WO2014038454A1 - パターン形成方法、構造体、櫛型電極の製造方法、及び二次電池 - Google Patents
パターン形成方法、構造体、櫛型電極の製造方法、及び二次電池 Download PDFInfo
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- WO2014038454A1 WO2014038454A1 PCT/JP2013/073058 JP2013073058W WO2014038454A1 WO 2014038454 A1 WO2014038454 A1 WO 2014038454A1 JP 2013073058 W JP2013073058 W JP 2013073058W WO 2014038454 A1 WO2014038454 A1 WO 2014038454A1
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a pattern forming method for forming a plurality of patterns made of the same or different pattern materials on a support, a structure having a pattern formed by this pattern forming method, and a comb electrode using the pattern forming method. And a secondary battery having a comb-shaped electrode manufactured by the manufacturing method.
- Patent Document 1 describes that a comb-shaped electrode was produced by depositing a positive electrode active material in a guide hole formed using a resist composition by electrophoresis. .
- the present invention has been made in view of the above situation, and a pattern forming method capable of forming a plurality of patterns made of the same or different pattern materials on a support in a short time, and this pattern formation. It aims at providing the structure provided with the pattern formed by the method, the manufacturing method of the comb electrode using the said pattern formation method, and the secondary battery which has the comb electrode manufactured by this manufacturing method.
- the inventors of the present invention have intensively studied to solve the above problems. As a result, it has been found that the above problems can be solved by filling the pattern material into the guide holes by a screen printing method when forming the pattern, and the present invention has been completed. Specifically, the present invention provides the following.
- a first aspect of the present invention is a pattern forming method for forming n (n is an integer of 2 or more) patterns made of the same or different pattern materials on a support, and the positive pattern is formed on the surface of the support.
- the resist composition is applied to form the first resist layer.
- k is an integer from 1 to (n-1)
- the kth resist layer In order up to the case of (n-1), the following (1) to (3): (1) forming guide holes penetrating the first to kth resist layers by exposure and development; (2) Filling the guide hole with the kth pattern material by screen printing; and (3) a positive resist composition on the kth resist layer and the kth pattern material filled in the guide hole.
- the second aspect of the present invention is a structure including a pattern formed by the pattern forming method.
- a third aspect of the present invention is a method for manufacturing a comb-shaped electrode in which the positive electrode and the negative electrode are each formed in a comb shape, and the positive electrode and the negative electrode are alternately arranged at the comb-shaped tooth portions.
- a fourth aspect of the present invention is a secondary battery having a comb electrode manufactured by the above manufacturing method.
- a pattern forming method capable of forming a plurality of patterns made of the same or different pattern materials on a support in a short time, a structure provided with a pattern formed by this pattern forming method, The manufacturing method of the comb-shaped electrode using the pattern formation method, and the secondary battery which has the comb-shaped electrode manufactured by this manufacturing method can be provided.
- the English letters in the figure indicate the type of comb electrode.
- the numbers in the figure represent the number of cycles.
- a positive resist composition is applied to the surface of the support 1 shown in FIG. 1A to form the first resist layer 2.
- the first resist layer 2 As a method for forming the first resist layer 2 by applying a positive resist composition to the surface of the support 1, a known method can be used without any particular limitation. As will be described later, guide holes 3a and 3b for forming pattern material layers 4a and 4b are formed in the first resist layer 2. Since the guide holes 3a and 3b serve as templates for forming the pattern material layers 4a and 4b, it is necessary to form the guide holes 3a and 3b to have a depth sufficient to form the pattern material layers 4a and 4b. Since the thickness of the first resist layer 2 will be the depth of the guide holes 3a and 3b in the future, it is appropriately determined in consideration of the required depth of the guide holes 3a and 3b. Examples of the thickness of the first resist layer 2 include 10 to 100 ⁇ m, but are not particularly limited.
- a known resist composition can be used without particular limitation, and may be either a non-chemical amplification system or a chemical amplification system.
- the non-chemically amplified positive resist composition include those containing at least a quinonediazide group-containing compound and an alkali-soluble resin.
- the chemically amplified positive resist composition has, for example, an acid dissociable leaving group, and the leaving group is desorbed by the action of an acid generated from a photoacid generator upon exposure to alkali. Examples include a resin having increased solubility, and a resin containing at least a photoacid generator.
- the process shown in FIG. 1C will be described.
- the first resist layer 2 is selectively exposed through a desired mask.
- the part which will become the guide hole 3a in the future becomes soluble in the developer, and the part which will not become the guide hole 3a in the future remains insoluble in the developer.
- the first resist layer 2 that has undergone selective exposure is developed. Development can be performed by a known method using a known developer. Examples of such a developer include an alkaline aqueous solution. Examples of the developing method include an immersion method and a spray method.
- a guide hole 3a penetrating to the surface of the support 1 is formed.
- the guide hole 3a is used as a mold for depositing a pattern material in a step (described later) shown in FIG.
- the first resist layer 2 in which the guide holes 3a are formed is subjected to after-curing that irradiates active energy rays such as ultraviolet rays or post-baking that is an additional heat treatment, as necessary.
- the first resist layer 2 is further improved in solvent resistance and plating solution resistance required in the step of filling the pattern material by performing after-cure or post-bake.
- the first pattern material is filled into the guide hole 3a formed in the step shown in FIG. 1C by screen printing. That is, the first pattern material layer 4a is formed on the surface of the support 1 using the guide hole 3a as a mold.
- the screen printing method can be executed by, for example, using a commercially available screen printing machine and appropriately adjusting the squeegee pressure, the squeegee speed, the squeegee material used, the hardness, the polishing angle, and the like.
- a positive resist composition 2 is applied on the first resist layer 2 and the first pattern material (that is, the first pattern material layer 4a) filled in the guide hole 3a.
- a second resist layer 5 is formed.
- the second resist layer 5 functions as a protective layer for the first pattern material layer 4a. That is, when the guide hole 3b is formed as described later without forming the second resist layer 5, the first pattern material layer 4a comes into contact with the developer and flows out in the process.
