JP2013058376A - Solid electrolyte particle, solid electrolyte membrane and method for producing solid electrolyte particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid electrolyte particle suitable for the densification of a solid electrolyte membrane.SOLUTION: A solid electrolyte particle 1 comprises an amorphous solid electrolyte and has a scale-like shape. In the solid electrolyte particle, an aspect ratio of a thickness with respect to a distribution particle size of the solid electrolyte particle is preferably 1×10-5×10. More preferably, the amorphous solid electrolyte includes an oxide solid electrolyte. Further, the oxide solid electrolyte preferably includes an electrolyte selected from the group consisting of LAGP:LiAlGe(PO)(where, 0≤X≤2 is satisfied), LiPO, LiPON and LiNbO.

Description

  The present invention relates to solid electrolyte particles used for various applications including electrodes for all solid state batteries, a solid electrolyte membrane containing the solid electrolyte particles, and a method for producing the solid electrolyte particles.

  With the rapid spread of information-related equipment and communication equipment such as personal computers, video cameras, and mobile phones in recent years, development of batteries that are used as power sources has been regarded as important. Also in the automobile industry and the like, development of high-power and high-capacity batteries for electric vehicles or hybrid vehicles is being promoted. Currently, lithium batteries are attracting attention among various batteries from the viewpoint of high energy density.

  Since lithium batteries currently on the market use electrolytes containing flammable organic solvents, safety devices can be installed to prevent temperature rise during short circuits, and improvements in structure and materials can be made to prevent short circuits. Necessary. In contrast, a lithium battery in which the electrolyte is changed to a solid electrolyte layer using an oxide solid electrolyte, a sulfide solid electrolyte, or the like and the battery is fully solidified does not use a flammable organic solvent in the battery. It is considered that the safety device can be simplified and the manufacturing cost and productivity are excellent.

  However, the all-solid battery has a problem that the ionic conductivity of the electrolyte is lower than that of the liquid battery, and both the active material and the electrolyte are crystalline. Various measures have been taken to increase the capacity of solid state batteries. For example, Patent Document 1 discloses a method for producing a solid electrolyte structure in which an electrode active material and a solid electrolyte are integrated in order to improve the bonding interface between the electrode active material and the solid electrolyte.

JP 2009-238739 A

Generally, as a method of forming a solid electrolyte membrane, the solid electrolyte membrane is formed by laminating solid electrolyte particles by a method such as slurry coating or compacting, and forming into a membrane shape, and sintering as necessary to increase the strength. Is formed.
In order to increase the capacity of the battery, the solid electrolyte membrane is required to be densified. As a densification method, it is conceivable that fine and uniform spherical solid electrolyte particles are stacked to form a dense packing. . However, when a solid electrolyte membrane is formed using an oxide solid electrolyte, the oxide solid electrolyte is harder than, for example, a sulfide solid electrolyte, and there is no technique for controlling the particle shape. Have difficulty. Therefore, there is a problem that cracking occurs when an electrolyte membrane made of an oxide solid electrolyte is thinned.

  The present invention has been accomplished in view of the above circumstances, and an object thereof is to provide solid electrolyte particles suitable for densification of a solid electrolyte membrane.

  In the present invention, solid electrolyte particles comprising an amorphous solid electrolyte and having a scaly shape are provided.

In this invention, the solid electrolyte particle whose aspect ratio of the thickness with respect to the distribution particle diameter of the said solid electrolyte particle is 1 * 10 ^<-2 > -5 * 10 ^{< -1} > is provided.

  In the present invention, the amorphous solid electrolyte provides solid electrolyte particles containing an oxide solid electrolyte.

In the present invention, the oxide solid electrolyte is composed of LAGP: Li _{1 + X} Al _X Ge _2-X (PO ₄ ) ₃ (where 0 ≦ X ≦ 2), Li ₃ PO ₄ , LiPON, and LiNbO ₃ . Solid electrolyte particles comprising an electrolyte selected from the group are provided.

  The present invention provides a solid electrolyte membrane comprising the solid electrolyte particles.

  The present invention provides a solid electrolyte membrane in which the solid electrolyte particles are oriented in the plane direction of the membrane in the solid electrolyte membrane.

