Composite current collector and full tab cell

Abstract

The utility model provides a kind of composite current collector and full tab electric core, composite current collector, comprising: base film and metal layer;The base film includes through hole area, a plurality of through holes are provided in the through hole area;The through hole penetrates the base film;Metal layer is respectively arranged on the opposite surface of the base film;The metal layer is electrically connected by the through hole between;Wherein, the through hole area completely covers the base film, or, the through hole area at least covers the side edge area of opposite two sides on the base film, and the side edge area is as full tab area.The technical scheme provided by the utility model saves preparation procedure, reduces electric core internal resistance, and is beneficial to the improvement of electric core energy density.

Description

Technical Field

[0001] This utility model relates to the field of battery technology, and in particular to a composite current collector and a omni-tab battery cell. Background Technology

[0002] Current collectors are used to gather the current generated by the active materials in a battery to form an output current. Existing current collectors generally use metal foil as the current collector, forming an electron conduction channel. Currently, in the preparation of composite current collectors, conductive metal layers are formed on both sides of a polymer base film through methods such as physical vapor deposition. Since the polymer layer in the middle of the composite current collector is non-conductive, the two ends of the tab foil are usually welded to the conductive metal layer of the composite current collector to transport the current from the battery cell. Double-sided welding increases the internal resistance of the battery cell and also increases the thickness of the current collector, which is detrimental to improving the energy density of the battery cell. Utility Model Content

[0003] This invention provides a composite current collector and omni-tab battery cell, which saves manufacturing processes, reduces the internal resistance of the battery cell, and is conducive to improving the energy density of the battery cell.

[0004] In a first aspect, embodiments of the present invention provide a composite current collector, comprising: a base film and a metal layer;

[0005] The base film includes a through-hole region, and multiple through-holes are provided in the through-hole region; the through-holes penetrate the base film; metal layers are respectively provided on opposite surfaces of the base film; the metal layers are electrically connected to each other through the through-holes; wherein, the through-hole region completely covers the base film, or, the through-hole region at least covers the side regions on opposite sides of the base film, and the side regions serve as full tab regions.

[0006] Optionally, the through holes are arranged in a matrix array within the through hole region;

[0007] Alternatively, within the through-hole region, the through-holes are arranged in a row along a first direction and offset from a row of through-holes arranged adjacent to each other in a second direction, forming a staggered arrangement that intersects with the through-holes adjacent to each other in the second direction; wherein the first direction is perpendicular to the second direction.

[0008] Optionally, the through hole is circular or elliptical.

[0009] Optionally, when the through-hole is circular, the diameter is 1-5 μm; when the through-hole is elliptical, the length of the major axis is 1-5 μm; and the density of the through-holes is 10-200 per cm³. 2 .

[0010] Optionally, the composite current collector further includes a riveting layer; the riveting layer is disposed between the metal layer and the base film; the riveting layer is connected through the through hole.

[0011] Optionally, the riveting layer is one or more of copper alloy, nickel, nickel alloy, titanium, silver, aluminum, or aluminum alloy.

[0012] Optionally, the thickness of the riveting layer is 10-100 nm.

[0013] Optionally, the composite current collector further includes a protective layer disposed on the surface of the metal layer.

[0014] Optionally, the thickness of the protective layer is less than or equal to one-tenth of the thickness of the metal.

[0015] Secondly, embodiments of the present invention provide a omnipolar battery cell, including the composite current collector described in any embodiment of the present invention.

[0016] The technical solution provided by this utility model embodiment provides that by setting through holes in the full or part of the area of ​​the base film, the metal layers on the opposite surface of the base film are electrically connected through the through holes. Compared with the prior art, this can eliminate the double-sided transfer welding process and reduce the internal resistance of the battery cell, which is beneficial to improving the energy density of the battery cell. Attached Figure Description

[0017] Figure 1 A top view of the composite current collector is provided for an embodiment of this utility model;

[0018] Figure 2 A top view schematic diagram of another composite current collector is provided for embodiments of this utility model;

[0019] Figure 3 This invention provides a schematic diagram of the cross-sectional structure at AA' of a composite current collector according to an embodiment of the present invention;

[0020] Figure 4 A top view schematic diagram of another composite current collector is provided for embodiments of this utility model;

