Patent Description:
All-solid secondary batteries are known as safe secondary batteries because flammable organic solvents are not necessary. Instead of a flammable organic solvent, an all-solid secondary battery is mainly composed of a powder laminate made of a powder material. Thus, an all-solid secondary battery improves safety but suffers from problems that stem from a powder material.

One of the problems is the mixing of the power materials of adjacent layers in the powder laminate during the formation of the powder laminate. In order to solve the problem, a method of forming a layer on a dry layer to avoid mixing powder materials is proposed, the layer being formed by spraying slurry having the material of the layer onto the dry layer. Such a method is disclosed in, for example, <CIT>.

<CIT> discloses a device for manufacturing a solid secondary battery, wherein a dispersion liquid is sprayed electrostatically an a substrate, by which time the liquid portion is evaporated, to produce a solid electrolyte layer.

<CIT> discloses an apparatus for making solid secondary batteries by electrostatic screen printing in which mixed powders for the first and second electrodes are mixed having different mixtures prior to electrostatic deposition and pressed under pressure. No further details regarding the state of the powders or any further processing after the pressing step are provided.

<CIT> discloses an apparatus for making solid secondary lithium batteries using solid electrolyte, especially sulfide based, which has reduced short circuiting, by stacking a positive electrode material powder, an electrolyte material powder and a negative electrode material powder in sequence. The powders are mixed and may be electrostatic-screen deposited.

In the method of <CIT>, a wet process is used with slurry prepared by dissolving a powder material in a solvent. In a method of a wet process, impurities such as a solvent remain in a powder laminate unless the impurities are completely removed from the powder laminate. Moreover, a part from which impurities have been removed may be left as a cavity in the powder laminate. Such impurities and cavity do not act as batteries and thus impurities and/or a cavity remaining in the powder laminate may deteriorate battery performance in an all-solid secondary battery including the powder laminate.

An object of the present invention is to provide an installation for manufacturing an all-solid secondary battery so as to improve the performance of the battery. It is a further object to provide a respective manufacturing method.

In order to solve the problem, an installation for manufacturing an all-solid secondary battery according to claim <NUM> is provided.

Advantageously, the powder laminate includes a positive layer, a solid-electrolyte layer, and a negative layer, and the electrostatic film-forming device includes a positive-electrode electrostatic film-forming machine for forming the positive layer, an electrolyte electrostatic film-forming machine for forming the solid-electrolyte layer, and a negative-electrode electrostatic film-forming machine for forming the negative layer.

With advantage, the conveying device includes a positive-electrode conveyor for conveying the powder material for forming the positive layer to the positive-electrode electrostatic film-forming machine and a negative-electrode conveyor for conveying the powder material for forming the negative layer to the negative-electrode electrostatic film-forming machine, and
the installation further includes an electrolyte conveyor for conveying the powder material for forming the solid-electrolyte layer to the electrolyte electrostatic film-forming machine.

Additionally, the solid-electrolyte layer may be a layer made of a sulfide based solid electrolyte.

Advantageously, the electrostatic film-forming device includes a powder loading member to be loaded with the powder material and a direct-current power supply that drops, by an electrostatic force, the powder material, with which the powder loading member is loaded, and forms the powder material into the powder films.

Advantageously, targets to be pressurized by the pressure device are the powder films formed by the electrostatic film-forming device and current collectors on which the powder films are placed, the current collectors have at least rough surfaces on which the powder films are placed, and
the installation further includes a pressurizing charger/discharger for charging and discharging an electrodes body having the powder laminate interposed between the two current collectors while applying a pressure to the electrodes body.

With advantage, the cutting-removing device forms the powder laminate by cutting and removing the outer end portion of the stacked powder films, and
the powder laminate to be formed is cut by the cutting-removing device such that an interface between the negative/positive layer and the solid-electrolyte layer has a larger area than an interface between the positive/negative layer and the solid-electrolyte layer, and the powder laminate has a side inclined as a cut surface.

Advantageously, the cutting-removing device cuts the powder films while stiffness inside a cutting position of the powder films is higher than stiffness outside the cutting position.

With advantage, the cutting-removing device includes a die for holding the powder films and a punch for stamping the powder films held by the die at a speed of at most <NUM>/sec,.

Said above-stated problem is also solved by a method for manufacturing an all-solid secondary battery according to claim <NUM>.

Advantageous embodiments of the invention are characterized by the features of the dependent claims.

According to the installation and the method for manufacturing the all-solid secondary battery, the impurities such as a solvent are not left contrary to a wet-process method and a cavity formed by removing impurities is not left in the formed powder laminate. This can improve the battery performance of the all-solid secondary battery manufactured from the powder laminate.

An installation for manufacturing an all-solid secondary battery according to a first embodiment of the present invention will be described below in accordance with the accompanying drawings.

Referring to <FIG>, the configuration of the all-solid secondary battery manufactured by the manufacturing installation will be simply described below.

As illustrated in <FIG>, an all-solid secondary battery <NUM> includes a powder laminate <NUM> in which powder films are stacked. Specifically, the powder laminate <NUM> includes a positive layer <NUM>, a negative layer <NUM>, and a solid-electrolyte layer <NUM> disposed between the positive layer <NUM> and the negative layer <NUM>. Each of the positive layer <NUM>, the negative layer <NUM>, and the solid-electrolyte layer <NUM> may be a single powder film or a laminate of multiple powder films. The all-solid secondary battery <NUM> further includes a positive current collector <NUM> and a negative current collector <NUM> that are disposed with the powder laminate <NUM> interposed therebetween in the thickness direction. Hereinafter, the positive current collector <NUM>, the negative current collector <NUM>, and the powder laminate <NUM> interposed between the positive current collector <NUM> and the negative current collector <NUM> will be referred to as an electrodes body <NUM> to <NUM>. The electrodes body <NUM> to <NUM> may include an insulating member, which is not illustrated, disposed between the positive current collector <NUM> and the negative current collector <NUM> and outside of the powder laminate <NUM>. The all-solid secondary battery <NUM> optionally includes an outer package <NUM>, such as a laminated pack <NUM> or a can, which contains the electrodes body <NUM> to <NUM>. When the electrodes body <NUM> to <NUM> is contained in the outer package <NUM>, the positive current collector <NUM> and the negative current collector <NUM> are electrically connected to the outside of the outer package <NUM>.

The materials of the main components of the all-solid secondary battery <NUM> will be described below.

As the positive current collector <NUM> and the negative current collector <NUM>, thin plates and foil members that are made of copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), indium (In), lithium (Li), tin (Sn), and an alloy thereof are used, or films made of the materials are used. The thin plates and foil members are <NUM> to <NUM> in thickness. Moreover, the surfaces of the positive current collector <NUM> and the negative current collector <NUM> are preferably roughened in view of improvement in adhesion to the powder laminate <NUM> containing powder. Roughening is processing for increasing surface roughness by etching or the like. An insulating sheet made of polymeric materials, e.g., a PET film is used as an insulating member.

The positive layer <NUM> and the negative layer <NUM> are layers made of a mixture of, with a predetermined ratio, a positive-electrode active material and a negative-electrode active material that ensure an electron conduction path among particles in order to deliver and receive electrons, and a solid electrolyte having ion conduction. The solid electrolyte having lithium-ion conduction is mixed with the positive-electrode active material and the negative-electrode active material, thereby providing ion conduction in addition to electron conduction. This can ensure the ion conduction path among particles.

The positive-electrode active material suitable for the positive layer <NUM> is not particularly limited as long as the material enables the insertion and desorption of lithium ions. For example, the positive-electrode active material may be selected from oxides such as a lithium-nickel composite oxide (LiNixM<NUM>-xO<NUM>), lithium cobalt oxide (LiCoO<NUM>), lithium nickel oxide (LiNiO<NUM>), lithium-nickel-cobalt-aluminum composite oxide (LiNi<NUM>Co<NUM>Al<NUM>O<NUM>, NCA layered oxide), lithium manganese oxide (e.g., spinel-type lithium manganese oxide LiMn<NUM>O<NUM>), and composite oxides with excessive Li (Li<NUM>MnO<NUM>-LiMO<NUM>), and compounds other than oxides. Compounds other than oxides include, for example, an olivine compound (LiMPO<NUM>) and a sulfur-containing compound (e.g., Li<NUM>S). In the chemical formulas, M indicates a transition metal. At least one positive-electrode active material can be used alone or in combination. In view of ease in securing a high capacity, a lithium-containing oxide containing at least one selected from the group consisting of Co, Ni, and Mn is preferable. The lithium-containing oxide may further contain typical metallic elements such as Al.