  The present invention provides a solid electrolyte membrane in which the solid electrolyte particles are sintered in the solid electrolyte membrane.

  In the present invention, a solid electrolyte membrane having a relative density of 80 to 95 is provided.

  The present invention provides a method for producing solid electrolyte particles, characterized in that mechanical energy is applied from a predetermined direction to raw material particles made of an amorphous solid electrolyte.

  In the present invention, the method for applying mechanical energy from the predetermined direction provides a method for producing solid electrolyte particles, wherein the raw material particles are sandwiched between two pressurized media and crushed.

  In the present invention, there is provided a method for producing solid electrolyte particles, wherein the method of sandwiching and crushing between the two pressurized media is a bead mill stirring method.

  In this invention, the distribution particle diameter of the said raw material particle provides the manufacturing method of the solid electrolyte particle which is 0.5 micrometer-10 micrometers.

  The present invention provides a method for producing solid electrolyte particles, wherein the raw material particles are made of an amorphous solid electrolyte containing an oxide solid electrolyte.

In the present invention, the oxide solid electrolyte is composed of LAGP: Li _{1 + X} Al _X Ge _2-X (PO ₄ ) ₃ (where 0 ≦ X ≦ 2), Li ₃ PO ₄ , LiPON, and LiNbO ₃ . A method for producing solid electrolyte particles comprising an electrolyte selected from the group is provided.

  According to the present invention, solid electrolyte particles suitable for densification of a solid electrolyte membrane can be provided.

It is explanatory drawing explaining the solid electrolyte particle of this invention. 2 is a SEM image of solid electrolyte particles obtained in Example 1. FIG. 2 is a SEM image of solid electrolyte particles obtained in Example 1. FIG. 3 is a SEM image of solid electrolyte particles obtained in Comparative Example 1. 2 is a graph showing the aspect ratio of the solid electrolyte particles obtained in Example 1. FIG. It is a SEM image of the solid electrolyte particle obtained in Example 2-1. It is a SEM image of the solid electrolyte membrane obtained in Example 2-2. 4 is a SEM image of the solid electrolyte membrane obtained in Comparative Example 2.

The present invention provides solid electrolyte particles comprising an amorphous solid electrolyte and having a scaly shape.
Hereinafter, the configuration and embodiments of the present invention will be described in detail. Although the present invention will be described in detail with reference to the drawings and examples, the present invention is not limited to these drawings and examples.

First, the solid electrolyte particles of the present invention will be described. The solid electrolyte particles of the present invention have a scaly shape and are amorphous. FIG. 1 is a perspective view showing an example of the solid electrolyte particles of the present invention. The solid electrolyte particles of the present invention are characterized by having a scaly shape as shown in FIG. Here, the scaly shape in the present invention is a flat particle, the flat surface is substantially scaly, and an extremely long protrusion (for example, a dendrite or a starfish arm) ). The outer edge of the flat surface is not necessarily a smooth arc shape as long as it has a substantially perfect circle shape or an oval shape as a whole. For example, the outer edge of the flat surface may be a jagged irregular edge. In addition, the scale-like solid electrolyte particles may be a flat lump by fusing part of the scale-like particles contained in the particle group.
From the viewpoint of forming a dense and difficult-to-break electrolyte thin film, the aspect ratio of the thickness to the distribution particle size of the solid electrolyte particles is preferably 1 × 10 ^{−2 to} 5 × 10 ⁻¹ . That is, as shown in FIG. 1, the longest line segment on the main surface of the solid electrolyte particle 1 is defined as a line segment A, and the longest line segment orthogonal to the line segment A is defined as a line segment B. The thickness of the particle 1 is defined as thickness C. In the present invention, a shape in which A to C satisfy a relationship of B = 0.2 A to A and C = 0.01 A to 0.5 A is preferable. The line segment A, line segment B, and thickness C can be measured using, for example, a scanning electron microscope (SEM).
As a method for measuring the aspect ratio, for example, the particle size distribution measurement of the solid electrolyte particles is performed, the particle size of the solid electrolyte particles and the particle size distribution range are obtained, and the thickness of the solid electrolyte particles is measured using SEM, The aspect ratio of the thickness with respect to the distribution particle size of the solid electrolyte particles can be measured.
The particle size distribution measurement method is not particularly limited, and examples thereof include a dynamic light scattering method, a laser diffraction / scattering method, and an image imaging method.
The particle size distribution measuring device is not particularly limited, and examples thereof include a laser diffraction / scattering type wet particle size distribution measuring device.
The thickness C of the solid electrolyte particles is preferably in the range of 0.01 μm to 0.5 μm, for example, and more preferably in the range of 0.01 μm to 0.1 μm.
The particle size distribution range of the solid electrolyte particles is preferably within a range of 0.1 μm to 5 μm, for example, more preferably within a range of 0.1 μm to 1 μm, and a range of 0.1 μm to 5 μm. It is preferable to exclude those that do not fit in.