- the second resist layer 5 as described above, it is possible to prevent the first pattern material layer 4a from coming out of contact with the developer.
- the type of positive resist composition and the coating method are the same as those described above for the process shown in FIG.
- the positive resist composition used in the step shown in FIG. 1 (e) may be the same as the positive resist composition used in the step shown in FIG. 1 (b). It is preferable to use a different one.
- the thickness of the second resist layer 5 is not particularly limited as long as the function of the first pattern material layer 4a as a protective layer is ensured, but the guide formed in the process shown in FIG.
- the thickness is appropriately determined in consideration of the depth required for the hole 3b, and 1 to 20 ⁇ m is exemplified.
- the process shown in FIG. In this step first, the first resist layer 2 and the second resist layer 5 are selectively exposed through a desired mask. As a result, the part that will become the guide hole 3b in the future becomes soluble in the developer, and the part that will not become the guide hole 3b in the future remains insoluble in the developer.
- the first resist layer 2 and the second resist layer 5 that have undergone selective exposure are developed.
- the developer and the developing method are the same as those described for the step shown in FIG.
- a guide hole 3b penetrating to the surface of the support 1 is formed.
- the guide hole 3b is used as a mold for depositing a pattern material in the step (described later) shown in FIG.
- the first resist layer 2 and the second resist layer 5 in which the guide holes 3b are formed are subjected to post-bake, which is an after-curing process that irradiates active energy rays such as ultraviolet rays or the like, as necessary.
- the first resist layer 2 and the second resist layer 5 are further subjected to after-cure or post-bake, so that, as will be described later, the solvent resistance and plating solution resistance required in the process of filling the pattern material are further increased. improves.
- the second pattern material is filled into the guide hole 3b formed in the step shown in FIG. That is, the second pattern material layer 4b is formed on the surface of the support 1 using the guide hole 3b as a mold.
- the peeling method is not particularly limited, and an immersion method, a spray method, a shower method, a paddle method, or the like can be used.
- the stripping solution include a 3 to 15% by mass sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, organic amine, tetramethylammonium hydroxide, triethanolamine, N-methylpyrrolidone, dimethyl sulfoxide, and acetone. It is done.
- the peeling treatment time is not particularly limited, but is, for example, about 1 to 120 minutes.
- the stripping solution may be heated to about 25 to 60 ° C.
- two patterns made of the first and second pattern materials can be formed on the support.
- N patterns of can be formed on the support.
- the pattern material is not particularly limited and is appropriately selected depending on the use of the pattern to be formed. Examples thereof include a positive electrode material / negative electrode material, a phosphor (RGB), a medical marker, and a product tag.
- the structure according to the present invention includes a pattern formed by the pattern forming method described above.
- Examples of such a structure include a battery, and specifically, a secondary battery having a comb-shaped electrode.
- Examples of the comb-shaped electrode include those in which a positive electrode and a negative electrode are each formed in a comb shape, and the positive electrode and the negative electrode are arranged to face each other in a comb-shaped tooth portion. More specifically, there are comb-shaped electrodes 11a and 11b shown in FIG.
- the comb electrodes 11a and 11b will be briefly described with reference to FIG.
- the comb-shaped electrodes 11a and 11b are each formed in a comb shape, and are formed so as to face each other so that they are alternately combined at comb-shaped teeth.
- the comb electrode 11a is a positive electrode
- the comb electrode 11b is a negative electrode.
- a separator (not shown) that separates the space or both is provided between the comb-shaped electrode 11a and the comb-shaped electrode 11b, and both are electrically separated.
- the comb-shaped electrodes 11a and 11b are formed on the surface of the substrate 14 whose surface is a nonconductor.
- An example of such a substrate 14 is a silicon substrate having an oxide film on the surface.
- the comb electrode 11a which is a positive electrode, has a current collector 12a for taking out current and a positive electrode active material layer 13a formed on the surface of the current collector 12a.
- the current collector 12a is formed in a comb shape in plan view.
- the positive electrode active material layer 13a is formed on the surface of the current collector 12a having a comb shape, and is formed in a comb shape in plan view, like the current collector 12a.
- the current collector 12a is made of metal, preferably gold, to impart conductivity. And in order to ensure the adhesiveness between the electrical power collector 12a and the board
- the adhesion providing layer is appropriately determined in consideration of the material of the current collector 12a and the material of the substrate 14. As an example, when the current collector 12a is made of gold and the substrate 14 is made of silicon, a titanium thin film is preferably used as the adhesion-imparting layer.
- the thickness of the current collector 12a and the thickness of the adhesion providing layer are not particularly limited and can be arbitrarily determined. As an example, the thickness of the current collector 12a may be 100 nm, and the thickness of the adhesion providing layer may be 50 nm, but is not limited thereto.
- the comb-shaped electrode 11b which is a negative electrode includes a current collector 12b for taking out current and a negative electrode active material layer 13b formed on the surface of the current collector 12b. Since the other matters of the comb-shaped electrode 11b are the same as those of the comb-shaped electrode 11a as the positive electrode, the description thereof is omitted.
- An electrolyte (not shown) is provided between the comb electrode 11a as the positive electrode and the comb electrode 11b as the negative electrode. Thereby, an electrode reaction occurs in each of the comb-shaped electrode 11a and the comb-shaped electrode 11b, and current can be extracted from the current collector 12a and the current collector 12b.
- the thickness of the teeth can be 10 to 50 ⁇ m
- the distance between two adjacent teeth can be 30 to 70 ⁇ m
- the thickness of the active material layer can be 10 to 50 ⁇ m.
- a lithium ion secondary battery includes a transition metal oxide such as lithium cobaltate as a material constituting the positive electrode active material layer 13a, and a material constituting the negative electrode active material layer 13b includes carbon. , Graphite, lithium titanate and the like.
