invention provides an electrode assembly, which comprises a positive plate, a negative plate and a diaphragm, wherein the positive plate, the diaphragm and the negative plate are arranged in a stacked manner and are wound to form the electrode assembly;
The positive plate comprises a positive current collector and a positive active material layer coated on at least one side of the surface of the positive current collector, and the single-sided density of the positive active material layer is 120g/m 2~300g/m2;
The positive electrode active material layer comprises a first area and a second area, wherein the first area is positioned on a winding inner ring of the positive electrode plate, the second area is positioned on a winding outer ring of the positive electrode plate, a plurality of etching lines are arranged in the first area of the positive electrode active material layer along the thickness direction parallel to the positive electrode plate, and a plurality of embossments are arranged in the second area of the positive electrode plate.
Optionally, the winding number of the first area is 1/4-1/2 of the total winding number of the positive plate.
Optionally, the sum of the volumes of the etching areas of all the etching lines is 1% -2% of the volume of the positive electrode active material layer.
Optionally, the depth of the etching lines is 25% -40% of the thickness of the positive electrode active material layer, the distance between two adjacent etching lines is 0.5 mm-1.5 mm, and the width of each etching line is 60-105 μm.
Optionally, the depth of the etching lines is 30% -35% of the thickness of the positive electrode active material layer, the distance between two adjacent etching lines is 0.8-1.2 mm, and the width of each etching line is 75-90 μm.
Optionally, the winding number of the second area is 1/2-3/4 of the total winding number of the positive plate.
Alternatively, the sum of the volumes of all the embossed regions is 1.5% to 7% of the volume of the positive electrode active material layer.
Optionally, the embossed area occupies 10% -50% of the area of the second area.
Optionally, the depth of the embossing is 2% -10% of the thickness of the positive electrode active material layer along the thickness direction parallel to the positive electrode sheet.
Optionally, the single-sided density of the positive electrode active material layer is 200g/m 2~300g/m2;
The negative electrode plate precursor comprises a negative electrode current collector and a negative electrode active material layer coated on at least one side of the surface of the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material and CMC;
and the negative electrode plate precursor is subjected to high-temperature treatment to obtain the negative electrode plate, so that CMC in the negative electrode active material layer is carbonized to form conductive carbon black.
Optionally, the high-temperature treatment temperature of the cathode plate precursor is 200-300 ℃, and the high-temperature treatment time of the cathode plate precursor is 3-7h.
Optionally, the negative electrode active material comprises a silicon-carbon material, wherein the silicon content accounts for 3-15% of the mass of the silicon-carbon material.
The second aspect of the present invention provides a method for preparing an electrode assembly, comprising the steps of:
S1, acquiring a positive plate, a negative plate and a diaphragm;
S2, etching a plurality of etching lines in a first area of the positive electrode active material layer of the positive electrode plate, and pressing embossing in a second area of the positive electrode active material layer of the positive electrode plate;
S3, sequentially stacking and winding the positive plate, the diaphragm and the negative plate to form an electrode assembly, wherein the first area is located in a winding inner ring of the positive plate, and the second area is located in a winding outer ring of the positive plate.
A third aspect of the present invention provides a battery comprising a battery case, an electrolyte and an electrode assembly as described above, or an electrode assembly prepared by the method of preparing an electrode assembly as described above.
According to the electrode assembly provided by the invention, the first area of the positive electrode active material layer of the inner ring of the winding core is etched and marked, the liquid retention amount can be increased by the groove position of the etching line, the N/P value of the winding core can be increased, the N/P value loss of the inner ring of the winding core is compensated, the CB value of the circular arc area of the positive electrode plate can be obviously increased, the lithium precipitation problem caused by the low CB value of the electrode plate is avoided, the lithium precipitation problem of the circular arc area of the winding core can be improved by the groove position-lifted liquid retention amount of the etching line, the thickness and the density of the positive electrode active material layer of the outer ring of the winding core can be effectively improved by embossing the second area of the positive electrode active material layer of the winding core, the positive electrode gram capacity exertion under large area density can be improved by embossing, more electrolyte can be stored, more contact area can be increased, the lithium removing channel is increased, the double discharge capacity of the winding core and the dynamic performance of the winding core are effectively improved, and the first effect of a battery is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that need to be used in the description of the embodiments of the present invention will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic cross-sectional view of a positive plate according to an embodiment of the present invention;
FIG. 2 is a schematic top view of a positive plate according to an embodiment of the present invention;
FIG. 3 is a schematic cross-sectional view of a negative electrode sheet precursor provided in an embodiment of the present invention;
FIG. 4 is a schematic cross-sectional view of a negative electrode sheet according to an embodiment of the present invention;
FIG. 5 is a schematic cross-sectional view of an electrode assembly according to an embodiment of the present invention;
Reference numerals in the drawings of the specification are as follows:
100-electrode assembly, 1-positive plate, 11-positive current collector, 12-positive active material layer, 121-first region, 1211-etched line, 122-second region, 1221-embossed, 2-negative plate, 21-negative current collector, 22-negative active material layer, 221-CMC, 3-separator.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the description of the present invention, it should be understood that the terms "longitudinal," "radial," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like indicate orientations or positional relationships that are based on the orientation or positional relationships shown in the drawings, merely to facilitate describing the present invention and simplify the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
In the description of the present invention, unless explicitly stated or limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected, mechanically connected, electrically connected, directly connected, indirectly connected via an intervening medium, or in communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test methods used in the examples described below are conventional methods unless otherwise specified, and the materials, reagents, etc., used are commercially available reagents and materials unless otherwise specified.