Moreover, in view of the improvement of rate characteristics, the positive-electrode active material may have an active material surface coated with a coating material. The coating material may be, for example, Li<NUM>Ti<NUM>O<NUM>, LiTaO<NUM>, Li<NUM>NbO<NUM>, LiAlO<NUM>, Li<NUM>ZrO<NUM>, Li<NUM>WO<NUM>, Li<NUM>TiO<NUM>, Li<NUM>B<NUM>O<NUM>, Li<NUM>PO<NUM>, Li<NUM>MoO<NUM>, LiBO<NUM>, alumina (Al<NUM>O<NUM>), or carbon (C).

The negative-electrode active material suitable for the negative layer <NUM> is a mixture of a negative-electrode active material and a lithium-ion conductive solid electrolyte or a negative-electrode active material used alone. The negative-electrode active material is not particularly limited as long as the insertion and desorption of a lithium ion can be performed. Known negative-electrode active materials used for all-solid batteries are usable. The negative-electrode active material may be, for example, a single element, an alloy, or a compound of metals or semimetals that allow the insertion and desorption of a lithium ion in addition to a carbonaceous material that allows the insertion and desorption of a lithium ion. Examples of the carbonaceous material include graphite (e.g., natural graphite or artificial graphite), hard carbon, and amorphous carbon. A single element and an alloy of metals or semimetals may be a lithium metal, an alloy thereof, or Si as a single element. A compound may be, for example, an oxide, a sulfide, a nitride, a hydrate, or silicide (e.g., lithium silicide). For example, a titanium oxide or a silicon oxide may be used as an oxide. At least one negative-electrode active material may be used alone or in combination. For example, a silicon oxide and a carbonaceous material may be used in combination.

Solid electrolytes are roughly classified into organic polymer electrolytes (also referred to as organic solid electrolytes) and inorganic solid electrolytes. Any one of the electrolytes may be used. Inorganic solid electrolytes are roughly classified into oxide materials and sulfide materials, any one of the materials may be used. Moreover, a crystalline or amorphous inorganic solid electrolyte may be appropriately selected. In other words, a solid electrolyte can be appropriately selected from materials including an organic compound, an inorganic compound, and a mixture of the compounds. Specifically, materials usable as solid electrolytes include, for example, a lithium-ion conductive solid electrolyte and a sulfide inorganic-solid electrolyte that is known for ion conduction higher than those of other inorganic compounds. Moreover, materials usable as solid electrolytes include lithium-containing metal oxides (at least one metal) such as Li<NUM>-SiO<NUM> and Li<NUM>-SiO<NUM>-P<NUM>O<NUM>, a lithium-containing metal nitride such as LixPyO<NUM>-zN<NUM>, lithium-containing sulfide based glass such as Li<NUM>S-P<NUM>S<NUM> system, Li<NUM>S-SiS<NUM> system, Li<NUM>S-B<NUM>S<NUM> system, Li<NUM>S-GeS<NUM> system, Li<NUM>S-SiS<NUM>-Lil system, Li<NUM>S-SiS<NUM>-Li<NUM>PO<NUM> system, Li<NUM>S-Ge<NUM>S<NUM> system, Li<NUM>S-GeS<NUM>-P<NUM>S<NUM> system, and Li<NUM>S-GeS<NUM>-ZnS system, PEO (polyethylene oxide), PVDF (polyvinylidene difluoride), lithium phosphate (Li<NUM>PO<NUM>), and a lithium-containing transition-metal oxide such as a lithium titanium oxide. A sulfide (sulfide inorganic-solid electrolyte) is preferably used as the inorganic solid electrolyte. For example, at least one sulfide containing Li<NUM>S and at least one element selected from the group consisting of the group <NUM> element, the group <NUM> element, and the group <NUM> element in the periodic table is preferably used. The elements of groups <NUM> to <NUM> in the periodic table are not particularly limited. For example, P, Si, Ge, As, Sb, and Al may be used. P, Si, and Ge are preferable and P is particularly preferable. Moreover, a sulfide containing these elements (particularly P) and Li is also preferable. The solid electrolyte suitable for the solid-electrolyte layer <NUM> may be identical to or different from the solid electrolyte used for the positive layer <NUM> and the negative layer <NUM>.

The positive-electrode active material, the negative-electrode active material, and the solid electrolyte are not limited to the foregoing materials. Ordinary materials in the field of batteries are also usable.

Referring to <FIG>, an installation <NUM> for manufacturing the all-solid secondary battery <NUM> will be described below.

As illustrated in <FIG>, the manufacturing installation <NUM> includes a mixer <NUM> for mixing multiple kinds (e.g., two kinds in <FIG>) of powder materials A and S, a conveying device <NUM> for conveying a powder material AS mixed by the mixer <NUM>, and an electrostatic film-forming device <NUM> for forming the powder film from the powder material AS conveyed by the conveying device <NUM>. The electrostatic film-forming device <NUM> also forms the powder laminate <NUM> by stacking the formed powder films, that is, forming another powder film on the formed powder film. In the manufacturing installation <NUM>, a process from the multiple kinds of powder materials A and S to the formation of the powder laminate <NUM> or later is a dry process.

As indicated in <FIG>, the powder materials A and S to be mixed by the mixer <NUM> are, for example, a first powder material A that is a powder material of a positive-electrode active material or a negative-electrode active material and a second powder material S that is a powder material of a solid electrolyte or the like. The multiple kinds of powder materials A and S preferably have small variations in particle size and thus may be extracted and used in a predetermined particle-size range through a sizing operation after processing using a ball mill or the like.

The mixer <NUM> mixes the multiple kinds of powder materials A and S to a uniform state by, for example, processing using a ball mill or the like. The degree of uniformity in mixing is determined according to the degree of mixing. For example, the color densities of the mixed powder material AS are measured at multiple points and the degree of mixing is determined according to the distribution or the standard deviation of the color densities measured at the multiple points. The multiple kinds of powder materials A and S have different color densities and thus the measurement of the color densities of the mixed powder material AS can determine the ratios of the specific powder materials A and S in the mixed powder material AS. The degree of mixing is a value corresponding to the distribution or the standard deviation (that is, variations) of the measured color densities. Thus, the smaller the value, the higher the degree of uniformity in mixing. Hence, the mixer <NUM> mixes the multiple kinds of powder materials A and S until the degree of mixing falls to a predetermined value or less. The mixed powder material AS also preferably has small variations in particle size and thus may be extracted and used in a predetermined particle-size range through a sizing operation.

The conveying device <NUM> preferably conveys the powder material AS without vibrating the mixed powder material AS. Typically, a mixture of the multiple kinds of powder materials A and S having different particle sizes or densities may be separated into the powder materials A and S by vibrations. For this reason, the conveying device <NUM> does not vibrate the mixed powder material AS, thereby stably conveying the powder material AS (in a uniformly mixed state). Specifically, in order to avoid vibrations applied to the mixed powder material AS, the conveying device <NUM> has, for example, divided containers for conveying the powder material AS for the respective powder films to be formed by the electrostatic film-forming device <NUM>.

The electrostatic film-forming device <NUM> uses at least an electrostatic force for forming the powder films. In other words, the electrostatic film-forming device <NUM> may use other forces (including gravity, a vibrating force and/or a pressing force) for forming the powder films in addition to an electrostatic force. The electrostatic film-forming device <NUM> can form a flat powder film having a uniform thickness by using at least an electrostatic force. The electrostatic film-forming device <NUM> includes, for example, a powder loading member to be loaded with the powder material AS and a direct-current power supply that causes a drop of the powder material AS from the powder loading member to form the powder film by an electrostatic force. The powder loading member and the direct-current power supply are not illustrated. The electrostatic film-forming device <NUM> preferably includes a cleaning tool for cleaning, each time a predetermined number of powder films are formed, instruments used for forming the powder films. This prevents the powder material AS left on the instruments by the formation of the powder films from adversely affecting the formation of a subsequent powder film with the instruments. In the above description, the electrostatic film-forming device <NUM> in <FIG> also forms the powder laminate <NUM> by stacking the formed powder films, that is, forming another powder film on the formed powder film. However, the electrostatic film-forming device <NUM> may not form the powder laminate <NUM>. In this case, the manufacturing installation <NUM> is provided with another device for forming the powder laminate <NUM> by stacking the powder films formed by the electrostatic film-forming device <NUM>.

The installation <NUM> for manufacturing the all-solid secondary battery <NUM> may have other configurations. In any configuration, processes from the multiple kinds of powder materials A and S to the formation of at least the powder laminate <NUM> or later are all dry processes. In other words, configurations from a location for storing the multiple kinds of powder materials A and S to the process of forming at least the powder laminate <NUM> are all dry processes in the manufacturing installation <NUM>, the configurations including the mixer <NUM>, the conveying device <NUM>, and the electrostatic film-forming device <NUM>. In this case, the dry process is a liquid-free process. Since the manufacturing installation <NUM> is provided for a dry process, liquids such as a solvent are unused contrary to a wet process, causing no problems resulting from the use of solvents. In other words, in the powder laminate <NUM> formed by the dry process, the impurities such as a solvent are not left and a cavity formed by removing the impurities such as a solvent is not left. The manufacturing installation <NUM> naturally eliminates the need for a device for drying the powder laminate <NUM> unlike in a wet process.