- the electrolyte a salt such as lithium perchlorate and lithium hexafluorophosphate, and a carbonate ester compound such as ethylene carbonate, dimethyl carbonate and diethyl carbonate, which dissolve this salt
- examples include electrolytes containing acetonitrile and organic solvents such as a mixture of at least two of these, and gel electrolytes containing the above electrolytes and polymers such as polyethylene oxide, polypropylene oxide, polyacrylonitrile, and polymethacrylonitrile.
- examples of the active material include positive electrode active material particles such as LiCoO 2 , LiFePO 4 , and LiMn 2 O 4 , and negative electrode active material particles such as graphite, Li 4 Ti 5 O 12 , Sn alloy, and Si-based compounds. Is exemplified.
- the above active material is preferably used in the state of a dispersion dispersed in a dispersion medium.
- examples of the dispersion medium used include water, acetonitrile, N-methylpyrrolidone, acetone and ethanol.
- the amount of the dispersion medium used is preferably such an amount that the solid content concentration of the dispersion becomes 35 to 60% by mass.
- the dispersion liquid usually contains a binder such as styrene butadiene rubber (SBR) or polyvinylidene fluoride.
- the dispersion may further contain a conductive aid such as carbon black (for example, acetylene black) and a dispersant such as carboxymethylcellulose.
- a conductive aid such as carbon black (for example, acetylene black) and a dispersant such as carboxymethylcellulose.
- the contents of the active material, the binder, the conductive aid, and the dispersant in the solid content of the dispersion are not particularly limited.
- the content of the active material is preferably 85 to 99% by mass
- the content of the binder is preferably 1 to 15% by mass
- the content of the conductive auxiliary agent is The content of the dispersant is preferably 0 to 7% by mass.
- the salt content is preferably adjusted so that the concentration of metal atoms (for example, lithium atoms) constituting the salt is 0.2 to 2.0M.
- the polymer content is preferably 2 to 80% by mass.
- the electrolyte solution further includes an unsaturated cyclic carbonate compound such as vinylene carbonate; a halogen-substituted carbonate compound such as fluoroethylene carbonate; a cyclic sulfonic acid compound such as 1,3-propane sultone; a cyclic sulfite such as ethylene sulfite.
- an ester compound such as 12-crown-4; and additives such as aromatic compounds such as benzene and toluene may be included.
- the concentration of the additive is preferably 0.1 to 20% by mass.
- the comb electrodes 11a and 11b shown in FIG. 2 are described with reference to FIG. 1, for example, by forming a conductive layer on the surface of the substrate 14 and patterning the conductive layer to form current collectors 12a and 12b.
- the pattern forming method according to the embodiment of the present invention can be used to form a positive electrode and a negative electrode on the current collectors 12a and 12b.
- the conductive layer and the current collectors 12a and 12b can be formed by the method described in Patent Document 1, for example.
- the positive electrode and the negative electrode use, for example, the current collectors 12a and 12b in FIG. 2 as the support 1 in FIG. 1, and the positive electrode active material layer 13a in FIG. 2 as the first pattern material layer 4a in FIG.
- the second pattern material layer 4b in FIG. 1 can be formed on the current collectors 12a and 12b by performing pattern formation according to FIG. 1 using the negative electrode active material layer 13b in FIG.
- Comb electrodes 11a and 11b shown in FIG. 2 were produced using a screen printing method.
- Formation of current collector First, an aluminum film (thickness: 200 nm) was formed as a conductive layer on the surface of a silicon substrate having an oxide film by a sputtering method. On this substrate, the positive resist composition 1 of Synthesis Example 1 was applied by spin coating to form a 1.5 ⁇ m resist layer and dried at 120 ° C. for 1 minute. Then, selective exposure (ghi mixed line, exposure amount: 100 mJ / cm 2 ) was performed on the resist layer using a mask having a pattern corresponding to the comb electrodes 11a and 11b shown in FIG.
- Formation of active material layer-1) 38.7 g of LiFePO 4 particles, 2.58 g of acetylene black as a conductive additive, 0.43 g of carboxymethyl cellulose as a dispersing agent, and 1.29 g of styrene butadiene rubber (SBR) as a binder are mixed (mass ratio is 90: 6). 1: 3), and 57 g of water was further added and mixed to obtain a dispersion having a solid content of 43% by mass. This dispersion is rotated and rotated at 2000 rpm for 10 minutes with a rotating / revolving mixer (trade name: Awatori Nertaro, manufactured by Shinky Co., Ltd.), and further mixed and dispersed. The resulting mixture is used as a positive electrode active material. It was.
- the silicon wafer on which the guide hole was formed was screen printed, the guide hole was filled with the positive electrode active material, and dried at 100 ° C. for 5 minutes to form a positive electrode active material layer.
- Screen printing uses a screen printing machine (MT-320T type, manufactured by Micro Tech Co., Ltd.) equipped with a silicon squeegee having a hardness of 60 ° polished at an angle of 45 °, using a squeegee pressure of 180 MPa and a squeegee speed of 15 It was performed at 0.0 mm / s.
- the resist composition 2 of Synthesis Example 2 is applied to the surface of the silicon wafer on which the positive electrode active material is deposited by spin coating to form a 10 ⁇ m resist layer, and dried at 140 ° C. for 1 minute to form a protective layer. Formed. (Guide hole production-2) Using a positive mask having the same shape in plan view as the formed comb-shaped current collector 12b, the resist layer located on the upper side of the comb-shaped current collector is exposed (ghi mixed line, exposure amount 60 mJ / cm 2). )did. Next, as an activation step, baking was performed at 85 ° C. for 3 minutes, and development was performed with an alkaline developer. As a result, a comb-shaped guide hole having the same shape as the current collector 12b in plan view was formed on the surface of the silicon wafer while protecting the positive electrode active material with the protective layer. The current collector 12b was exposed at the bottom of the guide hole.
