JP2016167434A - Method for manufacturing secondary battery and secondary battery - Google Patents
Method for manufacturing secondary battery and secondary battery Download PDFInfo
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- JP2016167434A JP2016167434A JP2015047698A JP2015047698A JP2016167434A JP 2016167434 A JP2016167434 A JP 2016167434A JP 2015047698 A JP2015047698 A JP 2015047698A JP 2015047698 A JP2015047698 A JP 2015047698A JP 2016167434 A JP2016167434 A JP 2016167434A
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- 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
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- 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
Abstract
Description
本発明は、二次電池の製造方法および二次電池に関し、特に、印刷法を用いて製造される二次電池に適用して有効なものに関する。 The present invention relates to a method for manufacturing a secondary battery and a secondary battery, and particularly relates to a battery that is effective when applied to a secondary battery manufactured using a printing method.
たとえば、特許文献１には、固体二次電池の製法の簡易化とともに優れた急放電特性、自己放電特性、さらに長寿命を有する固体二次電池が開示されている。当該固体二次電池は、電解質層を挟んで２枚の正極材料を主とする正極層を配し、これと間隔を保って同じく２枚の負極材料を主とする負極層を電解質層を挟んで配し、おのおの２枚の正極層間、負極層間をたとえば孔を通して、それぞれの電極材料で電気的に接続した構成を有する。そして、電解質と結着剤を主とする電解質層および電極材料と電解質と結着剤を主とする正極層の少なくとも一方を、印刷法によって形成することが開示されている。 For example, Patent Document 1 discloses a solid secondary battery that has excellent rapid discharge characteristics, self-discharge characteristics, and a long life as well as simplification of the manufacturing method of the solid secondary battery. In the solid secondary battery, a positive electrode layer mainly composed of two positive electrode materials is arranged with an electrolyte layer sandwiched therebetween, and a negative electrode layer mainly composed of two negative electrode materials is sandwiched between the electrolyte layers while keeping an interval therebetween. And the two positive electrode layers and the negative electrode layer are electrically connected with each electrode material through, for example, holes. Then, it is disclosed that at least one of an electrolyte layer mainly composed of an electrolyte and a binder and an electrode material, a positive electrode layer mainly composed of an electrolyte and a binder is formed by a printing method.
特許文献２には、電解質部の厚みが薄く、電解質部の抵抗の低減、電池内部抵抗の低減を図ることができ、しかも、生産性を向上させることができる全固体電池が開示されている。当該全固体電池は、電極活物質を含有する正電極部と、電極活物質を含有する負電極部と、固体電解質からなる電解質部とを有する電池本体と、電池本体に形成された正集電部及び負集電部とを備えた全固体電池であり、電池本体は、後に正電極部となる第１成形体、後に電解質部となる第２成形体、後に負電極部となる第３成形体の順に層状に積層してなる３層構造の積層成形体を、同時焼成１回で、且つ、１００ｋｇ／ｃｍ2以上の加圧下で、焼成一体化されて構成されていることが開示されている。また、３層構造の積層成形体が、圧粉法や印刷法、若しくはテープ積層法、又はその組合せにより形成された積層成形体であることが開示されている。 Patent Document 2 discloses an all-solid-state battery in which the thickness of the electrolyte portion is thin, the resistance of the electrolyte portion can be reduced, the internal resistance of the battery can be reduced, and the productivity can be improved. The all solid state battery includes a battery body having a positive electrode part containing an electrode active material, a negative electrode part containing an electrode active material, and an electrolyte part made of a solid electrolyte, and a positive current collector formed on the battery body. Part and a negative current collector, the battery body is a first molded body that will later become a positive electrode part, a second molded body that will later be an electrolyte part, and a third molded body that will later be a negative electrode part. It is disclosed that a laminated molded body having a three-layer structure formed by laminating layers in the order of the body is configured to be integrally fired at the same time and under a pressure of 100 kg / cm 2 or more. Yes. Moreover, it is disclosed that the laminated molded body having a three-layer structure is a laminated molded body formed by a compacting method, a printing method, a tape lamination method, or a combination thereof.