  According to the present invention, since the solid electrolyte particles have a scaly shape, the ratio of the main surface to the thickness is sufficiently large, so that the solid electrolyte particles can contact each other by surface contact, not point contact, The electrolyte membrane can be densified.

(Method for producing solid electrolyte particles)
Hereinafter, the manufacturing method of the solid electrolyte particle of this invention is demonstrated.
By applying mechanical energy to the raw material particles made of an amorphous solid electrolyte from a predetermined direction, the solid electrolyte particles that are flattened and subdivided to have a scale-like shape can be formed.

The raw material particles made of an amorphous solid electrolyte are softer than the crystallized solid electrolyte, so even when a hard solid electrolyte such as an oxide solid electrolyte is used, mechanical energy is applied from a predetermined direction. It is flattened and subdivided into scaly particles.
Here, “amorphous” means a state in which a predetermined crystal peak is not detected by the X-ray diffraction method.
The distribution particle size of the raw material particles is not particularly limited, but is preferably in the range of 0.5 μm to 10 μm in diameter.
The solid electrolyte used in the present invention is not particularly limited as long as it is an amorphous substance. For example, an oxide solid electrolyte, a sulfur-based solid electrolyte, or the like is used.
In particular, the present invention is extremely effective when an electrolyte membrane is formed using a solid electrolyte that is essentially a relatively hard material and whose particle shape is difficult to control. An oxide solid electrolyte is a material suitable for the present invention because it is a material that is essentially relatively hard per se.
As an amorphous body of an oxide solid electrolyte, for example, a NASICON type oxide represented by the general formula Li _{1 + X} Al _X Ge _2-X (PO ₄ ) ₃ (0 ≦ x ≦ 2) can be mentioned, In particular, Li _1.5 Al _0.5 Ge _1.5 (PO ₄ ) ₃ [hereinafter referred to as LAGP] is preferable.
Moreover, Li ₃ PO ₄ , LiPON, LiNbO _3, etc. may be mentioned as other amorphous bodies of the oxide solid electrolyte.

  As a method of adding mechanical energy to the raw material particles from a predetermined direction, a method in which the raw material particles are sandwiched between two pressurized media and crushed can be employed. For example, mechanical milling can be performed. . Mechanical milling is basically a process of atomizing a material, but the present inventors, when using an amorphous solid electrolyte, are not crystalline but have a certain amount of particles. It has been found that since it is soft, it is crushed instead of being crushed when subjected to an impact from the beads, and solid electrolyte particles having a specific scaly shape are obtained.

  The solid electrolyte slurry when slurrying the solid electrolyte raw material particles contains at least the solid electrolyte, and may further contain an alcohol dispersant. The alcohol dispersant is not particularly limited as long as it can obtain solid electrolyte particles having a scaly shape.

  Specific examples of the alcohol dispersant include ethanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, 2-ethylhexanol, and dodecanol. Of these, ethanol is preferable. The ratio of the alcohol dispersant in the solid electrolyte slurry is not particularly limited, but is preferably in the range of 50 wt% to 70 wt%, for example.

  Mechanical milling is not particularly limited as long as it is a method of mixing a solid electrolyte while imparting mechanical energy. For example, a bead mill, a ball mill, a vibration mill, a turbo mill, a mechano-fusion, a disk mill, etc. In particular, a bead mill is preferable.

