JP2013088048A - Electrode drying method and electrode drying device - Google Patents
Electrode drying method and electrode drying device Download PDFInfo
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- 238000001035 drying Methods 0.000 title claims abstract description 176
- 239000002904 solvent Substances 0.000 claims abstract description 119
- 239000012298 atmosphere Substances 0.000 claims abstract description 59
- 239000011267 electrode slurry Substances 0.000 claims abstract description 30
- 238000001704 evaporation Methods 0.000 claims abstract description 21
- 230000008020 evaporation Effects 0.000 claims abstract description 18
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- 239000011888 foil Substances 0.000 abstract description 42
- 239000002002 slurry Substances 0.000 abstract description 8
- 230000006866 deterioration Effects 0.000 abstract description 3
- 238000004904 shortening Methods 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 25
- 238000011084 recovery Methods 0.000 description 14
- 238000005204 segregation Methods 0.000 description 13
- 238000000576 coating method Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000032258 transport Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
- B05C9/08—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material and performing an auxiliary operation
- B05C9/14—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying liquid or other fluent material and performing an auxiliary operation the auxiliary operation involving heating or cooling
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B13/00—Machines and apparatus for drying fabrics, fibres, yarns, or other materials in long lengths, with progressive movement
- F26B13/10—Arrangements for feeding, heating or supporting materials; Controlling movement, tension or position of materials
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
- F26B21/02—Circulating air or gases in closed cycles, e.g. wholly within the drying enclosure
- F26B21/04—Circulating air or gases in closed cycles, e.g. wholly within the drying enclosure partly outside the drying enclosure
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Coating Apparatus (AREA)
- Drying Of Solid Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
本発明は、電極乾燥方法、および電極乾燥装置に関する。 The present invention relates to an electrode drying method and an electrode drying apparatus.
リチウムイオン二次電池は、蓄電密度が大きく、充放電を繰り返し行っても蓄電性能をよく保つことから、自動車や家電製品の電源として広く用いられている。 Lithium ion secondary batteries are widely used as power sources for automobiles and home appliances because they have a high storage density and maintain good storage performance even after repeated charging and discharging.
リチウムイオン二次電池の電極形成過程においては、まず、正極のアルミニウム箔、負極の銅箔のような電極箔上に、溶媒を含むスラリー状態の電極スラリーを一定重量塗布することによって電極層を形成する。次に、電極乾燥装置の乾燥炉の中において、電極層に含まれる溶媒を揮発させて乾燥させ、電極層の固形分と電極箔とを固着させている。 In the process of forming an electrode of a lithium ion secondary battery, first, an electrode layer is formed by applying a certain weight of a slurry slurry containing a solvent on an electrode foil such as a positive electrode aluminum foil or a negative electrode copper foil. To do. Next, in the drying furnace of the electrode drying apparatus, the solvent contained in the electrode layer is volatilized and dried to fix the solid content of the electrode layer and the electrode foil.
電極乾燥工程においては、乾燥炉内において、電極箔の上下面から熱風を吹きつける方法が一般的である（例えば、特許文献１、および２を参照）。熱風による場合の乾燥条件の主なものとして、熱風の温度、熱風の吹き付け量、および乾燥時間がある。 In the electrode drying step, a method of blowing hot air from the upper and lower surfaces of the electrode foil in a drying furnace is common (see, for example, Patent Documents 1 and 2). The main drying conditions in the case of hot air include the temperature of hot air, the amount of hot air sprayed, and the drying time.
電極乾燥装置には、電極の生産性を上げるために乾燥時間の短縮を図ることが要請されている。このような要請に対して、乾燥条件（熱風の場合における熱風の温度、および熱風の吹き付け量）を大きく変化させると、電極内部の微細構造に影響が及んでしまい、電極性能が低下することがある。電極性能の劣化を招かない範囲内において乾燥条件を変化させなければならないため、乾燥時間の短縮に対して効果的な対策をとることができない。 The electrode drying apparatus is required to shorten the drying time in order to increase the productivity of the electrode. In response to such a request, if the drying conditions (the temperature of hot air in the case of hot air and the amount of hot air blown) are changed significantly, the fine structure inside the electrode will be affected, and the electrode performance may deteriorate. is there. Since the drying conditions must be changed within a range that does not cause deterioration of electrode performance, it is not possible to take effective measures for shortening the drying time.
電極内部の微細構造に影響が及んでしまう理由は、乾燥温度を高温にしたり、熱風量を増加させたりすると、スラリー状態の電極層において、表面における溶媒の揮発速度と、深部からの溶媒の拡散速度との差が大きくなって、電極スラリー中のバインダーが偏析してしまうことに起因していると考えられる。このようなバインダーの偏析が生じると、電極箔と塗膜である電極層との間の十分な密着力を得ることができなくなる。強密着の塗膜が得られないと、初期における電池内の抵抗値のみならず、充放電を繰り返した後の電池内の抵抗値も高くなり、電極性能の低下を招くことになる。 The reason why the fine structure inside the electrode is affected is that when the drying temperature is increased or the amount of hot air is increased, the volatilization rate of the solvent on the surface and the diffusion of the solvent from the deep part in the electrode layer in the slurry state. It is considered that the difference from the speed is increased and the binder in the electrode slurry is segregated. When such segregation of the binder occurs, it becomes impossible to obtain sufficient adhesion between the electrode foil and the electrode layer as the coating film. If a strongly adherent coating film is not obtained, not only the resistance value in the battery at the initial stage but also the resistance value in the battery after repeated charge / discharge increases, leading to a decrease in electrode performance.
そこで、本発明の目的は、電極性能の低下を招くことなく、スラリー状態の電極層に含まれる溶媒を効率よく揮発させて、乾燥時間の短縮を図ることが可能な電極乾燥方法、および電極乾燥装置を提供することにある。 Accordingly, an object of the present invention is to provide an electrode drying method and an electrode drying method capable of efficiently evaporating the solvent contained in the electrode layer in a slurry state without reducing the electrode performance and shortening the drying time. To provide an apparatus.
上記目的を達成するための電極乾燥方法は、溶媒を含む電極スラリーを集電体に塗布することによって形成された電極層を乾燥炉の中において乾燥させる方法である。そして、前記電極層内に残存する溶媒濃度と前記乾燥炉内の雰囲気における溶媒濃度との濃度差を、前記雰囲気における溶媒濃度を高めることによって小さくしつつ、熱を付与して前記電極層を乾燥させている。 The electrode drying method for achieving the above object is a method in which an electrode layer formed by applying an electrode slurry containing a solvent to a current collector is dried in a drying furnace. Then, heat is applied to dry the electrode layer while reducing the concentration difference between the solvent concentration remaining in the electrode layer and the solvent concentration in the atmosphere in the drying furnace by increasing the solvent concentration in the atmosphere. I am letting.
また、上記目的を達成するための電極乾燥装置は、溶媒を含む電極スラリーを集電体に塗布することによって形成された電極層を乾燥炉の中において乾燥させる電極乾燥装置である。電極乾燥装置は、前記電極層内に残存する溶媒濃度と前記乾燥炉内の雰囲気における溶媒濃度との濃度差を、前記雰囲気における溶媒濃度を高めることによって小さくする蒸発速度調整部材と、前記電極層を乾燥させる熱を付与するヒーター部と、を有している。 Moreover, the electrode drying apparatus for achieving the said objective is an electrode drying apparatus which dries the electrode layer formed by apply | coating the electrode slurry containing a solvent to a collector in a drying furnace. An electrode drying apparatus includes: an evaporation rate adjusting member that reduces a concentration difference between a solvent concentration remaining in the electrode layer and a solvent concentration in the atmosphere in the drying furnace by increasing the solvent concentration in the atmosphere; and the electrode layer And a heater part for applying heat for drying the liquid.
