JP5948941B2 - Method for producing electrode active material layer, electrode active material layer, electrode body and lithium ion secondary battery - Google Patents

Description

  The present invention relates to a method for producing an electrode active material layer, an electrode active material layer, an electrode body, a lithium ion secondary battery, and the like.

Layered crystals such as lithium cobaltate (LiCoO ₂ ), lithium nickelate (LiNiO ₂ ), and graphite advance electrode reactions by inserting / extracting lithium ions between layers (intercalation / deintercalation). Therefore, it is widely used as a positive electrode or negative electrode active material for lithium secondary batteries (see, for example, Patent Document 1).
However, an electrode active material layer composed of a layered crystal electrode active material has an intercalation layer in the crystal that is oriented in parallel to the electrode active material layer (current collector layer). Insertion / desorption is difficult to occur, and there is a problem that the utilization rate of the active material is small and the capacity is small.

JP-A-8-180904

  An object of the present invention is to provide an electrode active material layer manufacturing method capable of easily manufacturing an electrode active material layer capable of easily inserting / extracting Li ions from an electrolyte, and Li ions from an electrolyte. An electrode active material layer capable of easily inserting / extracting lithium, an electrode body capable of easily inserting / extracting Li ions from an electrolyte, and battery capacity and battery output It is to provide a lithium ion secondary battery excellent in the above.

Such an object is achieved by the present invention described below.
The method for producing an electrode active material layer of the present invention is a method for producing an electrode active material layer for a lithium ion secondary battery,
Forming a first layer in which a layered crystal electrode active material is oriented in a normal direction of the layered crystal layer;
Forming a plurality of holes in the surface of the first layer.
Thereby, the electrode active material layer in which the interlayer part of the layered crystal is exposed can be easily manufactured. As a result, insertion / extraction of Li ions to / from the electrolyte is facilitated, the active material utilization rate is increased, and the battery capacity and battery output of the lithium ion secondary battery can be improved.

In the manufacturing method of the electrode active material layer of this invention, it is preferable to have the process of performing an ion etching process to the internal peripheral surface of the said hole.
Thereby, the exposure of the interlayer part of a layered crystal can be made more remarkable, and insertion / extraction of Li ion to / from the electrolyte can be performed more easily.
In the method for producing an electrode active material layer of the present invention, the ion etching treatment is preferably performed by providing a mask at a site other than the hole.
Thereby, erosion of the upper part of the electrode active material layer can be suppressed, and the yield of the electrode active material layer can be increased.

In the method for producing an electrode active material layer of the present invention, it is preferable that the ion etching process uses inert gas ions.
Thereby, it is possible to relatively easily remove the ion species implanted into the electrode active material layer during ion etching from the final electrode active material layer.
In the manufacturing method of the electrode active material layer of this invention, it is preferable to have the process of heat-processing at the absolute temperature of 1/2 or more of melting | fusing point of the said electrode active material after the process of performing the said ion etching process.
Thereby, the crystallinity of the electrode active material on the inner peripheral surface of the hole can be made higher.

In the manufacturing method of the electrode active material layer of this invention, it is preferable to have the process of heat-processing at 300 degreeC or more after the process of performing the said ion etching process.
Thereby, it is possible to more easily remove ionic species implanted into the electrode active material layer during ion etching.
In the electrode active material layer of the present invention, the diameter of the hole is preferably 10 μm or more and 5000 μm or less.
This makes it possible to more easily insert / desorb Li ions while maintaining the mechanical strength of the electrode active material layer.

In the electrode active material layer of the present invention, the ratio of the area occupied by the pores on the surface of the electrode active material layer when viewed in plan is preferably 0.004% or more and 70% or less.
This makes it possible to more easily insert / desorb Li ions while maintaining the mechanical strength of the electrode active material layer.
The electrode active material layer of the present invention is manufactured by the method for manufacturing an electrode active material layer of the present invention.
Thereby, the electrode active material layer which can perform insertion / detachment | desorption of Li ion from electrolyte easily can be provided.

The electrode active material layer of the present invention is an electrode active material layer for a lithium ion secondary battery,
The electrode active material of the layered crystal includes a first layer oriented in the normal direction of the layer of the layered crystal,
A plurality of holes are formed from the surface of the first layer.
Thereby, the electrode active material layer which can perform insertion / detachment | desorption of Li ion from electrolyte easily can be provided.