Various conditions of mechanical milling are set so that desired solid electrolyte particles can be obtained. For example, when using a bead mill, a slurry solid electrolyte and grinding beads are added, and the treatment is performed at a predetermined rotation speed and time.
The number of platen rotations when performing the bead mill is preferably, for example, in the range of 2500 rpm to 5000 rpm, and more preferably in the range of 2550 rpm to 4550 rpm.
Moreover, it is preferable that the processing time at the time of performing a bead mill exists in the range of 0.5 hour-3 hours, for example.
The liquid feed flow rate of the slurry solid electrolyte is preferably in the range of 0.1 L / min to 0.2 L / min. Examples of the material of the beads include PSZ (partially stabilized zirconia, PARTIALLY STABILIZED ZIRCONIA), alumina, and the like. The particle size of the beads is not particularly limited, but a diameter in the range of 0.1 mm to 1 mm is preferable.

The mechanical milling may be dry mechanical milling or wet mechanical milling, but the latter is preferred. It is because it can prevent that a raw material composition adheres to wall surfaces, such as a container. Examples of the liquid used for wet mechanical milling include aprotic liquids.
Examples of the aprotic liquid include ketones such as acetone; alkanes that are liquid at room temperature (25 ° C.); aromatic hydrocarbons such as benzene, toluene, and xylene. In addition, the addition amount of the said liquid is not specifically limited, What is necessary is just the quantity which can obtain a desired solid electrolyte particle.

(Solid electrolyte membrane)
The solid electrolyte membrane in the present invention is a member that becomes a solid electrolyte layer, and the solid electrolyte membrane can be formed by compacting the solid electrolyte particles. As another method, a solid electrolyte membrane is formed by preparing a slurry containing solid electrolyte particles, applying the solid electrolyte particle slurry to the surface of a film-forming support, drying, rolling, and cutting. be able to.
Examples of the slurry application method include a blade method (for example, a doctor blade method), an inkjet method, and the like.
The film-forming support is peeled from the solid electrolyte membrane. The timing for peeling off the film-forming support can be set as appropriate. As the film-forming support, for example, a general one such as a release-treated PET film can be used.
The drying of the solid electrolyte particle slurry is not particularly limited, and examples thereof include heat drying, vacuum drying, and heat drying under reduced pressure. The drying atmosphere is not particularly limited, and can be performed, for example, in an air atmosphere.
The obtained solid electrolyte membrane can enhance the strength of the membrane by sintering as necessary. Various conditions such as heating temperature and atmosphere in sintering can be set as appropriate.

The solid electrolyte particle slurry contains at least solid electrolyte particles, a binder, and a solvent, and may further contain a plasticizer and a dispersant.
The solid electrolyte particle content in the solid electrolyte particle slurry is preferably, for example, 40 wt% to 80 wt%, and particularly preferably 60 wt% to 70 wt%.
Examples of the binder include polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), and the like. Among these, PVB is preferable from the viewpoint of film strength during thin film formation.
The binder content in the solid electrolyte particle slurry is preferably, for example, 3 wt% to 8 wt%, and particularly preferably 3 wt% to 5 wt%.
Examples of the solvent include solvents having a boiling point of 200 ° C. or less, such as acetone, ethanol, 1-butanol, N-methyl-2-pyrrolidone (NMP), and the like.

The plasticizer imparts flexibility and elasticity to the solid electrolyte membrane, and contributes to improving the handleability of the solid electrolyte membrane and improving the adhesion with the adjacent layers. Examples thereof include dibutyl phthalate, polyacrylate, polyvinyl acetate, cellulose acetate, and dioctyl phthalate (DOP).
The dispersant is intended to improve the dispersibility of the solid electrolyte particles in the solid electrolyte particle slurry, and may be selected depending on the solid electrolyte particles to be used. Examples thereof include carboxylic acid-based, amine-based, and phosphoric acid-based materials. Specifically, polymers such as G-700 (manufactured by Kyoeisha Chemical Co., Ltd.) and KD-9 (manufactured by CRODA) as the carboxylic acid system, and polymers such as KD-2 (manufactured by CRODA) and SOLSPERS 41000 (manufactured by Lubrizol) as the amine system. Examples of amine-based and phosphoric acid-based materials include SOLSPERS 20000 (manufactured by Lubrizol).
The method for preparing the solid electrolyte particle slurry is not particularly limited, but a method of dispersing the solid electrolyte particles in a solvent in which a binder is dispersed is preferable.

