JP2009123610A - All-solid polymer battery and its manufacturing method - Google Patents

All-solid polymer battery and its manufacturing method Download PDF

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JP2009123610A
JP2009123610A JP2007298260A JP2007298260A JP2009123610A JP 2009123610 A JP2009123610 A JP 2009123610A JP 2007298260 A JP2007298260 A JP 2007298260A JP 2007298260 A JP2007298260 A JP 2007298260A JP 2009123610 A JP2009123610 A JP 2009123610A
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JP5571281B2 (en
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Tomohiro Ueda
智博 植田
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Panasonic Corp
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Priority to PCT/JP2008/001573 priority patent/WO2009001526A1/en
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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
    • 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

<P>PROBLEM TO BE SOLVED: To provide an all-solid polymer battery in which an increase of an internal resistance during being stored is controlled and high-rate discharging characteristics after being stored are excellent. <P>SOLUTION: The all-solid polymer battery includes a positive electrode layer, an negative electrode layer containing lithium and a dry polymer electrolyte layer arranged between the positive electrode layer and the negative electrode layer, and between the negative electrode layer and the electrolyte layer, there is formed an amorphous lithium nitride layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、ドライポリマー電解質を用いた全固体型ポリマー電池およびその製造方法に関する。   The present invention relates to an all solid-state polymer battery using a dry polymer electrolyte and a method for producing the same.

非水電解質電池は、正極と負極との間に液状電解質を含むセパレータを介在させたタイプの電池と、正極と負極との間に固体電解質を介在させたタイプの電池（以下、全固体型電池とする）とに大別することができる。全固体型電池は、液漏れのおそれがないため、電池の安全性や信頼性が高く、また電池の薄型化や積層化が可能であるという長所を有する。   Non-aqueous electrolyte batteries include a battery of a type in which a separator containing a liquid electrolyte is interposed between a positive electrode and a negative electrode, and a battery of a type in which a solid electrolyte is interposed between a positive electrode and a negative electrode (hereinafter, all-solid-state battery). And). An all-solid-state battery has advantages in that the battery has high safety and reliability because the liquid does not leak, and the battery can be thinned and stacked.

全固体型電池に使用される固体電解質としては、無機材料や有機材料が用いられる。無機材料からなる固体電解質は、イオン伝導性が高いが、脆性が高いために可撓性を有する膜に加工することが困難である。一方、有機材料からなる固体電解質には、例えば、有機高分子からなるドライポリマー電解質が用いられる。ドライポリマー電解質は、無機材料と比較して柔軟性が高く、薄膜の形成が可能である点から、薄型で高エネルギー密度を有する電池の固体電解質材料として期待されている。   An inorganic material or an organic material is used as the solid electrolyte used in the all solid state battery. A solid electrolyte made of an inorganic material has high ionic conductivity, but it is difficult to process into a flexible film because of high brittleness. On the other hand, as the solid electrolyte made of an organic material, for example, a dry polymer electrolyte made of an organic polymer is used. Dry polymer electrolytes are expected to be thin and have a high energy density because they are more flexible than inorganic materials and can form thin films.

ドライポリマー電解質としては、ポリエチレンオキサイドと、リチウム塩またはナトリウム塩のような支持塩とを複合化したドライポリマー電解質が知られている。しかし、このドライポリマー電解質を用いた場合、室温でのイオン伝導率が１０-4〜１０-7Ｓ・ｃｍ-1と低いため、高負荷放電時に得られる電池容量が低下する。 As a dry polymer electrolyte, a dry polymer electrolyte in which polyethylene oxide and a supporting salt such as a lithium salt or a sodium salt are combined is known. However, when this dry polymer electrolyte is used, since the ionic conductivity at room temperature is as low as 10 −4 to 10 −7 S · cm −1 , the battery capacity obtained during high load discharge decreases.

これに対しては、例えば、非特許文献１記載の、短いエチレンオキサイド鎖を側鎖に配することで分子配列を無定形化した、室温で１０-4Ｓ・ｃｍ-1以上のイオン伝導率を有するドライポリマー電解質を用いることが考えられる。しかしながら、このドライポリマー電解質を全固体型電池に用いた場合、保存後に内部抵抗が大きくなり、電池容量が減少する。 For this, for example, the ion conductivity of 10 −4 S · cm −1 or more at room temperature described in Non-Patent Document 1, in which a short ethylene oxide chain is arranged in a side chain to make the molecular arrangement amorphous. It is conceivable to use a dry polymer electrolyte having However, when this dry polymer electrolyte is used for an all-solid battery, the internal resistance increases after storage, and the battery capacity decreases.

また、ドライポリマー電解質を用いた全固体型ポリマー電池は、液状電解質やゲルポリマー電解質を用いた電池と比較して、保存時に内部抵抗が増大し、電池特性が劣化しやすい。これは、活物質とドライポリマー電解質との反応性が高いことが原因であると考えられる。特に、負極活物質にリチウムまたはリチウム合金を用いた場合、ドライポリマー電解質の分解が起こりやすく、負極活物質と電解質との界面部に絶縁性被膜が生成しやすい。負極界面部に絶縁性被膜が生成すると、活物質と電解質との接触面積が減少し、負極界面部の抵抗が大きくなる。その結果、電池の内部抵抗が増大する。   In addition, an all solid-state polymer battery using a dry polymer electrolyte has an increased internal resistance during storage and is likely to deteriorate battery characteristics as compared with a battery using a liquid electrolyte or a gel polymer electrolyte. This is considered due to the high reactivity between the active material and the dry polymer electrolyte. In particular, when lithium or a lithium alloy is used as the negative electrode active material, the dry polymer electrolyte is likely to be decomposed, and an insulating film is likely to be formed at the interface between the negative electrode active material and the electrolyte. When an insulating film is formed at the negative electrode interface, the contact area between the active material and the electrolyte decreases, and the resistance at the negative electrode interface increases. As a result, the internal resistance of the battery increases.

ところで、特許文献１では、内部短絡のない高信頼性の電池を得るために、リチウム負極のドライポリマー電解質との対向面に、結晶性窒化リチウム（Ｌｉ3Ｎ）からなる薄層（厚み５〜１０μｍ）を設けることが提案されている。結晶性Ｌｉ3Ｎに関して、非特許文献２では、窒素とリチウムの直接反応によって生成し、単結晶ではｃ軸と垂直な方向で１．２×１０-3Ｓ・ｃｍ-1、ｃ軸と平行な方向で１×１０-5Ｓ・ｃｍ-1、また多結晶では７×１０-4Ｓ・ｃｍ-1と比較的高いイオン伝導率を示すことが報告されている。しかし、特許文献１記載の方法でも、保存時の内部抵抗の上昇を抑制することは困難である。
特開昭６３―２９８９８０号公報 ポリマーバッテリーの最新技術II、金村聖志監修、ｐ１１３、シーエムシー出版 固体アイオニクス、工藤徹一、苗木和夫著、ｐ７６、講談社 By the way, in Patent Document 1, in order to obtain a highly reliable battery without an internal short circuit, a thin layer (thickness 5 to 5) made of crystalline lithium nitride (Li 3 N) is formed on the surface of the lithium negative electrode facing the dry polymer electrolyte. 10 μm) has been proposed. With respect to crystalline Li 3 N, in Non-Patent Document 2, it is produced by a direct reaction between nitrogen and lithium, and in a single crystal, 1.2 × 10 −3 S · cm −1 in a direction perpendicular to the c-axis, parallel to the c-axis. 1 × 10 −5 S · cm −1 in various directions and 7 × 10 −4 S · cm −1 in polycrystals have been reported to exhibit a relatively high ion conductivity. However, even with the method described in Patent Document 1, it is difficult to suppress an increase in internal resistance during storage.
JP 63-298980 A The latest polymer battery technology II, supervised by Seiji Kanamura, p113, CM Publishing Solid ionics, Tetsuichi Kudo, Kazuo Naegi, p.76, Kodansha

そこで、本発明は、上記従来の問題を解決するため、ドライポリマー電解質を用いた場合でも、保存時の内部抵抗の増大が抑制され、高率放電特性に優れた全固体型ポリマー電池を提供することを目的とする。   Accordingly, the present invention provides an all-solid-state polymer battery excellent in high-rate discharge characteristics, in which increase in internal resistance during storage is suppressed even when a dry polymer electrolyte is used, in order to solve the above-described conventional problems. For the purpose.