A method of using the installation <NUM> for manufacturing the all-solid secondary battery <NUM>, in other words, a method of manufacturing the all-solid secondary battery <NUM> by using the manufacturing installation <NUM> will be described below.

First, the mixer <NUM> mixes the multiple kinds of powder materials A and S. In other words, the mixer <NUM> provides a mixing step of mixing the multiple kinds of powder materials A and S.

Subsequently, the powder material AS mixed by the mixer <NUM> is conveyed from the mixer <NUM> to the electrostatic film-forming device <NUM> by the conveying device <NUM>. In other words, the conveying device <NUM> provides a conveying step of conveying the mixed powder material AS from the mixer <NUM> to the electrostatic film-forming device <NUM>.

Thereafter, the electrostatic film-forming device <NUM> forms the powder film from the mixed powder material AS by using at least an electrostatic force. In other words, the electrostatic film-forming device <NUM> provides an electrostatic-film forming step of forming the powder film from the mixed powder material AS by using at least an electrostatic force. The electrostatic film-forming device <NUM> or another device then forms the powder laminate <NUM> by stacking the formed powder films. In other words, the electrostatic film-forming device <NUM> or another device provides a powder-laminate forming step of forming the powder laminate <NUM> by stacking the powder films.

The mixing step, the conveying step, the electrostatic-film forming step, and the powder-laminate forming step are all dry processes. Hence, in the powder laminate <NUM> formed by these steps, impurities are not left and a cavity formed by removing the impurities is not left. The powder laminate <NUM> is interposed between the positive current collector <NUM> and the negative current collector <NUM> as illustrated in <FIG>, so that the electrodes body <NUM> to <NUM> is obtained. The electrodes body <NUM> to <NUM> is each stacked as one layer or multiple layers and is optionally contained in the outer package <NUM>, e.g., the laminated pack <NUM> or the can, forming the all-solid secondary battery <NUM>.

As has been discussed, according to the installation <NUM> for manufacturing the all-solid secondary battery <NUM>, the impurities such as a solvent are not left contrary to a wet-process method and a cavity formed by removing impurities is not left in the formed powder laminate <NUM>. This can improve the battery performance of the all-solid secondary battery <NUM> manufactured from the powder laminate <NUM>. Moreover, according to the installation <NUM> for manufacturing the all-solid secondary battery <NUM>, a device for drying the powder laminate <NUM> is not necessary, thereby simplifying the overall configuration and reducing the cost for manufacturing the all-solid secondary battery <NUM>.

An installation <NUM> for manufacturing an all-solid secondary battery <NUM> according to a second embodiment will be described below in accordance with the accompanying drawings. The second embodiment will more specifically describe the first embodiment. Configurations omitted in the first embodiment will be mainly discussed below. The same configurations as those of the first embodiment are indicated by the same reference numerals and the explanation thereof is omitted.

As illustrated in <FIG>, in the installation <NUM> for manufacturing the all-solid secondary battery <NUM> according to the second embodiment, a first powder material A is a powder material of a positive-electrode active material or a negative-electrode active material and a second powder material S is a powder material of a sulfide based solid electrolyte.

A conveying device <NUM> for conveying a powder material AS mixed by a mixer <NUM> includes a positive-electrode conveyor <NUM> for conveying the powder material AS for forming a positive layer <NUM> and a negative-electrode conveyor <NUM> for conveying the powder material AS for forming a negative layer <NUM>. The manufacturing installation <NUM> includes an electrolyte conveyor <NUM> for conveying a powder material S of the sulfide based solid electrolyte that is the second powder material S, as a powder material conveyor in addition to the conveying device <NUM>. The positive-electrode conveyor <NUM>, the electrolyte conveyor <NUM>, and the negative-electrode conveyor <NUM> may all have the same configuration or different configurations.

An electrostatic film-forming device <NUM> includes a positive-electrode electrostatic film-forming machine <NUM> for forming the positive layer <NUM>, an electrolyte electrostatic film-forming machine <NUM> for forming a solid-electrolyte layer <NUM>, and a negative-electrode electrostatic film-forming machine <NUM> for forming the negative layer <NUM>. In the electrostatic film-forming device <NUM>, the positive-electrode electrostatic film-forming machine <NUM>, the electrolyte electrostatic film-forming machine <NUM>, and the negative-electrode electrostatic film-forming machine <NUM> are sequentially disposed from the upstream side. Specifically, the electrostatic film-forming device <NUM> is configured such that the positive layer <NUM> is formed by the positive-electrode electrostatic film-forming machine <NUM>, the solid-electrolyte layer <NUM> is formed on the positive layer <NUM> by the electrolyte electrostatic film-forming machine <NUM>, and the negative layer <NUM> is formed on the solid-electrolyte layer <NUM> by the negative-electrode electrostatic film-forming machine <NUM> (that is, powder laminate <NUM> is formed). The positive-electrode electrostatic film-forming machine <NUM>, the electrolyte electrostatic film-forming machine <NUM>, and the negative-electrode electrostatic film-forming machine <NUM> may all have the same configuration or different configurations. The solid-electrolyte layer <NUM> formed by the electrolyte electrostatic film-forming machine <NUM> is made of the powder material S of a sulfide based solid electrolyte. Thus, the solid-electrolyte layer <NUM> is a layer made of a sulfide based solid electrolyte.

The installation <NUM> for manufacturing the all-solid secondary battery <NUM> according to the second embodiment includes a current-collector feeder <NUM> for feeding a positive current collector <NUM> and a negative current collector <NUM>. The current-collector feeder <NUM> feeds the positive current collector <NUM> to the positive-electrode electrostatic film-forming machine <NUM>, so that the positive layer <NUM> is formed on the positive current collector <NUM>. Furthermore, the current-collector feeder <NUM> feeds the negative current collector <NUM> to a pressure device <NUM>, which will be described later, so that the powder laminate <NUM> to be pressurized by the pressure device <NUM> is replaced with the electrodes body <NUM> to <NUM>. Before the positive layer <NUM>, the solid-electrolyte layer <NUM>, and the negative layer <NUM> are formed, the powder films may be leveled with a small pressure at any time. Furthermore, on the positive current collector <NUM> and/or the negative current collector <NUM> fed from the current-collector feeder <NUM>, a rough surface is formed in contact with the positive layer <NUM> and/or the negative layer <NUM>. The rough surface is formed on the positive current collector <NUM> and/or the negative current collector <NUM>, thereby roughening the positive layer <NUM> and/or the negative layer <NUM> in contact with the surface. In other words, roughness on the surface of the positive current collector <NUM> and/or the negative current collector <NUM> is transferred to the positive layer <NUM> and/or the negative layer <NUM>.

The installation <NUM> for manufacturing the all-solid secondary battery <NUM> according to the second embodiment further includes the pressure device <NUM> for pressurizing the electrodes body <NUM> to <NUM>, a cutting-removing device <NUM> for cutting and removing an outer end portion of the electrodes body <NUM> to <NUM> pressurized by the pressure device <NUM>, and a laminator <NUM> for sealing the electrodes body <NUM> to <NUM> into a laminated pack <NUM> after the outer end portion is cut and removed. In some cases, a layering device or a layering laminator is necessary.

The pressure device <NUM> pressurizes the electrodes body <NUM> to <NUM> in the thickness direction. The pressurization (hereinafter, will be also referred to as main pressurization) makes powder denser in the powder laminate <NUM> of the electrodes body <NUM> to <NUM>, thereby improving the battery performance. The pressure device <NUM> includes a pressing body, which is not illustrated, for pressurizing the electrodes body <NUM> to <NUM>. Before the main pressurization, the pressure device <NUM> may apply a lower pressure than that of the main pressurization under low-vacuum environments. If only the main pressurization is performed on the electrodes body <NUM> to <NUM>, gas in the powder laminate <NUM> of the electrodes body <NUM> to <NUM> may be rapidly pressed out by the main pressurization, increasing the possibility of a break in the powder laminate <NUM>. However, if a low pressure is applied to the electrodes body <NUM> to <NUM> in advance under low-vacuum environments (hereinafter, will be also referred to as vacuum provisional pressurization), gas in the powder laminate <NUM> is properly discharged in advance and thus is not rapidly pressed out in the subsequent main pressurization, so that the powder laminate <NUM> is hardly broken. The pressure device <NUM> may be manually operated or operated by another controller, which is not illustrated, in order to perform the vacuum provisional pressurization and the main pressurization. If an operation is performed by another controller, the controller includes a vacuum temporary pressure unit that causes the pressure device <NUM> to perform vacuum provisional pressurization and a main pressure unit that causes the pressure device <NUM> to perform the main pressurization.

