CN115775874A - A kind of positive electrode active material and preparation method thereof, battery, electrical device - Google Patents

Abstract

The application discloses a positive electrode active material, a preparation method thereof, a battery, and an electric device. The positive electrode active material includes a core layer and a cladding layer arranged on the surface of _the core layer, the cladding layer includes nanomaterials, and the nanomaterials include RuOCl and _M2O3 , wherein M includes at least one of Al, Ga, In or Y . The present application significantly improves the electrical performance of the positive electrode active material by coating the nanomaterial composed of RuOCl and M ₂ O ₃ on the surface of the cobalt-free layered positive electrode active material.

Description

A kind of positive electrode active material and preparation method thereof, battery, electrical device

technical field

The present application relates to the field of new energy technology, in particular to a positive electrode active material and a preparation method thereof, a battery, and an electrical device.

Background technique

Lithium-ion batteries have received a lot of attention as the core of electric vehicles and energy storage and conversion. Studies have shown that cathode active materials play a decisive role in battery energy density, safety, and service life. Among many cathode active materials, ternary cathode active materials, especially high-nickel NCMs, have been extensively studied. However, Ni-rich layered oxide cathodes suffer from many surface side effects and microstructural defects, such as residual lithium compounds, HF attack, structural degradation, intergranular/intragranular cracks, and low conductivity during cycling, ultimately resulting in reduced battery cycle life. In cobalt-free layered cathode materials, due to the lack of cobalt, the electronic conductivity of the material is poor, the migration speed of lithium ions is slow, the mixing of lithium and nickel is serious, and the layered structure becomes poor, especially for cobalt-free nickel-rich layered cathode materials. The cycle life of the active material has a great influence.

Contents of the invention

The application provides a positive electrode active material, a preparation method thereof, a battery, and an electrical device, which solve the problem of poor cycle performance of the current cobalt-free layered positive electrode active material.

According to the positive electrode active material provided in the first aspect of the present application, it includes a core layer and a cladding layer disposed on the surface of the core layer, the cladding layer includes nanomaterials, and the nanomaterials include RuOCl and M ₂ O ₃ , wherein M includes Al, Ga At least one of , In or Y.

Optionally, in other embodiments of the present application, the material of the core layer includes a compound of the chemical formula Li _b Ni _{x Mny} O ₂ , where 1.05≤b≤1.15, 0.5<x<1, and x+y=1.

Optionally, in other embodiments of the present application, the nanomaterial satisfies at least one of the following characteristics:

(a) D50 of nanomaterials is 50nm～200nm;

(b) The specific surface area of the nanomaterial is BET, and the unit is m ² /g, satisfying: 1000≤BET≤1500.

Optionally, in other embodiments of the present application, the molar ratio of RuOCl to M ₂ O ₃ is (0.01˜0.05):1.

Optionally, in other embodiments of the present application, the material of the core layer is a layered single crystal material, and the material of the core layer satisfies at least one of the following characteristics:

(i) D50 of the material of the core layer is 2 μm to 4 μm;

(ii) The material of the core layer has a specific surface area of 0.4 m ² /g to 0.8 m ² /g.

Optionally, in other embodiments of the present application, the mass ratio of the nanomaterial to the material of the core layer is (0.1˜1):100.

According to the preparation method of the positive electrode active material provided by the second aspect of the present application, comprising:

Provide nano carbon fiber cardboard;

A mixed solution of RuCl ₃ and chloride salt is added dropwise on the heated nano-carbon fiber cardboard to obtain nanomaterials;

Provide nuclear material;

The nanometer material and the core layer material are mixed and calcined to obtain the positive electrode active material.

Optionally, in other embodiments of the present application, the chloride salt includes at least one of AlCl ₃ , GaCl ₃ , InCl ₃ or YCl ₃ .

Optionally, in other embodiments of the present application, the core layer material includes a compound of the chemical formula Li _b Ni _{x Mny} O ₂ , wherein 1.05≦b≦1.15, 0.5<x<1, and x+y=1.

Optionally, in other embodiments of the present application, the heating temperature of the carbon nanofiber paperboard is 300°C-400°C.