正極活物質を含む正極層と、イオン伝導機能を備えた電解質層と、負極活物質を含む負極層とが順次積層された３層構造を有する全固体二次電池を、印刷法で形成しようとする場合、少なくとも正極層、電解質層または負極層となるインクを各々作製し、各層をそれぞれ対応するインクで印刷し、焼成し、次の層を順次積み重ねて作製することにより製造できる。このような製造方法においては、各層の印刷および焼成は大気中で行えるため、製造が容易になり、製造コストを低く抑えることが可能になるメリットがある。 An all-solid-state secondary battery having a three-layer structure in which a positive electrode layer including a positive electrode active material, an electrolyte layer having an ion conduction function, and a negative electrode layer including a negative electrode active material are sequentially laminated is formed by a printing method. In this case, at least a positive electrode layer, an electrolyte layer, or a negative electrode layer can be prepared, and each layer can be printed with a corresponding ink, fired, and the following layers can be sequentially stacked. In such a manufacturing method, since printing and baking of each layer can be performed in air | atmosphere, there exists a merit which manufacture becomes easy and it becomes possible to hold down manufacturing cost low.
しかし、上記した製造方法、つまり各層を単に印刷および焼成により形成しただけでは、各層の活物質、特に電解質層でリチウムイオンが十分に伝導しきれず、デバイスとして機能しない、つまり二次電池として使用するに十分な充放電を繰り返すことができないことが判明した。 However, when the above-described manufacturing method, that is, each layer is simply formed by printing and baking, lithium ions cannot be sufficiently conducted in the active material of each layer, particularly the electrolyte layer, and does not function as a device, that is, used as a secondary battery. It was found that sufficient charge / discharge could not be repeated.
本発明の目的は、少なくとも正極層、電解質層または負極層の各層が印刷および焼成により形成された二次電池に、充放電特性を発現させる技術を提供することにある。 An object of the present invention is to provide a technique for developing charge / discharge characteristics in a secondary battery in which at least each layer of a positive electrode layer, an electrolyte layer, or a negative electrode layer is formed by printing and baking.
上記課題を解決するために、本発明の第１の態様においては、（ａ）基板上に集電体を形成する工程と、（ｂ）前記集電体上に正極層を形成する工程と、（ｃ）前記正極層上に電解質層を積層形成する工程と、（ｄ）前記電解質層上に負極層を積層形成する工程と、（ｅ）前記負極層上にポリマー電解質を塗布し、前記負極層を透して前記電解質層に前記ポリマー電解質を供給する工程と、を有する二次電池の製造方法を提供する。 In order to solve the above problems, in the first aspect of the present invention, (a) a step of forming a current collector on a substrate, (b) a step of forming a positive electrode layer on the current collector, (C) a step of laminating and forming an electrolyte layer on the positive electrode layer; (d) a step of laminating and forming a negative electrode layer on the electrolyte layer; and (e) applying a polymer electrolyte on the negative electrode layer; And supplying the polymer electrolyte to the electrolyte layer through a layer.
前記（ｄ）工程と前記（ｅ）工程の間、および、前記（ｅ）工程の後に、前記基板上に形成した前記集電体、前記正極層、前記電解質層および前記負極層を加熱する工程、をさらに有してもよい。前記加熱が、大気圧未満の圧力で行われてもよい。前記正極層、前記電解質層および前記負極層から選択された１以上の部材の形成が、印刷および焼成による形成であってもよい。前記印刷および焼成が、大気雰囲気中で実施されてもよい。前記（ｅ）工程の前記ポリマー電解質の塗布が、印刷法による塗布であってもよい。前記（ｅ）工程の後、前記基板、前記集電体、前記正極層、前記電解質層および前記負極層を封止する工程、をさらに有してもよい。前記集電体が、前記電解質層の形成に用いるポリマー電解質に対し化学的に安定な導電体からなるものであってもよい。あるいは、前記（ａ）工程の後、前記（ｂ）工程の前に、前記集電体上に、前記ポリマー電解質の浸透を阻害する保護層を形成する工程、をさらに有してもよい。 Heating the current collector, the positive electrode layer, the electrolyte layer and the negative electrode layer formed on the substrate between the step (d) and the step (e) and after the step (e). , May further be included. The heating may be performed at a pressure less than atmospheric pressure. The formation of one or more members selected from the positive electrode layer, the electrolyte layer, and the negative electrode layer may be formed by printing and baking. The printing and baking may be performed in an air atmosphere. The application of the polymer electrolyte in the step (e) may be an application by a printing method. After the step (e), the method may further include a step of sealing the substrate, the current collector, the positive electrode layer, the electrolyte layer, and the negative electrode layer. The current collector may be made of a conductor that is chemically stable with respect to the polymer electrolyte used to form the electrolyte layer. Or after the said (a) process, before the said (b) process, you may further have the process of forming the protective layer which inhibits the penetration of the said polymer electrolyte on the said electrical power collector.