本発明の全固体型ポリマー電池は、正極層、リチウムを含む負極層、および前記正極層と前記負極層との間に配されたドライポリマー電解質層を備えた全固体型ポリマー電池であって、前記負極層と前記電解質層との間に非晶質のリチウム窒化物層が設けられていることを特徴とする。
前記リチウム窒化物層の表面をＸＰＳ分析した際に得られるＮの１ｓスペクトルが、結合エネルギー３９０．０〜３９６．０ｅＶの範囲において、３９３．５〜３９４．５ｅＶのみに極大ピークを有するのが好ましい。 The all solid state polymer battery of the present invention is an all solid state polymer battery comprising a positive electrode layer, a negative electrode layer containing lithium, and a dry polymer electrolyte layer disposed between the positive electrode layer and the negative electrode layer, An amorphous lithium nitride layer is provided between the negative electrode layer and the electrolyte layer.
It is preferable that the 1s spectrum of N obtained when XPS analysis of the surface of the lithium nitride layer has a maximum peak only at 393.5 to 394.5 eV in the range of binding energy 390.0 to 396.0 eV. .

本発明の第１の全固体型ポリマー電池の製造方法は、
（１）正極集電層の片面に正極層を配置し、正極積層体を得る工程、
（２）負極集電層の片面にリチウムを含む負極層を配置し、負極積層体を得る工程、
（３）前記負極積層体における前記負極層上に、ドライポリマー電解質の溶液を塗布した後、乾燥させて溶媒を除去し、前記負極層上にドライポリマー電解質層を形成し、中間積層体を得る工程、
（４）前記正極層と前記電解質層が対向するように、前記正極積層体と前記中間積層体とを重ね合わせ、電極複合体を得る工程、および
（５）前記電極複合体を密封する工程を含み、
前記工程（２）〜（５）を、窒素含有量０．１〜１０体積％の雰囲気下で実施することにより、前記電解質層と前記負極層との間に非晶質のリチウム窒化物層を形成することを特徴とする。 The first all solid-state polymer battery production method of the present invention comprises:
(1) A step of arranging a positive electrode layer on one side of the positive electrode current collecting layer to obtain a positive electrode laminate,
(2) Disposing a negative electrode layer containing lithium on one surface of the negative electrode current collecting layer to obtain a negative electrode laminate,
(3) After applying a solution of a dry polymer electrolyte on the negative electrode layer in the negative electrode laminate, the solvent is removed by drying, and a dry polymer electrolyte layer is formed on the negative electrode layer to obtain an intermediate laminate. Process,
(4) a step of superimposing the positive electrode laminate and the intermediate laminate so that the positive electrode layer and the electrolyte layer face each other to obtain an electrode composite; and (5) a step of sealing the electrode composite. Including
An amorphous lithium nitride layer is formed between the electrolyte layer and the negative electrode layer by performing the steps (2) to (5) in an atmosphere having a nitrogen content of 0.1 to 10% by volume. It is characterized by forming.

本発明の第２の全固体型ポリマー電池の製造方法は、
（Ａ）基材上にドライポリマー電解質の溶液を塗布した後、乾燥させて溶媒を除去し、基材上にドライポリマー電解質層を形成する工程、
（Ｂ）正極集電層の片面に正極層を配置し、正極積層体を得る工程、
（Ｃ）負極集電層の片面にリチウムを含む負極層を配置し、負極積層体を得る工程、
（Ｄ）前記基材からドライポリマー電解質層を剥離し、前記負極積層体における前記負極層上にドライポリマー電解質層を配置して中間積層体を得る工程、
（Ｅ）前記正極層と前記電解質層が対向するように、前記正極積層体と前記中間積層体とを重ね合わせ、電極複合体を得る工程、および
（Ｆ）前記電極複合体を密封する工程を含み、
前記工程（Ａ）を純窒素雰囲気下で実施し、前記工程（Ｂ）〜（Ｆ）を窒素含有量１０体積％以下の雰囲気下で実施することにより、前記電解質層と前記負極層との間に非晶質のリチウム窒化物層を形成することを特徴とする。 The method for producing the second all solid-state polymer battery of the present invention comprises:
(A) A step of applying a dry polymer electrolyte solution on a substrate and then drying to remove the solvent to form a dry polymer electrolyte layer on the substrate;
(B) A step of arranging a positive electrode layer on one side of the positive electrode current collecting layer to obtain a positive electrode laminate,
(C) a step of disposing a negative electrode layer containing lithium on one side of the negative electrode current collecting layer to obtain a negative electrode laminate,
(D) peeling the dry polymer electrolyte layer from the substrate and disposing the dry polymer electrolyte layer on the negative electrode layer in the negative electrode laminate to obtain an intermediate laminate;
(E) a step of superposing the positive electrode laminate and the intermediate laminate so that the positive electrode layer and the electrolyte layer face each other to obtain an electrode composite; and (F) a step of sealing the electrode composite. Including
By carrying out the step (A) in a pure nitrogen atmosphere and carrying out the steps (B) to (F) in an atmosphere having a nitrogen content of 10% by volume or less, between the electrolyte layer and the negative electrode layer. And forming an amorphous lithium nitride layer.

本発明によれば、保存時の内部抵抗の増大を抑制することができ、保存後の高率放電特性に優れた全固体型ポリマー電池を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the increase in internal resistance at the time of a preservation | save can be suppressed and the all-solid-state polymer battery excellent in the high rate discharge characteristic after a preservation | save can be provided.

本発明は、正極層、リチウムを含む負極層、および前記正極層と前記負極層との間に配されたドライポリマー電解質層を備えた全固体型ポリマー電池に関し、前記負極層と前記電解質層との間、すなわち負極界面部に非晶質のリチウム窒化物層が設けられた点に特徴を有する。
これにより、ドライポリマー電解質を用いた場合でも、保存時の負極界面部の抵抗（以下、界面抵抗とする。）の増大を抑制することができる。このため、保存時の電池の内部抵抗の増大が抑制され、保存後の高率放電特性に優れた全固体型ポリマー電池が得られる。 The present invention relates to an all-solid-state polymer battery comprising a positive electrode layer, a negative electrode layer containing lithium, and a dry polymer electrolyte layer disposed between the positive electrode layer and the negative electrode layer, the negative electrode layer and the electrolyte layer, In other words, the amorphous lithium nitride layer is provided at the interface portion of the negative electrode.
Thereby, even when a dry polymer electrolyte is used, an increase in the resistance of the negative electrode interface during storage (hereinafter referred to as interface resistance) can be suppressed. For this reason, an increase in the internal resistance of the battery during storage is suppressed, and an all solid-state polymer battery excellent in high-rate discharge characteristics after storage can be obtained.