本発明によれば、電極層内に残存する溶媒濃度と乾燥炉内の雰囲気における溶媒濃度との濃度差を、雰囲気における溶媒濃度を高めることによって小さくしつつ、熱を付与して電極層を乾燥させているので、電極層を緩やかに乾燥させて、バインダーの偏析が生じることを防止することができる。バインダーの偏析を生じさせない条件にて電極層を乾燥させることから、集電体と電極層との密着性が向上し、初期における電池内の抵抗値はもちろんのこと、充放電を繰り返した後の電池内の抵抗値も低くなり、電極性能の向上を図ることが可能となる。もって、電極性能の低下を招くことなく、スラリー状態の電極層に含まれる溶媒を効率よく揮発させて、乾燥時間の短縮を図ることが可能な電極乾燥方法、および電極乾燥装置を提供できた。 According to the present invention, heat is applied to dry the electrode layer while reducing the concentration difference between the solvent concentration remaining in the electrode layer and the solvent concentration in the atmosphere in the drying furnace by increasing the solvent concentration in the atmosphere. Therefore, it is possible to prevent the binder from segregating by gently drying the electrode layer. Since the electrode layer is dried under conditions that do not cause segregation of the binder, the adhesion between the current collector and the electrode layer is improved, and not only the initial resistance value in the battery but also after repeated charging and discharging. The resistance value in the battery is also lowered, and the electrode performance can be improved. Accordingly, it is possible to provide an electrode drying method and an electrode drying apparatus capable of efficiently evaporating the solvent contained in the electrode layer in a slurry state and reducing the drying time without causing deterioration in electrode performance.
以下、添付した図面を参照しながら、本発明の実施形態を説明する。なお、図面の説明において同一の要素には同一の符号を付し、重複する説明を省略する。図面の寸法比率は、説明の都合上誇張されており、実際の比率とは異なる。 Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. The dimensional ratios in the drawings are exaggerated for convenience of explanation, and are different from the actual ratios.
図１および図２に示すように、電極乾燥装置１０は、溶媒２１を含む電極スラリー２０を電極箔３０（集電体に相当する）に塗布することによって形成された電極層４０を乾燥炉５０の中において乾燥させる。この電極乾燥装置１０は、電極層４０が形成された電極箔３０を乾燥炉５０内において搬送する搬送部６０と、電極層４０内に残存する溶媒濃度と乾燥炉５０内の雰囲気５７における溶媒濃度との濃度差を、雰囲気５７における溶媒濃度を高めることによって小さくする蒸発速度調整部材７０と、電極層４０を乾燥させる熱を付与するヒーター部８０と、を有している。ヒーター部８０は、熱源として熱風を用いている。そして、電極層４０内に残存する溶媒濃度と乾燥炉５０内の雰囲気５７における溶媒濃度との濃度差を、雰囲気５７における溶媒濃度を高めることによって小さくしつつ、熱を付与して電極層４０を乾燥させている。以下、詳述する。 As shown in FIGS. 1 and 2, the electrode drying apparatus 10 is configured to dry an electrode layer 40 formed by applying an electrode slurry 20 containing a solvent 21 to an electrode foil 30 (corresponding to a current collector). Dry in. The electrode drying apparatus 10 includes a transport unit 60 that transports the electrode foil 30 on which the electrode layer 40 is formed in the drying furnace 50, a solvent concentration remaining in the electrode layer 40, and a solvent concentration in the atmosphere 57 in the drying furnace 50. The evaporation rate adjusting member 70 that reduces the difference in concentration by increasing the solvent concentration in the atmosphere 57 and the heater unit 80 that applies heat to dry the electrode layer 40 are included. The heater unit 80 uses hot air as a heat source. Then, while reducing the concentration difference between the solvent concentration remaining in the electrode layer 40 and the solvent concentration in the atmosphere 57 in the drying furnace 50 by increasing the solvent concentration in the atmosphere 57, heat is applied to make the electrode layer 40. It is dried. Details will be described below.
電極箔３０は、集電体として用いられる。電極箔３０は、適宜の材料、例えば、アルミニウム、銅、ニッケル、鉄、ステンレス鋼を用いることができる。具体的には、例えば、正極集電体にはアルミニウムなどの電極箔３０を用い、負極集電体には銅などの電極箔３０を用いることができる。電極箔３０の具体的な厚さについて特に制限はないが、例えば、アルミニウムの場合には２０μｍ、銅の場合には１０μ程度の薄膜である。 The electrode foil 30 is used as a current collector. The electrode foil 30 can be made of an appropriate material such as aluminum, copper, nickel, iron, and stainless steel. Specifically, for example, an electrode foil 30 such as aluminum can be used for the positive electrode current collector, and an electrode foil 30 such as copper can be used for the negative electrode current collector. Although there is no restriction | limiting in particular about the specific thickness of the electrode foil 30, For example, in the case of aluminum, it is a thin film of about 20 micrometers, and in the case of copper, it is about 10 micrometers.
電極スラリー２０には、正極を形成するために用いる正極スラリーと、負極を形成するために用いる負極スラリーとがある。 The electrode slurry 20 includes a positive electrode slurry used for forming a positive electrode and a negative electrode slurry used for forming a negative electrode.
正極スラリーは、例えば、正極活物質２２、導電助剤２４、およびバインダー２３を有し、溶媒２１を添加することで、所定の粘度にされる。正極活物質２２は、例えば、マンガン酸リチウムである。導電助剤２４は、例えば、アセチレンブラックである。バインダー２３は、例えば、ＰＶＤＦ（ポリフッ化ビニリデン）である。溶媒２１は、例えば、ＮＭＰ（ノルマルメチルピロリドン）である。なお、正極活物質２２は、マンガン酸リチウムに特に限定されないが、容量および出力特性の観点から、リチウム−遷移金属複合酸化物を適用することが好ましい。導電助剤２４は、例えば、カーボンブラックやグラファイトを利用することも可能である。バインダー２３および溶媒２１は、ＰＶＤＦおよびＮＭＰに限定されない。溶媒２１として水を用いることもできる。 The positive electrode slurry has, for example, a positive electrode active material 22, a conductive auxiliary agent 24, and a binder 23, and has a predetermined viscosity by adding a solvent 21. The positive electrode active material 22 is, for example, lithium manganate. The conductive auxiliary agent 24 is, for example, acetylene black. The binder 23 is, for example, PVDF (polyvinylidene fluoride). The solvent 21 is, for example, NMP (normal methyl pyrrolidone). The positive electrode active material 22 is not particularly limited to lithium manganate, but it is preferable to apply a lithium-transition metal composite oxide from the viewpoint of capacity and output characteristics. For example, carbon black or graphite can be used as the conductive assistant 24. The binder 23 and the solvent 21 are not limited to PVDF and NMP. Water can also be used as the solvent 21.