本発明の第２の態様においては、基板上に、集電体、正極層、電解質層、負極層が順次積層された二次電池であって、前記電解質層と前記負極層とがポリマー電解質を含む二次電池を提供する。前記正極層、電解質層および前記負極層が、印刷法により形成されたものであってもよい。 In a second aspect of the present invention, a secondary battery in which a current collector, a positive electrode layer, an electrolyte layer, and a negative electrode layer are sequentially laminated on a substrate, wherein the electrolyte layer and the negative electrode layer contain a polymer electrolyte. A secondary battery including the same is provided. The positive electrode layer, the electrolyte layer, and the negative electrode layer may be formed by a printing method.
なお、上記の発明の概要は、本発明の必要な特徴の全てを列挙したものではない。また、これらの特徴群のサブコンビネーションもまた、発明となりうる。 It should be noted that the above summary of the invention does not enumerate all the necessary features of the present invention. In addition, a sub-combination of these feature groups can also be an invention.
以下、発明の実施の形態を通じて本発明を説明するが、以下の実施形態は特許請求の範囲にかかる発明を限定するものではない。また、実施形態の中で説明されている特徴の組み合わせの全てが発明の解決手段に必須であるとは限らない。 Hereinafter, the present invention will be described through embodiments of the invention, but the following embodiments do not limit the invention according to the claims. In addition, not all the combinations of features described in the embodiments are essential for the solving means of the invention.
図１〜図５は、本実施形態の二次電池の製造方法を工程順に示した断面図である。まず、図１に示すように、基板１０２の上に集電体１０４を形成する。 1-5 is sectional drawing which showed the manufacturing method of the secondary battery of this embodiment in order of the process. First, as shown in FIG. 1, the current collector 104 is formed on the substrate 102.
基板１０２は、集電体１０４等、本実施の形態の製造方法で製造される二次電池の構成部材を支持する。構造部材が支持できる機械的強度を有する限り、基板１０２に材料、寸法、形状等の制限は無い。ただし、当該二次電池の製造工程において、焼成等熱処理が施されるので、熱処理に耐え得る程度の耐熱性を有することが好ましい。また、製造工程において使用される有機溶媒やリチウム塩等に対し化学的安定性を有することが好ましい。基板１０２として、たとえばガラス基板、金属箔、ＰＥＴ（ポリエチレンテレフタレート）等のフィルムを例示することができる。 The substrate 102 supports components of the secondary battery manufactured by the manufacturing method of the present embodiment, such as the current collector 104. As long as the structural member has a mechanical strength that can be supported, the substrate 102 is not limited in material, size, shape, and the like. However, since heat treatment such as firing is performed in the manufacturing process of the secondary battery, it is preferable to have heat resistance enough to withstand the heat treatment. Moreover, it is preferable that it has chemical stability with respect to the organic solvent used in a manufacturing process, lithium salt, etc. Examples of the substrate 102 include a glass substrate, a metal foil, and a film such as PET (polyethylene terephthalate).