上記リチウムを含む負極層は、例えば、リチウムまたはリチウム合金の活物質（以下、リチウム系活物質とする。）の層からなる。
リチウム系活物質に対して、リチウム窒化物はドライポリマー電解質より安定であるため、保存時の負極界面部におけるドライポリマー電解質の分解を抑制することができる。また、リチウム窒化物が非晶質であるため、界面抵抗を低減することができる。リチウム窒化物層が非晶質であると、窒素イオンと結合するリチウムイオンの状態が変化し、リチウム窒化物層内でリチウムイオンが拘束されにくくなり、イオン伝導性が向上する。このため、負極界面部（リチウム窒化物層）内におけるリチウムイオンの移動が速くなり、界面抵抗が小さくなると考えられる。 The negative electrode layer containing lithium is composed of, for example, a layer of lithium or a lithium alloy active material (hereinafter referred to as a lithium-based active material).
Since lithium nitride is more stable than a dry polymer electrolyte relative to a lithium-based active material, decomposition of the dry polymer electrolyte at the negative electrode interface during storage can be suppressed. In addition, since lithium nitride is amorphous, interface resistance can be reduced. If the lithium nitride layer is amorphous, the state of the lithium ions that bind to the nitrogen ions changes, making it difficult for lithium ions to be restrained in the lithium nitride layer and improving the ion conductivity. For this reason, it is considered that the movement of lithium ions in the negative electrode interface (lithium nitride layer) becomes faster and the interface resistance becomes smaller.

本発明の第１の全固体型ポリマー電池の製造方法は、ドライポリマー電解質層の作製およびドライポリマー電解質層を用いた電池組立てを、窒素含有量０．１〜１０体積％の雰囲気下で行う点に特徴を有する。すなわち、
（１）正極集電層の片面に正極層を配置し、正極積層体を得る工程、
（２）負極集電層の片面にリチウムを含む負極層を配置し、負極積層体を得る工程、
（３）前記負極積層体における前記負極層上に、ドライポリマー電解質の溶液を塗布した後、乾燥させて溶媒を除去し、前記負極層上にドライポリマー電解質層を形成し、中間積層体を得る工程、
（４）前記正極層と前記電解質層が対向するように、前記正極積層体と前記中間積層体とを重ね合わせ、電極複合体を得る工程、および
（５）前記電極複合体を密封する工程を含み、
前記工程（２）〜（５）を、窒素含有量０．１〜１０体積％の雰囲気下で実施することにより、前記電解質層と前記負極層との間に非晶質のリチウム窒化物層を形成する。 In the first method for producing an all-solid-state polymer battery of the present invention, the production of a dry polymer electrolyte layer and the assembly of the battery using the dry polymer electrolyte layer are performed in an atmosphere having a nitrogen content of 0.1 to 10% by volume. It has the characteristics. That is,
(1) A step of arranging a positive electrode layer on one side of the positive electrode current collecting layer to obtain a positive electrode laminate,
(2) Disposing a negative electrode layer containing lithium on one surface of the negative electrode current collecting layer to obtain a negative electrode laminate,
(3) After applying a solution of a dry polymer electrolyte on the negative electrode layer in the negative electrode laminate, the solvent is removed by drying, and a dry polymer electrolyte layer is formed on the negative electrode layer to obtain an intermediate laminate. Process,
(4) a step of superimposing the positive electrode laminate and the intermediate laminate so that the positive electrode layer and the electrolyte layer face each other to obtain an electrode composite; and (5) a step of sealing the electrode composite. Including
An amorphous lithium nitride layer is formed between the electrolyte layer and the negative electrode layer by performing the steps (2) to (5) in an atmosphere having a nitrogen content of 0.1 to 10% by volume. Form.

上記方法により、負極層における電解質層との接触面（負極界面部）に非晶質のリチウム窒化物層を確実かつ容易に形成することができる。工程（２）〜（５）において、雰囲気中の窒素含有量が１０体積％を超えると、負極界面部に結晶質のリチウム窒化物が生成しやすい。また、工程（２）〜（５）において、雰囲気中の窒素含有量が０．１体積％未満であると、リチウム窒化物層を確実に形成するのが困難である。
工程（１）は、工程（２）〜（５）と同様の雰囲気で実施してもよく、異なる雰囲気で実施してもよいが、作業効率の観点から、工程（１）も工程（２）〜（５）と同様の雰囲気で実施するのが好ましい。 By the above method, an amorphous lithium nitride layer can be reliably and easily formed on the contact surface (negative electrode interface portion) of the negative electrode layer with the electrolyte layer. In the steps (2) to (5), when the nitrogen content in the atmosphere exceeds 10% by volume, crystalline lithium nitride is likely to be generated at the negative electrode interface. In steps (2) to (5), if the nitrogen content in the atmosphere is less than 0.1% by volume, it is difficult to reliably form a lithium nitride layer.
Step (1) may be carried out in the same atmosphere as steps (2) to (5) or in a different atmosphere, but from the viewpoint of work efficiency, step (1) is also step (2). It is preferable to carry out in the same atmosphere as in (5).

本発明の第２の固体型ポリマー電池の製造方法は、電解質層の作製を純窒素雰囲気で行い、電解質層を用いた電池組立てを、窒素含有量１０体積％以下の雰囲気で行う点に特徴を有する。すなわち、
（Ａ）基材上にドライポリマー電解質の溶液を塗布した後、乾燥させて溶媒を除去し、基材上にドライポリマー電解質層を形成する工程、
（Ｂ）正極集電層の片面に正極層を配置し、正極積層体を得る工程、
（Ｃ）負極集電層の片面に負極層を配置し、負極積層体を得る工程、
（Ｄ）前記基材からドライポリマー電解質層を剥離し、前記負極積層体における前記負極層上にドライポリマー電解質層を配置して中間積層体を得る工程、
（Ｅ）前記正極層と前記電解質層が対向するように、前記正極積層体と前記中間積層体とを重ね合わせ、電極複合体を得る工程、および
（Ｆ）前記電極複合体を密封する工程を含み、
前記工程（Ａ）を純窒素雰囲気下で実施し、前記工程（Ｃ）〜（Ｆ）を窒素含有量１０体積％以下の雰囲気下で実施することにより、前記電解質層と前記負極層との間に非晶質のリチウム窒化物層を形成する。 The second solid-state polymer battery production method of the present invention is characterized in that the electrolyte layer is produced in a pure nitrogen atmosphere, and the battery assembly using the electrolyte layer is conducted in an atmosphere having a nitrogen content of 10% by volume or less. Have. That is,
(A) A step of applying a dry polymer electrolyte solution on a substrate and then drying to remove the solvent to form a dry polymer electrolyte layer on the substrate;
(B) A step of arranging a positive electrode layer on one side of the positive electrode current collecting layer to obtain a positive electrode laminate,
(C) A step of disposing a negative electrode layer on one side of the negative electrode current collecting layer to obtain a negative electrode laminate,
(D) peeling the dry polymer electrolyte layer from the substrate and disposing the dry polymer electrolyte layer on the negative electrode layer in the negative electrode laminate to obtain an intermediate laminate;
(E) a step of superposing the positive electrode laminate and the intermediate laminate so that the positive electrode layer and the electrolyte layer face each other to obtain an electrode composite; and (F) a step of sealing the electrode composite. Including
By performing the step (A) in a pure nitrogen atmosphere and performing the steps (C) to (F) in an atmosphere having a nitrogen content of 10% by volume or less, the electrolyte layer and the negative electrode layer Then, an amorphous lithium nitride layer is formed.