The cutting-removing device <NUM> cuts and removes the outer end portion of the electrodes body <NUM> to <NUM> because the battery performance is likely to deteriorate on the outer end portion. Only the central portion of the electrodes body <NUM> to <NUM> other than the outer end portion is used for the all-solid secondary battery <NUM>. Since the powder laminate <NUM> of the electrodes body <NUM> to <NUM> is formed by pressurizing powder materials, deformation and/or a short circuit are likely to occur on the outer end. In the event of deformation and/or a short circuit on the outer end of the powder laminate <NUM>, the outer end is cut and removed by the cutting-removing device <NUM>, thereby preventing deterioration of the battery performance due to the deformation and/or the short circuit. For the cutting-removing device <NUM>, for example, a method of stamping the central portion of the electrodes body <NUM> to <NUM> or a method of cutting the outer end portion of the electrodes body <NUM> to <NUM> (e.g., a chocolate break method) is used. In the method of stamping the central portion of the electrodes body <NUM> to <NUM>, the cutting-removing device <NUM> includes a die for holding the outer end portion of the electrodes body <NUM> to <NUM> and a punch for stamping the central portion of the electrodes body <NUM> to <NUM> with the outer end portion held by the die. The dies and the punch are not illustrated. In the method of cutting the outer end portion of the electrodes body <NUM> to <NUM> (specifically, the chocolate break method), the cutting-removing device <NUM> includes a cutter blade for forming a cutting groove along the inner edge of a portion to be cut on the electrodes body <NUM> to <NUM>, a retainer plate for retaining the central portion of the electrodes body <NUM> to <NUM> where the cutting groove is formed, and a separating tool for separating the outer end portion of the electrodes body <NUM> to <NUM> retained by the retainer plate, along the cutting groove by a bending moment.

The laminator <NUM> seals the electrodes body <NUM> to <NUM> into the laminated pack <NUM> after the outer end portion is cut and removed. The electrodes body <NUM> to <NUM> is each stacked as one layer or multiple layers. In the case of multiple layers, a current collector for electrically connecting the layers is optionally provided. The laminator <NUM> may include a vacuum pump for sealing the electrodes body <NUM> to <NUM> into the laminated pack <NUM> in a high-vacuum atmosphere. When the electrodes body <NUM> to <NUM> is sealed into the laminated pack <NUM> in a high-vacuum atmosphere, the electrodes body <NUM> to <NUM> of the manufactured all-solid secondary battery <NUM> always receive an atmospheric pressure from the outside due to a pressure difference between the inside and the outside of the laminated pack <NUM>. Thus, powder in the powder laminate <NUM> of the electrodes body <NUM> to <NUM> is kept dense.

In the installation <NUM> for manufacturing the all-solid secondary battery <NUM> according to the second embodiment, the mixer <NUM>, the conveying device <NUM>, the electrolyte conveyor <NUM>, the electrostatic film-forming device <NUM>, the current-collector feeder <NUM>, the pressure device <NUM>, the cutting-removing device <NUM>, and the laminator <NUM> are all provided for a dry process and are disposed in, for example, a dry room.

First, the mixer <NUM> mixes a powder material of a positive-electrode active material (first powder material A) and a powder material of a sulfide based solid electrolyte (second powder material S). A mixed powder material AS is conveyed to the positive-electrode electrostatic film-forming machine <NUM> by the positive-electrode conveyor <NUM>. Concurrently, the powder material of the sulfide based solid electrolyte (second powder material S) is conveyed to the electrolyte electrostatic film-forming machine <NUM> by the electrolyte conveyor <NUM>. Meanwhile, the mixer <NUM> mixes the powder material of the negative-electrode active material (first powder material A) and the powder material of the sulfide based solid electrolyte (second powder material S). The mixed powder material AS is conveyed to the negative-electrode electrostatic film-forming machine <NUM> by the negative-electrode conveyor <NUM>.

The positive-electrode electrostatic film-forming machine <NUM> forms the positive layer <NUM> on the positive current collector <NUM> fed from the current-collector feeder <NUM>. The electrolyte electrostatic film-forming machine <NUM> forms the solid-electrolyte layer <NUM> on the positive layer <NUM>. The negative-electrode electrostatic film-forming machine <NUM> forms the negative layer <NUM> on the solid-electrolyte layer <NUM>, thereby forming the powder laminate <NUM>.

The negative current collector <NUM> fed from the current-collector feeder <NUM> is placed on the negative layer <NUM> of the powder laminate <NUM> by the pressure device <NUM>, thereby forming the electrodes body <NUM> to <NUM>. Subsequently, the pressure device <NUM> performs the main pressurization on the electrodes body <NUM> to <NUM> or the vacuum provisional pressurization before the main pressurization. In other words, the pressure device <NUM> provides a main pressurization step of performing the main pressurization on the electrodes body <NUM> to <NUM> or a vacuum provisional pressurization step and the main pressurization step.

The cutting-removing device <NUM> cuts and removes the outer end portion of the electrodes body <NUM> to <NUM>. The battery performance is likely to deteriorate on the outer end portion. In other words, the cutting-removing device <NUM> provides a cutting-removing step of cutting and removing the outer end portion of the electrodes body <NUM> to <NUM>.

The laminator <NUM> seals the electrodes body <NUM> to <NUM> into the laminated pack <NUM> in a high-vacuum atmosphere after the outer end portion is cut and removed. The electrodes body <NUM> to <NUM> is each stacked as one layer or multiple layers. In the case of multiple layers, a current collector for electrically connecting the layers is optionally provided. In other words, the laminator <NUM> provides a laminating step of sealing the electrodes body <NUM> to <NUM> into the laminated pack <NUM> in a high-vacuum atmosphere.

As has been discussed, in the installation <NUM> for manufacturing the all-solid secondary battery <NUM> according to the second embodiment, powder in the powder laminate <NUM> is made denser through the main pressurization performed by the pressure device <NUM> in addition to the effect of the first embodiment, thereby further improving the battery performance. By performing, in particular, the vacuum provisional pressurization before the main pressurization, the powder laminate <NUM> becomes resistant to deformation, thereby further improving the battery performance.

The cutting-removing device <NUM> cuts and removes the outer end portion of the electrodes body <NUM> to <NUM> because the battery performance is likely to deteriorate on the outer end portion, and the central portion of the electrodes body <NUM> to <NUM> is used for the all-solid secondary battery because high battery performance is obtained at the central portion. Thus, the battery performance can be further improved.

Moreover, the laminator <NUM> causes the electrodes body <NUM> to <NUM> to always receive an atmospheric pressure from the outside. Thus, powder in the powder laminate <NUM> of the electrodes body <NUM> to <NUM> is kept dense so as to further improve the battery performance.

In the first and second embodiments, the positive layer <NUM> is first formed and then the negative layer <NUM> is formed. The negative layer <NUM> may be formed prior to the positive layer <NUM>. Specifically, in <FIG> and <FIG>, the positive layer <NUM>, the positive-electrode conveyor <NUM>, and the positive-electrode electrostatic film-forming machine <NUM> may be replaced with the negative layer <NUM>, the negative-electrode conveyor <NUM>, and the negative-electrode electrostatic film-forming machine <NUM>.

The first embodiment described the configuration of the all-solid secondary battery <NUM> in accordance with <FIG>. The configuration is not limited to the one illustrated in <FIG> as long as at least the powder laminate <NUM> is provided.

The manufacturing installation <NUM> may be provided with a pressurizing charger/discharger for charging and discharging (hereinafter, will be referred to as pressurizing charge/discharge) the electrodes body <NUM> to <NUM> while applying a pressure. The pressurizing charger/discharger was not described in the second embodiment. By the pressurizing charge and discharge of the electrodes body <NUM> to <NUM> (or stacked electrodes bodies <NUM> to <NUM>), the powder laminate <NUM> of the electrodes body <NUM> to <NUM> expands and shrinks while being pressed by the positive current collector <NUM> and the negative current collector <NUM>. This allows the powder laminate <NUM> to sufficiently catch the rough surfaces of the positive current collector <NUM> and the negative current collector <NUM>, thereby further improving the battery performance in an unpressurized state.

Additionally, the first and second embodiments did not describe the specific configurations of the electrostatic film-forming device <NUM> and the powder laminate forming step. For example, the electrostatic film-forming device <NUM> and the powder laminate forming step may be configured as follows:.

Referring to <FIG>, a first specific example of the electrostatic film-forming device <NUM> capable of forming a powder film with a uniform thickness will be described below.