[0021] Figure 5 A schematic diagram of the cross-sectional structure of another composite current collector is provided for embodiments of this utility model;

[0022] Figure 6 This invention provides an enlarged cross-sectional structural diagram of the through hole in an embodiment of the present invention;

[0023] Figure 7 A schematic diagram of the composition of a omnipolar battery cell is provided for an embodiment of this utility model;

[0024] Figure 8 This invention provides a schematic diagram of the tab cutting shape for a multi-tab battery cell according to an embodiment of the present invention. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of the embodiments of this utility model clearer, the technical solutions of the embodiments of this utility model will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this utility model, not all embodiments. Based on the embodiments of this utility model, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of this utility model.

[0026] Composite current collectors refer to those formed by depositing copper / aluminum atoms on the surface of a polymer base film to create composite copper foil current collectors or composite aluminum foil current collectors. This combines the mechanical and structural advantages of polymer films with the electrochemical performance advantages of copper and aluminum, replacing traditional aluminum foil and copper foil current collector materials for lithium batteries. It has advantages such as high safety, high energy density, and saving metal resources.

[0027] Because the polymer layer in the middle layer of the composite current collector is non-conductive, the two ends of the tab foil are typically welded to the metal conductive layer of the composite current collector to transmit current from the battery cell. Therefore, an ultrasonic tab bonding process needs to be added in the upstream process. This ultrasonic tab bonding process welds the two ends of the tab foil to the metal conductive layer of the composite current collector, achieving double-sided current conduction. This double-sided bonding process not only increases the internal resistance of the battery cell but also increases the overall thickness of the composite current collector, and is also detrimental to improving the energy density of the battery cell.

[0028] In view of this, Figure 1 This is a top view schematic diagram of a composite current collector according to an embodiment of the present invention. Figure 2 This provides a top view schematic diagram of another composite current collector for embodiments of the present invention. Figure 3 A schematic diagram of the cross-sectional structure at AA' of the composite current collector is provided in an embodiment of this utility model. See [link / reference]. Figures 1-3 It includes: a base film 110 and a metal layer 120;

[0029] The base film 110 includes a through-hole region, and multiple through holes are provided in the through-hole region; the through holes penetrate the base film 110; metal layers 120 are respectively provided on opposite surfaces of the base film 110; the metal layers 120 are electrically connected to each other through the through holes; wherein, the through-hole region completely covers the base film 110, or the through-hole region at least covers the side regions on opposite sides of the base film 110, and the side regions serve as the full tab region.

[0030] Specifically, the base film 110 is a polymer material film, which can be polyethylene terephthalate (PET), polypropylene (PP), polyimide (PI), etc. The base film 110 serves as an intermediate carrier for the composite current collector, supporting the metal layer 120. Considering the application requirements of the composite current collector, and taking into account the difficulty and cost of the manufacturing process, the preferred thickness of the base film 110 is between 3 μm and 6 μm; for example, the thickness of the base film 110 can be 3 μm, 4 μm, 5 μm, or 6 μm.

[0031] A via region is planned on the base film 110, and multiple vias are set in the via region. The shape of the vias can be circular, elliptical, or other regular shapes. The vias can be prepared by laser drilling, where holes are drilled within specific via regions. For example... Figure 2 As shown, the surface of the entire substrate mold can be planned with through-hole areas, meaning that the through-hole areas completely cover the surface of the substrate film 110, thus providing through-holes on the entire surface of the substrate mold. Figure 1 As shown, through-hole areas can also be planned in the side areas on both sides of the base mold, so that holes can be drilled on both sides of the base film 110, which will then serve as the full tab area.

[0032] An exemplary perforation process can be as follows: the base film 110 roll is placed on a laser perforation machine and continuously pulled and unwound. By setting perforation parameters, such as laser power, laser wavelength, spot diameter, and transmission speed, the perforation density and perforation size can be adjusted. In some embodiments, the perforation parameters can be set to 150–250 W, laser wavelength 1064 nm, spot diameter 1–5 μm, and transmission speed 10–50 m / min for laser perforation. Since the subsequent winding and unwinding processes in the composite current collector preparation process have certain requirements on the tensile strength of the base film 110, it is preferable to perform laser perforation on the side regions on both sides of the base film 110, which will subsequently serve as the full tab region.