上記方法により、負極層における電解質層との接触面（負極界面部）に非晶質のリチウム窒化物層を確実かつ容易に形成することができる。工程（Ｃ）〜（Ｆ）において、雰囲気中の窒素含有量が１０体積％を超えると、負極界面部に結晶質のリチウム窒化物が生成しやすい。
窒素含有量１０体積％以下の雰囲気としては、例えば、純アルゴン雰囲気が挙げられる。
工程（Ｂ）は、工程（Ａ）と同様の雰囲気で実施してもよく、工程（Ｃ）〜（Ｆ）と同様の雰囲気で実施してもよいが、作業効率の観点から、工程（Ｂ）は工程（Ｃ）〜（Ｆ）と同様の雰囲気で実施するのが好ましい。 By the above method, an amorphous lithium nitride layer can be reliably and easily formed on the contact surface (negative electrode interface portion) of the negative electrode layer with the electrolyte layer. In steps (C) to (F), when the nitrogen content in the atmosphere exceeds 10% by volume, crystalline lithium nitride is likely to be generated at the negative electrode interface.
Examples of the atmosphere having a nitrogen content of 10% by volume or less include a pure argon atmosphere.
Step (B) may be performed in the same atmosphere as in step (A) or in the same atmosphere as in steps (C) to (F), but from the viewpoint of work efficiency, step (B) ) Is preferably carried out in the same atmosphere as in steps (C) to (F).

上記製造方法で得られたリチウム窒化物が非晶質であることは、例えばＸＰＳ分析により確認することができる。リチウム窒化物が非晶質である場合、ＸＰＳ分析により得られるＮの１ｓスペクトルは、結合エネルギー３９０．０〜３９６．０ｅＶの範囲において、３９３．５〜３９４．５ｅＶのみに極大のピークを有する。これに対して、リチウム窒化物が結晶質Ｌｉ3Ｎである場合、ＸＰＳ分析により得られるＮの１ｓスペクトルは、結合エネルギー３９０．０〜３９６．０ｅＶの範囲において、３９３．５〜３９４．５ｅＶおよび３９１．５〜３９２．５ｅＶに極大のピークを有する。 It can be confirmed, for example, by XPS analysis that the lithium nitride obtained by the above production method is amorphous. When lithium nitride is amorphous, the 1s spectrum of N obtained by XPS analysis has a maximum peak only at 393.5 to 394.5 eV in the range of binding energy 390.0 to 396.0 eV. In contrast, when the lithium nitride is crystalline Li 3 N, the 1s spectrum of N obtained by XPS analysis is 393.5 to 394.5 eV and a binding energy of 390.0 to 396.0 eV and It has a maximum peak at 391.5 to 392.5 eV.

負極界面部におけるリチウムイオン伝導性の向上効果および保存時の内部抵抗上昇の抑制効果が顕著に得られるため、上記製造方法で得られる非晶質のリチウム窒化物層の厚みは、５０〜１０００ｎｍが好ましい。
また、保存時の内部抵抗上昇の抑制効果が顕著に得られるため、負極層における上記非晶質のリチウム窒化物層の被覆率は、３０〜１００％が好ましい。
上記製造方法で得られた非晶質のリチウム窒化物層は、負極層がリチウム合金活物質層からなる場合、リチウムおよび窒素以外にリチウム合金中に含まれる元素を含んでいてもよい。
上記製造時の窒素を含む雰囲気としては、例えば窒素およびアルゴンガス等の不活性ガスの混合雰囲気が挙げられる。 Since the effect of improving lithium ion conductivity at the negative electrode interface and the effect of suppressing the increase in internal resistance during storage can be obtained remarkably, the thickness of the amorphous lithium nitride layer obtained by the above production method is 50 to 1000 nm. preferable.
Moreover, since the inhibitory effect of the increase in internal resistance during storage is remarkably obtained, the coverage of the amorphous lithium nitride layer in the negative electrode layer is preferably 30 to 100%.
When the negative electrode layer is made of a lithium alloy active material layer, the amorphous lithium nitride layer obtained by the above production method may contain an element contained in the lithium alloy in addition to lithium and nitrogen.
As an atmosphere containing nitrogen at the time of the said manufacture, the mixed atmosphere of inert gas, such as nitrogen and argon gas, is mentioned, for example.

以下、本発明の一実施の形態として扁平形全固体型ポリマー電池を、図９を参照しながら説明する。図９は、本発明の扁平型全固体型ポリマー電池の概略縦断面図である。
図９に示すように、電池は、負極積層体１１、ドライポリマー電解質層１、および正極積層体１２からなる電極複合体を含む。負極積層体１１は、負極層（リチウム系活物質層）２（例えば、厚み１〜３００μｍ）および負極集電層４（例えば、厚み５〜２００μｍ）からなる。正極積層体１２は、正極層３（例えば、厚み１〜１００μｍ）および正極集電層５（例えば、厚み５〜２００μｍ）からなる。負極層２と正極層３とが対向するように、負極積層体１１と正極積層体１２とがドライポリマー電解質層１（例えば、厚み１０〜２００μｍ）を介して配されている。すなわち、負極層２と正極層３との間にドライポリマー電解質層１が配されている。ドライポリマー電解質層１と負極層２との間に非晶質のリチウム窒化物層７が形成されている。電極複合体を構成する各層は円板状であり、正極集電層５および負極集電層４は、正極層３、負極層２、および電解質層１よりも径が大きい。正極集電層５の周縁部と負極集電層４の周縁部との間に、正極３、負極層２および電解質層１を囲むようにシール材６が配されている。このようにシール材６を用いることにより電極複合体が密封されている。 Hereinafter, a flat all solid-state polymer battery according to an embodiment of the present invention will be described with reference to FIG. FIG. 9 is a schematic longitudinal sectional view of the flat type all solid-state polymer battery of the present invention.
As shown in FIG. 9, the battery includes an electrode composite including a negative electrode laminate 11, a dry polymer electrolyte layer 1, and a positive electrode laminate 12. The negative electrode laminate 11 includes a negative electrode layer (lithium-based active material layer) 2 (for example, a thickness of 1 to 300 μm) and a negative electrode current collecting layer 4 (for example, a thickness of 5 to 200 μm). The positive electrode laminate 12 includes a positive electrode layer 3 (for example, a thickness of 1 to 100 μm) and a positive electrode current collecting layer 5 (for example, a thickness of 5 to 200 μm). A negative electrode laminate 11 and a positive electrode laminate 12 are arranged via a dry polymer electrolyte layer 1 (for example, a thickness of 10 to 200 μm) so that the negative electrode layer 2 and the positive electrode layer 3 face each other. That is, the dry polymer electrolyte layer 1 is disposed between the negative electrode layer 2 and the positive electrode layer 3. An amorphous lithium nitride layer 7 is formed between the dry polymer electrolyte layer 1 and the negative electrode layer 2. Each layer constituting the electrode composite has a disk shape, and the positive electrode current collecting layer 5 and the negative electrode current collecting layer 4 have a larger diameter than the positive electrode layer 3, the negative electrode layer 2, and the electrolyte layer 1. A sealing material 6 is disposed between the peripheral edge of the positive electrode current collecting layer 5 and the peripheral edge of the negative electrode current collecting layer 4 so as to surround the positive electrode 3, the negative electrode layer 2, and the electrolyte layer 1. Thus, the electrode composite is sealed by using the sealing material 6.