集電体１０４は、後に説明する正極層および負極層に接続され、正極層および負極層から電荷を集め、供給する。集電体１０４は、金属を含み、たとえばアルミニウム、銅、ステンレス鋼とすることができる。ただし、後に説明するポリマー電解質に対し化学的に安定な導電体からなることが好ましい。集電体１０４の形成には、メッキ法、スパッタ法等を用いることができる。被膜のパターニングには、たとえばフォトマスクを用いた金属層等のエッチング法またはリフトオフ法により形成できる。 The current collector 104 is connected to a positive electrode layer and a negative electrode layer, which will be described later, and collects and supplies charges from the positive electrode layer and the negative electrode layer. The current collector 104 includes a metal, and can be, for example, aluminum, copper, or stainless steel. However, it is preferably made of a chemically stable conductor with respect to the polymer electrolyte described later. For forming the current collector 104, a plating method, a sputtering method, or the like can be used. The film can be patterned by, for example, an etching method such as a metal layer using a photomask or a lift-off method.
次に、図２に示すように、集電体１０４の上に正極層１０６を形成する。正極層１０６は、正極活物質および導電材がバインダー樹脂で固着された層である。正極活物質としてリチウム含有複合酸化物、たとえばＬｉＭｎ２Ｏ４が例示できる。導電材としてたとえばアセチレンブラックが例示できる。バインダー樹脂としてポリエチレンオキサイド（ＰＥＯ）樹脂、エチレン／プロピレンオキサイド共重合体、ポリフッ化ビニリデン（ＰＶｄＦ）樹脂が例示できる。正極層１０６には、リチウム塩たとえばリチウムビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）が添加されても良い。 Next, as illustrated in FIG. 2, the positive electrode layer 106 is formed on the current collector 104. The positive electrode layer 106 is a layer in which a positive electrode active material and a conductive material are fixed with a binder resin. Examples of the positive electrode active material include lithium-containing composite oxides such as LiMn 2 O 4 . An example of the conductive material is acetylene black. Examples of the binder resin include polyethylene oxide (PEO) resin, ethylene / propylene oxide copolymer, and polyvinylidene fluoride (PVdF) resin. A lithium salt such as lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) may be added to the positive electrode layer 106.
正極層１０６は、印刷および焼成により形成できる。すなわち、正極層１０６の印刷用のインクとして、適切な溶媒で粘度調整されたバインダー樹脂に正極活物質および導電材を混錬したものを調製し、例えばスクリーン印刷により正極層１０６のパターンに印刷する。当該印刷パターンを、たとえば１２０℃、３０分の条件で焼成し、正極層１０６を形成する。印刷および焼成は、大気雰囲気中で実施することができる。なお、正極層１０６の平滑化と密着性向上のため、たとえば１５０℃、１分間の条件で熱プレス処理を行っても良い。 The positive electrode layer 106 can be formed by printing and baking. That is, as a printing ink for the positive electrode layer 106, a binder resin whose viscosity is adjusted with an appropriate solvent is prepared by kneading a positive electrode active material and a conductive material, and printed on the pattern of the positive electrode layer 106 by screen printing, for example. . The printed pattern is baked, for example, at 120 ° C. for 30 minutes to form the positive electrode layer 106. Printing and baking can be performed in an air atmosphere. In addition, in order to smooth the positive electrode layer 106 and improve the adhesiveness, for example, heat press treatment may be performed under conditions of 150 ° C. for 1 minute.
次に、図３に示すように、正極層１０６の上に電解質層１０８を積層形成する。電解質層１０８は、任意のリチウムイオン導電性の酸化物（ＬＩＳＩＣＯＮ系固体電解質等）を含み、ポリマー電解質を含む。電解質層１０８は、図示するように正極層１０６を覆うように形成してもよい。電解質層１０８として、リチウムビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）等のリチウムイオン塩が添加されたエチレン／プロピレンオキサイド共重合体に固体電解質粉末、たとえばＬｉ２Ｏ−Ａｌ２Ｏ３−ＴｉＯ２−Ｐ２Ｏ５系固体電解質（ＬＡＴＰ）粉末を分散させた電解質層を例示することができる。電解質層１０８として、シート状に形成されたガラスセラミックス等の電解質を、正極層１０６上に配置しても良い。また、電解質層１０８は、印刷および焼成により形成してもよい。印刷および焼成は、大気雰囲気中で実施することができる。当該印刷パターンを、たとえば１００℃、６０分の条件で焼成し、電解質層１０８を形成する。 Next, as illustrated in FIG. 3, an electrolyte layer 108 is stacked on the positive electrode layer 106. The electrolyte layer 108 includes any lithium ion conductive oxide (such as a LISICON solid electrolyte), and includes a polymer electrolyte. The electrolyte layer 108 may be formed so as to cover the positive electrode layer 106 as illustrated. As the electrolyte layer 108, a solid electrolyte powder such as Li 2 O—Al 2 O 3 —TiO 2 — is added to an ethylene / propylene oxide copolymer to which a lithium ion salt such as lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) is added. An electrolyte layer in which P 2 O 5 based solid electrolyte (LATP) powder is dispersed can be exemplified. As the electrolyte layer 108, an electrolyte such as a glass ceramic formed in a sheet shape may be disposed on the positive electrode layer 106. The electrolyte layer 108 may be formed by printing and baking. Printing and baking can be performed in an air atmosphere. The printed pattern is baked, for example, at 100 ° C. for 60 minutes to form the electrolyte layer 108.
