CN114695868A - Silicon-based prelithiation material and preparation method and application thereof - Google Patents
Silicon-based prelithiation material and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
Abstract
The invention provides a silicon-based prelithiation material and a preparation method and application thereof, wherein the silicon-based prelithiation material has a structural general formula of LixSiOyWherein 1 is<x is less than or equal to 6, and y is less than or equal to 4 and more than or equal to 2. The silicon-based prelithiation material may also be composited with a carbon material. The two materials can be applied to the preparation of the positive pole piece of the lithium battery, and then the lithium battery is prepared. The lithium battery assembled by the silicon-based prelithiation material has obvious lithium supplementing effect on the lithium battery and high theoretical capacity, and the residual substances after the lithium removal of the material are mainly SiO2，SiO2Is an inorganic filling ceramic material commonly used for preparing polymer electrolytes, does not bring side effects to batteries and is beneficial to improving the safety.
Description
Technical Field
The invention belongs to the technical field of lithium battery materials, and particularly relates to a silicon-based pre-lithiation material as well as a preparation method and application thereof.
Background
Because of the advantages of high voltage, large capacity, high energy density, no memory effect, long cycle life and the like, the lithium ion battery is widely applied to the fields of consumer electronics products, energy storage power grids, electric vehicles and the like as an important energy storage device, and the lithium ion battery is also required to have higher capacity and energy density according to current market demands. However, in the current lithium ion battery, graphite is used as a negative electrode material, and during the first charge and discharge process, an organic electrolyte solution is reduced and decomposed on the surface of the graphite to form a Solid Electrolyte Interface (SEI) film, so that a large amount of active lithium from a positive electrode is permanently consumed, reversible active lithium in the battery is reduced, the first coulombic efficiency is low, and the capacity and energy density of the battery are reduced. Existing graphite anodes typically suffer from 5% to 10% loss of first week irreversibly active lithium, which is more of the first week irreversibly active lithium loss for high capacity anodes, such as hard carbon, silicon carbon anodes, and the like.
The most important method for solving the problem is to pre-lithiate the anode/cathode before the cycle, and compensate the irreversible loss caused by the SEI film formation by lithium supplement, so as to improve the capacity and energy density of the battery. Generally, a negative electrode pre-lithium method uses lithium foil for lithium supplement and lithium powder for lithium supplement, such as patents CN201480026582 and CN201210056121, and this lithium supplement method is very effective and has little influence on the cell structure, but the lithium foil/lithium powder has very strict requirements on the environment, is difficult to control, has a certain operation safety hazard, has very high requirements on equipment, and greatly increases the cost of the cell. Therefore, the use of lithium-rich materials for lithium supplementation of the positive electrode may be a very promising prelithiation technique, and the development of high-quality lithium-rich materials becomes an urgent task.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a silicon-based prelithiation material, a preparation method and application thereof. The technical scheme of the invention is as follows:
in a first aspect, the invention provides a silicon-based prelithiation material, the structural general formula of which is LixSiOyWherein 1 is<x≤6，2≤y≤4。
Further, the preparation method of the silicon-based prelithiation material comprises the following steps: ball-milling and mixing a lithium source and a silicon source; then sintering; and cooling to room temperature after sintering is finished, and then primarily crushing and crushing the obtained material again to obtain the silicon-based pre-lithiation material.
Furthermore, the particle size of the lithium source and the silicon source is 10nm-100 um.
Further, the lithium source is at least one selected from lithium carbonate, lithium hydroxide and lithium acetate.
Further, the silicon source is at least one selected from silicon dioxide, silicon carbonate, silicon acetate, ethyl orthosilicate and coal gangue.
Further, the sintering temperature is 600-950 ℃.
Further, the silicon-based prelithiation material has a particle size of 50nm-50 um.
In a second aspect, the invention provides a silicon-based prelithiation material compounded by carbon materials, wherein the carbon materials are coated on the surface of the silicon-based prelithiation material.
Furthermore, the mass ratio of the carbon material to the silicon-based pre-lithiation material is 1 (20-1000).
Further, the carbon material is selected from one or more of amorphous carbon, graphene, carbon nanotubes and conductive graphite.
In a third aspect, the invention provides an application of the silicon-based pre-lithiation material and the silicon-based pre-lithiation material compounded by the carbon material in preparation of a lithium battery positive pole piece.