図９に示す構造の全固体型ポリマー電池は、例えば、以下の２つの方法により作製することができる。
本発明の第１の製造方法の一例を以下に示す。窒素含有量０．１〜１０体積％の雰囲気下で以下の工程（電解質層１の作製および電解質層１を用いた電池の組立て）を実施する。負極集電層４の片面に負極層２を圧着し、負極積層体１１を得る。ついで、負極層２の上にドライポリマー電解質の溶液をキャストし、溶媒を乾燥除去して、電解質層１を得る。このようにして、負極積層体１１と電解質層１の中間積層体を得る。その後、正極集電層５の片面に正極層３を被着させて正極積層体１２を得る。正極層３と電解質層１とが対向するように、正極積層体１２と中間積層体とを重ね合わせて、正極積層体１２、負極積層体１１、および両層間に配されたドライポリマー電解質層１からなる電極複合体を得る。電極複合体の周縁部にシール材６を配して電極複合体を密封する。このようにして、全固体型ポリマー電池２１を組立てる。より具体的には、図９では、正極集電層５および負極集電層４が、正極層３、負極層２、および電解質層１よりも径が大きいため、正極集電層５の周縁部と、負極集電層４の周縁部との間に、シール材６を配する。正極集電層５、負極集電層４、およびシール部材６により、正極層３、負極層２、および電解質層１を封止する。 The all-solid-state polymer battery having the structure shown in FIG. 9 can be produced, for example, by the following two methods.
An example of the 1st manufacturing method of this invention is shown below. The following steps (preparation of electrolyte layer 1 and assembly of a battery using electrolyte layer 1) are performed under an atmosphere having a nitrogen content of 0.1 to 10% by volume. The negative electrode layer 2 is pressure-bonded to one surface of the negative electrode current collecting layer 4 to obtain the negative electrode laminate 11. Next, a solution of the dry polymer electrolyte is cast on the negative electrode layer 2, and the solvent is removed by drying to obtain the electrolyte layer 1. In this way, an intermediate laminate of the negative electrode laminate 11 and the electrolyte layer 1 is obtained. Thereafter, the positive electrode layer 3 is deposited on one surface of the positive electrode current collecting layer 5 to obtain the positive electrode laminate 12. The positive electrode laminate 12 and the intermediate laminate are overlapped so that the positive electrode layer 3 and the electrolyte layer 1 face each other, and the positive electrode laminate 12, the negative electrode laminate 11, and the dry polymer electrolyte layer 1 disposed between both layers. An electrode composite consisting of is obtained. The electrode composite is sealed by disposing a sealing material 6 on the peripheral edge of the electrode composite. In this way, the all solid-state polymer battery 21 is assembled. More specifically, in FIG. 9, since the positive electrode current collecting layer 5 and the negative electrode current collecting layer 4 have a larger diameter than the positive electrode layer 3, the negative electrode layer 2, and the electrolyte layer 1, The sealing material 6 is disposed between the negative electrode current collecting layer 4 and the peripheral edge portion thereof. The positive electrode current collecting layer 5, the negative electrode current collecting layer 4, and the seal member 6 seal the positive electrode layer 3, the negative electrode layer 2, and the electrolyte layer 1.

上記製造方法で、リチウム窒化物層が形成される理由としては、以下の２つが考えられる。
１つは、電解質層１を窒素含有雰囲気で作製する際、ドライポリマー電解質の溶液中に窒素が溶存する。その後、負極層２上にドライポリマー電解質の溶液をキャストした際、電解質層１中に溶存する窒素が電解質層１と接触する負極層２中のリチウム系活物質と反応して、リチウム窒化物が生成するためと考えられる。もう一つは、雰囲気中の窒素とリチウム系活物質が直接反応して、負極層２の表面にリチウム窒化物が生成するためと考えられる。 There are two possible reasons why the lithium nitride layer is formed by the above manufacturing method.
First, when the electrolyte layer 1 is produced in a nitrogen-containing atmosphere, nitrogen is dissolved in the dry polymer electrolyte solution. Thereafter, when a dry polymer electrolyte solution is cast on the negative electrode layer 2, nitrogen dissolved in the electrolyte layer 1 reacts with the lithium-based active material in the negative electrode layer 2 in contact with the electrolyte layer 1, so that lithium nitride is formed. It is thought to generate. Another reason is that nitrogen in the atmosphere and the lithium-based active material directly react to generate lithium nitride on the surface of the negative electrode layer 2.

次に、本発明の第２の製造方法の一例を以下に示す。純窒素雰囲気において、ポリエチレンテレフタレート（ＰＥＴ）のフィルム等からなる基材上にドライポリマー電解質の溶液をキャストし、その後溶媒を乾燥除去して、基材上にドライポリマー電解質層１を形成する。その後、基材上に形成されたドライポリマー電解質層１を純アルゴン雰囲気下に移動させる。これ以降の工程（上記ドライポリマー電解質層の作製以外の工程）は、すべて純アルゴン雰囲気にて実施する。負極集電体４の片面に負極層２を圧着して、負極積層体１１を得る。ついで、ドライポリマー電解質層１を基材から剥離し、負極層２の上に載置する。このようにして、負極積層体１１とドライポリマー電解質層１からなる中間積層体を得る。その後、正極集電層５の片面に正極層３を被着させて正極積層体１２を得る。正極層３と電解質層１とが対向するように、正極積層体１２と中間積層体とを重ね合わせて、正極積層体１２、負極積層体１１、および両層間に配されたドライポリマー電解質層１からなる電極複合体を得る。上記と同様に電極複合体の周縁部にシール材６を配置して、電極複合体を封止する。このようにして、全固体型ポリマー電池２１を組立てる。
上記２つの方法のいずれにおいても、負極界面部に確実に非晶質のリチウム窒化物層を形成することができる。負極界面部に非晶質のリチウム窒化物層を効率よく形成することができる点で、上記方法による電池組立て後にエージングを行うのが好ましい。 Next, an example of the 2nd manufacturing method of this invention is shown below. In a pure nitrogen atmosphere, a dry polymer electrolyte solution is cast on a substrate made of a polyethylene terephthalate (PET) film or the like, and then the solvent is removed by drying to form the dry polymer electrolyte layer 1 on the substrate. Thereafter, the dry polymer electrolyte layer 1 formed on the substrate is moved under a pure argon atmosphere. All subsequent steps (steps other than the production of the dry polymer electrolyte layer) are performed in a pure argon atmosphere. The negative electrode layer 2 is pressure-bonded to one surface of the negative electrode current collector 4 to obtain the negative electrode laminate 11. Next, the dry polymer electrolyte layer 1 is peeled from the substrate and placed on the negative electrode layer 2. In this way, an intermediate laminate comprising the negative electrode laminate 11 and the dry polymer electrolyte layer 1 is obtained. Thereafter, the positive electrode layer 3 is deposited on one surface of the positive electrode current collecting layer 5 to obtain the positive electrode laminate 12. The positive electrode laminate 12 and the intermediate laminate are overlapped so that the positive electrode layer 3 and the electrolyte layer 1 face each other, and the positive electrode laminate 12, the negative electrode laminate 11, and the dry polymer electrolyte layer 1 disposed between both layers. An electrode composite consisting of is obtained. The sealing material 6 is arrange | positioned to the peripheral part of an electrode complex similarly to the above, and an electrode complex is sealed. In this way, the all solid-state polymer battery 21 is assembled.
In either of the two methods, an amorphous lithium nitride layer can be reliably formed at the negative electrode interface. Aging is preferably performed after battery assembly by the above method in that an amorphous lithium nitride layer can be efficiently formed at the negative electrode interface.