- Formation of active material layer-2) 38.7 g of Li 4 Ti 5 O 12 particles, 2.58 g of acetylene black as a conductive additive, 0.43 g of carboxymethyl cellulose as a dispersing agent, and 1.29 g of SBR as a binder are mixed (mass ratio is 90: 6: 1). : 3), and 57 g of water was further added and mixed to obtain a dispersion having a solid content of 43% by mass. This dispersion was rotated and rotated at 2000 rpm for 10 minutes in a rotating / revolving mixer (trade name: Awatori Nertaro, manufactured by Shinky Co., Ltd.), and further mixed and dispersed. The resulting mixture was used as a negative electrode active material. It was.
- the silicon wafer on which the guide hole was formed was screen printed, the guide hole was filled with the negative electrode active material, and dried at 100 ° C. for 5 minutes to form a negative electrode active material layer.
- Screen printing uses a screen printing machine (MT-320T type, manufactured by Micro Tech Co., Ltd.) equipped with a silicon squeegee having a hardness of 60 ° polished at an angle of 45 °, using a squeegee pressure of 180 MPa and a squeegee speed of 15 It was performed at 0.0 mm / s.
- Comb-shaped electrodes 11a and 11b shown in FIG. 2 were produced using an injection method. (Formation of current collector) In the same manner as in Example 1, comb-shaped current collectors 12a and 12b were formed.
- the resist composition of Synthesis Example 1 was applied to the surface of the silicon wafer on which the current collector was formed by spin coating to form a 50 ⁇ m resist layer and dried at 140 ° C. for 5 minutes. Then, using a positive mask having the same shape in plan view as the formed comb-shaped current collector, the resist layer positioned above the comb-shaped current collector is exposed (ghi mixed line, exposure amount: 60 mJ / cm). 2 ). Next, as an activation step, baking was performed at 85 ° C. for 3 minutes, and development was performed with an alkaline developer. As a result, comb-shaped guide holes were formed on the surface of the silicon wafer. The current collector was exposed at the bottom of the guide hole.
- Example 2 The cross-sections of the comb electrodes 11a and 11b obtained in Example 1 were observed with SEM and EDX (energy dispersive X-ray spectroscopy). The results are shown in FIG. As shown in FIG. 3A, in the comb-shaped electrodes 11a and 11b, it was confirmed that the positive electrode active material and the negative electrode active material were filled without variation according to the shape of the guide hole. Further, as shown in FIG. 3B, it was observed that phosphorus was present in the positive electrode, and it was confirmed that the positive electrode active material was filled. On the other hand, as shown in FIG. 3C, it was observed that titanium was present in the negative electrode, and it was confirmed that the negative electrode active material was filled.
- Example 3 When preparing the positive electrode active material, the mass ratio of LiFePO 4 particles, acetylene black, carboxymethyl cellulose, and SBR was changed to 87: 6: 5: 2, and the solid content concentration of the dispersion was changed to 42% by mass. When preparing the negative electrode active material, the mass ratio of Li 4 Ti 5 O 12 particles, acetylene black, carboxymethyl cellulose, and SBR was changed to 87: 6: 5: 2, and the solid content concentration of the dispersion was 42% by mass. Comb electrodes 11a and 11b shown in FIG. 2 were produced in the same manner as in Example 1 except that the change was made.
- the resist surface was observed with an optical microscope. As a result, no positive electrode active material or negative electrode active material residue extending in a strip shape in the moving direction of the squeegee was observed on the resist surface. Moreover, when the produced comb-shaped electrode was observed by SEM, the beard-like residue of the positive electrode active material or the negative electrode active material was not observed.
- the positive electrode active material or the negative electrode active material by reducing the amount of acetylene black, which is a conductive auxiliary agent, from 12% by mass to 6% by mass, a whisker-like residue of the positive electrode active material or the negative electrode active material is generated. It was found that a short circuit between the electrodes can be prevented.
- the secondary battery was charged and discharged by setting the current value to 20 ⁇ A (Example 4), 160 ⁇ A (Example 5), or 225 ⁇ A (Example 6).
- a charge / discharge curve is shown in FIG.
- Table 1 shows the value of the discharge capacity read from this charge / discharge curve. Note that the letters A to C in FIG. 4 represent the comb electrodes A to C, respectively.
- the secondary battery having the comb-shaped electrode manufactured using the pattern forming method according to the present invention increases the overall size of the comb-shaped electrode and increases the area occupied by the active material. It was found that the discharge capacity was improved by increasing the width. Further, from comparison between Examples 5 and 6, it was found that when the area of the comb-shaped electrode is the same, the discharge capacity is improved by narrowing the interval between teeth and widening the area occupied by the active material.
- Example 7 and 8 Except for changing the thickness of the active material layer as shown in Table 2, in the same manner as in Example 4 or 5, fabrication of the comb electrodes 11a and 11b shown in FIG. 2, fabrication of the secondary battery, and charging and Discharge was performed. In Examples 7 and 8, the current value was set to 90 ⁇ A (Example 7) or 353 ⁇ A (Example 8). A charge / discharge curve is shown in FIG. Further, Table 2 shows the discharge capacity value read from the charge / discharge curve. For comparison, FIG. 5 and Table 2 also show the results of Examples 4 and 5. Moreover, the English letters A, B, D, and E in FIG. 5 represent the comb-shaped electrodes A, B, D, and E, respectively.
- the secondary battery having the comb-shaped electrode manufactured using the pattern forming method according to the present invention has a thicker active material layer. It was found that the discharge capacity is improved.
- Example 9 ⁇ Longer life by adding additives>
- Example 9 In the same manner as in Example 8, the fabrication of the comb electrodes 11a and 11b shown in FIG. 2, the fabrication of the secondary battery, and the charging and discharging were performed. Charging and discharging were repeated for 100 cycles, and the charging capacity and discharging capacity at 1, 5, 10, 25, 50, and 100th cycle were measured.
- FIG. 6 shows the discharge capacity retention ratio in each cycle when the discharge capacity in the first cycle is 100%.
- Example 10 In the same manner as in Example 9, except that a solution containing 5% by weight vinylene carbonate in addition to 1M LiClO 4 (solvent is a mixed solution of ethylene carbonate and diethyl carbonate having a volume ratio of 1: 1) was used as the electrolyte solution.
