The disclosure of Japanese Patent Application No. 2011-204943 filed on Sep. 20, 2011 including specification, drawings and claims is incorporated herein by reference in its entirety.
1. Field of the Invention
This invention relates to a method for manufacturing a battery electrode by applying an application liquid containing an active material to a base material and a method for manufacturing a battery using the electrode.
2. Description of the Related Art
As a method for producing a chemical battery such as a lithium-ion secondary battery, the applicant of this application previously disclosed a technology for forming one electrode by applying an application liquid containing an active material in stripes on a surface of a base material, which will become a current collector, and laminating an electrolyte layer and another electrode on the one electrode (JP2011-070788A). In this technology, by a nozzle-scan coating method for moving and scanning a nozzle including discharge openings for discharging an application liquid relative to the base material surface, the application liquid containing the active material is applied to the base material surface from the nozzle in which a multitude of discharge openings are arranged in a predetermined direction to form a multitude of stripe-shaped active material pattern elements parallel to each other.
In the nozzle-scan coating method for discharging the application liquid while the nozzle is moved to scan relative to the base material surface, the application liquid discharged from the discharge openings and adhered to the base material spreads around at the start of application and, finally, pattern element start ends may become wider than other parts.
On the other hand, higher density of active material pattern elements is also required to further improve battery performance, more specifically, battery capacity and charge/discharge characteristics, and it is necessary to narrow intervals between parallel pattern elements. In this case, in the above conventional technology, there is a possibility that the adjacent pattern elements touch each other due to the spread of the application liquid at the start of application and it is difficult to deal with such a request as to increase the density of the pattern elements. In this respect, there is a room for improvement in the above conventional technology.
This invention was developed in view of the above problem, an object thereof is to provide a technology capable of contributing to an improvement in battery performance by forming stripe-shaped pattern elements at narrower intervals than before while avoiding contact between the pattern elements in a technology for manufacturing a battery electrode by applying an application liquid containing active material.
To achieve the above object, the present invention is a battery electrode manufacturing method for manufacturing a battery electrode in which a plurality of stripe-shaped active material pattern elements parallel to each other are arranged on a surface of a base material, comprising: a first application step of applying an application liquid containing an active material in a stripe on the surface of the base material by moving and scanning a nozzle for discharging the application liquid in a predetermined scanning direction relative to the surface of the base material, thereby forming a first active material pattern element; and a second application step of applying an application liquid containing an active material in a stripe by moving and scanning a nozzle for discharging the application liquid in the scanning direction relative to the surface of the base material, thereby forming a second active material pattern element adjacent to the first active material pattern element, wherein a start position of the first active material pattern element and a start position of the second active material pattern element are made different in the scanning direction.
In the thus configured invention, the start positions are made different from each other in the scanning direction between the first and second active material pattern elements adjacent to each other. Thus, even if start end parts of the respective first and second active material pattern elements spread wider than a supposed-to-be pattern element width, a possibility of contact of the both pattern elements is reduced as compared with a case where the respective start positions are located at the same position in the scanning direction. It seems that there is a little problem when the adjacent active material pattern elements are merely in contact only at start end parts thereof. However, realistically, if the adjacent pattern elements touch each other at the start end parts, a wide pattern element is often formed with the both pattern elements kept united by a movement of the nozzle relative to the base material. Thus, the shape and surface area of the active material pattern elements become different from desired ones, wherefore expected battery performance cannot be obtained.
In the invention, a probability of contact between the pattern elements is reduced by making the start positions of the adjacent pattern elements different in the scanning direction. Thus, it is possible to form active material pattern elements, which are a plurality of adjacent stripe-shaped pattern elements at narrower intervals than before, while avoiding contact between the pattern elements.
Note that, in this invention, contact between the active material pattern elements adjacent to each other is prevented. Thus, the adjacent active material pattern elements are not limited to those of the same type and may have different compositions. For example, active material pattern elements for a positive electrode and those for a negative electrode may be alternately arranged on the base material. In this sense, the application liquid used in the first application step and that used in the second application step in the invention are not limited to the same application liquid.