The electrode body of the present invention is characterized by comprising the electrode active material layer of the present invention and a collector electrode.
Thereby, the interlayer part of the layered crystal is exposed, and an electrode body in which insertion / extraction of Li ions from / to the electrolyte can be easily performed can be provided.
The lithium ion secondary battery of the present invention is characterized in that the electrode body of the present invention is used as a positive electrode or a negative electrode.
Thereby, the lithium ion secondary battery excellent in battery capacity and battery output can be provided.

It is sectional drawing which shows an example of an electrode active material layer. It is typical sectional drawing for demonstrating one form of a structure of the electrode body provided with the electrode active material layer. It is typical sectional drawing for demonstrating one form of a structure of a lithium ion secondary battery.

Hereinafter, preferred embodiments of the present invention will be described in detail.
<Electrode active material layer for lithium ion secondary battery>
First, prior to the description of the manufacturing method for the lithium ion secondary battery of the present invention, the electrode active material layer manufactured by the manufacturing method will be described in detail.
FIG. 1 is a cross-sectional view illustrating an example of an electrode active material layer.

As shown in FIG. 1, the electrode active material layer 1 includes a layered crystal electrode active material 11 oriented in the layer direction, that is, the normal direction of the layer, and a plurality of pores 12.
The electrode active material 11 is a layered crystal material and is oriented in the layer direction of the electrode active material layer 1. The electrode active material 11 is a substance that can advance an electrode reaction by inserting / desorbing (intercalating / deintercalating) lithium ions between layers.

By the way, the electrode active material layer composed of the layered crystal electrode active material has an intercalation layer in the crystal oriented in parallel to the electrode active material layer (current collector layer), so that Li ions from the electrolyte Insertion / desorption is difficult to occur, and there is a problem that the utilization rate of the active material is small and the capacity is small.
In contrast, the electrode active material layer 1 has a plurality of holes 12 formed on the surface by the manufacturing method of the present invention, which will be described later, and the interlayer part of the layered crystal is exposed. Li ion insertion / desorption can be easily performed. As a result, the active material utilization rate is increased, and the battery capacity and battery output of the lithium ion secondary battery can be improved.

Specifically, as the electrode active material, a layered crystal electrode active material for a positive electrode, such as LiMnO ₂ , LiCoO ₂ , LiCo _1-x Ni _x O ₂ , LiNiO ₂ , V ₂ O ₅ , Nb ₂ O ₅ , Examples thereof include layered crystal electrode active materials for negative electrodes such as niobium pentoxide (Nb ₂ O ₅ ) and graphite.
In addition, as a material which comprises the electrode active material layer 1, other than the said electrode active material, for example, a conductive support agent, a sintering aid, a binder resin, etc. may be included.

A plurality of holes 12 are provided on the surface of the electrode active material layer 1.
As shown in FIG. 1, the hole 12 may be a through hole like the hole 12 </ b> A, or may be a non-through hole, i.e., a concave shape like the hole 12 </ b> B. In the case of the through hole, it is possible to prevent the etching residue from adhering to the bottom of the hole 12 in an ion etching process described later.

On the inner peripheral surface of the hole 12 (holes 12A and 12B), the interlayer part of the layered crystal is exposed. Thereby, insertion / extraction of Li ion between electrolytes can be performed easily.
The inner wall of the hole portion 12 is preferably subjected to ion etching treatment. Thereby, the exposure of the interlayer part of a layered crystal can be made more remarkable, and insertion / extraction of Li ion to / from the electrolyte can be performed more easily.

The average diameter of the holes 12 is preferably 10 μm or more and 5000 μm or less, and more preferably 20 μm or more and 100 μm or less. Thereby, insertion / extraction of Li ion can be performed more easily while maintaining the mechanical strength of the electrode active material layer 1.
Further, the ratio of the area occupied by the holes 12 on the surface of the electrode active material layer 1 when the electrode active material layer 1 is viewed in plan is preferably 0.004% or more and 70% or less, and 0.2% or more. More preferably, it is 35% or less. Thereby, insertion / extraction of Li ion can be performed more easily while maintaining the mechanical strength of the electrode active material layer 1.
The average thickness of the electrode active material layer 1 as described above (the average thickness of the portion other than the hole 12) is preferably from 0.1 μm to 500 μm, and more preferably from 100 μm to 300 μm. Thereby, the active material utilization factor can be further improved.