As shown in fig. 1-2, in one embodiment, the first aspect of the present invention provides an electrode assembly 100, which includes a positive electrode sheet 1, a negative electrode sheet 2, and a separator 3, wherein the positive electrode sheet 1, the separator 3, and the negative electrode sheet 2 are stacked, and wound to form the electrode assembly 100;
The positive plate 1 comprises a positive electrode current collector 11 and a positive electrode active material layer 12 coated on at least one side of the surface of the positive electrode current collector 11, wherein the single-sided density of the positive electrode active material layer 12 is 120g/m 2~300g/m2;
The positive electrode active material layer 12 includes a first region 121 and a second region 122, the first region 121 is located at a winding inner ring of the positive electrode sheet 1, the second region 122 is located at a winding outer ring of the positive electrode sheet 1, a plurality of etching lines 1211 are provided along the first region 121 of the positive electrode active material layer 12 parallel to the thickness direction of the positive electrode sheet 1, and a plurality of embossments 1221 are provided at the second region 122 of the positive electrode sheet 1.
In the winding type winding core with the conventional structure, the current density of the inner ring of the winding core is larger, the polarization is larger, the winding tension of the winding core of the inner ring is larger, the problem of lower N/P value of the winding core is easily caused, and the curvature of the arc area of the positive plate 1 is large, so that the CB value is lower at the moment.
In an embodiment, the first area 121 of the positive electrode active material layer 12 of the inner ring of the winding core is etched and marked, so that the liquid retention amount of the groove of the etching line 1211 can be increased, the N/P value of the winding core can be increased, the N/P value loss of the inner ring of the winding core can be compensated, the CB value of the arc area of the positive electrode plate 1 can be obviously increased, the lithium precipitation problem caused by the low CB value of the positive electrode plate can be avoided, and the liquid retention amount of the groove of the etching line 1211 can be increased, so that the lithium precipitation problem of the arc area of the winding core can be improved.
Further, the length of the etched line 1211 is the same as the width of the first region 121, or the length of the etched line 1211 is slightly smaller than the width of the first region 121, so that the liquid retention amount is increased by the groove position of the etched line 1211.
In an embodiment, the second area 122 of the positive electrode active material layer 12 of the outer ring of the winding core is subjected to embossing 1221, the thickness and density of the positive electrode active material layer 12 of the positive electrode sheet 1 can be effectively improved by the embossing 1221, the positive electrode gram capacity exertion under the large area density can be improved by the embossing 1221, more electrolyte can be stored by the embossing 1221, more contact area is increased, the lithium removing channel is increased, the double discharging capacity of the winding core and the dynamic performance of the winding core are effectively improved, and the initial efficiency of the battery is improved.
Specifically, the embossments 1221 are formed by rolling the second region 122 of the positive electrode active material layer 12 using an embossing roller, and the embossments 1221 are formed in any one of a circle, a square, a diamond, a triangle, a hexagon, a trapezoid, and an ellipse, and in a preferred embodiment, the embossments 1221 are formed in a circular shape.
As shown in fig. 1-2, in one embodiment, the winding fold of the first region 121 is 1/4-1/2 of the total winding fold of the positive electrode sheet 1.
Specifically, the winding number of the first region 121 is any one point value or a range of any two point values of 1/4, 3/10, 7/20, 2/5, 9/20 or 1/2 of the total winding number of the positive electrode sheet 1, and in a preferred embodiment, the winding number of the first region 121 is 3/10-9/20 of the total winding number of the positive electrode sheet 1.
When the winding fold number of the first area 121 is 1/4-1/2 of the total winding fold number of the positive plate 1, the high capacity of the winding core can be maintained, meanwhile, the long cycle performance of the winding core is considered, the problem of lithium precipitation in the arc area of the positive plate 1 can be effectively solved, when the winding fold number of the first area 121 is smaller than 1/4 of the total winding fold number of the positive plate 1, the CB value change in the arc area of the positive plate 1 is not obvious, the lithium precipitation in the arc area is not obvious, and when the winding fold number of the first area 121 is larger than 1/2 of the total winding fold number of the positive plate 1, the problems of larger CB value in the arc area of the positive plate 1 and larger core capacity loss are caused.
As shown in fig. 1-2, in one embodiment, the sum of the volumes of the etched areas of all of the etched lines 1211 is 1% -2% of the volume of the positive electrode active material layer 12.
Specifically, the sum of the volumes of the etched regions of all the etched lines 1211 is any one point value or a range of any two point values of 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2% of the volume of the positive electrode active material layer 12. In a preferred embodiment, the sum of the volumes of the etched areas of all of the etched lines 1211 is 1.2% -1.8% of the volume of the positive electrode active material layer 12.
Specifically, when the sum of the volumes of the etching areas of all the etching lines 1211 is 1% -2% of the volume of the positive electrode active material layer 12, the high capacity of the winding core can be maintained, the long cycle performance of the winding core can be considered, the problem of lithium analysis in the arc area of the positive electrode sheet 1 can be effectively solved, when the sum of the volumes of the etching areas of all the etching lines 1211 is less than 1% of the volume of the positive electrode active material layer 12, the CB value change in the arc area of the positive electrode sheet 1 is not obvious, the lithium analysis in the arc area is not obvious, and when the sum of the volumes of the etching areas of all the etching lines 1211 is greater than 2% of the volume of the positive electrode active material layer 12, the problems of larger CB value in the arc area of the positive electrode sheet 1 and larger capacity loss of the winding core can be caused.