負極スラリーは、例えば、負極活物質２２、導電助剤２４、およびバインダー２３を有し、溶媒２１を添加することで、所定の粘度にされる。負極活物質２２は、例えば、グラファイトである。導電助剤２４、バインダー２３、および溶媒２１は、例えば、アセチレンブラック、ＰＶＤＦ、およびＮＭＰである。なお、負極活物質２２は、グラファイトに特に限定されず、ハードカーボンや、リチウム−遷移金属複合酸化物を利用することも可能である。導電助剤２４は、例えば、カーボンブラックやグラファイトを利用することも可能である。バインダー２３および溶媒２１は、ＰＶＤＦおよびＮＭＰに限定されない。溶媒２１として水を用いることもできる。 The negative electrode slurry has, for example, a negative electrode active material 22, a conductive auxiliary agent 24, and a binder 23, and has a predetermined viscosity by adding the solvent 21. The negative electrode active material 22 is, for example, graphite. The conductive auxiliary agent 24, the binder 23, and the solvent 21 are, for example, acetylene black, PVDF, and NMP. The negative electrode active material 22 is not particularly limited to graphite, and hard carbon or a lithium-transition metal composite oxide can also be used. For example, carbon black or graphite can be used as the conductive assistant 24. The binder 23 and the solvent 21 are not limited to PVDF and NMP. Water can also be used as the solvent 21.
電極箔３０に正極スラリーを塗布することによって形成した正極の電極層４０および負極スラリーを塗布することによって形成した負極の電極層４０を、乾燥炉５０において乾燥し、正極および負極を形成する。このとき、電極スラリー２０に含まれる溶媒２１としてのＮＭＰは、揮発することによって電極スラリー２０から除去する。 The positive electrode layer 40 formed by applying the positive electrode slurry to the electrode foil 30 and the negative electrode layer 40 formed by applying the negative electrode slurry are dried in a drying furnace 50 to form the positive electrode and the negative electrode. At this time, NMP as the solvent 21 contained in the electrode slurry 20 is removed from the electrode slurry 20 by volatilization.
電極乾燥装置１０の乾燥炉５０は、熱風通路および電極箔３０の搬送路を形成するケーシング９０を有している。乾燥炉５０内は、複数（図示例にあっては、６個）に区画した乾燥ゾーン５１〜５６から構成されている。乾燥ゾーン５１〜５６ごとに、蒸発速度調整部材７０とヒーター部８０とを設けている。説明の便宜上、電極箔３０を搬送する方向の上流側から順に（図１において左側から順に）、第１の乾燥ゾーン５１、第２の乾燥ゾーン５２、第３の乾燥ゾーン５３、第４の乾燥ゾーン５４、第５の乾燥ゾーン５５、および第６の乾燥ゾーン５６という。ケーシング９０内に仕切り壁９１を設けることによって、第１〜第６のそれぞれの乾燥ゾーン５１〜５６を形成している。搬送部６０を配置するために、ケーシング９０の端面、および仕切り壁９１には開口部を設けている。第１〜第６の乾燥ゾーン５１〜５６のそれぞれには、搬送される電極箔３０の上方位置から熱風を供給するための上ノズル９２と、搬送される電極箔３０の下方位置から熱風を供給するための下ノズル９３と、乾燥ゾーン５１〜５６内を排気するための排気口９４とを設けている。上ノズル９２、下ノズル９３および排気口９４は、乾燥ゾーン５１〜５６内の熱風を撹拌し、熱風が通路内を均一に流れる位置に設定されている。 The drying furnace 50 of the electrode drying apparatus 10 includes a casing 90 that forms a hot air passage and a conveyance path for the electrode foil 30. The inside of the drying furnace 50 is composed of drying zones 51 to 56 divided into a plurality (six in the illustrated example). An evaporation rate adjusting member 70 and a heater unit 80 are provided for each of the drying zones 51 to 56. For convenience of explanation, the first drying zone 51, the second drying zone 52, the third drying zone 53, and the fourth drying are sequentially performed from the upstream side in the direction in which the electrode foil 30 is conveyed (in order from the left side in FIG. 1). These are referred to as zone 54, fifth drying zone 55, and sixth drying zone 56. By providing the partition wall 91 in the casing 90, the first to sixth drying zones 51 to 56 are formed. In order to arrange the transport unit 60, an opening is provided in the end surface of the casing 90 and the partition wall 91. In each of the first to sixth drying zones 51 to 56, hot air is supplied from an upper nozzle 92 for supplying hot air from an upper position of the conveyed electrode foil 30, and from a lower position of the conveyed electrode foil 30. A lower nozzle 93 for exhausting air and an exhaust port 94 for exhausting the inside of the drying zones 51 to 56 are provided. The upper nozzle 92, the lower nozzle 93, and the exhaust port 94 are set to positions where the hot air in the drying zones 51 to 56 is stirred and the hot air flows uniformly in the passage.
図示例の蒸発速度調整部材７０は、乾燥炉５０から排出された排気を雰囲気５７内に供給するための配管系１００を備えている。乾燥炉５０から排出された排気を再利用することによって、雰囲気５７における溶媒濃度を高めている。蒸発速度調整部材７０はまた、排気の温度を結露温度まで下げることなく雰囲気５７内に供給する。排気を再利用するため、低コストで量産を実現することもできる。 The illustrated evaporation rate adjusting member 70 includes a piping system 100 for supplying exhaust discharged from the drying furnace 50 into the atmosphere 57. By reusing the exhaust discharged from the drying furnace 50, the solvent concentration in the atmosphere 57 is increased. The evaporation rate adjusting member 70 also supplies the atmosphere 57 without reducing the temperature of the exhaust gas to the dew condensation temperature. Since the exhaust gas is reused, mass production can be realized at low cost.
配管系１００には、各排気口９４と溶媒回収装置１１０とを接続する第１配管１０１、溶媒回収装置１１０の出口と乾燥ゾーン５１〜５６ごとに設けられた熱交換器１２０の入口とを接続する第２配管１０２と、熱交換器１０５の出口と上下のノズル９２、９３とを接続する第３配管１０３と、溶媒回収装置１１０をバイパスして排気を流下させるバイパス管１０４とを含んでいる。溶媒回収装置１１０は、溶媒回収器１１１と送風ファン１１２とを有し、過剰なＮＭＰを液体にして回収するとともに、回収した溶媒２１の一部を雰囲気５７内に供給する空気（給気）に再び混合する。バイパス管１０４には、熱媒体（例えば、蒸気や蒸気還流水）との間で熱交換を行って空気を加熱する熱交換器１０５と、バイパスさせる排気量を調整するためのバルブ１０６が設けられている。第１配管１０１には、溶媒回収装置１１０の入口側の排気温度を測定する温度センサー１０７を設け、第２配管１０２には、溶媒回収装置１１０の出口側の給気温度を測定する温度センサー１０８を設けている。出口側の温度センサー１０８は、バイパス管１０４が第２配管１０２に合流した後の位置において、給気温度を測定する。第２配管１０２には、給気の溶媒濃度を測定する濃度センサー１０９を設けている。溶媒回収装置１１０は、給気の溶媒濃度を定められた濃度とするように、給気に再び混合させる溶媒量を制御する。 The piping system 100 is connected to the first piping 101 connecting each exhaust port 94 and the solvent recovery device 110, the outlet of the solvent recovery device 110, and the inlet of the heat exchanger 120 provided for each of the drying zones 51 to 56. A second pipe 102 that connects the outlet of the heat exchanger 105 and the upper and lower nozzles 92 and 93, and a bypass pipe 104 that bypasses the solvent recovery device 110 and flows down the exhaust gas. . The solvent recovery device 110 includes a solvent recovery device 111 and a blower fan 112, recovers excess NMP as a liquid, and supplies air (supply air) that supplies a part of the recovered solvent 21 to the atmosphere 57. Mix again. The bypass pipe 104 is provided with a heat exchanger 105 that heats air by exchanging heat with a heat medium (for example, steam or steam reflux water), and a valve 106 for adjusting the amount of exhaust to be bypassed. ing. The first pipe 101 is provided with a temperature sensor 107 that measures the exhaust temperature on the inlet side of the solvent recovery device 110, and the temperature sensor 108 that measures the supply air temperature on the outlet side of the solvent recovery device 110 is provided in the second pipe 102. Is provided. The outlet-side temperature sensor 108 measures the supply air temperature at a position after the bypass pipe 104 joins the second pipe 102. The second pipe 102 is provided with a concentration sensor 109 that measures the solvent concentration of the supply air. The solvent recovery device 110 controls the amount of solvent mixed with the supply air so that the solvent concentration of the supply air becomes a predetermined concentration.