- solvent is a mixed solution of ethylene carbonate and diethyl carbonate having a volume ratio of 1: 1.
- FIG. 6 shows the discharge capacity retention ratio in each cycle when the discharge capacity in the first cycle is 100%.
- Example 11 3 parts by mass of polyethylene oxide having a mass average molecular weight of 80,000, 10 parts by mass of acetonitrile, and 7.2 parts by mass of 1M LiClO 4 solution (solvent is a 1: 1 volume ratio ethylene carbonate / diethyl carbonate mixed solution)
- solvent is a 1: 1 volume ratio ethylene carbonate / diethyl carbonate mixed solution
- An electrolyte solution was prepared. After 1,000 ⁇ l of this electrolyte solution was dropped into a guide formed on an SiO 2 substrate and surrounded by an ethylene propylene diene rubber plate having a thickness of 3 mm and a width of 2 mm, and dried at 80 ° C. for 30 minutes, When the state was observed, it was gelled.
- the surface resistance was measured with a tester in the air within 3 minutes after the completion of drying, and it was 100 k ⁇ .
- the gel electrolyte was subjected to impedance measurement as follows. An 8 mm ⁇ ⁇ 60 ⁇ m thick polyimide film having a 5 mm ⁇ through hole is adhered to a 2 mm thick Au substrate, and the electrolyte containing polyethylene oxide is formed in the recess formed by the Au substrate and the through hole. The solution was added dropwise and dried at 80 ° C. for 20 minutes.
- the electrolyte solution containing polyethylene oxide was dropped into the gap between the obtained comb-shaped electrodes 11a and 11b and dried at 80 ° C. for 20 minutes.
- a secondary battery in which the gap was filled with the gel electrolyte was produced.
- the electric current value was set to 50 microamperes, and charging and discharging were performed. Charging and discharging were repeated for 100 cycles, and the charging capacity and discharging capacity at 1, 25, 50, 75 and 100th cycles were measured.
- a charge / discharge curve is shown in FIG.
- the number in FIG. 7 represents the number of cycles.
- the secondary battery having a comb-shaped electrode manufactured by using the pattern forming method according to the present invention has good charge / discharge characteristics even when a gel electrolyte is used.
- Example 12 About the comb-shaped electrode produced in Example 4, C rate was set to 1C, 2C, 5C, 10C, 20C, or 40C, and it charged and discharged like Example 4. A charge / discharge curve is shown in FIG. Table 4 shows the discharge capacity retention ratio at each C rate when the discharge capacity at 1 C is 100%.
- the secondary battery having the comb-shaped electrode manufactured by using the pattern forming method according to the present invention has a good discharge capacity maintenance rate even when the C rate is increased, and was manufactured by the injection method. It turned out that it has the performance equivalent to the secondary battery which has a comb-shaped electrode.
- Example 13 The comb-shaped electrode produced in Example 4 was charged and discharged in the same manner as in Example 4. Charging and discharging were repeated 250 cycles, and the charging capacity and discharging capacity were measured in a predetermined cycle.