ドライポリマー電解質層１は、例えばエーテル酸素やエステル酸素など電子供与性を有する酸素原子を分子内に含むポリマー（以下、単に酸素含有ポリマーとする）と、ポリマー中に溶解するリチウム塩とからなる。このようなドライポリマー電解質では、エーテル酸素やエステル酸素がリチウムイオンに配位する。酸素含有ポリマーとしては、例えば、ポリエチレンオキサイド、ポリプロピレンオキサイド、エチレンオキサイドとプロピレンオキサイドとの共重合体、エチレンオキサイド単位もしくはプロピレンオキサイド単位からなるポリマー、またはポリカーボネートが用いられる。   The dry polymer electrolyte layer 1 is made of, for example, a polymer containing oxygen atoms having electron donating properties such as ether oxygen and ester oxygen (hereinafter simply referred to as oxygen-containing polymer) and a lithium salt dissolved in the polymer. In such a dry polymer electrolyte, ether oxygen and ester oxygen are coordinated to lithium ions. As the oxygen-containing polymer, for example, polyethylene oxide, polypropylene oxide, a copolymer of ethylene oxide and propylene oxide, a polymer composed of ethylene oxide units or propylene oxide units, or polycarbonate is used.

リチウム塩がポリマー骨格に溶解・解離するためには、リチウムイオンと対アニオン間の相互作用に匹敵するリチウムイオンとポリマー骨格間の強い相互作用が必要となる。上述したように、酸素含有ポリマーでは、酸素がリチウムイオンに配位可能なため、ドライポリマー電解質中においてリチウム塩は解離し溶解する。ポリマー鎖（骨格）のセグメント運動により、この解離したリチウムイオンはポリマー内を移動可能なため、ドライポリマー電解質はイオン伝導性を有する。   In order for the lithium salt to dissolve and dissociate in the polymer skeleton, a strong interaction between the lithium ion and the polymer skeleton, which is comparable to the interaction between the lithium ion and the counter anion, is required. As described above, in the oxygen-containing polymer, oxygen can be coordinated to lithium ions, so that the lithium salt is dissociated and dissolved in the dry polymer electrolyte. Since the dissociated lithium ions can move in the polymer due to the segmental movement of the polymer chain (skeleton), the dry polymer electrolyte has ion conductivity.

リチウム塩としては、例えば、ＬｉＣｌＯ4、ＬｉＢＦ4、ＬｉＰＦ6、ＬｉＡｌＣｌ4、ＬｉＳｂＦ6、ＬｉＳＣＮ、ＬｉＣＦ3ＳＯ3、ＬｉＡｓＦ6、低級脂肪族カルボン酸リチウム、ＬｉＣｌ、ＬｉＢｒ、ＬｉＩ、クロロボランリチウム、四フェニルホウ酸リチウム、ＬｉＮ（ＣＦ3ＳＯ2）2、またはＬｉＮ（Ｃ2Ｆ5ＳＯ2）2が挙げられる。これらを単独で用いてもよく、２種以上を組み合わせて用いてもよい。上記リチウム塩の中でも、ＬｉＮ（ＣＦ3ＳＯ2）2、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2、またはＬｉＣｌＯ4が好ましい。これらのリチウム塩を用いた場合、ドライポリマー電解質のリチウム系活物質に対する安定性が向上し、良好な負極界面部を実現することができる。 Examples of the lithium salt, LiClO 4, LiBF 4, LiPF 6, LiAlCl 4, LiSbF 6, LiSCN, LiCF 3 SO 3, LiAsF 6, lithium lower aliphatic carboxylate, LiCl, LiBr, LiI, chloroborane lithium, Four Examples include lithium phenylborate, LiN (CF 3 SO 2 ) 2 , or LiN (C 2 F 5 SO 2 ) 2 . These may be used alone or in combination of two or more. Among the lithium salts, LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , or LiClO 4 is preferable. When these lithium salts are used, the stability of the dry polymer electrolyte with respect to the lithium-based active material is improved, and a good negative electrode interface can be realized.

ドライポリマー電解質に、その目的を損なわない限りにおいて他の成分を添加してもよい。例えば、強度や膜質の均一性を向上させる目的で、各種無機フィラーを添加してもよい。添加によりイオン伝導性をさらに向上させることも可能である。上記無機フィラーとしては、例えば、アルミナやシリカなどの微粒子が挙げられる。ドライポリマー電解質は、リチウム塩とグライム類の固体の結晶性錯体を含んでいてもよい。
ドライポリマー電解質の支持体に多孔質シートを用いてもよい。多孔質シートには、例えば、ポリプロピレン、ポリエチレン、ポリエチレンテレフタレート、もしくはポリフェニレンサルファイドなどの不織布、またはポリプロピレンもしくはポリエチレンの微多孔性フィルムが用いられる。 Other components may be added to the dry polymer electrolyte as long as the purpose is not impaired. For example, various inorganic fillers may be added for the purpose of improving strength and uniformity of film quality. It is possible to further improve the ionic conductivity by addition. Examples of the inorganic filler include fine particles such as alumina and silica. The dry polymer electrolyte may contain a solid crystalline complex of a lithium salt and glymes.
A porous sheet may be used as a support for the dry polymer electrolyte. For the porous sheet, for example, a nonwoven fabric such as polypropylene, polyethylene, polyethylene terephthalate, or polyphenylene sulfide, or a microporous film of polypropylene or polyethylene is used.

正極層３は、例えば、正極活物質、導電材、および結着剤の混合物（正極合剤）からなる。
正極積層体１２は、例えば、正極集電層５の片面に、正極活物質、導電材、及び結着剤を混練して得られた正極合剤からなる正極層３を圧着させることにより得られる。また、正極積層体１２は、例えば、正極集電層５の片面に、正極合剤を脱水Ｎ−メチル−２−ピロリドン、エチレングリコールエーテル類などの液体中に溶解または分散させたスラリーを塗布、乾燥した後、圧延するなどの方法により被着させて、正極層３を形成することにより得られる。 The positive electrode layer 3 is made of, for example, a mixture (positive electrode mixture) of a positive electrode active material, a conductive material, and a binder.
The positive electrode laminate 12 is obtained, for example, by pressing a positive electrode layer 3 made of a positive electrode mixture obtained by kneading a positive electrode active material, a conductive material, and a binder on one surface of the positive electrode current collecting layer 5. . Moreover, the positive electrode laminate 12 is, for example, applied to one surface of the positive electrode current collecting layer 5 with a slurry in which the positive electrode mixture is dissolved or dispersed in a liquid such as dehydrated N-methyl-2-pyrrolidone or ethylene glycol ethers. After drying, it is obtained by forming the positive electrode layer 3 by applying it by a method such as rolling.