Further, the method for preparing the positive pole piece of the lithium battery comprises the following steps: mixing and homogenizing the silicon-based pre-lithiation material or the silicon-based pre-lithiation material compounded by the carbon material, the positive electrode material, the conductive agent and the adhesive, then coating the mixture on an aluminum foil current collector, pre-drying and rolling the mixture, and then drying the mixture in vacuum for 8 to 16 hours at the temperature of between 80 and 120 ℃ to obtain the lithium-based lithium-ion battery.
In a fourth aspect, the invention provides a lithium battery, which includes the above positive electrode plate.
Compared with the existing prelithiation material, the invention has the following advantages and beneficial effects:
firstly, the silicon-based prelithiation material of the invention has the advantages of simple and easily obtained raw materials and low price.
Secondly, the silicon-based prelithiation material disclosed by the invention is simple in synthesis method, does not need special environmental treatment, and is easy to realize industrial production.
Thirdly, the silicon-based pre-lithiation material has obvious lithium supplementing effect and high theoretical capacity, and substances remained after the material is subjected to lithium removal are mainly SiO2，SiO2Is an inorganic filling ceramic material commonly used for preparing polymer electrolyteIt does not cause any adverse effect on the battery and contributes to improvement of safety.
Drawings
Fig. 1 is a scanning electron micrograph of a prelithiated material provided in example 1 of the present invention.
Fig. 2 is an XRD diffractogram of the prelithiated material provided in example 1 of the present invention.
Fig. 3 is a first week charge diagram of a prelithiated material provided in example 1 of the present invention.
Detailed Description
In the embodiment of the invention, the ball milling and mixing equipment can be one of a double-motion mixer, a three-dimensional mixer, a V-shaped mixer, a single-cone double-helix mixer, a groove type helical ribbon mixer and a horizontal type gravity-free mixer.
In the embodiment of the invention, the sintering equipment can be one of a box furnace, a tube furnace, a roller kiln and a rotary furnace.
In an embodiment of the invention, the crushing plant may be selected from one of a jaw crusher, a cone crusher, a counterimpact crusher, a hammer crusher and a roller crusher.
In the embodiment of the present invention, the pulverization apparatus may select one of a flat jet mill, a fluidized bed jet mill, a circulating jet mill, an impact mill, an expansion mill, a ball mill pulverizer, a high-speed rotary projectile mill, and a high-speed rotary impact mill.
In the description of the present invention, it is to be noted that those whose specific conditions are not specified in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturers. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
Example 1 provides a silicon-based pre-lithium material Li4SiO4The preparation process comprises weighing lithium hydroxide with particle size of 1um and silica material with particle size of 200nm according to corresponding stoichiometric ratioAnd (2) mixing the two materials in a molar ratio of lithium ions to silicon ions of 4.1:1 in a ball mill, adding water serving as a dispersing agent, and performing revolution at a revolution speed of 600rpm and rotation at a rotation speed of 300rpm for 5 hours. Taking out the mixture, placing the mixture in a tube furnace for sintering at 850 ℃ under the argon atmosphere for 10 hours, and naturally cooling. Crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain Li4SiO4The pre-lithiated material has a particle size of 50nm to 50um, and the morphology is shown in a Scanning Electron Microscope (SEM) diagram of FIG. 1, and the X-ray diffraction (XRD) result is shown in FIG. 2.
Preparing a positive pole piece: the prepared silicon-based prelithiation material Li4SiO4The conductive agent Super P and the adhesive PVDF are mixed according to the mass ratio of 80:10:10, and NMP is used as a dispersing agent; coating the obtained slurry on an aluminum foil current collector, wherein the coating thickness is 200 um; and rolling the obtained pole piece, drying the pole piece in vacuum at 110 ℃ for 12 hours, and cutting the pole piece into a circular piece with the diameter of 12mm for later use.
Assembling the button cell: at 1.0mol/L LiPF6EC/EMC (3:7v/v) as electrolyte, Li plate with diameter of 14mm as negative electrode, Cellgard-2400 type separator, CR2032 button cell assembled in a glove box filled with argon.
Electrochemical testing: a constant-current charge-discharge mode test was carried out using a charge-discharge instrument, model No. CT2001A, available from Wuhan blue electronics, Inc., at a test temperature of 25 deg.C, a voltage range of 3.0-4.4V, and a current density of 50 mAh/g. The first cycle charge and discharge of the silicon-based pre-lithium material of example 1 are shown in FIG. 3, and the result shows that the specific charge capacity is 660 mAh/g.