排気の温度を結露温度まで下げることなく雰囲気５７内に供給するために、測定した給気温度に基づいて、バイパス管１０４を流下させる排気風量を制御する。溶媒回収装置１１０をバイパスして流下する排気は、溶媒回収装置１１０を通過した空気に比べて高温であることから、給気温度を高めて給気温度を一定に保つことができる。バイパス管１０４に設けた熱交換器１０５によってバイパス管１０４を流下する排気を加温することによって、給気温度がさらに低下した場合においても給気温度を一定に保つことができる。排気の温度を結露温度まで下げることなく雰囲気５７内に供給することによって、配管系１００における結露を防止するための特段の対策、例えば断熱材の配置などが不要となる。これにともなって、設備費の低減に寄与することができる。 In order to supply the exhaust gas to the atmosphere 57 without lowering the exhaust temperature to the dew condensation temperature, the amount of exhaust air flowing through the bypass pipe 104 is controlled based on the measured supply air temperature. Since the exhaust gas that flows down by bypassing the solvent recovery device 110 has a higher temperature than the air that has passed through the solvent recovery device 110, the supply air temperature can be increased to keep the supply air temperature constant. By heating the exhaust gas flowing down the bypass pipe 104 by the heat exchanger 105 provided in the bypass pipe 104, the supply air temperature can be kept constant even when the supply air temperature further decreases. By supplying the temperature of the exhaust gas into the atmosphere 57 without lowering it to the dew condensation temperature, special measures for preventing dew condensation in the piping system 100, for example, the arrangement of a heat insulating material, etc. are not required. In connection with this, it can contribute to reduction of an installation cost.
第１〜第３の配管１０１〜１０３には、ダンパー類を設けていない。結露を防止するためである。 The first to third pipes 101 to 103 are not provided with dampers. This is to prevent condensation.
乾燥ゾーン５１〜５６ごとに設けられた熱交換器１２０は、熱媒体（例えば、蒸気や蒸気還流水）との間で熱交換を行って空気を加熱する。乾燥ゾーン５１〜５６ごとに雰囲気５７の温度を測定する温度センサー１２１を設けている。各熱交換器１２０によって給気を加温することによって、上下のノズル９２、９３から噴出す熱風温度を制御して、各乾燥ゾーン５１〜５６の温度を設定した温度に保つことができる。熱風の温度は、環境温度や電極スラリー２０の種類などによって種々異なることから特に限定されないが、例えば１００±４０℃である。 The heat exchanger 120 provided for each of the drying zones 51 to 56 heats the air by exchanging heat with a heat medium (for example, steam or steam reflux water). A temperature sensor 121 that measures the temperature of the atmosphere 57 is provided for each of the drying zones 51 to 56. By heating the supply air by each heat exchanger 120, the temperature of hot air ejected from the upper and lower nozzles 92, 93 can be controlled, and the temperature of each drying zone 51-56 can be maintained at a set temperature. The temperature of the hot air is not particularly limited because it varies depending on the environmental temperature, the type of the electrode slurry 20, and the like, but is 100 ± 40 ° C., for example.
乾燥時において、各乾燥ゾーン５１〜５６の雰囲気５７中には、再利用する排気に含まれている溶媒２１と、電極層４０から揮発した溶媒２１とが含まれる。乾燥時の雰囲気５７の溶媒濃度は適宜設定可能であるが、強密着性の電極層４０を得るためには、例えば、１０００ＰＰＭ以下となるように制御することが好ましい。 At the time of drying, the atmosphere 57 in each of the drying zones 51 to 56 includes the solvent 21 contained in the exhaust gas to be reused and the solvent 21 volatilized from the electrode layer 40. The solvent concentration of the atmosphere 57 at the time of drying can be set as appropriate. However, in order to obtain the strongly adherent electrode layer 40, for example, it is preferable to control it to be 1000 PPM or less.
電極層４０は、残留ＮＭＰが２００ｐｐｍ以下となるまで乾燥される。熱源に蒸気を使用するのは容易に入手可能な熱源であるからであるのと、溶媒２１にＮＭＰ（融点−２４℃、沸点２０４℃）を使用していることから、比較的低温度１００℃前後での連続乾燥が可能となるからである。 The electrode layer 40 is dried until the residual NMP becomes 200 ppm or less. The reason why steam is used as the heat source is that it is an easily available heat source, and NMP (melting point −24 ° C., boiling point 204 ° C.) is used as the solvent 21, so that a relatively low temperature of 100 ° C. This is because continuous drying before and after is possible.
蒸発速度調整部材７０は、配管系１００、および溶媒回収装置１１０などによって構成されている。ヒーター部８０は、配管系１００、溶媒回収装置１１０、熱交換器１０５、１２０、および熱交換器１０５、１２０に供給する熱媒体の温度や流量を調整するための図示しない部材などによって構成されている。 The evaporation rate adjusting member 70 includes a piping system 100, a solvent recovery device 110, and the like. The heater unit 80 includes a piping system 100, a solvent recovery device 110, heat exchangers 105 and 120, and a member (not shown) for adjusting the temperature and flow rate of the heat medium supplied to the heat exchangers 105 and 120. Yes.
搬送部６０は、電極スラリー２０を塗布する前の電極箔３０を供給する供給ロール６１と、電極層４０を乾燥させた後の電極箔３０を巻き取る巻取りロール６２と、供給ロール６１と巻取りロール６２との間に配置され電極箔３０の下面を保持する複数のサポートロール６３と、を有している。供給ロール６１には、電極箔３０を予め巻回してある。巻取りロール６２には、巻取りロール６２を回転駆動するモータＭを接続してある。モータＭを駆動して巻取りロール６２を回転駆動すると、電極箔３０は、供給ロール６１から繰り出され、乾燥炉５０内を搬送され、巻取りロール６２に巻き取られる。このようにして、搬送部６０は、長尺状の電極箔３０をロール・トゥ・ロール方式によって連続的に搬送する。 The transport unit 60 includes a supply roll 61 that supplies the electrode foil 30 before the electrode slurry 20 is applied, a winding roll 62 that winds up the electrode foil 30 after the electrode layer 40 is dried, a supply roll 61 and a winding roll. A plurality of support rolls 63 that are arranged between the take-up roll 62 and hold the lower surface of the electrode foil 30. The electrode foil 30 is wound around the supply roll 61 in advance. A motor M that rotationally drives the winding roll 62 is connected to the winding roll 62. When the motor M is driven and the take-up roll 62 is rotationally driven, the electrode foil 30 is unwound from the supply roll 61, conveyed in the drying furnace 50, and taken up by the take-up roll 62. Thus, the conveyance part 60 conveys the elongate electrode foil 30 continuously by a roll-to-roll system.