Another aspect of the invention is a battery manufacturing method for manufacturing a battery, comprising: an electrode manufacturing step of manufacturing an electrode by the battery electrode manufacturing method described above; and an electrolyte layer forming step of forming an electrolyte layer covering the active material pattern elements by applying an application liquid containing an electrolyte material to a surface of the electrode where the active material pattern elements are formed.
In the thus configured invention, a battery is manufactured by laminating another functional layer through application on an electrode free from contact between the adjacent pattern elements as described above and including stripe-shaped active material pattern elements arranged at narrow intervals. That is, according to this invention, it is possible to manufacture a high-performance battery including an active material layer formed by stripe-shaped pattern elements arranged at a high density and having a large surface area.
The above and further objects and novel features of the invention will more fully appear from the following detailed description when the same is read in connection with the accompanying drawing. It is to be expressly understood, however, that the drawing is for purpose of illustration only and is not intended as a definition of the limits of the invention.
The lower surface of the positive-electrode active material layer 14 has an uneven structure in conformity with the unevenness on the upper surface of the solid electrolyte layer 13, whereas the upper surface thereof is a substantially flat surface. The positive-electrode current collector 15 is laminated on the upper surface of the positive-electrode active material layer 14, whereby the lithium-ion secondary battery module 1 is formed. A lithium-ion battery is formed by appropriately arranging tab electrodes or laminating a plurality of modules on this lithium-ion battery module 1.
Here, known materials for lithium-ion batteries can be used as materials for the respective layers. For example, a copper foil and an aluminum foil can be respectively used as the negative-electrode current collector 11 and the positive-electrode current collector 15. Further, a material mainly containing LiCoO2 (LCO) can be, for example, used as a positive-electrode active material and a material mainly containing Li4Ti5O12 (LTO) can be, for example, used as a negative-electrode active material. Furthermore, a mixture of polyethylene oxide and polystyrene can be, for example, used as the solid electrolyte layer 13. Note that the materials for the respective functional layers are not limited to these.
The lithium-ion secondary battery module 1 having such a composition and structure is thin and flexible. Since the negative-electrode active material layer 12 is formed to have an uneven space structure as shown and, thereby, increase its surface area with respect to its volume, an area facing the positive-electrode active material layer 14 via the thin solid electrolyte layer 13 can be increased to ensure high efficiency and high output. In this way, the lithium-ion secondary battery having the above structure can be small in size and have high performance.
Subsequently, an application liquid containing a negative-electrode active material is applied to one surface of the copper foil by a nozzle dispensing method, in particular, by a nozzle-scan coating method for relatively moving a nozzle for dispensing the application liquid with respect to an application target surface (Step S102). An organic LTO material containing the negative-electrode active material described above can be, for example, used as the application liquid. A mixture of the above negative-electrode active material, acetylene black or ketjen black as a conduction aid, polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA) or polytetrafluoroethylene (PTFE) as a binder, N-methyl-2-pyrrolidone (NMP) as a solvent and the like can be used as the application liquid. Note that, besides LTO described above, graphite, metal lithium, SnO2, alloys and the like can be used as the negative-electrode active material.
In the nozzle-scan coating method, a nozzle 21 perforated with one or more dispense openings is arranged above a copper foil 11. The nozzle 21 is relatively moved at a constant speed in an arrow direction Ds with respect to the copper foil 11 while dispensing a fixed amount of an application liquid 22 from the dispense opening(s). By doing so, the application liquid 22 is applied on the copper foil 11 in a stripe extending in the Y-direction. By providing the nozzle 21 with a plurality of dispense openings, a plurality of stripes can be formed by one movement. By repeating this movement according to need, the application liquid can be applied in stripes on the entire surface of the copper foil 11. By drying and curing the application liquid, the negative-electrode active material layer 12 is formed on the upper surface of the copper foil 11. A photo-curable resin may be added to the application liquid and the application liquid may be cured by light irradiation after application.