In the solid electrolyte membrane in the present invention, the solid electrolyte particles are preferably oriented in the plane direction of the membrane. The solid electrolyte membrane in the present invention is preferably a sintered body of solid electrolyte particles. This is because the solid electrolyte membrane can be densified.
The content of the solid electrolyte particles having a scale-like shape in the solid electrolyte membrane is preferably in the range of 40% by weight to 80% by weight, and more preferably in the range of 60% by weight to 70% by weight.
The thickness of the solid electrolyte membrane of the present invention is, for example, in the range of 0.5 μm to 50 μm from the viewpoint of preventing the occurrence of drying unevenness during film formation when the solid electrolyte particles are oriented in the plane direction of the membrane. It is preferable.
The relative density of the solid electrolyte membrane of the present invention is preferably in the range of 80 to 95, for example, from the viewpoint of densification.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.

(Example 1) Production of solid electrolyte particles having a scale-like shape LAGP which is an amorphous powder was used as raw material particles. The average particle diameter of the raw material particles was 5 μm. Next, LAGP 60g and ethanol 340g were mixed so that it might become a LAGP15 wt% solution, and the solid electrolyte slurry was prepared. Then, PSZ beads (diameter 0.3 mm) are put into a bead mill container, the container is attached to a bead mill stirrer, and the prepared solid electrolyte slurry is fed to the container at a feed flow rate of 0.15 L / min, and mechanical milling is performed. It was.
Mechanical milling is performed at a base plate rotation speed of 2590 rpm between 0 min (operation start) and 30 min, at a base plate rotation speed of 3240 rpm between 30 min and 75 min, and the base plate between 75 min and 180 min (operation end). The rotation was performed at 3885 rpm.
After the start of operation (a) after 60 min and (b) after 180 min (end of operation), samples were collected and observed for shape using a scanning electron microscope (SEM). The SEM image diagrams of (a) and (b) are shown in FIGS. 2 and 3, respectively.

(Comparative Example 1)
In Example 1, a sample at the time of (c) 0 min (operation start) of mechanical milling was collected and shape observation was performed using SEM. An SEM image of (c) is shown in FIG.

(SEM observation results)
As shown in FIG. 4 of Comparative Example 1 according to the SEM image diagram, the raw material particles at the start of mechanical milling did not have a scaly shape, but as shown in FIG. 2 of Example 1, mechanical milling was started. The particles obtained 60 minutes later had a scaly shape. Further, as shown in FIG. 3 of Example 1, 180 minutes after the start of mechanical milling, it had a scaly shape that was thinner than the particles shown in FIG. Further, as shown in FIGS. 2 and 3 of Example 1, some of the obtained solid electrolyte particles were fused to form a flat lump. The thickness of the solid electrolyte particles was measured from the SEM image of the solid electrolyte particles collected 180 minutes after the start of mechanical milling operation in Example 1 (b).

(Particle size distribution measurement)
Particle size distribution measurement was performed on the solid electrolyte particles collected 180 minutes after the start of mechanical milling operation in Example 1 (b). As the particle size distribution measuring device, a laser diffraction / scattering type wet particle size distribution measuring device (Nikkiso Microtrack) was used. The average particle diameter of the solid electrolyte particles and the distribution range of the particle diameter were specified by the particle size distribution measurement, and the aspect ratio of the thickness to the distribution particle diameter was measured. The results are shown in Table 1 and FIG.

In Example 1, the thickness of the solid electrolyte particles was 0.01 μm to 0.5 μm, and the particle size distribution range of the solid electrolyte particles was 0.1 μm to 5 μm. As shown in Table 1 and FIG. 5, the aspect ratio of the thickness to the distribution particle diameter of the solid electrolyte particles was in the range of 1 × 10 ^{−2 to} 5 × 10 ⁻¹ .

(Example 2-1) Production of solid electrolyte particles having scale-like shape A slurry was prepared in the same manner as in Example 1. Then, PSZ beads (diameter 0.5 mm) are put into a bead mill container, the container is attached to a bead mill stirrer, and the prepared solid electrolyte slurry is fed to the container at a feed flow rate of 0.15 L / min, and mechanical milling is performed. It was.
Mechanical milling was performed for 60 minutes at a base plate rotation number of 4525 rpm.
A sample after completion of the operation was collected and observed for shape using SEM. An SEM image diagram is shown in FIG. As shown in FIG. 6, the particles had a scaly shape, and some of the obtained solid electrolyte particles were fused to form a flat lump.