次に、図４に示すように、電解質層１０８の上に負極層１１０を積層形成する。負極層１１０は、負極活物質がバインダー樹脂で固着された層である。負極活物質としてハードカーボンが例示できる。バインダー樹脂としてポリエチレンオキサイド（ＰＥＯ）樹脂、エチレン／プロピレンオキサイド共重合体、ポリフッ化ビニリデン（ＰＶｄＦ）樹脂が例示できる。負極層１１０には、リチウム塩たとえばリチウムビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）が添加されても良い。 Next, as shown in FIG. 4, a negative electrode layer 110 is formed on the electrolyte layer 108 by lamination. The negative electrode layer 110 is a layer in which a negative electrode active material is fixed with a binder resin. An example of the negative electrode active material is hard carbon. Examples of the binder resin include polyethylene oxide (PEO) resin, ethylene / propylene oxide copolymer, and polyvinylidene fluoride (PVdF) resin. Lithium salt such as lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) may be added to the negative electrode layer 110.
負極層１１０は、印刷および焼成により形成できる。すなわち、負極層１１０の印刷用のインクとして、適切な溶媒で粘度調整されたバインダー樹脂に負極活物質を混錬したもの調製し、例えばスクリーン印刷により負極層１１０のパターンに印刷する。当該印刷パターンを、たとえば１２０℃、３０分の条件で焼成し、負極層１１０を形成する。印刷および焼成は、大気雰囲気中で実施することができる。なお、負極層１１０の平滑化と密着性向上のため、たとえば１５０℃、１分間の条件で熱プレス処理を行っても良い。 The negative electrode layer 110 can be formed by printing and baking. That is, as the ink for printing the negative electrode layer 110, a binder resin whose viscosity is adjusted with an appropriate solvent is prepared by kneading the negative electrode active material, and printed on the pattern of the negative electrode layer 110 by screen printing, for example. The printed pattern is baked, for example, at 120 ° C. for 30 minutes to form the negative electrode layer 110. Printing and baking can be performed in an air atmosphere. In addition, in order to smooth the negative electrode layer 110 and improve adhesiveness, for example, heat pressing may be performed under conditions of 150 ° C. for 1 minute.
負極層１１０の形成後、基板１０２上に形成した集電体１０４、正極層１０６、電解質層１０８および負極層１１０の全体を加熱する。加熱の条件は、たとえば１２０℃、２４時間とすることができる。加熱は、大気圧未満の圧力、たとえばロータリーポンプ等の真空ポンプで到達できる減圧圧力の下で行うことが好ましい。 After the formation of the negative electrode layer 110, the current collector 104, the positive electrode layer 106, the electrolyte layer 108, and the negative electrode layer 110 formed over the substrate 102 are heated. The heating conditions can be, for example, 120 ° C. and 24 hours. The heating is preferably performed under a pressure lower than atmospheric pressure, for example, a reduced pressure that can be reached by a vacuum pump such as a rotary pump.