As shown in fig. 1-2, in one embodiment, the depth of the etched lines 1211 is 25% -40% of the thickness of the positive electrode active material layer 12, the distance between two adjacent etched lines 1211 is 0.5 mm-1.5 mm, and the width of the etched lines 1211 is 60 μm-105 μm.
Specifically, the depth of all the etched lines 1211 is a range of values consisting of any one point value or any two point values of 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40% of the thickness of the positive electrode active material layer 12.
Specifically, when the depth of the etched line 1211 is 25% -40% of the thickness of the positive electrode active material layer 12, the high capacity of the winding core can be maintained, the long cycle performance of the winding core can be considered, the problem of lithium analysis in the arc area of the positive electrode sheet 1 can be effectively solved, when the depth of the etched line 1211 is smaller than 25% of the thickness of the positive electrode active material layer 12, the current density of the inner ring of the winding core is larger, the polarization is larger, the winding tension of the winding core of the inner ring is larger, the problem of lower N/P value of the winding core is easily caused, and when the depth of the etched line 1211 is larger than 40% of the thickness of the positive electrode active material layer 12, the N/P value of the winding core is increased, but the high temperature performance of the winding core is deteriorated, and meanwhile the capacity loss of the winding core is obvious.
Specifically, the spacing between adjacent two etched lines 1211 is 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, or 1.5mm, or a range of values consisting of any two point values.
Specifically, when the interval between two adjacent etching lines 1211 is 0.5 mm-1.5 mm, the high capacity of the winding core can be maintained, meanwhile, the long cycle performance of the winding core is considered, the problem of lithium analysis in the negative arc area corresponding to the positive plate 1 can be effectively solved, when the interval between two adjacent etching lines 1211 is smaller than 0.5mm, the N/P value of the winding core is increased, but the high temperature performance of the winding core is deteriorated, meanwhile, the capacity loss of the winding core is obvious, when the interval between two adjacent etching lines 1211 is larger than 1.5mm, the N/P value of the inner winding core is changed less, the improvement on the negative arc area corresponding to the positive plate 1 is not obvious, and meanwhile, the capacity is lost.
Specifically, the width of the etched line 1211 is 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, or 105 μm, or a range of values consisting of any one point value or any two point values.
Specifically, when the width of the etching line 1211 is 60 μm to 105 μm, the high capacity of the winding core can be maintained, the long cycle performance of the winding core is considered, and the problem of lithium analysis in the arc area of the positive plate 1 can be effectively improved, when the width of the etching line 1211 is smaller than 60 μm, the CB value change of the arc area of the negative electrode corresponding to the positive plate 1 is not obvious, the lithium analysis in the arc area is not obvious, and when the width of the etching line 1211 is larger than 105 μm, the problems of larger CB value of the arc area of the negative electrode corresponding to the positive plate 1, larger capacity loss of the winding core and deterioration of high-temperature cycle retention rate can be caused.
1-2, In a preferred embodiment, the etched lines 1211 have a depth of 30% -35% of the thickness of the positive electrode active material layer 12, the spacing between two adjacent etched lines 1211 is 0.8 mm-1.2 mm, and the width of the etched lines 1211 is 75 μm-90 μm.
As shown in fig. 1-2, in one embodiment, the winding fold of the second region 122 is 1/2-3/4 of the total winding fold of the positive electrode sheet 1.
Specifically, the winding number of the second region 122 is any one point value or any range value formed by two point values of 1/2, 11/20, 3/5, 13/20, 7/10 or 3/4 of the total winding number of the positive electrode sheet 1, and in a preferred embodiment, the winding number of the second region 122 is 11/20-7/10 of the total winding number of the positive electrode sheet 1.
When the winding fold number of the second area 122 is 1/2-3/4 of the total winding fold number of the positive plate 1, the high capacity of the winding core can be maintained, meanwhile, the long cycle performance of the winding core is considered, the problem of lithium analysis in the arc area of the positive plate 1 can be effectively solved, when the winding fold number of the second area 122 is smaller than 1/2 of the total winding fold number of the positive plate 1, the problems of larger CB value in the arc area of the positive plate 1 and larger capacity loss of the winding core can be caused, and when the winding fold number of the second area 122 is larger than 3/4 of the total winding fold number of the positive plate 1, the CB value change in the arc area of the positive plate 1 is not obvious, and the improvement of lithium analysis in the arc area is not obvious.
As shown in fig. 1-2, in one embodiment, the sum of the volumes of all of the embossed 1221 areas is 1.5% -7% of the volume of the positive electrode active material layer 12.
Specifically, the sum of the volumes of all the areas of the embossments 1221 is 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, or 7% of the volume of the positive electrode active material layer 12, or a range of values consisting of any one or any two of the point values, and in a preferred embodiment, the sum of the volumes of all the areas of the embossments 1221 is 3% -5% of the volume of the positive electrode active material layer 12.