リチウム系活物質としては、従来から用いられているリチウム単体またはリチウム合金が挙げられる。リチウム合金としては、例えば、Ｌｉ−Ｓｉ合金、Ｌｉ−Ｓｎ合金、Ｌｉ−Ａｌ合金、Ｌｉ−Ｇａ合金、Ｌｉ−Ｍｇ合金、またはＬｉ−Ｉｎ合金が用いられる。
正極活物質としては、リチウム電池の正極活物質として使用可能なものであればよい。具体的には、例えば、（ＣＦ）n、（Ｃ2Ｆ）n、ＭｎＯ2、ＴｉＳ2、ＭｏＳ2、ＦｅＳ2、ＬｉxaＣｏＯ2、ＬｉxaＮｉＯ2、ＬｉxaＭｎＯ2、ＬｉxaＣｏyＮｉ1-yＯ2、ＬｉxaＣｏyＭ1-yＯz、ＬｉxaＮｉ1-yＭyＯz、ＬｉxbＭｎ2Ｏ4、またはＬｉxbＭｎ2-yＭyＯ4が挙げられる。ここで、上記式中の元素Ｍは、Ｎａ、Ｍｇ、Ｓｃ、Ｙ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ａｌ、Ｃｒ、Ｐｂ、Ｓｂ、およびＢからなる群より選択される少なくとも一種であり、ｘａ＝０〜１．２、ｘｂ＝０〜２．０、ｙ＝０〜０．９、およびｚ＝２．０〜２．３を満たす。上記のｘａおよびｘｂは、充放電開始前の値であり、充放電により増減する。また、上記以外に、正極活物質として、例えば、バナジウム酸化物もしくはそのリチウム化合物、ニオブ酸化物もしくはそのリチウム化合物、有機導電性物質を用いた共役系ポリマー、シェブレル相化合物、またはオリビン系化合物が用いられる。これらを単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the lithium-based active material include conventionally used lithium simple substance or lithium alloy. As the lithium alloy, for example, a Li—Si alloy, a Li—Sn alloy, a Li—Al alloy, a Li—Ga alloy, a Li—Mg alloy, or a Li—In alloy is used.
As a positive electrode active material, what can be used as a positive electrode active material of a lithium battery should just be used. Specifically, for example, (CF) n , (C 2 F) n , MnO 2 , TiS 2 , MoS 2 , FeS 2 , Li xa CoO 2 , Li xa NiO 2 , Li xa MnO 2 , Li xa Co y Ni 1-y O 2 , Li xa Co y M 1-y O z , Li xa Ni 1- y My O z , Li xb Mn 2 O 4 , or Li xb Mn 2- y My O 4 . Here, the element M in the above formula is at least one selected from the group consisting of Na, Mg, Sc, Y, Mn, Fe, Co, Ni, Cu, Zn, Al, Cr, Pb, Sb, and B. Xa = 0-1.2, xb = 0-2.0, y = 0-0.9, and z = 2.0-2.3. Said xa and xb are values before the start of charging / discharging, and increase / decrease by charging / discharging. In addition to the above, as the positive electrode active material, for example, vanadium oxide or a lithium compound thereof, niobium oxide or a lithium compound thereof, a conjugated polymer using an organic conductive material, a chevrel phase compound, or an olivine compound is used. It is done. These may be used alone or in combination of two or more.

導電材としては、例えば、天然黒鉛や人造黒鉛などのグラファイト類、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、もしくはサーマルブラックなどのカーボンブラック類、炭素繊維や金属繊維などの導電性繊維類、アルミニウム粉などの金属粉末類、酸化亜鉛やチタン酸カリウムなどの導電性ウィスカー類、酸化チタンなどの導電性金属酸化物、またはフェニレン誘導体などの有機導電性材料が挙げられる。   Examples of the conductive material include graphites such as natural graphite and artificial graphite, carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black, and conductive materials such as carbon fiber and metal fiber. Organic conductive materials such as conductive fibers, metal powders such as aluminum powder, conductive whiskers such as zinc oxide and potassium titanate, conductive metal oxides such as titanium oxide, and phenylene derivatives.

結着剤としては、例えば、ポリフッ化ビニリデン（ＰＶｄＦ）、ポリテトラフルオロエチレン、ポリエチレン、ポリプロピレン、アラミド樹脂、ポリアミド、ポリイミド、ポリアミドイミド、ポリアクリルニトリル、ポリアクリル酸、ポリアクリル酸メチル、ポリアクリル酸エチル、ポリアクリル酸ヘキシル、ポリメタクリル酸、ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリメタクリル酸ヘキシル、ポリ酢酸ビニル、ポリビニルピロリドン、ポリエーテル、ポリエーテルサルフォン、ヘキサフルオロポリプロピレン、スチレンブタジエンゴム、またはカルボキシメチルセルロースが挙げられる。また、正極表面から深部に至るまでイオンが容易に到達することができるため、結着剤としては、エチレングリコールエーテル類を含むドライポリマー電解質を用いるのが好ましい。これらは、単独で用いてもよく、２種以上を組み合わせて用いてもよい。   Examples of the binder include polyvinylidene fluoride (PVdF), polytetrafluoroethylene, polyethylene, polypropylene, aramid resin, polyamide, polyimide, polyamideimide, polyacrylonitrile, polyacrylic acid, polymethyl acrylate, and polyacrylic acid. Ethyl, polyhexyl acrylate, polymethacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polyhexyl methacrylate, polyvinyl acetate, polyvinyl pyrrolidone, polyether, polyether sulfone, hexafluoropolypropylene, styrene butadiene rubber, or Carboxymethylcellulose is mentioned. In addition, since ions can easily reach from the positive electrode surface to the deep part, it is preferable to use a dry polymer electrolyte containing ethylene glycol ethers as the binder. These may be used alone or in combination of two or more.

シール材６には、電池分野で常用される材料を使用すればよい。例えば、シール材６には、合成樹脂材料が用いられる。
本発明において用いられるドライポリマー電解質は一次電池および二次電池のいずれにも使用可能である。本発明の全固体型ポリマー電池の形態としては、扁平型、コイン型、円筒型、角型、またはラミネート型などが挙げられるが、その形態は特に限定されない。また、積層型、捲回型、またはバイポーラ型の電池でもよい。 As the sealing material 6, a material commonly used in the battery field may be used. For example, a synthetic resin material is used for the sealing material 6.
The dry polymer electrolyte used in the present invention can be used for either a primary battery or a secondary battery. Examples of the form of the all solid-state polymer battery of the present invention include a flat form, a coin form, a cylindrical form, a square form, and a laminate form, but the form is not particularly limited. In addition, a stacked type, a wound type, or a bipolar type battery may be used.

以下に、本発明の実施例を詳細に説明するが、本発明はこれらの実施例に限定されない。なお、以下の実施例における評価用セルおよび全固体型ポリマー電池の組立ては、すべて、室温でかつ−５０℃以下に露点管理された雰囲気で実施した。   Examples of the present invention will be described in detail below, but the present invention is not limited to these examples. In addition, the assembly of the evaluation cell and the all-solid-state polymer battery in the following examples were all performed in an atmosphere in which the dew point was controlled at room temperature and −50 ° C. or lower.

《実施例１》
図１に示す評価用セル（両極がリチウム電極からなる対称セル）を以下の手順で作製した。セルの作製は、窒素３．５体積％およびアルゴン９６．５体積％の雰囲気のグローブボックス中にて行った。
アセトニトリル１００ｇに、粘度平均分子量１００，０００のポリエチレンオキサイド（Ｓｉｇｍａ−Ａｌｄｒｉｃｈ製）１０ｇおよびジメトキシエタン（ＤＭＥ）１０ｇを溶解させてポリエチレンオキサイドのアセトニトリル溶液を得た。そして、このアセトニトリル溶液にＬｉＮ（ＣＦ3ＳＯ2）2を、リチウムイオン濃度［Ｌｉ］とポリマー中のエチレンオキサイド部のエーテル酸素濃度［ＥＯ］とのモル比率［Ｌｉ］／［ＥＯ］が０．０５となるように添加した。このようにして、ドライポリマー電解質のアセトニトリル溶液を得た。 Example 1
An evaluation cell shown in FIG. 1 (a symmetric cell in which both electrodes are lithium electrodes) was produced by the following procedure. The cell was manufactured in a glove box having an atmosphere of 3.5% by volume of nitrogen and 96.5% by volume of argon.
In 100 g of acetonitrile, 10 g of polyethylene oxide (manufactured by Sigma-Aldrich) having a viscosity average molecular weight of 100,000 and 10 g of dimethoxyethane (DME) were dissolved to obtain an acetonitrile solution of polyethylene oxide. Then, LiN (CF 3 SO 2 ) 2 is added to this acetonitrile solution, and the molar ratio [Li] / [EO] of the lithium ion concentration [Li] and the ether oxygen concentration [EO] of the ethylene oxide portion in the polymer is 0.00. It added so that it might become 05. In this way, an acetonitrile solution of the dry polymer electrolyte was obtained.