- FIG. 9A shows the capacity retention rate in each cycle when the charge capacity and discharge capacity in the first cycle are 100%.
- FIG. 9B shows the Coulomb efficiency (that is, discharge capacity / charge capacity) in each cycle. From these results, the secondary battery having the comb-shaped electrode manufactured by using the pattern forming method according to the present invention has a stable capacity maintenance rate even after 250 cycles, and the Coulomb efficiency is 98.8%. It was found that the high value was maintained.
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Abstract
Description
図1は、本発明の実施形態に係るパターン形成方法を示す横断面図である。図1を参照して、本発明の実施形態に係るパターン形成方法について説明する。なお、図1では、n=2の場合について説明する。
この工程において、まず、所望のマスクを介して、1番目のレジスト層2を選択露光させる。これにより、将来ガイド孔3aとなる部分が現像液に対して可溶となり、将来ガイド孔3aとならない箇所が現像液に対して不溶のままとなる。
この工程では、図1(c)で示される工程で形成されたガイド孔3aに、スクリーン印刷法により、1番目のパターン材料を充填する。即ち、ガイド孔3aを鋳型として、支持体1の表面に1番目のパターン材料層4aを形成させる。
この工程では、1番目のレジスト層2と、ガイド孔3aに充填された1番目のパターン材料(即ち、1番目のパターン材料層4a)との上に、ポジ型レジスト組成物を塗布して2番目のレジスト層5を形成させる。2番目のレジスト層5は、1番目のパターン材料層4aの保護層として機能する。即ち、2番目のレジスト層5を形成させないで、後述のとおり、ガイド孔3bを形成させると、その過程で1番目のパターン材料層4aが現像液に触れて、流出してしまう。上述のとおりに2番目のレジスト層5を形成させることで、1番目のパターン材料層4aが現像液に触れて流出してしまうのを防ぐことができる。
この工程において、まず、所望のマスクを介して、1番目のレジスト層2及び2番目のレジスト層5を選択露光させる。これにより、将来ガイド孔3bとなる部分が現像液に対して可溶となり、将来ガイド孔3bとならない箇所が現像液に対して不溶のままとなる。
この工程では、図1(f)で示される工程で形成されたガイド孔3bに、スクリーン印刷法により、2番目のパターン材料を充填する。即ち、ガイド孔3bを鋳型として、支持体1の表面に2番目のパターン材料層4bを形成させる。
この工程では、1番目のレジスト層2及び2番目のレジスト層5を除去する。具体的には、例えば、剥離液を用いて、これらのレジスト層を剥離する方法が挙げられる。この場合、剥離方法は、特に限定されず、浸漬法、スプレー法、シャワー法、パドル法等を用いることができる。また、剥離液としては、例えば、3~15質量%の水酸化ナトリウム水溶液、水酸化カリウム水溶液、有機アミン、テトラメチルアンモニウムヒドロキシド、トリエタノールアミン、N―メチルピロリドン、ジメチルスルホキシド、アセトン等が挙げられる。剥離処理時間は、特に限定されないが、例えば1~120分間程度である。なお、剥離液は、25~60℃程度に加温してもよい。
なお、図1では、n=2の場合について説明したが、nが3以上の場合については、図1(c)~(e)で示される工程を必要回数繰り返すことにより、同一又は異なるパターン材料からなるn個のパターンを支持体上に形成することができる。
櫛型電極11aと櫛型電極11bとの間には、空間又は両者を隔離するセパレータ(図示せず)が設けられ、両者が電気的に分離される。櫛型電極11a及び11bは、表面が不導体である基板14の表面に形成される。このような基板14としては、表面に酸化膜を有するシリコン基板が例示される。
m-クレゾール及びp-クレゾールの混合物(m-クレゾール/p-クレゾール=6/4(質量比))とホルムアルデヒドとを酸触媒の存在下で常法により付加縮合して得たクレゾール型ノボラック樹脂(質量平均分子量30000)70質量部と、感光剤として1,4-ビス(4-ヒドロキシフェニルイソプロピリデニル)ベンゼンのナフトキノン-1,2-ジアジド-5-スルホン酸ジエステル15質量部と、可塑剤としてポリメチルビニルエーテル(質量平均分子量100000)15質量部とに対して、溶剤としてプロピレングリコールモノメチルエーテルアセテート(PGMEA)を固形分濃度が40質量%になるように添加してから、混合して溶解させ、レジスト組成物1を得た。このレジスト組成物1は、ノボラック系であり、非化学増幅系であり、ポジ型である。
m-クレゾール及びp-クレゾールの混合物(m-クレゾール/p-クレゾール=6/4(質量比))とホルムアルデヒドとを酸触媒の存在下で常法により付加縮合して得たクレゾール型ノボラック樹脂(質量平均分子量10000)52.5質量部と、ポリヒドロキシスチレン樹脂VPS-2515(日本曹達社製) 10質量部と、下記式(1)で表される樹脂27.5質量部と、下記式(2)で表される樹脂10質量部と、酸発生剤として下記式(3)で表される化合物2質量部と、増感剤として1,5-ジヒドロキシナフタレン2質量部と、添加剤としてトリエチルアミン0.01質量部及びサリチル酸0.02質量部と、溶剤としてPGMEA 107質量部及びガンマブチロラクトン6質量部とを混合して溶解させることによりレジスト組成物2を得た。このレジスト組成物2は、化学増幅系であり、ポジ型である。
スクリーン印刷法を用いて、図2に示す櫛型電極11a及び11bを作製した。
(集電体の形成)
まず、酸化膜を有するシリコン基板の表面に、スパッタ法により、導電層としてアルミニウム膜(厚さ:200nm)を形成した。この基板上に、合成例1のポジ型レジスト組成物1をスピンコート法により塗布し、1.5μmのレジスト層を形成させ、120℃にて1分間乾燥させた。そして、図2に示す櫛型電極11a及び11bに対応するパターンを有するマスクを用いて、レジスト層に選択露光(ghi混合線、露光量100mJ/cm2)を行った。次いで、TMAH2.38質量%のアルカリ現像液で1分間現像した。現像後に、アルミニウムエッチング液(H3PO4:HNO3:H2O=4:1:1.6(質量比))でディップ法によりエッチングし、アルミニウムパターンを形成して、櫛型集電体12a及び12bを形成した。
集電体の形成されたシリコンウェーハの表面に、合成例1のレジスト組成物をスピンコート法により塗布し、50μmのレジスト層を形成させ、140℃にて5分間乾燥させた。そして、形成された櫛型の集電体12aと平面視で同一形状となるポジマスクを使用して、櫛型の集電体の上部に位置するレジスト層に露光(ghi混合線、露光量60mJ/cm2)した。次いで、活性化工程として85℃にて3分間ベークを行い、アルカリ現像液で現像した。これにより、シリコンウェーハの表面に、集電体12aと平面視で同一形状となる櫛型形状のガイド孔を形成させた。なお、ガイド孔の底部には、集電体12aが露出していた。