電極スラリー２０の塗布は、電極箔３０を搬送しつつ、塗布部９５によって行う。塗布部９５は、溶媒２１を含むスラリー状の電極スラリー２０を電極箔３０に塗布するコーター９６を有している。コーター９６は、電極箔３０に対向し、電極箔３０を搬送しながら間欠的に電極スラリー２０を塗布する。これにより、電極スラリー２０は、一定の間隔の隙間を空けて間欠的に配列する。コーター９６を使っての間欠塗工方式では、ロール・トゥ・ロール方式で供給される集電箔に、粘度１０，０００〜３００，０００ｃｐｓ程度（固形分６３．４±１０％）としたスラリーを、コーター９６塗工部分で片面（Ｗｅｔ膜厚１３０±１０μｍ、Ｄｒｙ膜厚８７±１０μｍ）程度の均一塗工を行い連続生産する方法が一般的である。 Application | coating of the electrode slurry 20 is performed by the application part 95, conveying the electrode foil 30. FIG. The application unit 95 includes a coater 96 that applies the slurry-like electrode slurry 20 containing the solvent 21 to the electrode foil 30. The coater 96 faces the electrode foil 30 and intermittently applies the electrode slurry 20 while conveying the electrode foil 30. Thereby, the electrode slurry 20 is intermittently arranged with a gap of a constant interval. In the intermittent coating method using the coater 96, a slurry having a viscosity of about 10,000 to 300,000 cps (solid content: 63.4 ± 10%) is applied to the current collector foil supplied by the roll-to-roll method. In general, the coater 96 is coated with a uniform coating on one side (Wet film thickness 130 ± 10 μm, Dry film thickness 87 ± 10 μm) for continuous production.
電極乾燥装置１０は、溶媒回収装置１１０、バイパス管１０４のバルブ１０６、ヒーター部８０、モータＭ、および塗布部９５の作動を制御するコントローラー１３０を有している。コントローラー１３０は、ＣＰＵおよびメモリを主体として構成され、動作を制御するためのプログラムがメモリに記憶されている。コントローラー１３０は、塗布部９５の作動を制御して、電極スラリー２０の塗布量、塗布厚さなどを調整し、ヒーター部８０の作動を制御して、給気の温度、風量などを調整する。コントローラー１３０はまた、モータＭの作動を制御して、電極箔３０の搬送速度を調整する。 The electrode drying apparatus 10 includes a controller 130 that controls the operation of the solvent recovery apparatus 110, the valve 106 of the bypass pipe 104, the heater unit 80, the motor M, and the coating unit 95. The controller 130 is mainly composed of a CPU and a memory, and a program for controlling the operation is stored in the memory. The controller 130 controls the operation of the application unit 95 to adjust the application amount and application thickness of the electrode slurry 20, and controls the operation of the heater unit 80 to adjust the temperature of the supply air, the air volume, and the like. The controller 130 also controls the operation of the motor M to adjust the conveyance speed of the electrode foil 30.
本実施形態の作用を説明する前に、乾燥炉５０に供給する給気の温度や風量を大きく変化させたときに生じる不具合について説明する。 Before describing the operation of the present embodiment, a problem that occurs when the temperature or air volume of the supply air supplied to the drying furnace 50 is greatly changed will be described.
乾燥工程において変化する品質指標の一つとして、電極層４０と電極箔３０との間の密着性がある。一般的に、乾燥工程においては、下記の式（１）（２）（３）にしたがって、溶媒２１であるＮＭＰを緩やかに揮発させて電極層４０を緩やかに乾燥させることによって、密着性が向上することが知られている。 One of the quality indexes that change in the drying process is the adhesion between the electrode layer 40 and the electrode foil 30. In general, in the drying step, adhesion is improved by gently evaporating NMP as the solvent 21 and gently drying the electrode layer 40 according to the following formulas (1), (2), and (3). It is known to do.
図３は、乾燥炉５０に供給する給気の温度や風量を大きく変化させたときに生じる不具合を示す図である。 FIG. 3 is a diagram illustrating a problem that occurs when the temperature or air volume of the supply air supplied to the drying furnace 50 is changed greatly.
熱風を用いた乾燥炉５０において乾燥速度の向上を図る場合には、熱風温度を高くするとともに風量を増加し、電極層４０の表面と雰囲気５７との界面部分における溶媒２１（ＮＭＰ）の除去量を増加させている。このような対応の場合、乾燥が早くなって、電極層４０の表面近傍にバインダー２３（ＰＶＤＦ）が偏析してしまう。このため、電極箔３０に強く密着した塗膜つまり強密着の電極層４０を得ることができなくなる。 When the drying rate is improved in the drying furnace 50 using hot air, the hot air temperature is increased and the air volume is increased, and the amount of solvent 21 (NMP) removed at the interface portion between the surface of the electrode layer 40 and the atmosphere 57 is increased. Is increasing. In such a case, drying is accelerated and the binder 23 (PVDF) is segregated near the surface of the electrode layer 40. For this reason, it becomes impossible to obtain a coating film strongly adhered to the electrode foil 30, that is, a strongly adhered electrode layer 40.
熱風温度を高くした場合にバインダー２３の偏析が生じる原因として、次のようなものを挙げることができる。すなわち、乾燥時においてはバインダー２３を溶媒２１に溶かしたものが電極層４０に含まれているので、電極層４０を高い温度の環境下にさらすと、電極層４０内において溶媒２１自体が対流を起こす。その結果、溶解しているバインダー２３が偏析してしまう。 The following can be cited as causes of segregation of the binder 23 when the hot air temperature is increased. That is, since the electrode layer 40 contains the binder 23 dissolved in the solvent 21 at the time of drying, the solvent 21 itself convects in the electrode layer 40 when the electrode layer 40 is exposed to a high temperature environment. Wake up. As a result, the dissolved binder 23 is segregated.
また、風量を増加した場合にバインダー２３の偏析が生じる原因として、次のようなものを挙げることができる。すなわち、電極層４０の表面近傍における溶媒２１（ＮＭＰ）だけが優先的に揮発して表面近傍だけが先に乾き（表面先乾き）、この表面先乾き部分に生じた亀裂やホールなどによる毛細管現象によって、ＮＭＰを深部から表面に向けて吸い上げる。その結果、溶解しているバインダー２３が偏析してしまう。 Moreover, the following can be mentioned as a cause of the segregation of the binder 23 when the air volume is increased. That is, only the solvent 21 (NMP) in the vicinity of the surface of the electrode layer 40 is preferentially volatilized and only the vicinity of the surface is dried first (surface pre-drying), and the capillary phenomenon due to cracks or holes generated in the surface pre-drying portion. The NMP is sucked from the depth toward the surface. As a result, the dissolved binder 23 is segregated.
乾燥時にバインダー２３の偏析を生じ得る乾燥条件では、表面粗さが大きく、密着力も弱いことから、電極箔３０と電極層４０との接触量あるいは接触面積が少なくなる。このため、初期における電池内の抵抗値のみならず、充放電を繰り返した後の電池内の抵抗値も高くなり、電極性能の低下を招くことになる。 Under drying conditions that can cause segregation of the binder 23 at the time of drying, the surface roughness is large and the adhesion is weak, so the contact amount or contact area between the electrode foil 30 and the electrode layer 40 is reduced. For this reason, not only the resistance value in the battery in the initial stage, but also the resistance value in the battery after repeated charge / discharge increases, leading to a decrease in electrode performance.
発生したバインダー２３の偏析を解消するために、乾燥後の電極をロールプレス機などによって圧縮する方法がある。しかしながら、乾燥が完了して電極層４０が固着した後に強制的に構造変化させることになるため、電極層４０の密着強度はさほど向上しない。しかも、低コストで量産を実現する観点から、乾燥工程の後に圧縮工程を付加することは避けることが望ましい。 In order to eliminate the segregation of the generated binder 23, there is a method in which the dried electrode is compressed by a roll press or the like. However, since the structure is forcibly changed after the drying is completed and the electrode layer 40 is fixed, the adhesion strength of the electrode layer 40 is not improved so much. Moreover, it is desirable to avoid adding a compression step after the drying step from the viewpoint of realizing mass production at a low cost.