At this point of time, an active material layer 12 is partly raised on the substantially flat surface of the copper foil 11. Thus, as compared with the case where the application liquid is simply applied to have a flat upper surface, a surface area can be increased with respect to the used amount of the active material. Therefore, the area facing a positive-electrode active material layer to be formed later can be increased to ensure a high output.
The flow chart of
The positive-electrode active material layer 14 is formed on a laminated body formed by laminating the copper foil 11, the negative-electrode active material layer 12 and the solid electrolyte layer 13 in this way (Step S104). The positive-electrode active material layer 14 is formed by applying a positive-electrode active material application liquid containing a positive-electrode active material by an appropriate coating method, e.g. a known knife coating method. An aqueous LCO material obtained by mixing the positive-electrode active material, acetylene black as a conduction aid, SBR as a binder, carboxymethylcellulose (CMC) as a dispersant and pure water as a solvent can be, for example, used as the application liquid containing the positive-electrode active material. Besides the above LCO, LiNiO2, LiFePO4, LiMnPO4, LiMn2O4 or compounds represented by LiMeO2 (Me=MxMyMz; Me, M are transition metal elements and x+y+z=1) such as LiNi1/3Mn1/3Co1/3O2 and LiNi0.8Co0.15Al0.05O2 can be used as the positive-electrode active material. Further, known coating methods capable of forming a flat film on a flat surface such as the knife coating method, a bar coating method and a spin coating method can be appropriately employed as the coating method.
By applying the application liquid containing the positive-electrode active material to the laminated body, the positive-electrode active material layer 14 which has a lower surface conforming to the unevenness on the surface of the electrolyte layer 13 and a substantially flat upper surface is formed. A metal foil, e.g. an aluminum foil which will become a positive-electrode current collector 15 is laminated on the upper surface of the positive-electrode active material layer 14 formed in this way (Step S105). At this time, it is desirable to superimpose the positive-electrode current collector 15 on the upper surface of the positive-electrode active material layer 14 formed in previous Step S104 before the positive-electrode active material layer 14 is cured. By doing so, the positive-electrode active material layer 14 and the positive-electrode current collector 15 can be tightly bonded to each other. Since the upper surface of the positive-electrode active material 14 is leveled, the positive-electrode current collector 15 can be easily laminated without forming any clearance. By doing so, the lithium-ion battery module 1 shown in
The above method for manufacturing a lithium-ion battery is basically the same as that disclosed in JP2011-070788 described above. However, in this embodiment, a step of forming the negative-electrode active material layer 12 in Step S102 is configured as follows to increase the density of the active material pattern elements 120 in the negative-electrode active material layer 12 by making the intervals between the multitude of stripe-shaped active material pattern elements 120 smaller than before.
Here, if it is thought to make the pattern element interval smaller than before, the adjacent pattern elements 121, 122 may touch each other due to the spread of the pattern element start ends Pa as shown in
However, realistically, once contact is established at the pattern element start ends, it is not easy to separate the two pattern elements again due to the surface tension of the application liquid. As the nozzle discharging the application liquid corresponding to each pattern element is moved to scan, a pattern element 123 is formed with two stripes of the application liquid, which are supposed to be separate, united as shown in
How far the start positions in the Y-direction between the adjacent pattern elements should be apart is considered with reference to
Note that, according to the knowledge of the inventors of this application, an increase amount of the width of the pattern element start end by the spread of the application liquid is at most about 20 to 30% if application conditions such as the viscosity of the application liquid, the opening diameter of the nozzle 21 and a scanning speed are appropriately managed. From this aspect, the difference ΔY between the start positions of the adjacent pattern elements may be simply set to be equal to or more than the arrangement pitch Lp of the pattern elements.
Next, a specific method for forming the above pattern elements by the nozzle-scan coating method is described. For example, the following procedure is thought as a method for forming a multitude of pattern elements parallel to each other with the start ends thereof arranged in a so-called offset manner.
At this time, it is possible to form an offset pattern in which the pattern element start ends in the Y-direction alternately differ between the adjacent pattern elements by making the position of the nozzle 21 relative to the base material 110 at the start of application different in the Y-direction. Note that the following two positional relationships can be thought between the pattern elements respectively formed by scanning movements in forward and backward directions.