(Example 2-2) Production of solid electrolyte membrane using solid electrolyte particles having scaly shape Solid electrolyte particles obtained in Example 2-1 were mixed with 100 parts by weight of solid electrolyte particles, solvent (ethanol and 1-butanol). The mixed solvent) was mixed at a ratio of 100 parts by weight, binder (PVB) 18 parts by weight, plasticizer (DOP) 9 parts by weight, and dispersant (polyamine) 5 parts by weight to prepare a solid electrolyte particle slurry. The prepared solid electrolyte particle slurry was blade-coated on the surface of the release PET film and allowed to dry naturally to form a solid electrolyte membrane. The thickness of the solid electrolyte membrane after drying was 20 μm. The shape of the obtained solid electrolyte membrane was observed using SEM. An SEM image diagram is shown in FIG.

(Comparative Example 2)
In Example 2-1, except that mechanical milling was not performed, a solid electrolyte membrane was formed by the same method as in Example 2-1 and Example 2-2, and the obtained solid electrolyte membrane was used using SEM. Shape observation was performed. An SEM image diagram is shown in FIG.

(SEM observation results)
As shown in FIG. 8 of Comparative Example 2 by the SEM image diagram, when mechanical milling is not performed, the film is cracked, but as shown in FIG. 7 of Example 2-2, mechanical milling is performed. When done, no cracks occurred in the membrane. The relative density of the solid electrolyte membrane in Example 2-2 is 90, the relative density of the solid electrolyte membrane in Comparative Example 2 is 80, and compared with Comparative Example 2, Example 2-2 is a solid electrolyte membrane. Dense lamination was possible.

1 Solid electrolyte particles having a scale-like shape

Claims (14)

  Solid electrolyte particles made of an amorphous solid electrolyte and having a scaly shape. The solid electrolyte particles according to claim 1, wherein an aspect ratio of a thickness to a distribution particle diameter of the solid electrolyte particles is 1 × 10 ^{−2 to} 5 × 10 ⁻¹ .   The solid electrolyte particle according to claim 1, wherein the amorphous solid electrolyte includes an oxide solid electrolyte. The oxide solid electrolyte is selected from the group consisting of LAGP: Li _{1 + X} Al _X Ge _2−X (PO ₄ ) ₃ (where 0 ≦ X ≦ 2), Li ₃ PO ₄ , LiPON, and LiNbO _3. The solid electrolyte particle according to any one of claims 1 to 3, comprising an electrolyte.   A solid electrolyte membrane comprising the solid electrolyte particles according to any one of claims 1 to 4.   The solid electrolyte membrane according to claim 5, wherein the solid electrolyte particles are oriented in a plane direction of the membrane in the solid electrolyte membrane.   The solid electrolyte membrane according to claim 5 or 6, wherein the solid electrolyte particles are sintered in the solid electrolyte membrane.   The solid electrolyte membrane according to claim 6 whose relative density is 80-95.   The method for producing solid electrolyte particles according to any one of claims 1 to 4, wherein mechanical energy is applied from a predetermined direction to the raw material particles made of an amorphous solid electrolyte.   The manufacturing method according to claim 9, wherein the method of applying mechanical energy from the predetermined direction is a method in which the raw material particles are sandwiched between two pressurized media and crushed.   The manufacturing method according to claim 9, wherein the method of sandwiching and crushing between the two pressurized media is a bead mill stirring method.   The manufacturing method according to any one of claims 9 to 11, wherein a distribution particle size of the raw material particles is 0.5 µm to 10 µm.   The manufacturing method according to any one of claims 9 to 12, wherein the raw material particles are made of an amorphous solid electrolyte containing an oxide solid electrolyte. The oxide solid electrolyte is selected from the group consisting of LAGP: Li _{1 + X} Al _X Ge _2-X (PO ₄ ) ₃ (where 0 ≦ X ≦ 2), Li ₃ PO ₄ , LiPON, and LiNbO _3. The manufacturing method of any one of Claims 8 thru | or 12 containing electrolyte.