As illustrated in <FIG>, the electrostatic film-forming device <NUM> includes a screen printing plate <NUM> that is electrically neutral and is not in contact with a target O where a powder film is to be formed, a rubbing member <NUM> that rubs the negatively (or positively) charged powder material AS into the screen printing plate <NUM> and drops the powder material AS onto the target O, a base <NUM> for placing the target O, and a direct-current power supply <NUM> for positively charging the base <NUM>.

The screen printing plate <NUM> has a mesh part <NUM> where the powder material AS is rubbed by the rubbing member <NUM>. The material of the mesh part <NUM> may be selected from, for example, polyester, nylon, stainless, or polyethylene. Other materials may be used according to the used powder material AS. If the powder material AS placed on the screen printing plate <NUM> is negatively charged, the screen printing plate <NUM> is preferably made of a material (nylon or rayon) positively charged in the triboelectric series or a metal such that the powder material AS is not positively charged by friction resulting from rubbing by the rubbing member <NUM>. If the powder material AS placed on the screen printing plate <NUM> is positively charged, the screen printing plate <NUM> is preferably made of a material (polyethylene or polyester) negatively charged in the triboelectric series or a metal such that the powder material AS is not negatively charged by friction resulting from rubbing by the rubbing member <NUM>.

The rubbing member <NUM> is, for example, a squeegee or a sponge. The rubbing member <NUM> may be replaced with an air-nozzle that drops the powder material AS from the screen printing plate <NUM> to the target O by blowing gas.

In order to negatively (or positively) charge the powder material AS placed on the screen printing plate <NUM>, the powder material AS is brought into contact with a plate carrying a negative (or positive) voltage, which is not illustrated. When the powder material AS is brought into contact with the plate, the negative plate (or positive plate) is vibrated so as to charge fine particles constituting the powder material AS. Instead of the method of vibrating the negative plate (or positive plate) in contact with the powder material AS, the powder material AS may be charged by friction or corona discharge. Thus, the powder material AS to be placed on the screen printing plate <NUM> is negatively (positively) charged before being placed on the screen printing plate <NUM>, ensuring negative (or positive) charge as compared with negative charge through the screen printing plate <NUM>.

As illustrated in <FIG>, if the powder material AS placed on the screen printing plate <NUM> is negatively charged, the base <NUM> is connected to the positive electrode of the direct-current power supply <NUM> so as to be positively charged. If the powder material AS placed on the screen printing plate <NUM> is positively charged, the base <NUM> is connected to the negative electrode of the direct-current power supply <NUM> so as to be negatively charged. This configuration is not illustrated.

Thus, according to the first specific example of the electrostatic film-forming device <NUM>, the powder material AS placed on the screen printing plate <NUM> is negatively (positively) charged with reliability, so that the powder material AS is uniformly dropped from the screen printing plate <NUM> to the target O positively (or negatively) charged through the base <NUM>. This can form the powder film having a uniform thickness.

The formation of the powder film with a uniform thickness by the electrostatic film-forming device <NUM> was examined in first to third experimental examples and a comparative example as follows:.

In the first experimental example, the electrostatic film-forming device <NUM> in <FIG> was used. On the screen printing plate <NUM> of the electrostatic film-forming device <NUM>, the mesh part <NUM> (opening) had a square shape, <NUM> meshes per inch, a wire diameter of <NUM>, and an opening of <NUM>. As powder materials placed on the screen printing plate <NUM>, <NUM> heavy calcium carbonates were used for experiments. In order to negatively charge the powder material, the powder material was brought into contact with the vibrating positive plate that carries a voltage of about -<NUM> V to -<NUM> V.

In the second experimental example, the polarity of charge in the first experimental example was reversed. Specifically, the powder material was positively charged and the base <NUM> was negatively charged. The second experimental example is identical to the first experimental example except for the polarity.

In the third experimental example, the rubbing member <NUM> of the first experimental example was replaced with an air-nozzle. The third experimental example is identical to the first experimental example except for the air-nozzle.

In the comparative example, the powder material was not charged before being placed on the screen printing plate <NUM> illustrated in <FIG>. The powder material was rubbed into the negatively charged screen printing plate <NUM> by the rubbing member <NUM>, so that the powder film was formed on the target O.

Table <NUM> shows data regarding the thicknesses of powder films formed in the examples. Table <NUM> shows the results of the first to third experimental examples and the comparative example that were all intended to form each powder film having a thickness of <NUM>.

As is evident from Table <NUM>, the powder films formed in the first to third experimental examples can have a more uniform thickness than in the comparative example.

Referring to <FIG>, a second specific example of the electrostatic film-forming device <NUM> capable of obtaining a desired thickness at any location in the powder film will be described below.

The electrostatic film-forming device <NUM> includes the screen printing plate <NUM> illustrated in <FIG> and a known configuration necessary for electrostatic film formation. Naturally, the configuration in <FIG> is usable other than the known configuration. The screen printing plate <NUM> in <FIG> includes the mesh part <NUM> (opening) where apertures and/or opening ratios vary among locations. The shape of the mesh part <NUM> is not limited to a rectangle. The mesh part <NUM> may be polygonal or circular in shape. The screen printing plate <NUM> is not always disposed in parallel with the target O where the powder film is formed. The screen printing plate <NUM> may be inclined (<NUM>° to <NUM>°) with respect to the target O. In the example of <FIG>, the mesh part <NUM> has a large aperture and a large opening ratio on a surrounding part (hereinafter, will be referred to as a first mesh part 38A) and a small aperture and a small opening ratio in a part (hereinafter, will be referred to as a second mesh part 38B) surrounded by the first mesh part 38A. By using the screen printing plate <NUM> having the mesh part <NUM>, the formed powder film has a large thickness corresponding to the first mesh part 38A having a large aperture and a large opening ratio and has a small thickness corresponding to the second mesh part 38B having a small aperture and a small opening ratio.

In the fourth experimental example, the screen printing plate <NUM> in <FIG> was used in the configuration of the comparative example. The screen printing plate <NUM> has an aperture of <NUM>, an opening ratio of <NUM>%, <NUM> meshes per inch, and a wire diameter of <NUM> in the first mesh part 38A and has an aperture of <NUM>, an opening ratio of <NUM>%, <NUM> meshes per inch, and a wire diameter of <NUM> in the second mesh part 38B. The screen printing plate <NUM> in parallel with the target O was disposed at a distance of <NUM> from the target O and carried a voltage of <NUM> kV. The powder material was dropped from the screen printing plate <NUM> to the target O by the rubbing member <NUM> while the voltage was applied, so that the powder film was formed. The powder film had a thickness of <NUM> to <NUM> at a point corresponding to the first mesh part 38A and had a thickness of <NUM> to <NUM> at a point corresponding to the second mesh part 38B.

By using the screen printing plate <NUM> including the mesh part <NUM> where apertures and/or opening ratios vary among locations, a desired thickness can be obtained at any point of the powder film.

Referring to <FIG>, a specific example of the powder-laminate forming step of obtaining a desired thickness at any location in the powder film will be described below.

Unlike in <FIG>, the powder laminate <NUM> formed in the powder-laminate forming step does not have a flat boundary between the positive layer <NUM> and the solid-electrolyte layer <NUM> and/or a flat boundary between the negative layer <NUM> and the solid-electrolyte layer <NUM>. For example, the boundary may have waviness as illustrated in <FIG>. However, it is preferable to perform stacking to flatten the overall powder laminate <NUM>. The solid-electrolyte layer <NUM> is increased in thickness on the end of the powder laminate <NUM>. Thus, even if the end of the laminate <NUM> is deformed, a short circuit is unlikely to occur on the end. In the powder laminate <NUM>, the outer surfaces of the positive layer <NUM> and the negative layer <NUM> (surfaces in contact with the positive current collector <NUM> and the negative current collector <NUM>) are flat as illustrated in <FIG> (the negative current collector <NUM> is omitted). The waviness is not caused by the roughness components of short wavelengths but is caused by the waviness components of long wavelengths. A cutoff value for discriminating between roughness components and waviness components preferably ranges from <NUM> to <NUM>. Moreover, regarding the waviness, the positive layer <NUM>, the solid-electrolyte layer <NUM>, and the negative layer <NUM> preferably satisfy the following formula: <MAT>.