LiFePO4粒子38.7g、導電助剤としてアセチレンブラック2.58g、分散剤としてカルボキシメチルセルロース0.43g、及び結着剤としてスチレンブタジエンゴム(SBR)1.29gを混合し(質量比は90:6:1:3)、更に57gの水を加えて混合し、固形分43質量%の分散液を得た。この分散液を自転・公転ミキサー(商品名:あわとり練太郎、(株)シンキー製)にて2000rpmで10分間回転させて、更に混合・分散を行い、得られた混合物を正極活物質として用いた。
正極活物質が堆積されたシリコンウェーハの表面に、合成例2のレジスト組成物2をスピンコート法により塗布し、10μmのレジスト層を形成させ、140℃にて1分間乾燥させて、保護層を形成させた。
(ガイド孔の作製-2)
形成された櫛型の集電体12bと平面視で同一形状となるポジマスクを使用して、櫛型の集電体の上部に位置するレジスト層に露光(ghi混合線、露光量60mJ/cm2)した。次いで、活性化工程として85℃にて3分間ベークを行い、アルカリ現像液で現像した。これにより、正極活物質を上記保護層により保護しつつ、シリコンウェーハの表面に、集電体12bと平面視で同一形状となる櫛型形状のガイド孔を形成させた。なお、ガイド孔の底部には、集電体12bが露出していた。
Li4Ti5O12粒子38.7g、導電助剤としてアセチレンブラック2.58g、分散剤としてカルボキシメチルセルロース0.43g、及び結着剤としてSBR1.29gを混合し(質量比は90:6:1:3)、更に57gの水を加えて混合し、固形分43質量%の分散液を得た。この分散液を自転・公転ミキサー(商品名:あわとり練太郎、(株)シンキー製)にて2000rpmで10分間回転させて、更に混合・分散を行い、得られた混合物を負極活物質として用いた。
最後にレジスト層をアセトンにて剥離して、櫛型電極11a及び11bを得た。スクリーン印刷法により電極活物質を充填するのに要した時間は、15分という非常に短い時間であった。
インジェクション法を用いて、図2に示す櫛型電極11a及び11bを作製した。
(集電体の形成)
実施例1と同様にして、櫛型集電体12a及び12bを形成した。
集電体の形成されたシリコンウェーハの表面に、合成例1のレジスト組成物をスピンコート法により塗布し、50μmのレジスト層を形成させ、140℃にて5分間乾燥させた。そして、形成された櫛型の集電体と平面視で同一形状となるポジマスクを使用して、櫛型の集電体の上部に位置するレジスト層に露光(ghi混合線、露光量60mJ/cm2)した。次いで、活性化工程として85℃にて3分間ベークを行い、アルカリ現像液で現像した。これにより、シリコンウェーハの表面に、櫛型形状のガイド孔を形成させた。なお、ガイド孔の底部には、集電体が露出していた。
マイクロピペットを使用して、上記で形成させたガイド孔のうち、正極に対応するものの周辺に実施例1の正極活物質を、負極に対応するものの周辺に実施例1の負極活物質を滴下し、櫛型パターンを有する各ガイド孔へ慎重に流しこんだ。その後、100℃にて5分間乾燥させ、活物質層を形成した。最後にレジスト層をアセトンにて剥離して、櫛型電極11a及び11bを得た。インジェクション法により電極活物質を充填するのに要した時間は、3時間という非常に長い時間であった。
実施例1で得られた櫛型電極11a及び11bの断面を、SEM及びEDX(エネルギー分散型X線分光法)で観察した。結果を図3に示す。図3(a)に示すとおり、櫛型電極11a及び11bにおいて、正極活物質及び負極活物質は、ガイド孔の形状に従って、ばらつきなく充填されていることが確認できた。また、図3(b)に示すとおり、正極にはリンが存在することが観察され、正極活物質が充填されていることが確認できた。一方、図3(c)に示すとおり、負極にはチタンが存在することが観察され、負極活物質が充填されていることが確認できた。
[実施例3]
正極活物質を調製する際、LiFePO4粒子、アセチレンブラック、カルボキシメチルセルロース、及びSBRの質量比を87:6:5:2に変更し、分散液の固形分濃度を42質量%に変更し、また、負極活物質を調製する際、Li4Ti5O12粒子、アセチレンブラック、カルボキシメチルセルロース、及びSBRの質量比を87:6:5:2に変更し、分散液の固形分濃度を42質量%に変更した以外は、実施例1と同様にして、図2に示す櫛型電極11a及び11bを作製した。
ガイド孔への正極活物質又は負極活物質の充填の直後に、レジスト表面を光学顕微鏡で観察した。その結果、レジスト表面に、スキージの移動方向に帯状に延びる正極活物質又は負極活物質の残渣は観察されなかった。
また、作製した櫛型電極をSEMで観察したところ、正極活物質又は負極活物質のひげ状の残渣は観察されなかった。
LiFePO4粒子、アセチレンブラック、カルボキシメチルセルロース、及びSBRの質量比を81:12:5:2に変更し、Li4Ti5O12粒子、アセチレンブラック2.58g、カルボキシメチルセルロース、及びSBRの質量比を81:12:5:2に変更した以外は、実施例3と同様にして、図2に示す櫛型電極11a及び11bを作製した。
ガイド孔への正極活物質又は負極活物質の充填の直後に、レジスト表面を光学顕微鏡で観察した。その結果、レジスト表面に、スキージの移動方向に帯状に延びる正極活物質又は負極活物質の残渣が観察された。
また、作製した櫛型電極をSEMで観察したところ、正極活物質又は負極活物質のひげ状の残渣は観察された。
[実施例4~6]
櫛型電極全体のサイズ、歯の太さ、隣接する2本の歯同士の間隔、歯の長さ、歯の本数、及び活物質層の厚さを表1に示すとおりに設定した以外は、実施例3と同様にして、図2に示す櫛型電極11a及び11bを作製した。
得られた櫛型電極11aと11bとの間隙を電解質液(1M LiClO4溶液、溶媒は体積比1:1の炭酸エチレン・炭酸ジエチル混合液)で満たして、二次電池を作製した。この二次電池について、電流値を20μA(実施例4)、160μA(実施例5)、又は225μA(実施例6)に設定して、充電及び放電を行った。充放電曲線を図4に示す。また、この充放電曲線から読み取った放電容量の値を表1に示す。なお、図4における英文字A~Cは、それぞれ櫛型電極A~Cを表す。
[実施例7及び8]
活物質層の厚さを表2に示すとおりに変更した以外は、実施例4又は5と同様にして、図2に示す櫛型電極11a及び11bの作製、二次電池の作製、並びに充電及び放電を行った。なお、実施例7及び8について、電流値の設定は90μA(実施例7)又は353μA(実施例8)とした。充放電曲線を図5に示す。また、この充放電曲線から読み取った放電容量の値を表2に示す。なお、比較のため、図5及び表2には、実施例4及び5の結果も示す。また、図5における英文字A、B、D、及びEは、それぞれ櫛型電極A、B、D、及びEを表す。
[実施例9]
実施例8と同様にして、図2に示す櫛型電極11a及び11bの作製、二次電池の作製、並びに充電及び放電を行った。充電及び放電を100サイクル繰り返して行い、1、5、10、25、50、及び100サイクル目の充電容量及び放電容量を測定した。1サイクル目の放電容量を100%としたときの各サイクルにおける放電容量維持率を図6に示す。