The battery provided according to the third aspect of the present application includes a positive electrode sheet, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer includes the above-mentioned positive electrode active material.

The electric device provided according to the fourth aspect of the present application includes the above-mentioned battery.

The positive electrode active material according to the embodiment of the present application has at least the following technical effects:

The positive electrode active material of the present application includes a cladding layer, and the cladding layer includes nanomaterials, and the nanomaterials include RuOCl and M ₂ O ₃ . Due to the many active sites of Ru, RuOCl is dispersed in _M2O3 with high acid resistance and high oxidation resistance, which increases the oxidation potential and slows down the corrosion of RuOCl. The synergistic effect of the _two makes the nanomaterial have excellent conductivity. and stability. Then, the nanomaterial and the core layer are mixed and coated to significantly improve the electrical performance of the positive electrode active material, especially the cycle performance.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that need to be used in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, other drawings can also be obtained based on these drawings without any creative effort.

Figure 1 is an electron microscope characterization test diagram of the surface morphology of the positive electrode active material provided by the embodiment of the present application;

Fig. 2 is a flow chart of the preparation method of the cathode active material provided by the present application.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the application with reference to the drawings in the embodiments of the application. Apparently, the described embodiments are only some of the embodiments of the application, not all of them. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts belong to the scope of protection of this application.

In this specification, the numerical range shown using "-" means the range which includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively.

Embodiments of the present application provide a positive electrode active material, a preparation method thereof, a battery, and an electrical device. Each will be described in detail below. It should be noted that the description sequence of the following embodiments is not intended to limit the preferred sequence of the embodiments.

The first aspect of the present application provides a positive electrode active material, including a core layer and a cladding layer disposed on the surface _of the core layer, the cladding layer includes nanomaterials, and the nanomaterials include RuOCl and _M2O3 , wherein M includes Al, Ga At least one of , In or Y. The nanomaterial is denoted as RuOCl@M ₂ O ₃ , and Figure 1 is an electron microscope characterization test diagram of the surface morphology of the positive electrode active material. Due to the many active sites of Ru, RuOCl is dispersed in _M2O3 with high acid resistance and high oxidation resistance, which increases the oxidation potential and slows down the corrosion of RuOCl. The synergistic effect of the _two makes the nanomaterial have excellent conductivity. and stability. Then, the nanomaterial and the core layer are mixed and coated to significantly improve the electrical performance of the positive electrode active material, especially the cycle performance.

In some embodiments of the present application, the material of the core layer includes a compound of the chemical formula Li _b Ni _{x Mny} O ₂ , wherein 1.05≦b≦1.15, 0.5<x<1, and x+y=1.

In some embodiments of the present application, the D50 of the nanomaterial may be 50nm-200nm, such as 70nm, 80nm, 90nm, 110nm, 120nm, 160nm, 170nm or any two numbers thereof. In some embodiments of the present application, the D50 of the nanomaterial may also be 100 nm˜180 nm. In some embodiments of the present application, the D50 of the nanomaterial may also be 130nm-150nm. The particle size of the nanomaterial is nanometer level, which makes the effect of coating better.

In some embodiments of the present application, the specific surface area BET of the nanomaterial is in m ² /g, which satisfies: 1000≤BET≤1500, for example, it can be 1050, 1150, 1250, 1350, 1450 or any two of them range. In some embodiments of the present application, 1100≤BET≤1400. In some embodiments of the present application, 1200≤BET≤1300. Nanomaterials have a larger specific surface area, which is conducive to improving the coating effect.

In some embodiments of the present application, the molar ratio of RuOCl and M ₂ O ₃ may be (0.01-0.05):1, (0.02-0.04):1, or 0.03:1. When the molar ratio of RuOCl and M ₂ O ₃ is within this range, the nanomaterial has excellent electrical conductivity and also increases the stability of the material, so that the electrical conductivity and stability are balanced. When the molar ratio is lower than the range, the active sites are less and the conductivity is weakened; when the molar ratio is higher than the range, the stability of the material is poor.