Specifically, when the sum of the volumes of all the areas of the embossments 1221 is 1.5% -7% of the volume of the positive electrode active material layer 12, the thickness and the density of the positive electrode active material layer 12 of the positive electrode sheet 1 can be effectively improved, the embossments 1221 can improve the positive electrode gram capacity exertion under the large area density, meanwhile, the embossments can reduce the initial thickness of the battery core, the volume energy density is improved, the embossments 1221 can store more electrolyte, increase more contact area, the lithium removing channel is increased, the doubling capacity of the winding core and the dynamic performance of the winding core are effectively improved, the initial effect of the battery is increased, when the sum of the volumes of all the areas of the embossments 1221 is smaller than 1.5% of the volume of the positive electrode active material layer 12, the storage performance of the electrolyte cannot be effectively improved, the problem of arc lithium precipitation is solved, when the sum of the volumes of the areas of all the embossments 1221 is larger than 7% of the volume of the positive electrode active material layer 12, the positive electrode sheet is easy to cause the breakage of the positive electrode sheet due to the excessive high torsion force, meanwhile, the positive electrode sheet is easy to cause the breakage of the positive electrode sheet, the excessive torsion, the aluminum foil is easy to break, and the aluminum foil is required to be more deeply stressed than 300 mu m.
As shown in fig. 1-2, in one embodiment, the area of the embossment 1221 is 10% -50% of the area of the second region 122.
Specifically, the area of embossment 1221 comprises 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% of the area of second region 122, or any range of values consisting of any two, and in a preferred embodiment, the area of embossment 1221 comprises 20% -40% of the area of second region 122.
Specifically, when the area of the embossing 1221 occupies 10% -50% of the area of the second area 122, the thickness and density of the positive electrode active material layer 12 of the positive electrode sheet 1 can be effectively improved, the embossing 1221 can improve the positive electrode gram capacity under large area density, the embossing 1221 can store more electrolyte, increase more contact area, increase lithium removing channels, effectively improve the doubling capacity of the winding core and the dynamic performance of the winding core, improve the initial efficiency of the battery, when the area of the embossing 1221 is smaller than 10% of the area of the second area 122, the positive electrode sheet 1 cannot effectively improve the storage performance of the electrolyte and improve the problem of arc lithium precipitation, and when the area of the embossing 1221 is larger than 50% of the area of the second area 122, the pressed area of the electrode sheet is increased. The aluminum foil may be broken during the circulation process, which affects the circulation retention rate.
As shown in fig. 1 to 2, in an embodiment, the depth of the embossment 1221 is 2% to 10% of the thickness of the positive electrode active material layer 12 in the direction parallel to the thickness of the positive electrode sheet 1.
Specifically, the depth of the embossment 1221 is any one point value or a range of any two point values of 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% of the thickness of the positive electrode active material layer 12, and in a preferred embodiment, the depth of the embossment 1221 is 4% -8% of the thickness of the positive electrode active material layer 12.
Specifically, when the depth of the embossing 1221 is 2% -10% of the thickness of the positive electrode active material layer 12, the thickness and density of the positive electrode active material layer 12 of the positive electrode sheet 1 can be effectively improved, the embossing 1221 can improve the positive electrode gram capacity exertion under large surface density, the embossing 1221 can store more electrolyte, increase more contact area, increase lithium removing channels, effectively improve the doubling capacity of the winding core and the dynamics performance of the winding core, improve the initial effect of the battery, when the depth of the embossing 1221 is less than 2% of the thickness of the positive electrode active material layer 12, the positive electrode sheet 1 can not effectively improve the storage performance of the electrolyte and improve the lithium precipitation problem, when the depth of the embossing 1221 is more than 10% of the thickness of the positive electrode active material layer 12, the positive electrode sheet is easy to cause the embossing area to be overpressure, the electrode sheet is easy to break due to overlarge embossing torque force, meanwhile, the gram capacity exertion of the overpressure part is low, when the embossing torque exceeds 300N, the electrode sheet can break, the embossing is too deep, the electrode sheet is required to be pressed down, and the electrode sheet is easy to cause the breaking of aluminum foil.
As shown in fig. 3 to 4, in one embodiment, the single-sided density of the positive electrode active material layer 12 is 200g/m 2~300g/m2;
The negative electrode sheet 2 precursor includes a negative electrode current collector 21 and a negative electrode active material layer 22 coated on at least one side of the surface of the negative electrode current collector 21, the negative electrode active material layer 22 including a negative electrode active material and CMC;
the precursor of the negative electrode sheet 2 is subjected to high temperature treatment to obtain the negative electrode sheet 2, and CMC in the negative electrode active material layer 22 is carbonized to form conductive carbon black.
When the single-sided density of the positive electrode active material layer 12 is 200g/m 2 or more, the deterioration of system dynamics is remarkable, and it is required to greatly improve the charge-discharge ability of the system.
Specifically, a vacuum baking process is introduced into the negative electrode active material of the negative electrode, CMC in the negative electrode is subjected to vacuum baking, the CMC is subjected to high-temperature treatment and carbonized into conductive carbon black, a conductive network is improved, and meanwhile, a large number of micropores are formed in the CMC in the carbonized area on the surface of the pole piece, so that electrolyte can be effectively stored, the low-temperature charging and discharging capacity is improved, and lithium precipitation is avoided. However, the defect is that after the pole piece is baked in high temperature and vacuum, the pole piece is thickened, the width of the winding core is increased during winding, and the battery core is easy to break, so that the baking time is not too long, the baking time is controlled within 5 hours, and the pole piece is thickened and broken.