[0033] Metal layers 120 are respectively disposed on opposite surfaces of the base film 110. The material of the metal layers 120 can be uniform and they serve as conductors. For example, the material of the metal layers 120 is copper, copper alloy, aluminum, or aluminum alloy, and they are prepared by methods such as magnetron sputtering, electroplating, or vacuum evaporation. The metal layers 120 on opposite surfaces of the base film 110 are electrically connected through through-holes, thereby eliminating the need for double-sided bonding required for the non-conductive base film 110. This also reduces the internal resistance of the battery cell, which is beneficial to improving the energy density of the battery cell. Considering parameters such as manufacturing process, cost, and energy density, the thickness of the metal layers 120 is between 100-2000 nm, with a preferred thickness of 500-1000 nm. For example, to increase the thickness of the conductive layer, a double-sided clamping electroplating method is preferred, where electroplating is performed by clamping the conductive layers on both sides of the base film 110. Due to the influence of current density from the sides to the middle of the film during the electroplating process, the current intensity is higher on the sides, so the electroplated metal layer 120 is formed preferentially. Furthermore, the metal layer 120 is thicker than the metal layer 120 in the middle of the film. Therefore, when laser-drilling the side areas of the base film 110, the metal layer 120 can be better filled into the vias on both sides of the base film 110, and the problem of inconsistent thickness between the sides and the middle can be solved. Moreover, when laser-drilling the side areas of the base film 110, in order to ensure the current density of the electrical connection between the metal layers 120 within the entire tab region, the via area must at least cover the side areas. That is, the width of the via area must be at least greater than the width of the entire tab region, where the width direction is the Y direction. This ensures the number of vias within the entire tab region, thereby guaranteeing the current density parameters within the entire tab region.

[0034] The technical solution provided by this utility model embodiment provides that by setting through holes in the full or part of the area of ​​the base film, the metal layers on the opposite surface of the base film are electrically connected through the through holes. Compared with the prior art, this can eliminate the double-sided transfer welding process and reduce the internal resistance of the battery cell, which is beneficial to improving the energy density of the battery cell.

[0035] See Figure 1 and Figure 2 Optionally, the vias are arranged in a matrix array within the via region; for example, the first direction is the X direction and the second direction is the Y direction, and the vias are arranged in an array with equal spacing in the first and second directions within the via region, or they can be arranged in a rectangular array with different spacing in the first X direction and the second Y direction, both of which can achieve electrical connection between the base film 110 and the metal layer 120 on the opposite surface.

[0036] Figure 4 A top view schematic diagram of another composite current collector is provided for embodiments of this utility model. See also... Figure 4Within the through-hole region, the through-holes are arranged in a row along the first direction X and are adjacent to a row of through-holes arranged in the second direction Y. The through-holes are offset in the first direction X, forming a staggered arrangement that intersects with the adjacent through-holes in the second direction Y; wherein, the first direction X is perpendicular to the second direction Y.

[0037] Specifically, staggered arrangement means that in the first direction X, the through holes in the i-th row and the through holes in the (i+1)-th row are not in the same column in the second direction Y, where i is an integer greater than or equal to 1. That is, the through holes in the (i+1)-th row are offset relative to the through holes in the i-th row in the first direction X. For example, the through holes in the second row are located on the perpendicular bisector of the line connecting adjacent through holes in the first row, thus forming an equilateral or isosceles shape of the center line, thereby forming various staggered arrangements to meet the design requirements of current density between metal layers 120.

[0038] Optionally, the through-holes can be circular or elliptical. Specifically, the through-holes are typically drilled using laser drilling. The base film roll 110 is placed on a laser drilling machine and continuously pulled and unwound. Drilling parameters, such as laser power, laser wavelength, spot diameter, and transmission speed, are set to adjust the drilling density and size. In some embodiments, the drilling parameters can be set to 150–250 W, laser wavelength 1064 nm, spot diameter 1–5 μm, and transmission speed 10–50 m / min for laser drilling. Therefore, the laser spot can be circular or elliptical. Optionally, when the through-hole is circular, the hole diameter is 1–5 μm; when the through-hole is elliptical, the length of the major axis is 1–5 μm; and the density of through-holes is 10–200 per cm. 2 Specifically, by setting the size of the through-holes, the material of the metal layer 120 can be fully filled, improving the electrical connection between the metal layers 120. Too low a density of through-holes will result in low current density, while too high a density will affect the tensile strength of the base film 110. Therefore, the density of through-holes is set to 10-200 per cm². 2 The preferred density of through holes is 30-80 per cm. 2 .