In some embodiments of the present application, the material of the core layer is a layered single crystal material, and the D50 of the material of the core layer may be 2 μm to 4 μm, such as 2.2 μm, 2.3 μm, 2.5 μm, 2.7 μm, 2.8 μm or A range consisting of any two numbers among them. When the D50 of the material of the core layer is in this range, the DC resistance (DCR) is low, the capacity is normal, and the cycle stability is better. The D50 of the material of the core layer is lower than this range, the DCR is low, and the capacity is high, but its cycle stability is poor, the gas production is serious, and the safety performance is deteriorated; the D50 of the material of the core layer is higher than this range, the DCR increases, and the capacity On the low side.

In some embodiments of the present application, the specific surface area of the material of the core layer may be 0.4m ² /g-0.8m ² /g, for example, it may be 0.45m ² /g, 0.55m ² /g, 0.65m ² /g , 0.75m ² /g or any two of them. In some embodiments of the present application, the specific surface area of the material of the core layer may also be 0.5 m ² /g˜0.7 m ² /g. In some embodiments of the present application, the specific surface area of the material of the core layer may also be 0.6 m ² /g. The material fine powder of the core layer with the specific surface area within this range is less, and the surface of the particles is smoother. The specific surface area of the material of the core layer is higher than this range, the fine powder is more, the surface is rough, and the stability of the material of the core layer is poor.

In some embodiments of the present application, the mass ratio of the nanomaterial to the material of the core layer may be (0.1-1): 100, or (0.2-0.8): 100, or (0.5-0.7): 100 . When the mass ratio of the nanomaterial to the material of the core layer is within this range, the coating effect of the nanomaterial is better, the conductivity of the positive electrode active material is good, and the cycle performance is excellent. When the mass ratio is lower than the range, the thickness of the coating layer is small, and the circulation of the positive electrode active material is poor. When the mass ratio is higher than the range, the coating layer is thick, hinders ion diffusion, and cannot exert capacity.

Correspondingly, the second aspect of the present application provides a method for preparing a positive electrode active material, as shown in FIG. 2 , including:

S1: Provide nano-carbon fiber cardboard;

S2: adding the mixed solution of RuCl ₃ and chloride salt dropwise on the heated nano-carbon fiber cardboard to obtain nano-materials;

S3: Provide nuclear material;

S4: Mixing and calcining the nanometer material and the core layer material to obtain the positive electrode active material.

The obtained positive electrode active material is a cobalt-free layered single crystal positive electrode active material, which is denoted as Li _b Ni _{x Mny} O ₂ @aRuOCl@M ₂ O ₃ , where a is the molar ratio of RuOCl to M ₂ O ₃ .

The present application makes nanomaterials by adding RuCl ₃ and chloride salt mixed solution dropwise in heated nano-carbon fiber paperboard (CFP). Due to the porous structure of nano-CFP, the prepared nano-material has a large specific surface area and a particle size of nanometer level, which is beneficial to the later coating effect.

In some embodiments of the present application, the chloride salt includes at least one of AlCl ₃ , GaCl ₃ , InCl ₃ or YCl ₃ .

In some embodiments of the present application, the core layer material includes a compound of the chemical formula Li _b Ni _{x Mny} O ₂ , wherein 1.05≦b≦1.15, 0.5<x<1, and x+y=1.

In some embodiments of the present application, the heating temperature of the carbon nanofiber paperboard may be 300°C-400°C, or 320°C-380°C, or 350°C-370°C. The heating temperature within this range can make the agglomeration degree of the obtained nano material relatively small and the specific surface area large.

Specifically, in step S4, the calcining temperature can be 300°C-400°C, or 320°C-380°C, or 350°C-370°C; the calcining time can be 4-8 hours, or 5-7 hours, may also be 6 hours; the calcining atmosphere is oxygen or air.

During specific implementation, the preparation method of positive electrode active material comprises:

1) The carbon nanofiber paperboard (CFP) is first washed with acetone, ethanol and deionized water in sequence, then heated on a hot plate at 250°C to 300°C, and left to stand in the air for 20 minutes.

2) Weigh an appropriate amount of RuCl ₃ and chloride salt, and dissolve them in 100mL deionized water. Then drop the mixed solution on the nano-CFP heated to 300°C-400°C, and continue heating for 10min-30min to obtain the nanometer material.

3) Provide core material.