Example 2
Example 2 provides a silicon-based pre-lithium material Li2SiO3The preparation process comprises the steps of weighing lithium carbonate with the particle size of 500nm and silicon dioxide material with the particle size of 500nm according to corresponding stoichiometric ratio, wherein the molar ratio of lithium ions to silicon ions in the two materials is 2.1:1, placing the two materials in a V-shaped conical spiral mixer, mixing at a high speed of 400rpm for 1 hour. Taking out the mixture, placing in a muffle furnace under air atmosphereSintering at 800 deg.c for 8 hr, and natural cooling. Crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain Li2SiO3And (3) assembling the pre-lithiated material with the granularity of 50nm-50um according to the method of the embodiment 1, and carrying out electrochemical test, wherein the charging specific capacity is 380 mAh/g.
Example 3
Example 3 provides a silicon-based pre-lithium material Li8SiO6The preparation process comprises the steps of weighing lithium hydroxide with the particle size of 500nm and silicon dioxide material with the particle size of 200nm according to corresponding stoichiometric ratio, wherein the molar ratio of lithium ions to silicon ions in the two materials is 8.2:1, and mixing the two materials at high speed in a V-shaped conical spiral mixer, wherein the rotating speed is 400rpm, and the mixing time is 1 hour. Taking out the mixture, placing the mixture in a tube furnace for sintering at 850 ℃ under the argon atmosphere for 16 hours, and naturally cooling. Crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain Li8SiO6And (3) assembling the pre-lithiated material with the granularity of 50nm-50um according to the method of the example 1, and carrying out electrochemical test, wherein the charging specific capacity is 880 mAh/g.
Example 4
Example 4 provides a silicon-based pre-lithium material Li3SiO3.5The preparation process comprises the steps of weighing lithium carbonate with the particle size of 500nm and silicon carbonate with the particle size of 500nm according to corresponding stoichiometric ratio, wherein the molar ratio of lithium ions to silicon ions in the two materials is 3.1:1, and mixing the two materials at a high speed in a V-shaped conical spiral mixer, wherein the rotating speed is 400rpm, and the mixing time is 2 hours. Taking out the mixture, placing the mixture in a tube furnace to sinter at 900 ℃ in argon atmosphere for 12 hours, and naturally cooling. Crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain Li3SiO3.5And (3) assembling the pre-lithiated material with the granularity of 50nm-50um according to the method of the example 1, and carrying out electrochemical test, wherein the charging specific capacity is 510 mAh/g.
Example 5
Practice ofExample 5 provides a silicon-based pre-lithium material Li3.4SiO3.7The preparation process comprises the steps of weighing lithium hydroxide with the particle size of 2um and tetraethoxysilane material with the particle size of 500nm according to corresponding stoichiometric ratio, wherein the molar ratio of lithium ions to silicon ions in the two materials is 3.5:1, and mixing the two materials at a high speed in a V-shaped conical spiral mixer at the rotating speed of 400rpm for 2 hours. Taking out the mixture, placing the mixture in a tube furnace for sintering at 870 ℃ in nitrogen atmosphere for 12 hours, and naturally cooling. Crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain Li3.4SiO3.7The prelithiated material, with a particle size of 50nm-50um, was assembled into button cells and tested electrochemically according to the method of example 1, with a specific charge capacity of 625 mAh/g.
Example 6
Example 6 provides a silicon-based pre-lithium material Li5.6SiO4.8The preparation process comprises the steps of weighing lithium acetate with the particle size of 500nm and a silicon dioxide material with the particle size of 500nm according to corresponding stoichiometric ratio, wherein the molar ratio of lithium ions to silicon ions in the two materials is 5.7:1, and mixing the two materials at a high speed in a V-shaped conical spiral mixer at the rotating speed of 400rpm for 2 hours. Taking out the mixture, placing the mixture in a tube furnace to sinter at 900 ℃ in argon atmosphere for 8 hours, and naturally cooling. Crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain Li5.6SiO4.8And (3) assembling the pre-lithiated material with the granularity of 50nm-50um according to the method of the example 1, and carrying out electrochemical test, wherein the specific charge capacity is 720 mAh/g.
Example 7
Example 7 provides a silicon-based pre-lithium material Li7.2SiO5.6The preparation process comprises the steps of weighing lithium hydroxide with the particle size of 500nm and gangue material with the particle size of 1um according to corresponding stoichiometric ratio, wherein the molar ratio of lithium ions to silicon ions in the two materials is 7.3:1, and mixing the two materials at a high speed in a V-shaped conical spiral mixer at the rotating speed of 400rpm for 2 hours. Taking out the mixture, placing the mixture in a tube furnace to sinter at 900 ℃ in an argon atmosphereSintering for 12 hours, and naturally cooling. Crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain Li7.2SiO5.6And (3) assembling the pre-lithiated material with the granularity of 50nm-50um according to the method of the example 1, and carrying out electrochemical test, wherein the specific charge capacity is 840 mAh/g.