[0039] Figure 5 A schematic diagram of the cross-sectional structure of another composite current collector is provided for embodiments of this utility model. See also... Figure 5 The composite current collector also includes a riveting layer 130; the riveting layer 130 is disposed between the metal layer 120 and the base film 110; the riveting layer 130 is connected through a through hole 111.

[0040] Specifically, the riveting layer 130 is respectively disposed on the first surface and the second surface of the base film 110. The materials of the riveting layer 130 can be the same. The riveting layer 130 can be prepared by magnetron sputtering or vacuum evaporation. A riveting layer 130 with a thickness of 10-100nm is formed on the first surface and the second surface of the base film 110, and then a metal layer 120 is generated on the surface of the riveting layer 130, thereby using the riveting layer 130 to improve the bonding force between the base film 110 and the metal layer 120. Figure 6 This invention provides an enlarged cross-sectional structural diagram of the through hole in an embodiment of the present invention. See also: Figure 6 The material of the riveting layer 130 can be one or more of copper alloy, nickel, nickel alloy, titanium, silver, aluminum or aluminum alloy. Therefore, by using the riveting layer 130 to form a metallization layer on the inner wall of the through hole, the connection of the double-sided riveting layer 130 of the base film 110 is realized. Furthermore, the metallization layer is used to improve the connection effect between the metal layers 120, and to avoid the reduction of current density caused by insufficient filling of the metal layers 120 in the through hole.

[0041] See also Figure 5 Optionally, the composite current collector also includes a protective layer 140, which is disposed on the surface of the metal layer 120.

[0042] Specifically, the material of the protective layer 140 can be one or more of chromium oxide, cobalt oxide, graphite, carbon black, acetylene black, Ketjen black, carbon nanotubes, carbon nanofibers, and graphene. The protective layer 140 protects the metal layer 120 from chemical corrosion or physical damage. The preparation methods of the protective layer 140 include one or more of physical vapor deposition, in-situ forming, and coating. Vacuum evaporation and magnetron sputtering are preferred methods for vapor deposition; in-situ forming is preferred, where a metal oxide passivation layer is formed in situ on the surface of the metal layer 120; coating methods are preferred, such as die coating, blade coating, and extrusion coating. An excessively thick protective layer 140 will affect the conductivity of the metal layer 120, while an excessively thin protective layer 140 will affect the protective effect. Therefore, the thickness of the protective layer 140 is less than or equal to one-tenth of the thickness of the metal layer. Optionally, the thickness of the protective layer 140 is set between 10-100 nanometers, with a preferred thickness of 20-60 nanometers.

[0043] This embodiment of the invention also provides a omnipolar battery cell, which includes the composite current collector provided in any embodiment of the invention. Therefore, it has the same beneficial effects, and will not be elaborated upon here.

[0044] For example, this utility model embodiment also provides a process for preparing a composite current collector: a PET film with a thickness of 4.5 micrometers is selected, and laser perforation is performed on the side areas of both sides of the base film 110, wherein the width of the side area is 100 mm, the laser power is 200 W, the laser wavelength is 1064 nm, the spot diameter is 3 micrometers, and the fixed transmission speed is 20 m / min. This yields a current collector with a diameter of 3 micrometers and a density of 50 current collectors / cm². 2 The micropores are circular. The through-holes are arranged in a matrix.

[0045] Typically, aluminum foil current collectors are used for the positive electrode. Therefore, the base film 110 prepared above is placed in a vacuum evaporation chamber, and the high-purity aluminum wire (purity greater than 99.99%) in the metal evaporation chamber is melted and evaporated at a high temperature of 1300-2000℃. The evaporated metal atoms are deposited on the two surfaces of the base film 110. The evaporation process is repeated multiple times to form an aluminum metal conductive layer with a thickness of 1 micrometer.