4) Mix the nanomaterial obtained in (2) with the core layer material in (3) according to a certain ratio (the nanomaterial accounts for 0.1% to 1% of the core layer material), and mix it in a high-speed mixer at 3000rpm～4000rpm Stirring for 20-30 minutes, and then calcining the obtained mixed material, the calcination temperature is 300°C-500°C, the calcination time is 4h-8h, and the calcination atmosphere is oxygen or air to obtain the positive electrode active material.

In addition, the third aspect of the present application provides a battery, including a positive electrode sheet, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer includes the above-mentioned positive electrode active material.

During specific implementation, the above-mentioned positive electrode active material is stirred evenly with a conductive agent, a binder, and a solvent, and the positive electrode sheet is made into a positive electrode sheet through processes such as sieving, coating, rolling, slitting, and cutting.

Specifically, the type of the conductive agent is not limited, and any known conductive agent can be used. Examples of conductive agents may include, but are not limited to, carbon materials such as natural graphite, artificial graphite, Super P conductive carbon black, acetylene black, needle coke, carbon nanotubes, and graphene. The above-mentioned positive electrode conductive agents can be used alone or in any combination.

The type of binder used in the production of the positive electrode active material layer is not particularly limited, and in the case of the coating method, any binder may be dissolved or dispersed in the liquid medium used in electrode production. Examples of binders may include, but are not limited to, one or more of polyethylene, polypropylene, polyvinylidene fluoride (PVDF), polytetrafluoroethylene, fluorinated polyvinylidene fluoride, and the like. The above binders can be used alone or in any combination.

The type of solvent used to form the positive electrode slurry is not limited, as long as it can dissolve or disperse the positive electrode active material, conductive agent, and binder. Examples of the solvent used to form the positive electrode slurry may include any one of aqueous solvents and organic solvents. Examples of the aqueous medium may include, but are not limited to, water, a mixed medium of alcohol and water, and the like. Examples of organic-based media may include, but are not limited to, hexane, benzene, toluene, xylene, pyridine, acetone, tetrahydrofuran (THF), N-methylpyrrolidone (NMP), and the like.

Specifically, the battery includes a positive pole piece, a negative pole piece, a separator and an electrolyte, and the positive pole piece is the above-mentioned positive pole piece. During specific implementation, the above-mentioned positive electrode sheet, negative electrode sheet, separator, electrolyte, etc. are assembled into a lithium ion battery. The negative electrode material used for the negative electrode sheet can be one or more of artificial graphite, natural graphite, mesocarbon microspheres, amorphous carbon, lithium titanate or silicon-carbon alloy. Negative electrode materials also need to have the characteristics of high compaction density, high mass specific capacity and high volume specific capacity.

A fourth aspect of the present application provides an electrical device, including the above-mentioned battery.

In some embodiments, the electrical devices of the present application are, but not limited to, backup power sources, motors, electric vehicles, electric motorcycles, power-assisted bicycles, bicycles, electric tools, large household storage batteries, and the like.

The following will be described in conjunction with specific embodiments.

Embodiment 1,

This embodiment provides a method for preparing a positive electrode active material, comprising the following steps:

1) Carbon nanofiber paperboard (CFP) was first washed with acetone, ethanol and deionized water in sequence, then heated on a hot plate at 250°C, and left to stand in the air for 20 minutes;

2) Weigh 0.85g RuCl ₃ and 53.87g AlCl ₃ and dissolve them in 100mL deionized water to make a mixed solution. Then the mixed solution was dropped on the nano-CFP heated to 350°C, and the heating was continued for 20min. The prepared nanomaterial 0.02RuOCl@Al ₂ O ₃ has a median particle size D50 of 89nm and a BET of 1347m ² /g;

3) Provide a cobalt-free single crystal layered core layer material Li _1.1 Ni _0.75 Mn _0.25 O ₂ with a median particle size D50 of 2.88 μm and a specific surface area of 0.49 m ² /g;

4) Mix the nanomaterial and core material obtained above at a high speed according to the mass ratio of 0.4:100, stir at 3500rpm for 25min, and calcinate the mixed material at 350°C for 5h in an oxygen atmosphere to obtain the finished positive electrode active material Li _1.1 Ni _0.75 Mn _0.25 O ₂ @0.02RuOCl@Al ₂ O ₃ .