<Method for producing electrode active material layer for lithium ion secondary battery>
Next, the manufacturing method of the electrode active material layer described above will be described.
The manufacturing method of the electrode active material layer 1 according to the present embodiment includes a step of forming a first layer in which the electrode active material 11 of a layered crystal is oriented in the layer direction of the electrode active material layer 1, and a plurality of methods on the surface of the first layer. Forming the hole 12 (holes 12A, 12B), an ion etching process on the inner peripheral surface of the hole 12, and an annealing process.

Hereinafter, each step will be described in detail.
First, a first layer composed of a layered crystal electrode active material is formed.
The first layer can be formed by a method such as compacting, bulk formation such as slurry sintering, laser deposition (PLD) method, thin film formation such as RF sputtering, or the like.
Next, a plurality of holes 12 (holes 12A and 12B) are formed in the formed layer.

Examples of the method of forming the hole 12 include a method of forming by a punch press, a drill ring, or the like.
By forming the hole 12 in this manner, the interlayer part of the layered crystal can be easily exposed on the inner peripheral surface of the hole 12. As a result, insertion / extraction of Li ions to / from the electrolyte is facilitated, the active material utilization rate is increased, and the battery capacity and battery output of the lithium ion secondary battery can be improved.

  An ion etching process is performed on the inner peripheral surface of the hole 12. By the way, when a hole is opened by a punch press, a drill ring or the like, a part of the interlayer part of the layered crystal is crushed, and insertion / extraction of Li ions may not be sufficient. By performing ion etching in this manner, the portion where the interlayer portion of the layered crystal is crushed can be removed, and insertion / extraction of Li ions can be facilitated.

Specific examples of the ion etching method include processing using an ion beam (ion beam such as Ar or Xe). When inert gas ions are used in the ion beam, degassing and removal by an annealing process described later can be easily performed even if implanted into the electrode active material layer during ion etching.
The ion beam processing is performed by providing a mask in a portion other than the hole 12 formed by a punch press, a drill ring or the like. By providing the mask in this manner, erosion of the upper part of the electrode active material layer 1 can be suppressed, and the yield of the electrode active material layer 1 can be increased.
Examples of the material constituting the mask include metals such as Ni and W, carbon, and the like.

Thereafter, annealing is performed.
The annealing treatment refers to heat treatment at an absolute temperature that is 1/2 or more of the melting point of the electrode active material. For example, in the case of LiCoO ₂ , since the melting point is about 1373K, the heat treatment temperature is preferably 687K or more, and more preferably 700 ° C. or more.
By performing the annealing treatment, the crystallinity of the electrode active material on the inner peripheral surface of the hole 12 can be made higher.

Further, by performing the annealing process at 300 ° C. or higher, it is possible to more easily remove the ion species implanted into the electrode active material layer during ion etching.
Further, degassing can be promoted by performing the annealing treatment under reduced pressure.
As described above, the electrode active material layer 1 can be formed.
In addition, the manufacturing method of the electrode active material layer of this invention is not limited to the said method.

  As another example of the method for producing an electrode active material layer of the present invention, for example, a polymer structure having a plurality of fine protrusions and a layered crystal electrode active material are integrally formed by powder compaction, and a formed body is formed. By firing and removing the polymer structure by sintering, the first layer forming step and the hole forming step are simultaneously performed to form the electrode active material layer 1 having a plurality of hole portions 12. Also good. Thereafter, ion etching treatment and annealing treatment may be performed as described above.

<Electrode body for lithium ion secondary battery>
Next, the electrode body provided with the electrode active material layer described above will be described.
FIG. 2 is a schematic cross-sectional view for explaining one embodiment of the configuration of the electrode body including the electrode active material layer.
As shown in FIG. 2, the electrode body 10 includes the above-described electrode active material layer 1 and a collector electrode 2 provided on the opposite surface side of the hole 12 of the electrode active material layer 1.