[0046] 1g of graphene was uniformly dispersed in 999g of N-methylpyrrolidone (NMP) solution using ultrasonic dispersion to prepare a coating solution with a solid content of 0.1wt.%. The coating solution was then uniformly coated onto the surface of the metal conductive layer using a die coating process, with the coating amount controlled at 100nm. Finally, the coating was dried at 100℃ to form a protective layer 140.

[0047] Typically, copper foil current collectors are used for the negative electrode. Therefore, the prepared base film 110 is placed in a magnetron sputtering chamber, and a 20 nm thick alloy bonding layer 130 is deposited on the surface of the base film 110 using a nickel-chromium alloy target. Then, a 50 nm thick metal layer 120 is deposited on the same copper target (purity 99.99%). A 1 μm thick copper conductive layer is then deposited on both sides of the film using an electroplating process. Finally, 1 g of graphite is uniformly dispersed in 999 g of N-methylpyrrolidone (NMP) solution using ultrasonic dispersion to prepare a coating solution with a solid content of 0.1 wt.%. This coating solution is then uniformly coated onto the surface of the metal conductive layer using a die coating process, with the coating thickness controlled at 100 nm. Finally, the coating is dried at 100 °C to form a protective layer 140.

[0048] Figure 7 A schematic diagram of the composition of a omnipolar battery cell is provided for an embodiment of this utility model. See [link / reference]. Figure 7For example, this utility model embodiment also provides a process for preparing a full-tab battery cell: lithium cobalt oxide, conductive carbon black, and polyvinylidene fluoride are mixed in a weight ratio of 97.0:1.5:1.5, N-methylpyrrolidone (NMP) is added as a solvent, and a slurry with a solid content of 0.8 is prepared and stirred evenly; the slurry is uniformly coated on the non-perforated area of ​​the aluminum foil current collector prepared above to form a positive electrode active material layer. It is dried at 90°C, and the density of the active material in the positive electrode active material layer is cold-pressed to 4 g / cm³. Finally, rectangular sawtooth-shaped tabs are formed by laser cutting, ultimately obtaining the positive electrode sheet 710. The aluminum foil current collector serves as the positive electrode sheet 710, and the active material in the positive electrode active layer may include at least one of lithium cobalt oxide, lithium manganese iron phosphate, lithium manganese vanadium phosphate, lithium chromium iron phosphate, and lithium manganese oxide. In this embodiment, lithium cobalt oxide is used as an example.

[0049] Graphite, conductive carbon black, and styrene-butadiene rubber were mixed in a weight ratio of 95:2.5:2.5, and deionized water was added as a solvent to prepare a slurry with a solid content of 0.8%, which was then stirred evenly. The slurry was uniformly coated onto the non-perforated area of ​​the copper foil current collector prepared above to form a negative electrode active material layer, and the content of active material in the negative electrode active material layer was 96 g / m2. The mixture was dried at 110℃, and the density of the active material in the negative electrode active material layer was cold-pressed to 1.8 g / cm3. Finally, rectangular sawtooth-shaped tabs were formed by laser cutting, resulting in the negative electrode sheet 720. The copper foil current collector serves as the negative electrode sheet 720, and the active material in the negative electrode active layer includes at least one of graphite, soft carbon, or hard carbon; in this embodiment, graphite is used as an example.

[0050] The prepared positive electrode 710 and negative electrode 720 are wound to form a core by alternating negative electrode 710, separator 730, and positive electrode 720. The core is placed inside the casing, and the exposed negative electrode is directly contacted to the bottom of the battery casing and then welded using laser welding. The exposed positive electrode is directly contacted to the battery cover and then welded using laser welding. An electrolyte (LiPF6 EC / DMC solution, where the volume ratio of EC to DMC is 1:1) is injected, followed by formation and capacity testing. For example, a cylindrical lithium-ion battery with a cell diameter of 46 mm and a height of 80 mm is obtained.

[0051] Figure 8 This invention provides a schematic diagram of the tab cutting shape for a full-tab battery cell according to an embodiment of the present invention. (See attached diagram.) Figure 8 The shape of the tabs in the unfurnished area can be rectangular serrated, directly cut open, or triangular serrated.