次に、図５に示すように、負極層１１０の上にポリマー電解質１１２を塗布する。ポリマー電解質１１２は、負極層１１０を透して電解質層１０８にポリマー電解質１１２を供給する。ポリマー電解質１１２として、ポリエチレンオキサイド、もしくはエチレン／プロピレンオキサイド共重合体にリチウム塩を加え、有機溶媒で粘着化したものを例示することができる。リチウム塩として、リチウムビス（トリフルオロメタンスルホニル）イミド（ＬｉＴＦＳＩ）を例示することができる。ポリマー電解質１１２の塗布は、印刷により行っても良い。塗布工程では、ポリマー電解質に含まれるリチウムイオンの失活を防止するために、相対湿度３％ＲＨ以下の環境で行うことが望ましい。 Next, as shown in FIG. 5, a polymer electrolyte 112 is applied on the negative electrode layer 110. The polymer electrolyte 112 supplies the polymer electrolyte 112 to the electrolyte layer 108 through the negative electrode layer 110. Examples of the polymer electrolyte 112 include those obtained by adding a lithium salt to polyethylene oxide or an ethylene / propylene oxide copolymer and adhering with an organic solvent. An example of the lithium salt is lithium bis (trifluoromethanesulfonyl) imide (LiTFSI). The application of the polymer electrolyte 112 may be performed by printing. The coating process is preferably performed in an environment with a relative humidity of 3% RH or less in order to prevent deactivation of lithium ions contained in the polymer electrolyte.
ポリマー電解質１１２が電解質層１０８に供給されることにより、図４までの工程で十分に伝導しきれなかったリチウムイオンが電解質層１０８内を伝導できるようになり、電解質層１０８がイオン伝導体として機能するようになる。 By supplying the polymer electrolyte 112 to the electrolyte layer 108, lithium ions that could not be sufficiently conducted in the steps up to FIG. 4 can be conducted in the electrolyte layer 108, and the electrolyte layer 108 functions as an ion conductor. To come.
ポリマー電解質１１２を塗布した後、基板１０２、集電体１０４、正極層１０６、電解質層１０８および負極層１１０の全体を加熱することができる。加熱の条件は、たとえば１００℃、６０分間とすることができる。さらに、全体加熱したものに減圧加熱乾燥を加えることが好ましい。減圧加熱乾燥は、大気圧未満の圧力、たとえばロータリーポンプ等の真空ポンプで到達できる減圧圧力の下で、１００℃、２４時間乾燥することが好ましい。 After applying the polymer electrolyte 112, the entire substrate 102, current collector 104, positive electrode layer 106, electrolyte layer 108, and negative electrode layer 110 can be heated. The heating conditions can be, for example, 100 ° C. for 60 minutes. Furthermore, it is preferable to apply heat drying under reduced pressure to the whole heated product. The vacuum heat drying is preferably performed at 100 ° C. for 24 hours under a pressure lower than atmospheric pressure, for example, a reduced pressure that can be reached by a vacuum pump such as a rotary pump.
基板１０２、集電体１０４、正極層１０６、電解質層１０８および負極層１１０の全体は、たとえばＰＥＴ（ポリエチレンテレフタレート）等のフィルムで封止（ラミネート）することが好ましい。 The entire substrate 102, current collector 104, positive electrode layer 106, electrolyte layer 108, and negative electrode layer 110 are preferably sealed (laminated) with a film such as PET (polyethylene terephthalate).
以上のようにして、図６に示すような、ポリマー電解質１１２が、少なくとも電解質層１０８に含浸された二次電池１００が形成される。以上のようにして製造された二次電池１００は、基板１０２上に集電体１０４、正極層１０６、電解質層１０８および負極層１１０を形成した後、ポリマー電解質１１２を塗布してその成分を少なくとも電解質層１０８に浸透させるため、電解質層１０８内でリチウムイオンを十分に伝導させることができる。これにより二次電池１００を正常に充放電動作させることができる。 As described above, the secondary battery 100 in which the polymer electrolyte 112 is impregnated at least in the electrolyte layer 108 as shown in FIG. 6 is formed. In the secondary battery 100 manufactured as described above, the current collector 104, the positive electrode layer 106, the electrolyte layer 108, and the negative electrode layer 110 are formed on the substrate 102, and then the polymer electrolyte 112 is applied to at least the components. Since the electrolyte layer 108 is infiltrated, lithium ions can be sufficiently conducted in the electrolyte layer 108. Thereby, the secondary battery 100 can be normally charged / discharged.