次に、本実施形態の作用を説明する。 Next, the operation of this embodiment will be described.
モータＭを駆動して巻取りロール６２を回転駆動し、電極箔３０を、供給ロール６１から繰り出し、巻取りロール６２に巻き取る。コーター９６は、移動している電極箔３０の表面に間欠的に電極スラリー２０を塗布する。コントローラー１３０は、塗布部９５の作動を制御し、電極スラリー２０の塗布量、塗布厚さなどを調整している。ヒーター部８０は、熱風を、上下のノズル９２、９３から熱風通路内に供給する。電極箔３０の表面に溶媒２１を含む電極スラリー２０を塗布した後、乾燥炉５０内において、電極層４０に含まれる溶媒２１を揮発させる。電極箔３０を搬送しつつ、電極スラリー２０の塗布と、塗布した電極層４０の乾燥とを継続する。 The motor M is driven to rotationally drive the take-up roll 62, and the electrode foil 30 is unwound from the supply roll 61 and taken up on the take-up roll 62. The coater 96 intermittently applies the electrode slurry 20 to the surface of the moving electrode foil 30. The controller 130 controls the operation of the coating unit 95 and adjusts the coating amount and coating thickness of the electrode slurry 20. The heater unit 80 supplies hot air from the upper and lower nozzles 92 and 93 into the hot air passage. After applying the electrode slurry 20 containing the solvent 21 to the surface of the electrode foil 30, the solvent 21 contained in the electrode layer 40 is volatilized in the drying furnace 50. While conveying the electrode foil 30, the application of the electrode slurry 20 and the drying of the applied electrode layer 40 are continued.
電極層４０を乾燥炉５０の中において乾燥させるときには、蒸発速度調整部材７０は、配管系１００を介して、乾燥炉５０から排出された排気を雰囲気５７内に供給する。これにより、電極層４０内に残存する溶媒濃度と乾燥炉５０内の雰囲気５７における溶媒濃度との濃度差は、雰囲気５７における溶媒濃度が高められることによって小さくなる。さらに、ヒーター部８０は、電極層４０を乾燥させる熱を付与している。 When the electrode layer 40 is dried in the drying furnace 50, the evaporation rate adjusting member 70 supplies exhaust gas discharged from the drying furnace 50 into the atmosphere 57 via the piping system 100. As a result, the concentration difference between the solvent concentration remaining in the electrode layer 40 and the solvent concentration in the atmosphere 57 in the drying furnace 50 is reduced by increasing the solvent concentration in the atmosphere 57. Further, the heater unit 80 applies heat that dries the electrode layer 40.
このように雰囲気５７における溶媒濃度を高めつつ乾燥させると、乾燥速度の向上を図るために熱風温度を高くするとともに風量を増加しても、溶媒２１であるＮＭＰを緩やかに揮発させて電極層４０を緩やかに乾燥させることができる。電極層４０を緩やかに乾燥させるのではあるが、熱風温度を高くできるとともに風量を増加することができるので、全体として乾燥時間を短縮することができ、生産性を高めることができる。乾燥時間の短縮を図ることができることから、乾燥炉５０の長さを短くすることもできる。もって、電極の乾燥に要する投資を削減することが可能となる。 When drying is performed while increasing the solvent concentration in the atmosphere 57 as described above, even if the hot air temperature is increased and the air volume is increased in order to improve the drying speed, the NMP which is the solvent 21 is gradually volatilized and the electrode layer 40 is evaporated. Can be gently dried. Although the electrode layer 40 is gently dried, since the hot air temperature can be increased and the air volume can be increased, the drying time can be shortened as a whole, and the productivity can be increased. Since the drying time can be shortened, the length of the drying furnace 50 can be shortened. Therefore, the investment required for drying the electrode can be reduced.
雰囲気５７における溶媒濃度は、電極層４０内に残存する溶媒濃度を越えない濃度に高める必要がある。電極層４０の乾燥が進行しない状態を回避するためである。 The solvent concentration in the atmosphere 57 needs to be increased to a concentration not exceeding the solvent concentration remaining in the electrode layer 40. This is to avoid a state where the drying of the electrode layer 40 does not proceed.
図２に示したように、電極層４０を緩やかに乾燥させるので、バインダー２３の偏析が生じることを防止することができる。バインダー２３の偏析を生じさせない条件にて電極層４０を乾燥させているので、電極箔３０と電極層４０との密着性が向上し、電極箔３０と電極層４０との接触量あるいは接触面積が十分大きくなる。このため、初期における電池内の抵抗値はもちろんのこと、充放電を繰り返した後の電池内の抵抗値も低くなり、電極性能の向上を図ることが可能となる。 As shown in FIG. 2, since the electrode layer 40 is gently dried, segregation of the binder 23 can be prevented. Since the electrode layer 40 is dried under conditions that do not cause segregation of the binder 23, the adhesion between the electrode foil 30 and the electrode layer 40 is improved, and the contact amount or contact area between the electrode foil 30 and the electrode layer 40 is increased. Become big enough. For this reason, not only the resistance value in the battery in the initial stage, but also the resistance value in the battery after repeated charging and discharging is reduced, and the electrode performance can be improved.
第１〜第６の乾燥ゾーン５１〜５６ごとに、蒸発速度調整部材７０とヒーター部８０とを設けている。このため、第１〜第６の乾燥ゾーン５１〜５６ごとに、雰囲気５７における溶媒濃度を高めることによって濃度差を小さくしつつ、熱を付与して電極層４０を乾燥させることができる。複数の乾燥ゾーン５１〜５６に区画した場合にも、乾燥ゾーン５１〜５６ごとにバインダー２３の偏析が生じることを防止することができ、電極性能の向上を図った電極を製造することができる。 An evaporation rate adjusting member 70 and a heater unit 80 are provided for each of the first to sixth drying zones 51 to 56. Therefore, for each of the first to sixth drying zones 51 to 56, the electrode layer 40 can be dried by applying heat while reducing the concentration difference by increasing the solvent concentration in the atmosphere 57. Even when partitioned into a plurality of drying zones 51 to 56, segregation of the binder 23 can be prevented in each of the drying zones 51 to 56, and an electrode with improved electrode performance can be manufactured.
バインダー２３の偏析が生じないので、乾燥後の電極をロールプレス機などによって圧縮する必要がない。乾燥工程の後に圧縮工程を付加しなくてよいので、低コストで量産を実現することもできる。 Since the segregation of the binder 23 does not occur, there is no need to compress the dried electrode with a roll press or the like. Since it is not necessary to add a compression step after the drying step, mass production can be realized at low cost.
図４は、雰囲気５７における溶媒濃度を高めながら電極層４０を乾燥する実施形態と、雰囲気５７における溶媒濃度を高めることなく電極層４０を乾燥する対比例とのそれぞれにおける、炉内ＮＭＰ蒸気濃度の変化を示すグラフである。横軸は乾燥炉通過時間（秒）を示し、縦軸は炉内ＮＭＰ蒸気濃度を示している。なお、本実施形態の値は、雰囲気５７における溶媒濃度を高めた分を減算したものである。図において、実施形態は実線にて、対比例は破線にて示される。 FIG. 4 shows the in-furnace NMP vapor concentration in each of the embodiment in which the electrode layer 40 is dried while increasing the solvent concentration in the atmosphere 57 and the proportionality in which the electrode layer 40 is dried without increasing the solvent concentration in the atmosphere 57. It is a graph which shows a change. The horizontal axis represents the drying furnace passage time (second), and the vertical axis represents the in-furnace NMP vapor concentration. Note that the value of this embodiment is obtained by subtracting the amount by which the solvent concentration in the atmosphere 57 is increased. In the figure, the embodiment is indicated by a solid line, and the proportionality is indicated by a broken line.