[0052] This invention provides an embodiment for testing the electrochemical performance of batteries prepared with different parameters. The test conditions are: 2C discharge at 25°C. Five battery structures were set up for comparative testing. The cylindrical lithium-ion battery cell provided in the above embodiment was used as the first structure. The second structure differs from the first structure in that the diameter of the laser-drilled holes in the base film 110 treatment is 3 micrometers, and the density is 30 holes / cm². 2 The third group of structures differs from the first group in that the electrode tabs are formed by laser cutting to create triangular sawtooth-shaped tabs. The first group of comparative structures differs from the first group in that the base film 110 does not have through holes, and the positive electrode is welded to both sides of the composite aluminum foil current collector using aluminum foil transfer welding to form the positive electrode tab. The negative electrode is welded to both sides of the composite copper foil current collector using nickel foil transfer welding to form the negative electrode tab. The second group of comparative structures differs from the second group in that the diameter of the laser-drilled holes in the base film 110 is 3 micrometers, and the density is 10 holes / cm². 2 The micropores are circular. The electrochemical performance test results are shown in Table 1.

[0053] Table 1 shows the results of the electrochemical performance test.

[0054] Internal resistance (mΩ) Temperature rise (°C) after 2C discharge First group structure 1 2.5 Second group structure 1.3 3 Third group structure 0.9 2.3 First set of contrasting structures 3.5 6 The second set of contrast structures 2 5

[0055] Comparing the first set of structures with the first set of comparative structures, it can be concluded that by using the electrode sheet structure of this utility model, the transfer welding process can be omitted, thereby reducing the battery's internal resistance and temperature rise. Comparing the second set of structures with the second set of comparative structures, it can be concluded that when the density of through-holes on the base film 110 is low, it affects the current transmission on both sides of the composite current collector, leading to increased internal resistance and higher temperature rise. Comparing the third set of structures with the first set of structures, it can be concluded that when the electrode tabs are cut into a triangular serrated shape and wound into a cylindrical cell, there is less overlap between the electrode tabs, thus slightly reducing the cell's internal resistance.

[0056] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this utility model, and not to limit it. Although this utility model has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this utility model.

Claims

1. A composite current collector, characterized in that, include: Base film and metal layer; The base film includes a through-hole region, and multiple through-holes are provided in the through-hole region; the through-holes penetrate the base film; metal layers are respectively provided on opposite surfaces of the base film; the metal layers are electrically connected to each other through the through-holes; wherein, the through-hole region completely covers the base film, or, the through-hole region at least covers the side regions on opposite sides of the base film, and the side regions serve as full tab regions.

2. The composite current collector according to claim 1, characterized in that, The through holes are arranged in a matrix array within the through hole region; Alternatively, within the through-hole region, the through-holes are arranged in a row along a first direction and offset from a row of through-holes arranged adjacent to each other in a second direction, forming a staggered arrangement that intersects with the through-holes adjacent to each other in the second direction; wherein the first direction is perpendicular to the second direction.

3. The composite current collector according to claim 2, characterized in that, The through hole is circular or elliptical.

4. The composite current collector according to claim 3, characterized in that, When the through-hole is circular, its diameter is 1-5 μm; when the through-hole is elliptical, its major axis length is 1-5 μm; and the density of the through-holes is 10-200 per cm³. 2 .

5. The composite current collector according to claim 1, characterized in that, It also includes a riveting layer; the riveting layer is disposed between the metal layer and the base film; the riveting layer is connected through the through hole.

6. The composite current collector according to claim 5, characterized in that, The riveting layer is one of copper alloy, nickel, nickel alloy, titanium, silver, aluminum, or aluminum alloy.

7. The composite current collector according to claim 6, characterized in that, The thickness of the riveting layer is 10-100 nm.

8. The composite current collector according to claim 1, characterized in that, It also includes a protective layer disposed on the surface of the metal layer.

9. The composite current collector according to claim 8, characterized in that, The thickness of the protective layer is less than or equal to one-tenth of the thickness of the metal.

10. A omnipolar battery cell, characterized in that, Includes the composite current collector as described in any one of claims 1-9.

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