電解質液として、1M LiClO4に加えて5質量%炭酸ビニレンを含む溶液(溶媒は体積比1:1の炭酸エチレン・炭酸ジエチル混合液)を用いた以外は、実施例9と同様にして、二次電池を作製し、1、5、10、25、50、及び100サイクル目の充電容量及び放電容量を測定した。1サイクル目の放電容量を100%としたときの各サイクルにおける放電容量維持率を図6に示す。
[実施例11]
質量平均分子量80,000のポリエチレンオキシド3質量部、アセトニトリル10質量部、及び1M LiClO4溶液(溶媒は体積比1:1の炭酸エチレン・炭酸ジエチル混合液)7.2質量部を混合して、電解質液を調製した。
この電解質液1,000μlを、SiO2基板上に配置した厚さ3mmで幅2mmのエチレンプロピレンジエンゴム板で囲まれて形成されたガイドの中に滴下し、80℃で30分間乾燥させた後に状態を観察したところ、ゲル状になっていた。
上記のとおりに形成されたゲル状の電解質について、乾燥終了後3分以内に、大気下でテスターにて表面抵抗を測定したところ、100kΩであった。
上記ゲル状電解質について、以下のとおりにしてインピーダンス測定を行った。厚さ2mmのAu基板の上に、5mmφの貫通孔を有する8mmφ×厚さ60ミクロンのポリイミドフィルムを密着させ、上記のAu基板と貫通孔とで形成された凹部に、ポリエチレンオキシドを含む上記電解質液を滴下し、80℃で20分間乾燥させた。ポリイミドフィルム及び形成されたゲル状電解質の上に、厚さ2mmの別のAu基板を載せ、2枚の上記Au基板の間に下記条件で電圧をかけて、インピーダンスを測定したところ、5.66×10-4Scm-1であった。
条件:初期電圧0.2V、周波数範囲0.1~10,000Hz、振幅0.005V、休止時間2秒、温度23℃
櫛型電極全体のサイズ、歯の太さ、隣接する2本の歯同士の間隔、歯の長さ、歯の本数、及び活物質層の厚さを表3に示すとおりに設定した以外は、実施例3と同様にして、図2に示す櫛型電極11a及び11bを作製した。得られた櫛型電極11aと11bとの間隙に、ポリエチレンオキシドを含む上記電解質液を滴下し、80℃で20分間乾燥させた。これにより、上記間隙がゲル状電解質で満たされた二次電池を作製した。この二次電池について、電流値を50μAに設定して、充電及び放電を行った。充電及び放電を100サイクル繰り返して行い、1、25、50、75、及び100サイクル目の充電容量及び放電容量を測定した。充放電曲線を図7に示す。なお、図7における数字は、サイクル数を表す。
[実施例12]
実施例4で作製した櫛型電極について、Cレートを1C、2C、5C、10C、20C、又は40Cに設定して、実施例4と同様にして、充電及び放電を行った。充放電曲線を図8に示す。また、1Cにおける放電容量を100%としたときの各Cレートにおける放電容量維持率を表4に示す。
[実施例13]
実施例4で作製した櫛型電極について、実施例4と同様にして、充電及び放電を行った。充電及び放電を250サイクル繰り返して行い、所定のサイクルにおいて充電容量及び放電容量を測定した。1サイクル目の充電容量及び放電容量を100%としたときの各サイクルにおける容量維持率を図9(a)に示す。また、各サイクルにおけるクーロン効率(即ち、放電容量/充電容量)を図9(b)に示す。
これらの結果から、本発明に係るパターン形成方法を用いて製造された櫛型電極を有する二次電池は、250サイクル後も、容量維持率が安定しており、クーロン効率は98.8%という高い値を維持していることが分かった。
2 1番目のレジスト層
3a、3b ガイド孔
4a、4b パターン材料層
5 2番目のレジスト層
11a、11b 櫛型電極
12a、12b 集電体
13a、13b 活物質層
14 基板
Claims (4)
- 同一又は異なるパターン材料からなるn個(nは2以上の整数)のパターンを支持体上に形成するパターン形成方法であって、
前記支持体の表面にポジ型レジスト組成物を塗布して1番目のレジスト層を形成させ、
k番目(kは1~(n-1)の整数)のパターン材料及びk番目のレジスト層について、kが1の場合からkが(n-1)の場合まで順番に、下記(1)~(3):
(1)露光及び現像により、1番目からk番目までのレジスト層を貫通するガイド孔を形成させること、
(2)スクリーン印刷法により前記ガイド孔にk番目のパターン材料を充填すること、及び
(3)k番目のレジスト層と前記ガイド孔に充填された前記k番目のパターン材料との上に、ポジ型レジスト組成物を塗布して(k+1)番目のレジスト層を形成させること
を繰り返し、
露光及び現像により、1番目からn番目までのレジスト層を貫通するガイド孔を形成させ、
スクリーン印刷法により前記ガイド孔にn番目のパターン材料を充填し、
1番目からn番目までのレジスト層を除去することを含むパターン形成方法。 - 請求項1に記載のパターン形成方法により形成されるパターンを備える構造体。
- 正極及び負極がそれぞれ櫛型形状として形成され、前記正極及び負極が櫛型形状の歯の部分で互い違いに組み合うように対向配置された櫛型電極の製造方法であって、
基板の表面に導電層を形成させ、当該導電層をパターニングして集電体を形成させ、
請求項1に記載のパターン形成方法を用いて、前記集電体上に前記正極及び負極を形成させることを含む製造方法。 - 請求項3記載の製造方法により製造された櫛型電極を有する二次電池。
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EP13835967.4A EP2894697B1 (en) | 2012-09-07 | 2013-08-28 | Pattern forming method and interdigitated electrode manufacturing method |
US14/426,300 US9478791B2 (en) | 2012-09-07 | 2013-08-28 | Method for forming pattern, structural body, method for producing comb-shaped electrode, and secondary cell |
KR1020157008038A KR101645904B1 (ko) | 2012-09-07 | 2013-08-28 | 패턴 형성 방법, 구조체, 빗형 전극의 제조 방법 및 이차 전지 |
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TW201424094A (zh) | 2014-06-16 |
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US20150243965A1 (en) | 2015-08-27 |
EP2894697B1 (en) | 2017-05-03 |
KR101645904B1 (ko) | 2016-08-04 |
EP2894697A1 (en) | 2015-07-15 |
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US9478791B2 (en) | 2016-10-25 |
KR20150043517A (ko) | 2015-04-22 |
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