Embodiment 2,

The preparation method of the positive electrode active material in Example 2 is the same as in Example 1, the difference is that 0.85g RuCl ₃ and 71.14g GaCl ₃ are weighed to make a mixed solution, and finally the finished positive electrode active material Li _1.1 Ni _0.75 Mn _0.25 O ₂ @0.02 RuOCl@Ga ₂ O ₃ .

Embodiment 3,

The preparation method of the positive electrode active material in Example 3 is the same as in Example 1, the difference is that 0.42g RuCl ₃ and 53.87g AlCl ₃ are weighed to make a mixed solution, and finally the finished positive electrode active material Li _1.1 Ni _0.75 Mn _0.25 O ₂ @0.01 RuOCl@Al ₂ O ₃ .

Embodiment 4,

The preparation method of the positive electrode active material in Example 4 is the same as in Example 1, the difference is that 2.11g RuCl ₃ and 53.87g AlCl ₃ are weighed to make a mixed solution, and finally the finished positive electrode active material Li _1.1 Ni _0.75 Mn _0.25 O ₂ @0.05 RuOCl@Al ₂ O ₃ .

Embodiment 5,

The preparation method of the positive electrode active material in Example 5 is the same as in Example 1, except that the median particle diameter D50 of the provided core layer material is 3.42 μm and the specific surface area is 0.41 m ² /g.

Embodiment 6,

The preparation method of the positive electrode active material in Example 6 is the same as in Example 1, except that the median particle diameter D50 of the provided core layer material is 2.26 μm and the specific surface area is 0.69 m ² /g.

Embodiment 7,

The preparation method of the positive electrode active material in Example 7 is the same as that in Example 1, except that the mass ratio of the nanomaterial to the core layer material is 0.1:100.

Embodiment 8,

The preparation method of the positive electrode active material in Example 8 is the same as in Example 1, except that the mass ratio of the nanomaterial to the core layer material is 1:100.

Comparative example 1,

The preparation method of the positive electrode active material of Comparative Example 1 is the same as that of Example 1, except that the same proportion of Al ₂ O ₃ is directly coated on the surface of the provided cobalt-free layered core layer material.

Comparative example 2,

The preparation method of the positive electrode active material of Comparative Example 2 is the same as in Example 1, the difference is that 4.23g RuCl ₃ and 53.87g AlCl ₃ are weighed to make a mixed solution, and finally the finished positive electrode active material Li _1.1 Ni _0.75 Mn _0.25 O ₂ @0.1 RuOCl@Al ₂ O ₃ .

Comparative example 3,

The preparation method of the positive electrode active material of Comparative Example 3 is the same as that of Example 1, the difference is that the mass ratio of nanomaterials and core layer materials is 1.5:100.

The positive electrode active material prepared in Examples and Comparative Examples, conductive carbon black (SP), and polyvinylidene fluoride (PVDF) were added to N-methylpyrrolidone (NMP) in a mass ratio of 92:4:4, and after mixing uniformly Coated on aluminum foil, dried at 100°C for 4 hours, cut into positive electrode pieces with a diameter of 12 mm, assembled into button half cells, left to stand for 12 hours, and carried out electrochemical tests.

The test method is as follows, and the results shown in Table 1 are obtained:

Capacity test: Use Xinwei or Landian detection cabinet, charge at 0.1C, cut-off voltage 4.3V, discharge at 0.1C, cut-off voltage 3V.

Cycle test: Use Xinwei or Landian detection cabinet, charge at 0.5C, cut-off voltage 4.3V, discharge at 1C, cut-off voltage 3V, cycle for 50 cycles.

Table 1

Comparing Examples 1 to 8 and Comparative Example 1, the discharge capacity and cycle retention rate of Examples 1 to 8 are all higher than Comparative Example 1, and Examples 1 to 8 are coated with the nanomaterial of the present application, while Comparative Example 1 is only The use of Al ₂ O ₃ for coating shows that the use of nanomaterials of the present application for coating can significantly improve the electrical properties of the positive electrode active material, including cycle performance.