As illustrated in <FIG>, on the end of the powder laminate <NUM>, the positive layer <NUM> and the negative layer <NUM> preferably have small thicknesses, and the solid-electrolyte layer <NUM> preferably has a large thickness. If the powder laminate <NUM> in particular is polygonal in plan view, the solid-electrolyte layer <NUM> preferably has quite a large thickness at each corner relative to the thicknesses of the positive layer <NUM> and the negative layer <NUM>. This reduces the possibility of a short circuit on the ends of the positive layer <NUM> and the negative layer <NUM>. Furthermore, as illustrated in <FIG>, the negative layer <NUM> is preferably larger in thickness than the positive layer <NUM> at any point in the powder laminate <NUM>. The thickness of the negative layer <NUM> in particular is preferably set at <NUM> to <NUM> relative to the thickness of the positive layer <NUM>. This prevents a short circuit caused by the precipitation of Li in the negative layer <NUM> and the inhibition of the growth toward the positive layer <NUM>, and improves the cycle characteristics of the all-solid secondary battery <NUM>.

In the powder-laminate forming step, any method may be used as long as the powder laminate <NUM> having the waviness is formed. As has been discussed in the second specific example of the electrostatic film-forming device <NUM>, the powder laminate <NUM> having waviness may be formed by using the mesh part <NUM> (opening) where apertures and/or opening ratios vary among locations.

In the powder-laminate forming step, the positive layer <NUM>, the solid-electrolyte layer <NUM>, and the negative layer <NUM> may be pressurized each time the layer is formed. In this case, in order to pressurize the overall layers while leaving part of the waviness of the layers, the pressing member of the pressure device <NUM> is preferably made of an elastic material.

In the powder laminate <NUM>, the solid-electrolyte layer <NUM> may be increased in thickness and the positive layer <NUM> and the negative layer <NUM> may be reduced in thickness toward the end of the powder laminate <NUM> such that the only the solid-electrolyte layer <NUM> is provided on the outermost end. This configuration is not illustrated. It is preferable to flatten the overall powder laminate <NUM>.

Referring to <FIG>, the first to fourth specific examples of the cutting-removing device <NUM> for cutting and removing the outer end portion of the electrodes body <NUM> to <NUM> will be described below.

As illustrated in <FIG>, the cutting-removing device <NUM> is a device for using the method of stamping the central portion of the electrodes body <NUM> to <NUM> (at least the powder laminate <NUM>) and a device for inclining sides <NUM> at the central portion of the electrodes body <NUM> to <NUM> by stamping. Specifically, the cutting-removing device <NUM> includes an inclined-side forming die <NUM> for holding the outer end portion of the electrodes body <NUM> to <NUM> and an inclined-side forming punch <NUM> for stamping the central portion of the electrodes body <NUM> to <NUM> with the outer end portion held by the inclined-side forming die <NUM>.

The inclined-side forming die <NUM> includes a base surface <NUM> on which the electrodes body <NUM> to <NUM> is placed and a space portion <NUM> through which the inclined-side forming punch <NUM> passes. Moreover, it is not necessary to press downward the electrodes body <NUM> to <NUM> for being held, which are placed on the base surface <NUM>, by the inclined-side forming die <NUM>. This is because the powder laminate <NUM> serving as a main configuration of the electrodes body <NUM> to <NUM> is a brittle material including one powder film or stacked powder films and the powder laminate <NUM> being stamped is broken before being largely deformed. Hence, the inclined-side forming die <NUM> does not include a retainer plate for retaining the electrodes body <NUM> to <NUM>. Thereby the inclined-side forming die <NUM> holds the electrodes body <NUM> to <NUM> so as to accept deformation of the electrodes body <NUM> to <NUM> being stamped. The inclined-side forming die <NUM> may include the retainer plate. The used retainer plate holds the electrodes body <NUM> to <NUM> with a force so as to accept deformation of the electrodes body <NUM> to <NUM> being stamped.

The inclined-side forming punch <NUM> has a blade <NUM> extending from a tip <NUM> to an inner surface 77I. The blade <NUM> cuts the electrodes body <NUM> to <NUM> by stamping. The blade <NUM> has the tip <NUM> that is sharpened and is increased in thickness toward the inner surface 77I in order to incline the side <NUM> that is the cut surface of the electrodes body <NUM> to <NUM>. The blade <NUM> is not limited to an inner blade <NUM> extending from the tip <NUM> to the inner surface 77I. The blade <NUM> may extend from the tip <NUM> to both of the inner surface 77I and an outer surface 77O. Instead of the method of using the inclined-side forming die <NUM> and the inclined-side forming punch <NUM>, Thomson's method using a Thomson blade may be used.

A method of using the cutting-removing device <NUM> will be described below.

First, the electrodes body <NUM> to <NUM> is placed (an example of holding) on the inclined-side forming die <NUM> so as to cover the space portion <NUM>. Subsequently, the inclined-side forming punch <NUM> is lowered at a predetermined speed V and is passed through the space portion <NUM>, so that the electrodes body <NUM> to <NUM> is stamped by the inclined-side forming punch <NUM>. The stamping cuts the sides <NUM> of the electrodes body <NUM> to <NUM> into inclined surfaces.

In the electrodes body <NUM> to <NUM> with the inclined sides <NUM>, the interface between the negative layer <NUM> and the solid-electrolyte layer <NUM> has a larger area than the interface between the positive layer <NUM> and the solid-electrolyte layer <NUM>.

The reason why the electrodes body <NUM> to <NUM> is shaped thus will be described below.

In the presence of an extra positive layer that is not opposed to a negative layer in a battery for which lithium ions are used, for example, a lithium-ion secondary battery, suspended metallic lithium is deposited from the end of the negative layer disposed near the extra positive layer, thereby increasing the occurrence of a short cut. Thus, in a battery for which lithium ions are used, a negative layer typically has a larger area than a positive layer.

In this configuration, however, the negative layer includes a useless part that does not overlap the positive layer. Moreover, even if the negative layer has a larger area than the positive layer, when the positive layer is displaced and is not partially opposed to the negative layer, a short circuit is likely to occur. Thus, the area of the negative layer is determined in consideration of the alignment error of the positive layer. This disadvantageously leads to an excessively large area of the negative layer, resulting in upsizing of the battery.

Unlike in this configuration, such a problem does not occur in the electrodes body <NUM> to <NUM> in which the sides <NUM> are inclined and the interface between the negative layer <NUM> and the solid-electrolyte layer <NUM> has a larger area than the interface between the positive layer <NUM> and the solid-electrolyte layer <NUM> as illustrated in <FIG>. Furthermore, the electrodes body <NUM> to <NUM> with the inclined sides <NUM> can prevent a short circuit caused by deformation of the projecting portions of the positive layer <NUM> and the negative layer <NUM>. Such a short circuit is likely to occur in a conventional all-solid secondary battery.

The inclined sides <NUM> of the electrodes body <NUM> to <NUM> are not limited to flat surfaces as long as the sides <NUM> have continuously inclined surfaces. For example, the sides <NUM> may have curved surfaces such as a convex surface or a concave surface. If the inclined sides <NUM> of the electrodes body <NUM> to <NUM> are in particular curved convex surfaces, the end part of the electrodes body <NUM> to <NUM> is hardly deformed. If the electrodes body <NUM> to <NUM> has multiple sides like polygons in plan view, the number of inclined sides <NUM> is not limited.

The cutting-removing device <NUM> cuts the electrodes bodies such that the interface between the negative layer <NUM> and the solid-electrolyte layer <NUM> has a larger area than the interface between the positive layer <NUM> and the solid-electrolyte layer <NUM>. The cutting-removing device <NUM> may cut the electrodes bodies such that the interface between the positive layer <NUM> and the solid-electrolyte layer <NUM> has a larger area than the interface between the negative layer <NUM> and the solid-electrolyte layer <NUM>.

The electrodes body <NUM> to <NUM> are shaped by the cutting-removing device <NUM> as in the first specific example but a chocolate break method is used instead of stamping.

As illustrated in <FIG>, the cutting-removing device <NUM> includes a retainer plate <NUM> for vertically retaining the electrodes body <NUM> to <NUM>, a cutting-groove forming member (not illustrated) for forming a cutting groove <NUM> for breaking (an example of cutting) the outer end portion of the electrodes body <NUM> to <NUM>, and a loading part (not illustrated) for applying a load F to an end part of the electrodes body <NUM> to <NUM> having the cutting groove <NUM>.

The retainer plate <NUM> holds the electrodes body <NUM> to <NUM> with a force so as to accept deformation of the electrodes body <NUM> to <NUM> being broken.

The cutting-groove forming member forms the cutting groove <NUM> as a cut at the starting point of a break when the load F is applied to the end part of the electrodes body <NUM> to <NUM>. Thus, the cutting groove <NUM> is shaped so as to incline the side <NUM> of the electrodes body <NUM> to <NUM> when the side <NUM> is formed by a break. The cutting groove <NUM> may be formed from the positive current collector <NUM> or the negative current collector <NUM>. The cutting-groove forming member is not limited as long as the cutting groove <NUM> is formed by the member. For example, a cutter blade, a rotary blade (a roller with a blade), or a die having a projecting portion that matches the shape of the cutting groove <NUM> may be used.