Since the electrode active material layer 1 is the same as described above, the description thereof is omitted.
As a constituent material of the collector electrode 2, for example, a single metal selected from the group consisting of Cu, Ti, Fe, Co, Ni, Zn, Al, Ge, In, Au, Pt, Ag and Pd, Examples include alloys containing two or more selected elements.
Further, the collector electrode 2 can be attached after the electrode active material layer 1 is manufactured, or can be fired together with the electrode active material layer 1.
Examples of the method for attaching the collector electrode 2 include pressure bonding, sputter deposition, and vacuum deposition.
Since such an electrode body 10 has the above-described electrode active material layer 1 (electrode active material layer of the present invention), insertion / extraction of Li ions from the electrolyte can be easily performed.

《Lithium ion secondary battery》
Next, the lithium ion secondary battery provided with the electrode active material layer manufactured by the manufacturing method of the present invention will be described in detail.
FIG. 3 is a schematic cross-sectional view for explaining one embodiment of the configuration of the lithium ion secondary battery.

As shown in FIG. 3, the lithium ion secondary battery 100 is disposed so as to face the electrode body 10 described above and the electrode active material layer 1 of the electrode body 10, and an electrode body having a polarity opposite to that of the electrode body 10. 10 ′ and an electrolyte layer 5 disposed between the electrode body 10 and the electrode body 10 ′.
Since the electrode body 10 is the same as described above, the description thereof is omitted.
The electrode body 10 ′ includes an electrode active material layer 3 disposed on the electrode body 10 side and a collector electrode 4 disposed on the opposite side of the electrode body 10.

The electrode body 10 ′ has a polarity opposite to that of the electrode body 10. That is, when the electrode body 10 is a positive electrode, the electrode body 10 ′ is a negative electrode body, and when the electrode body 10 is a negative electrode, the electrode body 10 ′ is a positive electrode body.
The material which comprises the electrode active material layer 3 can mention the same thing as the electrode active material which comprises the electrode active material layer 1 mentioned above. The electrode active material layer 3 may also be provided with a hole.

Moreover, as a material which comprises the collector electrode 4, the thing similar to the material which comprises the collector electrode 2 mentioned above can be mentioned.
The electrolyte layer 5 is composed of an electrolyte or an electrolytic solution, and is disposed between the electrode body 10 and the electrode body 10 ′. The electrolyte layer 5 is formed over the inside of the hole 12 of the electrode active material layer 1.

  As the electrolyte constituting the electrolyte layer 5, any of an electrolytic solution, a liquid electrolyte, and a solid electrolyte can be used, but it is preferable to use a solid electrolyte. Thereby, it is possible to effectively prevent a trouble such as a short circuit from occurring while maintaining a high capacity and a high output. When an electrolytic solution or a liquid electrolyte is used, a separator (not shown) is provided between the electrode body 10 and the electrode body 10 '.

Examples of solid electrolytes include polymer electrolytes in which branched side chains, lithium-supported electrolyte salts, spacers, and the like are introduced into base polymers such as polyacrylic acid and polyethylene oxide, and SiO ₂ —P ₂ O ₅ —Li ₂ O, SiO _{2 -P 2 O 5 -LiCl, Li} 2 O-LiCl-B 2 O 3, Li 3.4 V 0.6 Si 0.4 O 4, Li 14 ZnGe 4 O 16, Li 3.6 V 0.4 Ge _0.6 O ₄ , Li _1.3 Ti _1.7 Al _0.3 (PO ₄ ) ₃ , Li _2.88 PO _3.73 N _0.14 , LiNbO ₃ , Li _0.35 La _0.55 TiO _{3, Li 7 La 3 Zr 2} 0 12, Li 2 S-SiS 2, Li 2 S-SiS 2 -LiI, Li 2 S-SiS 2 -P 2 S 5, LiPON, Li 3 N, Li _{, LiI-CaI 2, LiI-} CaO, LiAlCl 4, LiAlF 4, LiI-Al 2 O 3, LiF-Al 2 O 3, LiBr-Al 2 O 3, Li 2 O-TiO 2, La 2 O 3 -Li ₂ O—TiO ₂ , Li ₃ N, Li ₃ NI ₂ , Li ₃ N—LiI—LiOH, Li ₃ N—LiCl, Li ₆ NBr ₃ , LiSO ₄ , Li ₄ SiO ₄ , Li ₃ PO ₄ —Li ₄ SiO _{4, Li 4 GeO 4 -Li 3} VO 4, Li 4 SiO 4 -Li 3 VO 4, Li 4 GeO 4 -Zn 2 GeO 2, Li 4 SiO 4 -LiMoO 4, Li 3 PO 4 -Li 4 SiO 4, LiSiO ₄ -Li ₄ represented by ZrO ₄ or the like, oxides, sulfides, halides, crystalline, such as a nitride or amorphous, and these pairs Can be exemplified partially atoms other transition metals of the object, typically metal, alkali metal, alkaline earth, lanthanides, chalcogenides, solid solutions are substituted with halogen or the like, an inorganic solid electrolyte and so on.