As shown in fig. 1-2, in an embodiment, the temperature of the high-temperature treatment of the precursor of the negative electrode sheet 2 is 200 ℃ to 300 ℃, and the time of the high-temperature treatment of the precursor of the negative electrode sheet 2 is 3 to 7 hours.
Specifically, the temperature of the high-temperature treatment of the precursor of the negative electrode sheet 2 is 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃ or 300 ℃ or a range of values consisting of any one point value or any two point values, and in a preferred embodiment, the temperature of the high-temperature treatment of the precursor of the negative electrode sheet 2 is 22 ℃ to 280 ℃.
Specifically, the time of the high temperature treatment of the precursor of the negative electrode sheet 2 is 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h or 7h or a range of values formed by any two point values, and in a preferred embodiment, the time of the high temperature treatment of the precursor of the negative electrode sheet 2 is 4-6h.
Specifically, when the temperature of the high-temperature treatment of the anode plate 2 precursor is 200-300 ℃, and the time of the high-temperature treatment of the anode plate 2 precursor is 3-7 hours, CMC is subjected to high-temperature treatment and carbonized into conductive carbon black, so that a conductive network is improved, a large number of micropores are formed in CMC in a carbonized area on the surface of the anode plate, electrolyte can be effectively stored, the low-temperature charging and discharging capacity is improved, and lithium precipitation is avoided.
When the temperature of the high-temperature treatment of the precursor of the negative plate 2 is lower than 200 ℃, CMC cannot be carbonized into conductive carbon black, when the temperature of the high-temperature treatment of the precursor of the negative plate 2 is higher than 300 ℃, partial active substances are lost, the capacity is lower, the baking temperature is too high, the electrode plate is easy to bulk, the winding width is increased due to thickening of the electrode plate, the effect of breaking corners of an electric core is caused after circulation, when the time of the high-temperature treatment of the precursor of the negative plate 2 is less than 3 hours, the baking effect is poor, the effect of the electrode plate on the improvement of dynamics is not obvious, when the time of the high-temperature treatment of the precursor of the negative plate 2 is greater than 7 hours, the loss of the surface density of the negative plate is excessive, the capacity is obviously reduced, meanwhile, the thickness of the negative plate is increased for a long time, the effect of breaking corners of the electric core circulation is increased, the cracking phenomenon exists at the same time, and the capacity retention rate is rapidly reduced. High temperature treatment temperature, optimally selected 350 ℃ for 5h
As shown in fig. 1 to 2, in an embodiment, the anode active material includes a silicon-carbon material, wherein the silicon content is 3 to 15% by mass of the silicon-carbon material.
Specifically, the silicon content is 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15% of the mass of the silicon-carbon material, or any one or any two point values, and in a preferred embodiment, the silicon content is 5% -10% of the mass of the silicon-carbon material.
When the silicon content is 3-15% of the silicon-carbon material, the lithium-ion battery has the effects of high capacity, long circulation, low expansion and no lithium precipitation of the anode arc, when the silicon content is less than 3% of the silicon-carbon material, the improvement effect is not obvious, as the dynamics of low silicon doping amount is close to that of a graphite system, the dynamics is excellent, the effect of improving the performance is not obvious due to the supplement of a new process, and when the silicon content is more than 15% of the silicon-carbon material, the lithium-ion battery has the advantages of large circulation expansion, easy failure of the long period of a battery core, obvious lithium precipitation of the anode arc and obvious and difficult improvement of the performance deterioration.
The second aspect of the present invention provides a method of manufacturing an electrode assembly 100, comprising the steps of:
S1, acquiring a positive plate 1, a negative plate 2 and a diaphragm 3;
S2, etching a plurality of etching lines 1211 in a first area 121 of the positive electrode active material layer 12 of the positive electrode sheet 1, and pressing embossing 1221 in a second area 122 of the positive electrode active material layer 12 of the positive electrode sheet 1;
S3, sequentially stacking and winding the positive plate 1, the diaphragm 3 and the negative plate 2 to form the electrode assembly 100, wherein the first area 121 is positioned on the winding inner ring of the positive plate 1, and the second area 122 is positioned on the winding outer ring of the positive plate 1.
Specifically, in step S1, the positive electrode sheet 1 includes a positive electrode current collector 11 and a positive electrode active material layer 12 coated on at least one side of the surface of the positive electrode current collector 11, the positive electrode active material layer including a positive electrode active material, a conductive agent, and a binder.
In some embodiments, the positive active material includes one or more of lithium nickel cobalt manganate (N xMyCz, x+y+z=1), nickel cobalt aluminum ternary material (NCA), lithium iron manganese phosphate (LiFe xMnyPO4, x+y=1), lithium iron phosphate (LiFePO 4), lithium manganate (LiMn 2O4), lithium cobaltate (LiCoO 2), lithium nickelate (LiNiO 2), lithium-rich manganese base, lithium nickel manganate (LMNO), lithium vanadyl phosphate (Li 3V2(PO4)3,LiVOPO4).
In some embodiments, the positive electrode conductive agent includes one or more of graphite, superconducting carbon, acetylene black, carbon nanotubes, graphene, carbon nanofibers, metal powders, metal fibers, and polyphenylene derivatives.