第１の乾燥ゾーン５１は、予熱ゾーンであり、電極層４０から溶媒２１は揮発していない。 The first drying zone 51 is a preheating zone, and the solvent 21 is not volatilized from the electrode layer 40.
対比例においては、第２の乾燥ゾーン５２では、溶媒２１の揮発が急激に始まって、炉内ＮＭＰ蒸気濃度が急激に高くなる。第３、第４の乾燥ゾーン５３、５４では、炉内ＮＭＰ蒸気濃度の変動が大きい。そして、第５の乾燥ゾーン５５の出口部分では、電極層４０の乾燥がほぼ完了し、炉内ＮＭＰ蒸気濃度がゼロとなる。 In contrast, in the second drying zone 52, the volatilization of the solvent 21 starts abruptly and the in-furnace NMP vapor concentration increases rapidly. In the third and fourth drying zones 53 and 54, the variation of the in-furnace NMP vapor concentration is large. Then, at the outlet portion of the fifth drying zone 55, the drying of the electrode layer 40 is almost completed, and the in-furnace NMP vapor concentration becomes zero.
実施形態においては、第２の乾燥ゾーン５２では、炉内ＮＭＰ蒸気濃度の変化は対比例に比べて緩やかであり、電極層４０の乾燥が緩やかに始まっていることがわかる。第３〜第５の乾燥ゾーン５３〜５５では、炉内ＮＭＰ蒸気濃度の変動が比較的小さく、溶媒濃度範囲Δｃの範囲内に収まっている。炉内ＮＭＰ蒸気濃度の変動が対比例に比べて均一であり、電極層４０の乾燥が緩やかに進行していることがわかる。そして、第６の乾燥ゾーン５６の出口部分では、電極層４０の乾燥がほぼ完了し、炉内ＮＭＰ蒸気濃度がゼロとなる。 In the embodiment, in the second drying zone 52, it can be seen that the change in the in-furnace NMP vapor concentration is gradual compared with the proportionality, and the drying of the electrode layer 40 starts gradually. In the third to fifth drying zones 53 to 55, the fluctuation of the in-furnace NMP vapor concentration is relatively small and falls within the solvent concentration range Δc. It can be seen that the variation of the NMP vapor concentration in the furnace is more uniform than the proportionality, and the drying of the electrode layer 40 is proceeding slowly. And in the exit part of the 6th drying zone 56, drying of the electrode layer 40 is substantially completed and the NMP vapor | steam density | concentration in a furnace will be zero.
対比例における電極層４０の密着力は製品としてＮＧのレベルであったが、実施形態における電極層４０の密着力は製品としてＯＫのレベルを満足した。 The adhesion strength of the electrode layer 40 in the comparative example was NG as a product, but the adhesion strength of the electrode layer 40 in the embodiment satisfied the OK level as a product.
対比例の乾燥条件では、雰囲気５７における溶媒濃度を高めていないため、電極層４０内に残存する溶媒濃度と乾燥炉５０内の雰囲気５７における溶媒濃度との濃度差が大きく、第５の乾燥ゾーン５５の出口部分で電極層４０の乾燥がほぼ完了するほど、乾燥速度が速くなっている。しかしながら、電極層４０の密着力は製品としての要求を満足することができなかった。 Since the solvent concentration in the atmosphere 57 is not increased under the proportional drying conditions, the concentration difference between the solvent concentration remaining in the electrode layer 40 and the solvent concentration in the atmosphere 57 in the drying furnace 50 is large, and the fifth drying zone. The drying speed increases as the drying of the electrode layer 40 is almost completed at the outlet portion 55. However, the adhesive strength of the electrode layer 40 could not satisfy the demand as a product.
一方、実施形態の乾燥条件では、雰囲気５７における溶媒濃度を高めているため、電極層４０内に残存する溶媒濃度と乾燥炉５０内の雰囲気５７における溶媒濃度との濃度差が小さく、緩やかに電極層４０を乾燥させている。対比例に比べると乾燥速度は緩やかではあるが、熱風温度を高くできるとともに風量を増加することができるので、全体として乾燥時間を短縮することができる。しかも、電極層４０の密着力は製品としての要求を十分に満足することができた。 On the other hand, under the drying conditions of the embodiment, since the solvent concentration in the atmosphere 57 is increased, the difference in concentration between the solvent concentration remaining in the electrode layer 40 and the solvent concentration in the atmosphere 57 in the drying furnace 50 is small, and the electrode gradually increases. Layer 40 is dried. Although the drying speed is moderate as compared with the proportionality, the hot air temperature can be increased and the air volume can be increased, so that the drying time can be shortened as a whole. In addition, the adhesion of the electrode layer 40 was able to fully satisfy the product requirements.
以上説明したように、本実施形態によれば、電極乾燥装置１０に蒸発速度調整部材７０とヒーター部８０とを設け、電極層４０内に残存する溶媒濃度と乾燥炉５０内の雰囲気５７における溶媒濃度との濃度差を、雰囲気５７における溶媒濃度を高めることによって小さくしつつ、熱を付与して電極層４０を乾燥させている。このため、電極層４０を緩やかに乾燥させるので、バインダー２３の偏析が生じることを防止することができる。バインダー２３の偏析を生じさせない条件にて電極層４０を乾燥させているので、電極箔３０と電極層４０との密着性が向上し、初期における電池内の抵抗値はもちろんのこと、充放電を繰り返した後の電池内の抵抗値も低くなり、電極性能の向上を図ることが可能となる。電極層４０を緩やかに乾燥させているが、炉内温度等を高く設定できるので、スラリー状態の電極層４０に含まれる溶媒２１を効率よく揮発させて、全体として乾燥時間を短縮することができる。 As described above, according to the present embodiment, the electrode drying apparatus 10 is provided with the evaporation rate adjusting member 70 and the heater unit 80, the solvent concentration remaining in the electrode layer 40 and the solvent in the atmosphere 57 in the drying furnace 50. The electrode layer 40 is dried by applying heat while reducing the concentration difference from the concentration by increasing the solvent concentration in the atmosphere 57. For this reason, since the electrode layer 40 is gently dried, segregation of the binder 23 can be prevented. Since the electrode layer 40 is dried under conditions that do not cause segregation of the binder 23, the adhesion between the electrode foil 30 and the electrode layer 40 is improved, and charge / discharge is performed as well as the resistance value in the battery in the initial stage. The resistance value in the battery after the repetition is reduced, and the electrode performance can be improved. Although the electrode layer 40 is gently dried, since the furnace temperature and the like can be set high, the solvent 21 contained in the electrode layer 40 in a slurry state can be efficiently volatilized and the drying time can be shortened as a whole. .
乾燥炉５０内を複数の乾燥ゾーン５１〜５６に区画し、乾燥ゾーン５１〜５６ごとに、蒸発速度調整部材７０とヒーター部８０とを設け、乾燥ゾーン５１〜５６ごとに、雰囲気５７における溶媒濃度を高めることによって濃度差を小さくしつつ、熱を付与して電極層４０を乾燥させている。このため、複数の乾燥ゾーン５１〜５６に区画した場合にも、乾燥ゾーン５１〜５６ごとにバインダー２３の偏析が生じることを防止することができ、電極性能の向上を図った電極を製造することができる。 The inside of the drying furnace 50 is divided into a plurality of drying zones 51 to 56, the evaporation rate adjusting member 70 and the heater unit 80 are provided for each of the drying zones 51 to 56, and the solvent concentration in the atmosphere 57 is set for each of the drying zones 51 to 56. The electrode layer 40 is dried by applying heat while reducing the difference in concentration by increasing. For this reason, even when partitioned into a plurality of drying zones 51 to 56, it is possible to prevent the segregation of the binder 23 from occurring in each of the drying zones 51 to 56, and to manufacture an electrode with improved electrode performance. Can do.