The loading part generates a bending moment and/or a shearing stress at the cutting groove <NUM> so as to apply the load F that starts a break from the cutting groove <NUM>.

First, the electrodes body <NUM> to <NUM> is vertically retained by the retainer plate <NUM>. Subsequently, the cutting groove <NUM> for breaking (an example of cutting) the outer end portion of the electrodes body <NUM> to <NUM> is formed by the cutting-groove forming member. Thereafter, the loading part applies a load to the end part of the electrodes body <NUM> to <NUM> having the cutting groove <NUM>, thereby breaking the outer end portion from the cutting groove <NUM> so as to incline the side <NUM> of the electrodes body <NUM> to <NUM>.

In addition to the foregoing steps, for example, the cutting groove <NUM> is formed by the cutting-groove forming member in the following two patterns: In a first pattern, the cutting groove <NUM> is formed on the positive current collector <NUM> or the negative current collector <NUM> in advance before the powder laminate <NUM> is formed. In a second pattern, the cutting groove <NUM> is formed on the powder laminate <NUM> (or the electrodes body <NUM> to <NUM>) without retaining the powder laminate <NUM> (or the electrodes body <NUM> to <NUM>) with the retainer plate <NUM> after the powder laminate <NUM> (or the electrodes body <NUM> to <NUM>) is formed.

As illustrated in <FIG>, the cutting-removing device <NUM> is a device for using the method of stamping the central portion of the electrodes body <NUM> to <NUM> (at least the powder laminate <NUM>) but is not necessarily a device for inclining sides <NUM> at the central portion of the electrodes body <NUM> to <NUM> by stamping. The cutting-removing device <NUM> is a device for preventing roughness on the sides <NUM> formed by stamping. Specifically, the cutting-removing device <NUM> includes a die <NUM> for holding the outer end portion of the electrodes body <NUM> to <NUM> and a punch <NUM> for stamping the central portion of the electrodes body <NUM> to <NUM> with the outer end portion held by the die <NUM>.

The die <NUM> includes the base surface <NUM> on which the electrodes body <NUM> to <NUM> are placed and the space portion <NUM> through which the punch <NUM> passes. The die <NUM> has an inner wall <NUM> facing the space portion <NUM>. On the upper end of the inner wall <NUM>, a blade 74a is formed to cut the outer end portion of the electrodes body <NUM> to <NUM> by stamping with the punch <NUM>. The inner wall <NUM> is vertical at a predetermined height <NUM> or higher and is inclined at an angle θ1 so as to extend the space portion <NUM> downward at a height lower than the predetermined height <NUM>. The inner wall <NUM> has a flank surface 74e lower than the predetermined height <NUM>. The flank surface 74e prevents roughness on the sides <NUM> formed in the electrodes body <NUM> to <NUM> by stamping with the punch <NUM>. The flank surface 74e is preferably formed under the intermediate portion of the inner wall <NUM> in order to extend the life of the die <NUM>.

The punch <NUM> preferably has a shear angle in order to reduce thrust for stamping. The shear angle improves the accuracy of stamping depending upon the angle. The shear angle may be provided for one of the punch <NUM> and the die <NUM> or both of the punch <NUM> and the die <NUM>. The punch <NUM> has a clearance C set at about several to several tens µm from the inner wall <NUM> of the die <NUM>. The stamping speed V of the punch <NUM> is preferably set at <NUM>/sec or less. This is because an impact applied to the electrodes body <NUM> to <NUM>, which is fragile materials, by stamping is small at a low stamping speed V and thus deformation of the electrodes body <NUM> to <NUM> by stamping is prevented. Thus, the stamping speed is preferable at <NUM>/sec or lower and is further preferable at <NUM>/sec or lower. On the punch <NUM> and the die <NUM> (also the inclined-side forming punch <NUM> and the inclined-side forming die <NUM>), portions in contact with at least the electrodes body <NUM> to <NUM> are preferably coated with an insulating material in order to prevent a short circuit caused by stamping the electrodes body <NUM> to <NUM>.

First, the electrodes body <NUM> to <NUM> is placed on the die <NUM> so as to cover the space portion <NUM>. Subsequently, the punch <NUM> is lowered at the predetermined speed V and is passed through the space portion <NUM>, so that the electrodes body <NUM> to <NUM> are stamped by the punch <NUM>. The outer end portion of the electrodes body <NUM> to <NUM> is cut by stamping with the blade 74a and the central portion of the electrodes body <NUM> to <NUM> is lowered in the space portion <NUM>. At this point, the flank surface 74e prevents roughness on the sides <NUM> formed in the electrodes body <NUM> to <NUM>.

In all of the first to third specific examples of the cutting-removing device <NUM>, the electrodes body <NUM> to <NUM> is preferably cut while stiffness inside the cutting position of the electrodes body <NUM> to <NUM> is higher than that outside the cutting position. In other words, in all of the first to third specific examples of the cutting-removing device <NUM>, the electrodes body <NUM> to <NUM> is preferably cut such that stiffness at the central portion of the electrodes body <NUM> to <NUM> is higher than that on the outer end portion to be cut. With this configuration, strain caused by cutting is absorbed on the outer end portion having low stiffness, thereby preventing damage and defects on the central portion to be provided as a product.

For stamping of fragile materials such as the electrodes body <NUM> to <NUM> with high accuracy, the central portion of the electrodes body <NUM> to <NUM> is not to be stamped into a desired size by one-time stamping. It is preferable that the electrodes body <NUM> to <NUM> is stamped in a range slightly larger than the desired size and then the electrodes body <NUM> to <NUM> in the range slightly larger than the desired size is stamped into the desired size. In the stamping performed several times, particularly if a portion on the outer end has high stiffness, the portion having high stiffness is first removed by stamping, so that a range to be subsequently stamped can have higher stiffness than the outside of the range.

As illustrated in <FIG>, only the inner wall <NUM> of the die <NUM> in the cutting-removing device <NUM> is different from that of the cutting-removing device <NUM> described as the third specific example. In the third specific example of the cutting-removing device <NUM>, the electrodes body <NUM> to <NUM> is stamped one time by lowering the punch <NUM> one time, whereas in the fourth specific example of the cutting-removing device <NUM>, the inner wall <NUM> of the die <NUM> has multiple blades 74a to 74c having different internal diameters, so that the electrodes body <NUM> to <NUM> is stamped several times by lowering the punch <NUM> one time. Specifically, as illustrated in <FIG>, the die <NUM> in the cutting-removing device <NUM> has an upper blade 74a formed on the upper end of the inner wall <NUM>, an intermediate blade 74b formed under and inside the upper blade 74a, and a lower blade 74c formed under and inside the intermediate blade 74b. The inner wall <NUM> is slightly inclined so as to extend the space portion <NUM> downward from the upper blade 74a to the intermediate blade 74b and is horizontally extended at the height of the intermediate blade 74b. Moreover, the inner wall <NUM> is slightly inclined so as to extend the space portion <NUM> downward from the intermediate blade 74b to the lower blade 74c and is horizontally extended at the height of the lower blade 74c. The upper blade 74a, the intermediate blade 74b, and the lower blade 74c are optionally similar in shape. The lower blade 74c determines the outside shape of a product and thus is formed according to the desired outside shape of the product, whereas it is not necessary to form the upper blade 74a and the intermediate blade 74b like the lower blade 74c. The inner wall <NUM> is vertical from the lower blade 74c to the predetermined height <NUM> and is inclined at an angle θ2 so as to extend the space portion <NUM> downward at a height lower than the predetermined height <NUM>. The inner wall <NUM> has the flank surface 74e lower than the predetermined height <NUM>. The flank surface 74e prevents roughness on the sides <NUM> formed in the electrodes body <NUM> to <NUM> by stamping with the punch <NUM>.

First, the electrodes body <NUM> to <NUM> is placed on the die <NUM> so as to cover the space portion <NUM>. Subsequently, the punch <NUM> is lowered one time and is passed through the space portion <NUM>, so that the electrodes body <NUM> to <NUM> is stamped three times by the inclined-side forming punch <NUM>. Specifically, the punch <NUM> moves downward through the upper blade 74a, so that the electrodes body <NUM> to <NUM> is stamped in two sizes larger than a desired size. The punch <NUM> then moves downward through the intermediate blade 74b, so that the electrodes body <NUM> to <NUM> in two size larger than the desired size is stamped in one size larger than the desired size. Thereafter, the punch <NUM> moves downward through the lower blade 74c, so that the electrodes body <NUM> to <NUM> in one size larger than the desired size is stamped in the desired size. The electrodes body <NUM> to <NUM> in the desired size move downward through the space portion <NUM> under the lower blade 74c. The flank surface 74e prevents roughness on the formed sides <NUM>.