図７は、二次電池１００の充電特性を示すグラフであり、図８は、二次電池１００の放電特性を示すグラフである。両グラフにおいて、ＬｉＴＦＳＩが０．２５Ｍ（モル）および５Ｍに相当するポリマー電解質１１２をそれぞれ塗布した場合を対比して示す。ＬｉＴＦＳＩが０．２５モルの場合より５モルの場合の方が充電時間が短く、放電時間が長くなることがわかる。このことから、ポリマー電解質１１２の塗布により二次電池１００が機能し、ポリマー電解質のＬｉＴＦＳＩの濃度が高いほど、二次電池１００の充放電特性が良好であることがわかる。 FIG. 7 is a graph showing the charging characteristics of the secondary battery 100, and FIG. 8 is a graph showing the discharging characteristics of the secondary battery 100. In both graphs, the case where the polymer electrolyte 112 corresponding to LiTFSI of 0.25 M (mole) and 5 M is applied is shown in comparison. It can be seen that the charging time is shorter and the discharging time is longer in the case of 5 mol than in the case of LiTFSI of 0.25 mol. From this, it can be seen that the secondary battery 100 functions by the application of the polymer electrolyte 112, and the higher the LiTFSI concentration of the polymer electrolyte, the better the charge / discharge characteristics of the secondary battery 100.
なお、塗布するポリマー電解質１１２が集電体１０４を腐食するようなものである場合、集電体１０４の形成の後、正極層１０６の形成前に、集電体１０４上に、ポリマー電解質１１２の浸透を阻害する保護層２０２を形成することができる（図９参照）。図９は、保護層２０２を有する二次電池２００の断面を示す。 Note that in the case where the applied polymer electrolyte 112 corrodes the current collector 104, the polymer electrolyte 112 is formed on the current collector 104 after the current collector 104 is formed and before the positive electrode layer 106 is formed. A protective layer 202 that inhibits penetration can be formed (see FIG. 9). FIG. 9 shows a cross section of the secondary battery 200 having the protective layer 202.
保護層２０２として、印刷および焼成して形成されたカーボン層を熱プレスしたものを例示することができる。カーボン層にはバインダーが含まれ、当該バインダーには、熱硬化型のフェノール樹脂またはキシレン変性フェノール樹脂が好ましい。カーボン層を熱プレスすることで、ピンホールを無くし、ポリマー電解質の浸漬を阻害できる。また、カーボン層を熱プレスすることで、カーボン粒子間の距離を短くし（導電性カーボンの密度を高め）、導電率を高めることができる。 As the protective layer 202, a carbon layer formed by printing and baking is hot-pressed. The carbon layer contains a binder, and the binder is preferably a thermosetting phenol resin or a xylene-modified phenol resin. By hot pressing the carbon layer, pinholes can be eliminated and the immersion of the polymer electrolyte can be inhibited. Further, by hot pressing the carbon layer, the distance between the carbon particles can be shortened (the density of the conductive carbon is increased), and the conductivity can be increased.
また、上記した実施の形態では、主に二次電池の製造方法を説明したが、発明を二次電池として把握することも可能である。すなわち、基板１０２上に、集電体１０４、正極層１０６、電解質層１０８、負極層１１０が順次積層された二次電池であって、電解質層１０８と負極層１１０とがポリマー電解質を含む二次電池、として把握することが可能である。ここで、正極層１０６、電解質層１０８および負極層１１０が、印刷法により形成されたものであってもよい。 In the above-described embodiment, the method for manufacturing a secondary battery has been mainly described, but the invention can also be understood as a secondary battery. That is, a secondary battery in which a current collector 104, a positive electrode layer 106, an electrolyte layer 108, and a negative electrode layer 110 are sequentially stacked on a substrate 102, where the electrolyte layer 108 and the negative electrode layer 110 include a polymer electrolyte. It can be grasped as a battery. Here, the positive electrode layer 106, the electrolyte layer 108, and the negative electrode layer 110 may be formed by a printing method.