雰囲気５７における溶媒濃度を、電極層４０内に残存する溶媒濃度を越えない濃度に高めているので、電極層４０の乾燥が進行しない状態を回避することができる。 Since the solvent concentration in the atmosphere 57 is increased to a concentration that does not exceed the solvent concentration remaining in the electrode layer 40, it is possible to avoid a state in which the drying of the electrode layer 40 does not proceed.
蒸発速度調整部材７０は、乾燥炉５０から排出された排気を雰囲気５７内に供給するための配管系１００を備え、雰囲気５７における溶媒濃度を、乾燥炉５０から排出された排気を再利用して高めている。排気を再利用するため、低コストで量産を実現することもできる。 The evaporation rate adjusting member 70 includes a piping system 100 for supplying the exhaust discharged from the drying furnace 50 into the atmosphere 57, and the solvent concentration in the atmosphere 57 is reused by reusing the exhaust discharged from the drying furnace 50. It is increasing. Since the exhaust gas is reused, mass production can be realized at low cost.
蒸発速度調整部材７０は、排気の温度を結露温度まで下げることなく雰囲気５７内に供給している。このため、配管系１００における結露を防止するための特段の対策、例えば断熱材の配置などを講じる必要がなく、設備費の低減を図ることができる。 The evaporation rate adjusting member 70 supplies the atmosphere 57 without reducing the temperature of the exhaust gas to the condensation temperature. For this reason, it is not necessary to take special measures for preventing dew condensation in the piping system 100, for example, the arrangement of a heat insulating material, and the equipment cost can be reduced.
（改変例）
乾燥炉５０内を複数の乾燥ゾーン５１〜５６に区画した実施形態を示したが、乾燥ゾーンが一つだけの乾燥炉にも本発明を適用することはできる。各乾燥ゾーン５１〜５６の雰囲気５７に同じ溶媒濃度の給気を供給する実施形態を示したが、各乾燥ゾーン５１〜５６の雰囲気５７に異なる溶媒濃度の給気を供給するようにしてもよい。
(Modification example)
Although the embodiment in which the inside of the drying furnace 50 is partitioned into a plurality of drying zones 51 to 56 is shown, the present invention can be applied to a drying furnace having only one drying zone. Although the embodiment has been described in which supply air having the same solvent concentration is supplied to the atmosphere 57 of each drying zone 51 to 56, supply air having a different solvent concentration may be supplied to the atmosphere 57 of each drying zone 51 to 56. .
雰囲気５７における溶媒濃度を、乾燥炉５０から排出された排気を再利用して高める実施形態を示したが、本発明は、この場合に限定されるものではない。例えば、ＮＭＰなどの溶媒２１を噴霧することによって、雰囲気５７における溶媒濃度を高めるようにしても良い。 Although the embodiment has been described in which the solvent concentration in the atmosphere 57 is increased by reusing the exhaust discharged from the drying furnace 50, the present invention is not limited to this case. For example, the solvent concentration in the atmosphere 57 may be increased by spraying the solvent 21 such as NMP.
また、溶媒用のキャリアガスとして、窒素等の不活性ガスを用いても良い。 Further, an inert gas such as nitrogen may be used as the carrier gas for the solvent.
ヒーター部８０の熱源として熱風を用いた実施形態を示したが、赤外線ヒーターを用いてもよい。また、熱源としての熱風や赤外線ヒーターを組み合わせて用いてもよい。 Although the embodiment using hot air as the heat source of the heater unit 80 has been shown, an infrared heater may be used. Further, hot air or an infrared heater as a heat source may be used in combination.
電極箔３０を連続して搬送する形態を図示したが、バッチ式で搬送する形態でもよい。 Although the form which conveys the electrode foil 30 continuously was illustrated, the form conveyed by a batch type may be sufficient.
さらに、本発明は、電極スラリー２０を間欠的に塗布する場合に限られるものではなく、電極スラリー２０を連続塗布する場合にも適用できることは言うまでもない。 Further, the present invention is not limited to the case where the electrode slurry 20 is intermittently applied, and it goes without saying that the present invention can also be applied to the case where the electrode slurry 20 is continuously applied.
１０ 電極乾燥装置、
２０ 電極スラリー、
２１ 溶媒、
２２ 活物質、
２３ バインダー、
２４ 導電助剤、
３０ 電極箔（集電体）、
４０ 電極層、
５０ 乾燥炉、
５１〜５６ 乾燥ゾーン、
５７ 雰囲気、
６０ 搬送部、
７０ 蒸発速度調整部材、
８０ ヒーター部、
９０ ケーシング、
９１ 仕切り壁、
９２ 上ノズル、
９３ 下ノズル、
９４ 排気口、
９５ 塗布部、
９６ コーター、
１００ 配管系、
１０１ 第１配管、
１０２ 第２配管、
１０３ 第３配管、
１０４ バイパス管、
１０５ 熱交換器、
１０６ バルブ、
１０７、１０８ 温度センサー、
１０９ 濃度センサー、
１１０ 溶媒回収装置、
１１１ 溶媒回収器、
１１２ 送風ファン、
１２０ 熱交換器、
１２１ 温度センサー、
１３０ コントローラー。
10 electrode drying device,
20 electrode slurry,
21 solvent,
22 active material,
23 binder,
24 conductive aid,
30 electrode foil (current collector),
40 electrode layers,
50 drying ovens,
51-56 drying zone,
57 Atmosphere,
60 transport section,
70 evaporation rate adjusting member,
80 heater section,
90 casing,
91 partition wall,
92 Upper nozzle,
93 Lower nozzle,
94 exhaust port,
95 Application part,
96 coaters,
100 piping system,
101 first piping,
102 second piping,
103 3rd piping,
104 bypass pipe,
105 heat exchanger,
106 valves,
107, 108 temperature sensor,
109 concentration sensor,
110 solvent recovery device,
111 solvent collector,
112 Blower fan,
120 heat exchanger,
121 temperature sensor,
130 Controller.
Claims (9)
前記電極層内に残存する溶媒濃度と前記乾燥炉内の雰囲気における溶媒濃度との濃度差を、前記雰囲気における溶媒濃度を高めることによって小さくしつつ、熱を付与して前記電極層を乾燥させる電極乾燥方法。 A method of drying an electrode layer formed by applying an electrode slurry containing a solvent to a current collector in a drying furnace,
An electrode for drying the electrode layer by applying heat while reducing the concentration difference between the solvent concentration remaining in the electrode layer and the solvent concentration in the atmosphere in the drying furnace by increasing the solvent concentration in the atmosphere. Drying method.
前記電極層内に残存する溶媒濃度と前記乾燥炉内の雰囲気における溶媒濃度との濃度差を、前記雰囲気における溶媒濃度を高めることによって小さくする蒸発速度調整部材と、
前記電極層を乾燥させる熱を付与するヒーター部と、を有する電極乾燥装置。 An electrode drying apparatus for drying an electrode layer formed by applying an electrode slurry containing a solvent to a current collector in a drying furnace,
An evaporation rate adjusting member that reduces the concentration difference between the solvent concentration remaining in the electrode layer and the solvent concentration in the atmosphere in the drying furnace by increasing the solvent concentration in the atmosphere;
An electrode drying apparatus comprising: a heater unit that applies heat to dry the electrode layer.
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