Comparing Examples 1 to 4 and Comparative Example 2, the discharge capacity and cycle retention of Examples 1 to 4 are higher than that of Comparative Example 2, and the molar ratio of RuOCl and _Al2O3 in Examples 1 to ₄ is within the scope of the present application , indicating that when the molar ratio of RuOCl and Al ₂ O ₃ is within the range of the present application, the prepared nanomaterials have better stability, and the nanomaterials have a better effect after coating, which can significantly improve the electrical properties of the positive electrode active material.

Comparing Examples 7-8 and Comparative Example 3, the discharge capacity and cycle retention rate of Examples 7-8 are all higher than Comparative Example 3, and the mass ratio of nanomaterials and core layer materials in Examples 7-8 is within the scope of the present application It shows that when the mass ratio of the nanomaterial and the core layer material is within the scope of the present application, the coating effect of the nanomaterial is better, which can significantly improve the electrical properties of the positive electrode active material, and the positive electrode active material has good conductivity and excellent cycle performance. .

The present application significantly improves the electrical performance of the positive _electrode active material by coating the nanomaterial composed of RuOCl and _M2O3 on the surface of the cobalt-free layered positive electrode active material.

The anode active material provided by the application and its preparation method, battery, and electrical device have been introduced in detail above. In this paper, specific examples have been used to illustrate the principle and implementation of the application. The description of the above examples is only It is used to help understand the method and its core idea of this application; at the same time, for those skilled in the art, according to the idea of this application, there will be changes in the specific implementation and application scope. In summary, this specification The content should not be construed as a limitation of the application.

Claims (10)

1. The positive active material is characterized by comprising a core layer and a coating layer arranged on the surface of the core layer, wherein the coating layer comprises a nano material, and the nano material comprises RuOCl and M ₂ O ₃ Wherein M comprises at least one of Al, ga, in or Y.

2. The positive electrode active material according to claim 1, wherein the material of the core layer comprises Li _b Ni _x Mn _y O ₂ Wherein b is more than or equal to 1.05 and less than or equal to 1.15, x is more than 0.5 and less than 1, x + y =1.

3. The positive electrode active material according to claim 1, wherein the nanomaterial satisfies at least one of the following characteristics:

(a) The D50 of the nano material is 50 nm-200 nm;

(b) The nano material has a specific surface area BET of m ² (iv)/g, satisfying: BET is more than or equal to 1000 and less than or equal to 1500.

4. The positive active material of claim 1, wherein the RuOCl and the M ₂ O ₃ The molar ratio of (0.01-0.05): 1.

5. the positive electrode active material according to claim 1, wherein the material of the core layer is a layered single crystal material, and the material of the core layer satisfies at least one of the following characteristics:

(i) The D50 of the material of the nuclear layer is 2-4 mu m;

(ii) The specific surface area of the material of the core layer is 0.4m ² /g～0.8m ² /g。

6. The positive electrode active material according to claim 1, wherein the mass ratio of the nanomaterial to the material of the core layer is (0.1 to 1): 100.

7. a method for producing a positive electrode active material according to any one of claims 1 to 6, comprising:

providing a carbon nanofiber paperboard;

RuCl is added ₃ And the mixed solution of chloride is dripped on the heated carbon nanofiber paperboard to obtain a nanomaterial;

providing a core layer material;

and mixing and calcining the nano material and the core layer material to obtain the cathode active material.

8. The method for preparing a positive electrode active material according to claim 7, wherein the chloride salt comprises AlCl ₃ 、GaCl ₃ 、InCl ₃ Or YCl ₃ At least one of (a); and/or the presence of a gas in the gas,

the core layer material comprises a material of the chemical formula Li _b Ni _x Mn _y O ₂ Wherein b is more than or equal to 1.05 and less than or equal to 1.15, x is more than 0.5 and less than 1, x + y =1; and/or the presence of a gas in the atmosphere,

the heating temperature of the carbon nanofiber paperboard is 300-400 ℃.

9. A battery comprising a positive electrode tab, wherein the positive electrode tab comprises a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, and the positive electrode active material layer comprises the positive electrode active material as claimed in claim 7 or claim 8.

10. An electric device comprising the battery of claim 9.

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