The shape of the lithium ion secondary battery of the present invention is not particularly limited, and may be any shape such as a coin shape, a button shape, a sheet shape, a stacked shape, a cylindrical shape, a flat shape, a rectangular shape, and the like.
As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to these.
For example, the manufacturing method of the present invention may have a process other than the processes described above.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
[1] Production of electrode active material layer (Example 1)
(Formation of electrode active material layer for positive electrode)
A layered rock-salt crystal composed of LiCoO ₂ powder (manufactured by Aldrich) was prepared as a positive electrode active material for layered crystals.

Next, 3 wt% polyacrylic acid powder (manufactured by Aldrich) was added to the LiCoO ₂ powder as a binder and mixed in an agate mortar.
Next, 80 mg of the mixed powder was filled in a tablet molding machine (Specacac, 10 mmφ), and press molded at a pressure of 600 MPa.
The obtained tablet (first layer) was placed in an alumina crucible and baked in a muffle furnace at 1000 ° C. for 6 hours. By baking at this temperature, the polyacrylic acid in the tablet is completely burned out.
The size of the tablet after baking was 10 mmφ × 0.3 mm.
When the surface of this tablet was subjected to X-ray diffraction measurement (used X-ray: Cu Kα ray), it coincided with the diffraction pattern of LiCoO ₂ crystal (space group R3m # 166).

Of the obtained diffraction lines, the relative ratio of the total of 003, 006, 009 diffraction line intensities to the total of 003, 101, 006, 012, 104, 015, 009, 107 diffraction line intensities is obtained, and the ICDD standard pattern (ICDD Number: 01-070-2675), the former was 0.67, while the latter was 0.50, which was larger. This means that in the resulting tablets, LiCoO ₂ layer crystal than in the case of a non-oriented powder indicates that it is oriented parallel to the tablet surface.

(Formation of through holes)
The obtained tablet was fixed on a punching metal (material: SUS304, round hole 60 ° zigzag type, size 10 mm square, pitch 2 mm, hole diameter 1 mm) with hot wax (melting point: about 90 ° C.).
From the punching metal side, through the hole of the punching metal, 19 through holes were opened with an injection needle having an outer diameter of 0.07 mmφ. The injection needle was attached to an electric router for use.

(Ion beam processing)
Next, the surface of the tablet opposite to the punching metal side was fixed to a stainless steel jig, and the tablet was placed in the ion beam irradiation apparatus (SM-09010 manufactured by JEOL) together with the jig.
After installing the tablet, the inside of the ion beam irradiation apparatus was evacuated to 1 × 10 ⁻³ Pa.
Next, an argon (Ar) ion beam was irradiated for 8 hours from the punching metal side of the tablet under conditions of 6 kV and 150 μA.
The through-hole diameter after irradiation with the argon ion beam was 0.2 to 0.5 mmφ.
After irradiation with the ion beam, the irradiation device was returned to the atmosphere, and the tablet was taken out together with the jig.
The hot wax was heated again and the jig and punching metal were peeled from the tablets.

(Annealing treatment)
Next, the tablet was put in an alumina crucible and baked in an air atmosphere at 1000 ° C. for 3 hours in a muffle furnace.
By this baking, desorption of argon injected into the tablet by argon ion beam irradiation, recovery of crystal distortion introduced by ion beam irradiation, and burning of the hot wax component adhering in the argon ion beam irradiation step are performed.
Thus, a positive electrode active material layer was obtained.

(Comparative example)
(Formation of electrode active material layer for positive electrode)
A layered rock-salt crystal composed of LiCoO ₂ powder (manufactured by Aldrich) was prepared as a positive electrode active material for layered crystals.
Next, 3 wt% polyacrylic acid powder (manufactured by Aldrich) was added to the LiCoO ₂ powder as a binder and mixed in an agate mortar.