In the first example shown in
On the other hand, in the second example shown in
The nozzle 26 is moved to scan in the scanning direction Ds (Y-direction) relative to the base material 110 while the application liquid is discharged from the respective discharge openings 261, 262 arranged in this manner. This causes a plurality of stripe-shaped pattern elements 271, 272 parallel to each other and having start positions different in the Y-direction between the adjacent pattern elements are simultaneously formed on the base material 110 as shown in
Thereafter, as shown in
Note that, in these application examples, the end positions of the pattern elements are not particularly limited and may be located at the same position in the Y-direction for the following reason. At the end positions of application, notable spread of the pattern elements as at the start positions is not found. Even if contact may be established due to the spread of the pattern elements, the contact is limited to that position and the adjacent pattern elements are not united as shown in
As described above, in this embodiment, a plurality of stripe-shaped pattern elements parallel to each other are formed by applying the application liquid containing the active material on the base material. To prevent contact between the pattern elements due to the spread of pattern element start ends in doing this, the pattern element start positions are made different in a pattern element extending direction (nozzle moving/scanning direction) between the adjacent pattern elements. By doing so, active material pattern elements can be formed at narrower intervals than before by preventing a disorder of the pattern element shape resulting from contact of the adjacent pattern elements at the pattern element start ends. As a result, in this embodiment, it is possible to manufacture a battery electrode used to manufacture a battery with good capacity and charge/discharge characteristics.
As described above, in this embodiment, the pattern elements 221 in
Note that the invention is not limited to the above embodiment and various changes other than the above can be made without departing from the gist thereof. For example, in the above embodiment, the invention is applied to the method for manufacturing the all-solid-state battery by successively laminating the solid electrolyte layer, the positive-electrode active material layer and the positive-electrode current collector on the negative electrode 10 formed by the method described above. However, the invention can also be applied to a technology for manufacturing a battery not only using such a solid electrolyte, but also an electrolyte layer formed by an electrolytic solution and a technology for manufacturing an electrode for the battery.
Although the active material pattern elements adjacent to each other have the same composition in the above embodiment, there is no limitation to this. A battery in which positive and negative active materials are alternately arranged along a base material surface (see, for example, JP2006-147210A) has been also proposed as a battery including active material pattern elements having a three-dimensional structure besides the above one. The invention can be applied also in manufacturing an electrode used in such a battery. Further, although the invention is applied in manufacturing the negative electrode in the above embodiment, the invention can be, of course, applied in manufacturing a positive electrode.
Further, the materials of the current collectors, the active materials, the electrolyte and the like illustrated in the above embodiment are only examples and there is no limitation to these. Also in the case of manufacturing a lithium-ion battery using other materials used as constituent materials of lithium-ion batteries, the manufacturing method of the invention can be preferably applied. Further, without limitation to lithium-ion batteries, the invention can be applied to manufacturing in general of chemical batteries using other materials and electrodes used therein.
Although a mode of moving and scanning the nozzle relative to the base material is illustrated to facilitate the understanding of the principle of the invention in the above description, relative movements of the base material and the nozzle can be realized by moving either the nozzle or the base material. Rather, in terms of preventing a disorder of application due to vibration applied to the nozzle, it is more preferable to fix the nozzle and move the base material.
Further, in the invention for example, a plurality of active material pattern elements parallel to each other may be formed in the first application step; and the second active material pattern element may be formed between the first active material pattern elements adjacent to each other. By doing so, it is possible to form a plurality of active material pattern elements which are proximate to each other, but do not touch each other, and to manufacture a battery electrode with good performance.
In this case, positions of the nozzle relative to the surface of the base material at the start of application may be made different in the scanning direction and a direction perpendicular thereto between the first application step and the second application step, commonly using the nozzle including a plurality of discharge openings arranged in the direction perpendicular to the scanning direction in the first application step and the second application step. By doing so, it is not necessary to prepare individual nozzles to form the respective first and second active material pattern elements. Further, by making the positions of the nozzle relative to the surface of the base material at the start of application different between the first application step and the second application step, it is possible to easily form a plurality of stripe-shaped pattern elements whose start positions in the scanning direction differ from each other and which extend at different positions in the direction perpendicular to the scanning direction.