The cutting-removing device <NUM> is not limited to the first to fourth specific examples as long as the outer end portion of the electrodes body <NUM> to <NUM> (at least the powder laminate <NUM>) is cut and removed. Means for cutting the electrodes body <NUM> to <NUM> is not limited to those in the first to fourth specific examples. Cutting devices such as a laser, a Thomson blade, a shearing machine, and a cutter may be used.

The all-solid secondary battery <NUM> according to the present invention includes at least the powder laminate <NUM>. For example, without deteriorating the basic performance, the all-solid secondary battery <NUM> may have a structure that prevents hydrogen sulfide from leaking to the outside even if moisture enters the battery. Referring to <FIG>, the specific examples of the all-solid secondary battery <NUM> having such a structure will be described below.

As illustrated in <FIG>, for example, the all-solid secondary battery <NUM> includes a hydrogen sulfide absorbent <NUM>. The hydrogen sulfide absorbent <NUM> may be activated carbon, zeolite, a catalyst (zinc oxide) and/or dehydrator (diphosphorus pentaoxide or silica gel). Alternatively, the hydrogen sulfide absorbent <NUM> may be a porous body, for example, a nonwoven fabric, glass paper, or a plastic foam that contains the catalyst and/or the dehydrator. The hydrogen sulfide absorbent <NUM> is preferably <NUM> to several hundreds µm in thickness. If the thickness of the hydrogen sulfide absorbent <NUM> is larger than several hundreds µm, the electrodes body <NUM> to <NUM> and the all-solid secondary battery <NUM> wastefully have large outside dimensions and heavy weights. If the thickness is smaller than <NUM>, the effect of adsorbing hydrogen sulfide is weakened, so that hydrogen sulfide may leak to the outside. For example, if the hydrogen sulfide absorbent <NUM> is a catalyst (zinc oxide), the amount of hydrogen sulfide that can be adsorbed by the hydrogen sulfide absorbent <NUM> is theoretically <NUM> (sulfur is <NUM>) for <NUM> of zinc oxide according to a reaction formula (H<NUM>S + ZnO → ZnS + H<NUM>O).

The examples of the all-solid secondary battery <NUM> in <FIG> will be described below.

In the example of <FIG>, the all-solid secondary battery <NUM> schematically includes the hydrogen sulfide absorbent <NUM> in the electrodes body <NUM> to <NUM>. The hydrogen sulfide absorbent <NUM> is square in plan view, is mostly placed on the outer part of the positive layer <NUM> and inside the solid-electrolyte layer <NUM>, and is disposed on the positive current collector <NUM>. Also in the example of <FIG>, the negative layer <NUM> preferably has a larger area than the positive layer <NUM> in order to prevent the short circuit. In this case, the end of the powder laminate <NUM> does not have the positive layer <NUM> and thus has a smaller thickness than the central portion. If the end of the powder laminate <NUM> has a smaller thickness than the central portion, a force applied to the end of the powder laminate <NUM> is smaller than that of the central portion in the pressurization step, so that the structure is likely to be deformed on the end. Furthermore, even if the area of the negative layer <NUM> is equal to that of the positive layer <NUM>, the solid-electrolyte layer <NUM> having a larger area than the negative layer <NUM> and the positive layer <NUM> causes the powder laminate <NUM> to have a smaller thickness on the end than the central portion, so that the structure is likely to be similarly deformed on the end. However, the hydrogen sulfide absorbent <NUM> placed as illustrated in <FIG> suppresses the possibility of a smaller thickness on the end of the powder laminate <NUM> than the central portion, thereby preventing structure deformation on the end. Naturally, a short circuit is prevented because the negative layer <NUM> has a larger area than the positive layer <NUM>. The hydrogen sulfide absorbent <NUM> is not limited to the location in <FIG> and thus may be disposed between the positive layer <NUM> and the solid-electrolyte layer <NUM> or between the solid-electrolyte layer <NUM> and the negative layer <NUM>. If the end of the powder laminate <NUM> is structurally broken, for example, when a force applied to the end of the powder laminate <NUM> is extremely larger than that of the central portion in the pressurization step or if the powder laminate <NUM> has a smaller thickness on the central portion than the end, the hydrogen sulfide absorbent <NUM> may be disposed at the central portion of the powder laminate <NUM>.

In the example of <FIG>, the all-solid secondary battery <NUM> schematically includes the stacked electrodes bodies <NUM> to <NUM>. The current collectors <NUM> and <NUM> of the adjacent electrodes bodies <NUM> to <NUM> have the same polarity with the hydrogen sulfide absorbent <NUM> interposed therebetween. In the absence of the hydrogen sulfide absorbents <NUM> in the structure of <FIG>, the electrodes bodies <NUM> to <NUM> may not be accurately stacked with the same polarities opposed to each other because of a displacement of the electrodes bodies <NUM> to <NUM> and/or a deformation and/or a curvature of the electrodes bodies <NUM> to <NUM> in the pressurization step. However, in the case of the hydrogen sulfide absorbents <NUM> placed as illustrated in <FIG>, a pressure is not applied to each set of the electrodes bodies <NUM> to <NUM> but is applied to two (or more) sets of the electrodes bodies <NUM> to <NUM> with the hydrogen sulfide absorbent <NUM> interposed therebetween, thereby preventing the displacement, deformation, and curvature. This can precisely stack the electrodes bodies <NUM> to <NUM> while preventing hydrogen sulfide from leaking to the outside. In order to increase conductivity between the adjacent electrodes bodies <NUM> to <NUM>, the hydrogen sulfide absorbent <NUM> in <FIG> preferably contains a conductive material (e.g., activated carbon) serving as a chief material. The all-solid secondary battery <NUM> is not limited to the example of <FIG>. The current collectors <NUM> and <NUM> of the adjacent electrodes bodies <NUM> to <NUM> may have different polarities. The hydrogen sulfide absorbent <NUM> may contain an insulating material (a nonwoven fabric, glass paper, or a plastic foam as a chief material). The shape of the hydrogen sulfide absorbent <NUM> is not limited to a square in the plan view of <FIG>. The hydrogen sulfide absorbent <NUM> may be entirely shaped like a sheet disposed so as to compensate for a hollow caused by variations in the thickness of the electrodes bodies <NUM> to <NUM>.

In the example of <FIG>, the all-solid secondary battery <NUM> schematically includes the electrodes bodies <NUM> to <NUM> that are stacked and sealed into the outer package <NUM>. The current collectors <NUM> and <NUM> of the adjacent electrodes bodies <NUM> to <NUM> have the same polarity and the hydrogen sulfide absorbents <NUM> are respectively disposed between the uppermost current collector <NUM> or <NUM> and the outer package <NUM> and between the lowermost current collector <NUM> or <NUM> and the outer package <NUM>. Since extra spaces are respectively provided between the uppermost current collector <NUM> or <NUM> and the outer package <NUM> and between the lowermost current collector <NUM> or <NUM> and the outer package <NUM>, the hydrogen sulfide absorbents <NUM> are disposed using the spaces in <FIG>. If a pressure is applied from the outside of the outer package <NUM> after the stacked electrodes bodies <NUM> to <NUM> are sealed into the outer package <NUM>, the hydrogen sulfide absorbent <NUM> may be square in plan view in <FIG> or may be disposed so as to compensate for a hollow caused by variations in the thickness of the electrodes bodies <NUM> to <NUM>.

The all-solid secondary battery <NUM> in <FIG> are merely exemplary and thus may include another current collector. The hydrogen sulfide absorbent <NUM> is not always necessary, the ends of the powder films of the powder laminate <NUM> may be aligned, or stacked and connected electrodes may be sealed into the outer package <NUM>.

The all-solid secondary battery <NUM> that does not require pressurization when being used will be described below.

The all-solid secondary battery <NUM> does not need charge and discharge during discharge and charge. The all-solid secondary battery <NUM> is required to satisfy requirements (<NUM>) and (<NUM>) and preferably satisfies requirement (<NUM>) and/or requirement (<NUM>):.

Claim 1:
An installation (<NUM>) for manufacturing an all-solid secondary battery (<NUM>) provided with a dry powder laminate (<NUM>) including stacked powder films,
the installation (<NUM>) comprising:
a mixer (<NUM>) for mixing multiple kinds of dry powder materials (A, S);
a conveying device (<NUM>) for conveying the dry powder materials (A, S) mixed by the mixer (<NUM>);
an electrostatic film-forming device (<NUM>) for forming the powder films in a dry process from the dry powder materials conveyed by the conveying device (<NUM>), by using at least an electrostatic force;
a pressure device (<NUM>) for pressurizing the dry powder films formed by the electrostatic film-forming device (<NUM>); and
a cutting-removing device (<NUM>) for cutting and removing an outer end portion of the dry powder films pressurized by the pressure device (<NUM>).