Next, 80 mg of the mixed powder was filled in a tablet molding machine (Specacac, 10 mmφ), and press molded at a pressure of 600 MPa.
The obtained tablet (layer) was placed in an alumina crucible and baked in a muffle furnace at 1000 ° C. for 6 hours. By baking at this temperature, the polyacrylic acid in the tablet is completely burned out.

The size of the tablet after baking was 10 mmφ × 0.3 mm.
When the surface of this tablet was subjected to X-ray diffraction measurement (used X-ray: Cu Kα ray), it coincided with the diffraction pattern of LiCoO ₂ crystal (space group R3m # 166).
Of the obtained diffraction lines, the relative ratio of the total of 003, 006, 009 diffraction line intensities to the total of 003, 101, 006, 012, 104, 015, 009, 107 diffraction line intensities is obtained, and the ICDD standard pattern (ICDD Number: 01-070-2675), the former was 0.67, while the latter was 0.50, which was larger. This means that in the resulting tablets, LiCoO ₂ layer crystal than in the case of a non-oriented powder indicates that it is oriented parallel to the tablet surface.
Thus, a positive electrode active material layer was obtained.

[2] Manufacture of electrode body One side of the positive electrode active material layer of Examples and Comparative Examples was coated with silver ink dispersed in diethyl carbonate and dried at 180 ° C. to obtain a thickness. A 0.05 mm silver collector electrode was formed. Thereby, an electrode body was obtained.

[3] Manufacture of Lithium Ion Secondary Battery The electrode body manufactured as described above is used as a positive electrode, a resin separator (Celguard # 2500) is placed thereon, and a Li foil (10 mmφ × 0) as a negative electrode is placed thereon. .1mm) and placed in a test cell (Hosen HS cell). A test cell (lithium ion secondary battery) was formed by filling this with an electrolytic solution (Kishida Chemical LBG-96943). All the test cell formation steps were performed in a glove box (argon atmosphere).

[4] Evaluation The charge / discharge characteristics of the test cell using the electrode active material layers of the above examples and comparative examples were evaluated in a constant current mode of 10 μA.
As a result, in the test cell using the electrode active material layer of the example, the discharge capacity at the third cycle was 103 μAh.

In contrast, in the test cell using the electrode active material layer of the comparative example, the discharge capacity at the third cycle was 82 μAh.
As can be seen from this result, the lithium ion secondary battery using the electrode active material layer produced by the production method of the present invention was excellent in battery capacity and battery output.
The present invention can be widely applied not only in the description of the above-described embodiments but also in a range not departing from the gist of the present invention.

  DESCRIPTION OF SYMBOLS 1, 3 ... Electrode active material layer 2, 4 ... Collector electrode 5 ... Electrolyte layer 10, 10 '... Electrode body 11 ... Electrode active material 12, 12A, 12B ... Hole 100 ... Lithium ion secondary battery

Claims (7)

A method for producing an electrode active material layer for a lithium ion secondary battery, comprising:
Forming a first layer in which a layered crystal electrode active material is oriented so as to be parallel to the surface of the electrode active material layer ;
Forming a plurality of holes in the surface of the first layer;
And a step of subjecting the inner peripheral surface of the hole portion to an ion etching process . The ion etching process, the manufacturing method of the electrode active material layer according to claim 1 for providing a mask a part other than the hole. The ion etching process, the manufacturing method of the electrode active material layer according to claim 1 or 2 using inert gas ions. The electrode active material layer manufacturing method according to any one of claims 2 to 3 , further comprising a step of performing a heat treatment at an absolute temperature equal to or higher than ½ of a melting point of the electrode active material after the step of performing the ion etching treatment. Method. The manufacturing method of the electrode active material layer of any one of Claim 1 thru | or 4 which has the process of heat-processing at 300 degreeC or more after the process of performing the said ion etching process. The method for producing an electrode active material layer according to any one of claims 1 to 5 , wherein the hole has a diameter of 10 µm or more and 5000 µm or less. The ratio of the area which the said hole occupies in the electrode active material layer surface at the time of planar view is 0.004% or more and 70% or less, The electrode active material layer of any one of Claim 1 thru | or 6 Manufacturing method .

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