以上、本発明を実施の形態を用いて説明したが、本発明の技術的範囲は上記実施の形態に記載の範囲には限定されない。上記実施の形態に、多様な変更または改良を加えることが可能であることが当業者に明らかである。その様な変更または改良を加えた形態も本発明の技術的範囲に含まれ得ることが、特許請求の範囲の記載から明らかである。 As mentioned above, although this invention was demonstrated using embodiment, the technical scope of this invention is not limited to the range as described in the said embodiment. It will be apparent to those skilled in the art that various modifications or improvements can be added to the above-described embodiment. It is apparent from the scope of the claims that the embodiments added with such changes or improvements can be included in the technical scope of the present invention.
１００…二次電池、１０２…基板、１０４…集電体、１０６…正極層、１０８…電解質層、１１０…負極層、１１２…ポリマー電解質、２００…二次電池、２０２…保護層。 DESCRIPTION OF SYMBOLS 100 ... Secondary battery, 102 ... Board | substrate, 104 ... Current collector, 106 ... Positive electrode layer, 108 ... Electrolyte layer, 110 ... Negative electrode layer, 112 ... Polymer electrolyte, 200 ... Secondary battery, 202 ... Protective layer.
Claims (11)
（ｂ）前記集電体上に正極層を形成する工程と、
（ｃ）前記正極層上に電解質層を積層形成する工程と、
（ｄ）前記電解質層上に負極層を積層形成する工程と、
（ｅ）前記負極層上にポリマー電解質を塗布し、前記負極層を透して前記電解質層に前記ポリマー電解質を供給する工程と、
を有する二次電池の製造方法。 (A) forming a current collector on a substrate;
(B) forming a positive electrode layer on the current collector;
(C) stacking and forming an electrolyte layer on the positive electrode layer;
(D) laminating and forming a negative electrode layer on the electrolyte layer;
(E) applying a polymer electrolyte on the negative electrode layer, supplying the polymer electrolyte to the electrolyte layer through the negative electrode layer;
The manufacturing method of the secondary battery which has this.
請求項１に記載の製造方法。 Heating the current collector, the positive electrode layer, the electrolyte layer and the negative electrode layer formed on the substrate between the step (d) and the step (e) and after the step (e). The manufacturing method according to claim 1, further comprising:
請求項２に記載の製造方法。 The manufacturing method according to claim 2, wherein the heating is performed at a pressure less than atmospheric pressure.
請求項１から請求項３の何れか一項に記載の製造方法。 The manufacturing method according to any one of claims 1 to 3, wherein the formation of one or more members selected from the positive electrode layer, the electrolyte layer, and the negative electrode layer is formation by printing and baking.
請求項４に記載の製造方法。 The manufacturing method according to claim 4, wherein the printing and baking are performed in an air atmosphere.
請求項１から請求項５の何れか一項に記載の製造方法。 The manufacturing method according to any one of claims 1 to 5, wherein the application of the polymer electrolyte in the step (e) is application by a printing method.
請求項１から請求項６の何れか一項に記載の製造方法。 7. The method according to claim 1, further comprising: sealing the substrate, the current collector, the positive electrode layer, the electrolyte layer, and the negative electrode layer after the step (e). Manufacturing method.
請求項１から請求項７の何れか一項に記載の製造方法。 The manufacturing method according to any one of claims 1 to 7, wherein the current collector is made of a conductor that is chemically stable with respect to a polymer electrolyte used for forming the electrolyte layer.
請求項１から請求項７の何れか一項に記載の製造方法。 The step of forming a protective layer that inhibits permeation of the polymer electrolyte on the current collector after the step (a) and before the step (b). The manufacturing method as described in any one.
前記電解質層と前記負極層とがポリマー電解質を含む
二次電池。 A secondary battery in which a current collector, a positive electrode layer, an electrolyte layer, and a negative electrode layer are sequentially laminated on a substrate,
The secondary battery in which the electrolyte layer and the negative electrode layer include a polymer electrolyte.
請求項１０に記載の二次電池。 The secondary battery according to claim 10, wherein the positive electrode layer, the electrolyte layer, and the negative electrode layer are formed by a printing method.
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