In some embodiments, the positive electrode binder includes one or more of polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-tetrafluoroethylene-propylene terpolymers, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymers, tetrafluoroethylene-hexafluoropropylene copolymers, and fluoroacrylate-based resins.
In some embodiments, the positive electrode active material layer comprises, by mass, 95-99wt% of a positive electrode active material, 0.3-1.4wt% of a conductive agent, and 0.8-1.4wt% of a binder.
The mass ratio of the positive electrode active material in the positive electrode active material layer is in the above range, so that the positive electrode sheet has higher lithium removal and intercalation capacity, and the battery has higher capacity.
The positive electrode current collector 11 is selected from a metal material that can conduct electrons, preferably, the positive electrode current collector 11 includes one or more of nickel, tin, copper, carbon materials, and in a more preferred embodiment, the positive electrode current collector 11 is selected from aluminum foil.
The positive electrode sheet may be prepared according to a conventional method in the art. For example, the positive electrode active material layer is typically formed by applying a positive electrode slurry prepared from a positive electrode active material, a positive electrode conductive agent, a positive electrode binder and any other components to the positive electrode current collector 11, drying the same, and cold pressing the same. The solvent may be N-methylpyrrolidone (NMP), but is not limited thereto.
In some embodiments, the negative electrode sheet 2 includes a negative electrode current collector 21 and a negative electrode active material layer coated on one or both side surfaces of the negative electrode current collector 21, the negative electrode active material layer including a negative electrode active material, a conductive agent, and a binder.
In an embodiment, the negative electrode active material includes metallic lithium, metallic lithium alloy, and the like, a lithium-free negative electrode, and the like.
In some embodiments, the negative electrode conductive agent includes one or more of graphite, superconducting carbon, acetylene black, carbon nanotubes, graphene, carbon nanofibers, metal powders, metal fibers, and polyphenylene derivatives.
In some embodiments, the negative electrode binder includes one or more of CMC, styrene-butadiene rubber, polyacrylic acid, sodium polyacrylate, polyacrylamide, polyvinyl alcohol, polymethacrylic acid.
In some embodiments, the mass percentage of each component in the negative electrode active material layer is 96% -97% of negative electrode active material, 0.05% -0.5% of conductive agent and 1.5% -3.5% of binder.
The negative electrode current collector 21 is selected from a metal material that can conduct electrons, and preferably, the negative electrode current collector 21 includes one or more of Al, ni, tin, copper, stainless steel, and in a more preferred embodiment, the negative electrode current collector 21 is selected from copper foil.
The negative electrode sheet may be prepared according to a conventional method in the art. For example, the negative electrode active material layer is typically prepared by coating a negative electrode active material, a negative electrode conductive agent, a negative electrode binder, and any other components as a negative electrode slurry on the negative electrode current collector 21, and subjecting the negative electrode slurry to a high temperature treatment to obtain the negative electrode sheet 2. The solvent may be an aqueous solvent, but is not limited thereto.
In some embodiments, the diaphragm 3 comprises a base film and a coating layer, wherein the base film adopts a porous PP layer, so that the blocking Kong Gailv caused by high silicon side reaction is reduced, the viscosity is strong, a pole piece is firmly adhered, the coating layer adopts an oily diaphragm coating layer, and meanwhile, the ceramic layer is added to the coating layer, so that the liquid retention performance and the safety performance are improved, and the long-period circulation is improved.
A third aspect of the present invention provides a battery comprising a battery case, an electrolyte, and an electrode assembly 100 as described above, or an electrode assembly 100 prepared by the above-described method of preparing an electrode assembly 100.
In one embodiment, the electrolyte includes a lithium salt, a solvent, and an additive;
In some embodiments, the lithium salt may be selected from one or more of lithium hexafluorophosphate LiPF 6, lithium perchlorate LiClO 4, lithium tetrafluoroborate LiBF 4, lithium hexafluoroarsenate LiAsF 6, other organic lithium salts (such as lithium trifluoromethylsulfonate LiCF 3 SO, lithium bis (trifluoromethylsulfonyl) imide LiTFSI, lithium bis (fluorosulfonyl) imide LiTNFSI, lithium fluorosulfonyl-n-perfluorobutylsulfonyl imide LiFNFSI, lithium bisoxalato borate LiBOB, liN (CF 3SO2)2、LiC(SO2CF3)3);
The lithium salt is a source of Li + in the electrolyte, provides free shuttle ions for the battery and plays a role in transmitting ions inside the battery, and can form a protective layer on the surface of an electrode material, thereby having important influences on the capacity, cycle performance, power density, energy density and other performances of the battery.
In some embodiments, the solvent may be selected from one or more of ethylene carbonate EC, propylene carbonate PC, butylene carbonate BC, dimethyl carbonate DMC, diethyl carbonate DEC, ethylmethyl carbonate EMC, and butyrolactone BL, and the ether compound includes one or more of tetrahydrofuran THF, 2-methyl-tetrahydrofuran 2-Me-THF, dimethoxydimethyl ether DMM, and 1, 2-dimethoxyethane DME.
In some embodiments, the additive may be a general-purpose additive that includes film forming additives, conductive additives, flame retardant additives, overcharge protection additives, additives to control water and HF content in the electrolyte, improve low temperature performance, or may be an additive that improves the interfacial stability of the pole piece with the electrolyte, such as fluoroethylene carbonate FEC, and the like.