Further, the nozzle may include a first discharge opening for forming the first active material pattern element by discharging the application liquid and a second discharge opening for forming the second active material pattern element by discharging the application liquid and the second discharge opening may be provided at a position different from the first discharge opening in the scanning direction and a direction perpendicular thereto; and thereby the first application step and the second application step may be simultaneously performed by moving the nozzle relative to the base material. By providing the nozzle with the discharge openings whose positions differ in the direction perpendicular to the scanning direction, a plurality of active material pattern elements can be simultaneously formed by one scanning movement of the nozzle. At this time, if the positions of the adjacent discharge openings are made different in the scanning direction, the start positions of the pattern elements are made different between the adjacent pattern elements, whereby the object of the invention is achieved.
Particularly, a plurality of first discharge openings and a plurality of second discharge openings may be provided to the nozzle, the first discharge openings and the second discharge openings being respectively arranged in the direction perpendicular to the scanning direction. By doing so, it is possible to form a multitude of pattern elements by one scanning movement of the nozzle and improve throughput of pattern element formation.
Further, the start position of the second active material pattern element may be located upstream of the start position of the first active material pattern element in the scanning direction. In this case, the spread of the application liquid, which will become the second active material pattern element, at the start end part converges and the application liquid is applied with a stable width between the first active material pattern elements previously formed. Thus, a possibility that the spread of the application liquid, which will become the second active material pattern element, leads to contact with the already formed first active material pattern elements is reduced.
Alternatively, the start position of the second active material pattern element may be located downstream of the start position of the first active material pattern element in the scanning direction. In this case, the scanning movement of the nozzle can be started at a position away from the spread of the start end of the first active material pattern element, wherefore a disorder of the pattern elements caused by the contact of the tip of the nozzle with the already formed first active material pattern elements can be prevented.
Further, a distance between the start position of the first active material pattern element and the start position of the second active material pattern element in the scanning direction may be equal to or more than an arrangement pitch of the first active material pattern element and the second active material pattern element adjacent thereto in a direction perpendicular to the scanning direction. Here, an arrangement pitch between the first active material pattern element and the second active material pattern element adjacent thereto can be defined as a distance between the center lines of the respective first and second active material pattern elements in the direction perpendicular to the scanning direction.
The pattern element can spread at the start end in both the scanning direction and the direction perpendicular thereto. The spread is assumed to be of the same degree in the both directions. Then, if the spread width is likely to exceed the arrangement pitch of the pattern elements, i.e. the sum of the supposed-to-be pattern element width and pattern element interval, the pattern element spreads to a position where the adjacent pattern element is supposed to be formed. Thus, to begin with, it is difficult to arrange the pattern elements at such a pitch.
Conversely, if the arrangement pitch is so set that such a problem does not occur, contact of the adjacent pattern elements can be almost reliably avoided when the start positions are made different in the scanning direction by a distance equal to or more than this arrangement pitch.
According to the battery electrode and battery manufacturing methods according to this invention, it is possible to manufacture a battery electrode including a plurality of stripe-shaped active material pattern elements which do not touch each other and are proximately arranged. Therefore, performance such as capacity and charge/discharge characteristics of the battery using this can be improved.
This invention can be preferably applied to a technology for manufacturing a battery electrode using an active material and manufacturing a battery using this electrode and particularly can provide a battery with good capacity and charge/discharge characteristics by forming a plurality of stripe-shaped active material pattern elements at a high density on a base material.
Although the invention has been described with reference to specific embodiments, this description is not meant to be construed in a limiting sense. Various modifications of the disclosed embodiment, as well as other embodiments of the present invention, will become apparent to persons skilled in the art upon reference to the description of the invention. It is therefore contemplated that the appended claims will cover any such modifications or embodiments as fall within the true scope of the invention.
Number | Date | Country | Kind |
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2011-204943 | Sep 2011 | JP | national |