Example 8
Embodiment 8 provides a carbon-coated silicon-based pre-lithium material Li4SiO4Is denoted as C-Li4SiO4The preparation method comprises the following steps of: 2:1 lithium hydroxide having a particle size of 500nm, lithium carbonate having a particle size of 400nm and silica having a particle size of 500nm were mixed in a V-cone screw mixer at a high speed of 400rpm for 2 hours. Taking out the mixture, placing the mixture in a muffle furnace, sintering the mixture in air at 850 ℃ for 6 hours, and naturally cooling the mixture. Crushing the sintered semi-finished product by using a jaw crusher, and crushing by using a jet mill to obtain Li4SiO4The granularity is 50nm-50 um. Then the obtained Li is4SiO4Mixing the carbon-coated pre-lithiation material and conductive graphite in a high-energy ball mill at the revolution speed of 600rpm and the rotation speed of 300rpm for 4 hours to obtain the carbon-coated pre-lithiation material C-Li4SiO4. The button cell was assembled and electrochemically tested according to the method of example 1, and the specific charge capacity was 670mAh/g, and compared to example 1, the slightly increased capacity was due to the sample being carbon coated, which has better conductivity, and the electrochemical reaction was easier to perform kinetically, which is beneficial to the release of capacity.
Example 9
Example 9 provides a carbon-coated silicon-based pre-lithium material Li2SiO3Is denoted as C-Li2SiO3The preparation method comprises the following steps of: 1 lithium carbonate having a particle size of 400nm and silica having a particle size of 500nm were mixed in a V-conical helical mixer at a high speed of 400rpm for a mixing time of 2 hours. Taking out the mixture, placing the mixture in a muffle furnace to sinter at 800 ℃ in the air for 6 hours, and naturally cooling. The second half of the sintering processCrushing the product by using a jaw crusher, and crushing the crushed product by using a jet mill to obtain Li2SiO3The granularity is 50nm-50 um. Then the obtained Li is2SiO3Mixing the carbon-coated carbon nano tube and the multi-wall carbon nano tube in a high-energy ball mill, adding an NMP solvent as a dispersing agent, wherein the revolution speed is 600rpm, the rotation speed is 300rpm, and the mixing time is 4 hours to obtain the carbon-coated pre-lithiation material C-Li2SiO3. The button cell was assembled and electrochemically tested as in example 1, and had a specific charge capacity of 385 mAh/g.
Examples 10 to 21
Examples 10 to 21 are uses of the silicon-based prelithiation material in a conventional positive electrode plate, and the silicon-based prelithiation material used is the Li prepared by the methods of examples 1 and 84SiO4And carbon-coated C-Li4SiO4. The positive electrode material used includes Lithium Cobaltate (LCO), nickel cobalt aluminum ternary material (NCA), nickel cobalt manganese ternary material (NCM811, NCM622, and NCM523), lithium manganese iron phosphate (LFMP).
Preparing a positive pole piece: mixing the prepared silicon-based prelithiation material, the anode material, the conductive agent SuperP and the adhesive PVDF according to the mass ratio of 10:80:5:5, and taking NMP as a dispersing agent; coating the obtained slurry on an aluminum foil current collector, wherein the coating thickness is 200 um; and rolling the obtained pole piece, drying the pole piece in vacuum at 110 ℃ for 12 hours, and cutting the pole piece into a circular piece with the diameter of 12mm for later use.
Assembling the button cell: at 1.0mol/L LiPF6EC/EMC (3:7v/v) as electrolyte, Li plate with diameter of 14mm as negative electrode, Cellgard-2400 type separator, CR2032 button cell assembled in a glove box filled with argon.
Electrochemical testing: a constant-current charge-discharge mode test was performed using a charge-discharge instrument, model CT2001A, available from Wuhan blue electronics, Inc., at a test temperature of 25 ℃ and a charge current magnification of 0.05C.
The voltage range and the test result are shown in table 1, and it can be known from the test result that after the pre-lithium material is added, the first cycle charging specific capacity of the button cell can be improved, and the carbon-coated pre-lithium material has better conductivity and better lithium supplementing effect.