In a preferred embodiment, the fabrication of the battery comprises the steps of:
The electrode assembly 100 is placed in a battery shell formed by punching, the electrolyte prepared by the above is respectively injected into the electrode assembly 100, and the metal battery is obtained through the procedures of vacuum packaging, standing, formation and the like.
The advantageous effects of the present invention are further illustrated below with reference to examples.
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is described in further detail below with reference to examples. It should be understood that the examples of the present invention are for the purpose of illustration only and are not intended to be limiting, and that the examples of the present invention are not limited to the examples given in the specification. The specific experimental or operating conditions were not noted in the examples and were made under conventional conditions or under conditions recommended by the material suppliers.
It is to be further understood that the use of one or more method steps in the present invention does not exclude the presence of other method steps before or after the combination step or the insertion of other method steps between the explicitly mentioned steps, unless otherwise indicated, and that the use of a combined connection between one or more devices/means in the present invention does not exclude the presence of other devices/means before or after the combination device/means or the insertion of other devices/means between the explicitly mentioned two devices/means, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is merely a convenient tool for identifying the method steps and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention in which the invention may be practiced, as such changes or modifications in their relative relationships may be regarded as within the scope of the invention without substantial modification to the technical matter.
In the examples described below, reagents, materials and apparatus used, unless otherwise specified, are commercially available or are available by synthetic means well known in the art.
Table 1 designs of electrode assemblies of examples 1 to 11 and comparative examples 1 to 6;
Example 1
The embodiment is used for illustrating the electrode assembly and the battery disclosed by the invention, and comprises the following operation steps:
manufacturing a positive plate:
Mixing positive active materials of lithium cobaltate, a conductive agent CNT, a conductive agent SP and a binder PVDF according to the mass ratio of 98.2:0.3:0.6:0.9. The mixture was thoroughly stirred in NMP solvent to form a uniform positive electrode slurry. The viscosity of the positive electrode slurry meets 3500-5500mPas, the slurry is coated on at least one surface of the aluminum foil of the positive electrode current collector, and the positive electrode plate meeting the requirements is obtained after the procedures of drying, rolling, die cutting and the like.
The single-sided density of the positive electrode active material layer of the positive electrode sheet is 120g/m 2, the winding fold number of the first area is 1/4 of the total winding fold number of the positive electrode sheet, a plurality of etching lines are etched in the first area, the sum of the volumes of etching areas of all etching lines is 1.2% of the volume of the positive electrode active material layer, the depth of each etching line is 30% of the thickness of the positive electrode active material layer, the interval between every two adjacent etching lines is 1.5mm, the width of each etching line is 75 mu m, the winding fold number of the second area is 3/4 of the total winding fold number of the positive electrode sheet, embossing is performed in the second area, the sum of the volumes of all embossing areas is 1.5% of the volume of the positive electrode active material layer, the area of embossing accounts for 10% of the area of the second area, and the depth of embossing is 2% of the thickness of the positive electrode active material layer;
manufacturing a negative plate:
Mixing graphite serving as a cathode active material, silicon-carbon cathode serving as a cathode active material, CNT serving as a conductive agent, SP serving as a conductive agent, PAA serving as a binder, SBR serving as a binder and CMC-Li serving as a binder according to the mass ratio of 87.5:8.7:0.1:0.2:1.7:1.3:0.9. And fully stirring and mixing the mixture in deionized water solvent to form uniform negative electrode slurry. The slurry is coated on at least one surface of a copper foil of a negative current collector, and baked for 5 hours at 300 ℃ to obtain a negative plate.
Manufacturing a diaphragm:
The porous PP membrane comprises a base membrane and a coating layer, wherein a porous PP layer is used as the base membrane, and an oily membrane coating layer and a ceramic layer are arranged on the surface of the base membrane.
And (3) preparing an electrolyte:
The electrolyte comprises lithium salt, a solvent and an additive, wherein the lithium salt can be selected from lithium hexafluorophosphate LiPF6, the solvent adopts carbonic ester and carboxylic ester, and the additive is a film forming additive, such as Vinylene Carbonate (VC), acrylonitrile and fluoroethylene carbonate (FEC).
Sequentially stacking the positive plate, the diaphragm and the negative plate, enabling the diaphragm to be positioned between the positive plate and the negative plate to play a role in isolation, and then winding one ends of the positive plate, the diaphragm and the negative plate to form an electrode assembly;
and then placing the coiled electrode assembly in a battery shell, respectively injecting the electrolyte prepared by the steps into the baked and dried battery core, and carrying out the procedures of vacuum packaging, standing, formation and the like to obtain the battery.
Examples 2 to 11
Examples 2-11 are provided to illustrate the disclosed electrode assemblies, including most of the operating steps of example 1, with the difference that:
the various components, parameters and contents of the electrode assemblies shown in table 1 were employed.
Comparative examples 1 to 6
Comparative examples 1-6 are provided to illustrate the electrode assemblies disclosed herein, including most of the operating steps of example 1, with the difference that:
the various components, parameters and contents of the electrode assemblies shown in table 1 were employed.
Performance testing
The following performance tests were carried out on the batteries obtained in examples 1 to 11 and comparative examples 1 to 6 described above:
and (one) a doubling capability test:
testing at 25+ -2deg.C, discharging to 3.0V at 0.2C, standing for 10min
Filling with 0.8C 4.53V, cutting off current 0.05C, standing for 10min
Discharging to 3V at 0.2C, standing for 10min, and recording corresponding initial capacity C0
Filling with 0.8C, cutting off current 0.05C, standing for 10min
Discharging to 3V at 0.5C, standing for 10min, recording corresponding capacity C1,
The discharge capacity of 0.5C times is C1/C0.
(II) first efficiency test of the battery, namely the first discharge capacity/the first charge capacity
And (III) testing low-temperature discharge of the battery:
(1) Testing at 25+ -2deg.C, discharging to 3.0V at 0.2C, standing for 10min
(2) Filling with 0.8C 4.53V, cutting off current 0.05C, standing for 10min
(3) Discharging to 3V at 0.2C, standing for 10min, and recording corresponding initial capacity C0
(4) At 25℃4.53V was charged with 0.8℃and the off-current was 0.05C
(5) Standing at 0deg.C for 3H, then discharging to 3V at 0.2C, and recording discharge capacity C2
(6) 0 ℃ Discharge C2/C0.
(IV) high temperature cycle testing of batteries
(1) Recording initial voltage, thickness and internal resistance at normal temperature
(2) Standing at 45 ℃ for 2H
(3) Constant current and constant voltage of 0.5C to 4.53V, cut-off current of 0.05C, and standing for 10min
(4) Discharging to 3V at 0.5C, standing for 10min
(5) Repeating the step 3 and the step 4 for 500 times, and recording discharge data, 50/100/200/300/400/500 cycle voltage, internal resistance and thickness.
The test results are shown in Table 2.
Table 2 electrochemical performance of the cells
As can be seen from tables 1 and 2, when the number of windings in the first region is 1/4 to 1/2 of the total number of windings in the positive electrode sheet, or when the sum of the volumes of the etched regions of all the etched lines is 1% -2% of the volume of the positive electrode active material layer, or when the depth of the etched line is 25% -40% of the thickness of the positive electrode active material layer, or when the interval between two adjacent etched lines is 0.5mm to 1.5mm, or when the width of the etched line is 60 μm to 105 μm, or when the sum of the volumes of all the regions is 1.5% -7% of the volume of the positive electrode active material layer, or when the area of the embossed area is 10% -50% of the area of the second region, or when the depth of the embossed area is 2% -10% of the thickness of the positive electrode active material layer, the high capacity of the roll core can be maintained while the long cycle performance of the roll core can be improved, and the positive electrode sheet can be effectively analyzed.
When at least one of the above conditions is not satisfied, the change of the N/P value of the inner winding core is low, the improvement of the negative electrode arc area corresponding to the positive electrode sheet is not obvious, and the capacity is lost, or the CB value of the negative electrode arc area corresponding to the positive electrode sheet is larger, the capacity loss of the winding core is larger and the high-temperature cycle retention rate is deteriorated.
As can be seen from comparative examples 1-11 and comparative examples 3-6, when the temperature of the high temperature treatment of the negative electrode sheet precursor is 200 ℃ to 300 ℃ and the time of the high temperature treatment of the negative electrode sheet precursor is 3-7 hours, CMC is carbonized into conductive carbon black through the high temperature treatment, so that a conductive network is improved, and meanwhile, a large number of micropores are formed in CMC in the carbonized area on the surface of the electrode sheet, so that electrolyte can be effectively stored, the low temperature charging and discharging capacity is improved, and lithium precipitation is avoided.
When the temperature of high-temperature treatment of the cathode plate precursor is lower than 200 ℃, CMC cannot be carbonized into conductive carbon black, when the temperature of high-temperature treatment of the cathode plate precursor is higher than 300 ℃, partial active substances can be lost, the capacity is lower, meanwhile, the baking temperature is too high, the electrode plate is easy to bulk, the winding width is increased due to thickening of the electrode plate, and the effect of corner breaking of the battery cell is caused after circulation.
When the high-temperature treatment time of the cathode plate precursor is longer than 7 hours, the cathode surface density loss is excessive, the capacity is obviously reduced, the thickness of the cathode plate is increased for a long time, the effect of cell cycle corner breaking is achieved, meanwhile, the cracking phenomenon exists on the electrode plate, and the capacity retention rate is rapidly reduced.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (14)
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| JP2018148229A (en) * | 2018-05-29 | 2018-09-20 | 太陽誘電株式会社 | Electrochemical device and method for manufacturing the same |
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| CN115763997A (en) * | 2022-11-10 | 2023-03-07 | 力神（青岛）新能源有限公司 | A wound battery pole group and lithium-ion battery |
| CN221841870U (en) * | 2024-02-07 | 2024-10-15 | 珠海冠宇电池股份有限公司 | A battery |
| CN222168433U (en) * | 2024-03-12 | 2024-12-13 | 江苏正力新能电池技术股份有限公司 | Battery pole piece and battery cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018148229A (en) * | 2018-05-29 | 2018-09-20 | 太陽誘電株式会社 | Electrochemical device and method for manufacturing the same |
| CN111540879A (en) * | 2020-05-08 | 2020-08-14 | 珠海冠宇电池股份有限公司 | Positive plate, preparation method and lithium ion battery comprising positive plate |
| CN115763997A (en) * | 2022-11-10 | 2023-03-07 | 力神（青岛）新能源有限公司 | A wound battery pole group and lithium-ion battery |
| CN221841870U (en) * | 2024-02-07 | 2024-10-15 | 珠海冠宇电池股份有限公司 | A battery |
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