TABLE 1 test results for examples 10 to 21
| Positive electrode material | Pre-lithium material | Voltage range (V) | Specific capacity of first cycle charge (mAh/g) | |
| Control group 1 | LCO | - | 3～4.6 | 220 |
| Example 10 | LCO | Li4SiO4 | 3～4.6 | 235.4 |
| Example 11 | LCO | C-Li4SiO4 | 3～4.6 | 239 |
| Control group 2 | NCA | - | 3～4.2 | 205 |
| Example 12 | NCA | Li4SiO4 | 3～4.2 | 218 |
| Example 13 | NCA | C-Li4SiO4 | 3～4.2 | 220 |
| Control group 3 | NCM811 | - | 3～4.2 | 215 |
| Example 14 | NCM811 | Li4SiO4 | 3～4.2 | 228 |
| Example 15 | NCM811 | C-Li4SiO4 | 3～4.2 | 231 |
| Control group 4 | NCM622 | - | 3～4.3 | 190 |
| Example 16 | NCM622 | Li4SiO4 | 3～4.3 | 208 |
| Example 17 | NCM622 | C-Li4SiO4 | 3～4.3 | 211.6 |
| Control group 5 | NCM523 | - | 3～4.4 | 192 |
| Example 18 | NCM523 | Li4SiO4 | 3～4.4 | 213 |
| Example 19 | NCM523 | C-Li4SiO4 | 3～4.4 | 217.5 |
| Control group 6 | LFMP | - | 3～4.2 | 182 |
| Example 20 | LFMP | Li4SiO4 | 3～4.2 | 195 |
| Example 21 | LFMP | C-Li4SiO4 | 3～4.2 | 198 |
In the data in table 1, the control group is the existing button cell assembled battery, which has no lithium supplement material added thereto, and the button cell assembled batteries added with examples 1 and 8 have a significant difference of 13-25.5 mAh/g in first cycle specific charge capacity.
In conclusion, compared with the existing lithium supplement material, the silicon-based pre-lithiation material has an obvious lithium supplement effect, and the first-cycle charging specific capacity of the silicon-based pre-lithiation material applied to the button cell is greatly improved. In addition, after the material is subjected to lithium removal, substances remained are mainly SiO2，SiO2Is an inorganic filling ceramic material commonly used for preparing polymer electrolytes, does not bring side effects to batteries and is beneficial to improving the safety. .
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A silicon-based prelithiation material, characterized by: the structural general formula of the silicon-based prelithiation material is LixSiOyWherein 1 is<x≤6，2≤y≤4。
2. A silicon-based prelithiation material according to claim 1, wherein: the preparation method of the silicon-based prelithiation material comprises the following steps: ball-milling and mixing a lithium source and a silicon source; then sintering; and cooling to room temperature after sintering is finished, and then primarily crushing and crushing the obtained material again to obtain the silicon-based pre-lithiation material.
3. A silicon-based prelithiation material according to claim 2, wherein: the lithium source is at least one selected from lithium carbonate, lithium hydroxide and lithium acetate.
4. A silicon-based prelithiation material according to claim 2, wherein: the silicon source is at least one selected from silicon dioxide, silicon carbonate, silicon acetate, ethyl orthosilicate and coal gangue.
5. A silicon-based prelithiation material compounded by carbon materials is characterized in that: the material is prepared by coating a carbon material on the surface of the silicon-based prelithiation material.
6. The carbon material-composited silicon-based prelithiation material according to claim 5, wherein: the mass ratio of the carbon material to the silicon-based pre-lithiation material is 1 (20-1000).
7. The carbon material-composited silicon-based prelithiation material according to claim 5 or 6, wherein: the carbon material is selected from one or more of amorphous carbon, graphene, carbon nanotubes and conductive graphite.
8. The application of the silicon-based prelithiation material as set forth in any one of claims 1 to 4 or the silicon-based prelithiation material as set forth in any one of claims 5 to 7 in the preparation of a positive electrode plate of a lithium battery.
9. Use according to claim 8, characterized in that: the method for preparing the lithium battery positive pole piece comprises the following steps: mixing and homogenizing the silicon-based pre-lithiation material or the silicon-based pre-lithiation material compounded by the carbon material, the positive electrode material, the conductive agent and the adhesive, then coating the mixture on an aluminum foil current collector, pre-drying and rolling the mixture, and then drying the mixture in vacuum for 8 to 16 hours at the temperature of between 80 and 120 ℃ to obtain the lithium-based lithium-ion battery.
10. A lithium battery, characterized in that: comprising the positive electrode sheet of claim 8 or 9.
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