得られたドライポリマー電解質のアセトニトリル溶液を、リチウム箔４２（直径１０ｍｍ、厚み０．３ｍｍ）をあらかじめ圧着させたステンレス鋼製の封口板３１にキャストした。そして、室温で４８時間真空乾燥し、溶媒成分であるアセトニトリルとＤＭＥを除去し、電解質層４１を得た。
得られたドライポリマー電解質を熱抽出ＧＣ−ＭＳ測定した。その結果、ドライポリマー電解質からＤＭＥが検出された。微量のグライム溶媒（ＤＭＥ）は、ドライポリマー電解質中においてリチウムイオンと錯体を形成して、ドライポリマー電解質の導電性を高め、電池の保存後の高率放電特性を向上させる点で好ましい。 The obtained acetonitrile solution of the dry polymer electrolyte was cast onto a stainless steel sealing plate 31 to which a lithium foil 42 (diameter 10 mm, thickness 0.3 mm) was previously pressed. And it was vacuum-dried at room temperature for 48 hours, acetonitrile and DME which are solvent components were removed, and the electrolyte layer 41 was obtained.
The obtained dry polymer electrolyte was subjected to heat extraction GC-MS measurement. As a result, DME was detected from the dry polymer electrolyte. A very small amount of glyme solvent (DME) is preferable in that it forms a complex with lithium ions in the dry polymer electrolyte, increases the conductivity of the dry polymer electrolyte, and improves the high rate discharge characteristics after storage of the battery.

電解質層４１の上に、別のリチウム箔４２´（直径１０ｍｍ、厚み０．３ｍｍ）を圧着させて、封口板３１上に電極複合体を得た。一方、ステンレス製のケース３２の内底面に、皿バネ３５およびスペーサー３４を配した。なお、皿バネ３５およびスペーサー３４は、リチウム箔（電極）の厚み変化への対応および電極複合体とケース３２との隙間を埋める目的で設けられた。その後、このケース３２の開口端縁部を、封口板３１の周縁部にガスケット３３を介してかしめることにより、電極複合体をケース内に密封させた。このようにリチウム電極を用いてリチウム対称セル３０を作製した。   Another lithium foil 42 ′ (diameter 10 mm, thickness 0.3 mm) was pressure-bonded on the electrolyte layer 41 to obtain an electrode composite on the sealing plate 31. On the other hand, a disc spring 35 and a spacer 34 are arranged on the inner bottom surface of the stainless steel case 32. The disc spring 35 and the spacer 34 were provided for the purpose of responding to changes in the thickness of the lithium foil (electrode) and filling the gap between the electrode assembly and the case 32. Then, the electrode composite was sealed in the case by caulking the opening edge of the case 32 to the peripheral edge of the sealing plate 31 via the gasket 33. Thus, the lithium symmetrical cell 30 was produced using the lithium electrode.

リチウム対称セルを６０℃の恒温槽で３日間エージングした後、リチウム対称セルを分解し、リチウム箔を取り出し、リチウム箔のドライポリマー電解質の接触面を観察した。その観察結果を図２に示す。図２に示すように、リチウム表面に褐色の変色部が認められた。リチウム対称セル組立ての前には、この変色部は認められなかった。そこで、この変色部をＸＲＤ（Ｘ−ｒａｙ ｄｉｆｆｒａｃｔｉｏｎ、Ｘ線回折）およびＸＰＳ（Ｘ−ｒａｙ Ｐｈｏｔｏｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ、Ｘ線光電子分光法）で解析した。   After aging the lithium symmetric cell for 3 days in a thermostat at 60 ° C., the lithium symmetric cell was disassembled, the lithium foil was taken out, and the contact surface of the dry polymer electrolyte of the lithium foil was observed. The observation results are shown in FIG. As shown in FIG. 2, a brown discoloration portion was observed on the lithium surface. This discoloration was not observed before the lithium symmetrical cell assembly. Therefore, the discolored portion was analyzed by XRD (X-ray diffraction, X-ray diffraction) and XPS (X-ray Photoelectron Spectroscopy, X-ray photoelectron spectroscopy).

ＸＲＤ測定には、Ｘ線光電子分光装置（商品名：全自動多目的Ｘ線回折装置 X'Pert PRO、スペクトリス社製）を使用した。測定条件は、電圧：４５ｋＶ、電流：４０ｍＡ、走査モード：Ｃｏｎｔｉｎｕｏｕｓ、走査範囲：７〜９０℃、ステップ幅０．０２℃、走査速度：１００ｓ／ｓｔｅｐ、スリット幅（ＤＳ／ＳＳ／ＲＳ）：０．５°／０．５°／０．１ｍｍ、雰囲気：ヘリウムとした。   For XRD measurement, an X-ray photoelectron spectrometer (trade name: fully automatic multipurpose X-ray diffractometer X'Pert PRO, manufactured by Spectris) was used. Measurement conditions are voltage: 45 kV, current: 40 mA, scanning mode: Continuous, scanning range: 7 to 90 ° C., step width 0.02 ° C., scanning speed: 100 s / step, slit width (DS / SS / RS): 0 .5 ° / 0.5 ° / 0.1 mm, atmosphere: helium.

ＸＰＳ分析には、Ｘ線光電子分光装置（商品名：ＸＰＳ−７０００、理学電機工業（株）製）を使用した。測定条件は、Ｘ線源：Ｍｇ−Ｋα、電圧：１０ｋＶ、電流：１０ｍＡ、Ｘ線スポットサイズ：約９ｍｍ、真空度：１０-7Ｐａとした。帯電補正は、ハイドロカーボンの１ｓ電子の結合エネルギーまたはイオンエッチング（５０００ｎｍまでのイオンエッチング、加速電圧：５００Ｖ、角度：９０度、イオン電流密度：３２μＡ／ｃｍ2、エッチングレート：１ｎｍ／分）に用いたアルゴンの２ｐ電子の結合エネルギーを基準に行った。 For the XPS analysis, an X-ray photoelectron spectrometer (trade name: XPS-7000, manufactured by Rigaku Denki Kogyo Co., Ltd.) was used. The measurement conditions were as follows: X-ray source: Mg—Kα, voltage: 10 kV, current: 10 mA, X-ray spot size: about 9 mm, vacuum degree: 10 −7 Pa. Charging correction is used for binding energy of 1s electrons of hydrocarbon or ion etching (ion etching up to 5000 nm, acceleration voltage: 500 V, angle: 90 degrees, ion current density: 32 μA / cm 2 , etching rate: 1 nm / min) This was performed based on the binding energy of 2p electrons of argon.

ＸＲＤ測定の結果を図３に示す。図３に示すように、Ｌｉに由来する回折ピークは認められたが、それ以外の回折ピークは認められなかった。また、ＸＰＳで測定したＮの１ｓスペクトルを図４に示す。なお、図４中の各スペクトルは、下から順に、深さ０（最表面）、２、５、１０、２０、５０、１００、２００、３００、および５００ｎｍの場合を示す。図４に示すように、ＮとＬｉの結合に基づくピークが認められ、Ｎの１ｓスペクトルは、結合エネルギー３９０．０〜３９６．０ｅＶの範囲において、３９３．５〜３９４．５ｅＶのみに極大のピークを有するがことがわかった。
以上の結果から、負極界面部にできた褐色の変色部は非晶質のリチウム窒化物であることがわかった。すなわち、リチウム箔４２とドライポリマー電解質層４１との間、およびリチウム箔４２’とドライポリマー電解質４１との間に、それぞれ非晶質のリチウム窒化物層４７および４７’が形成されていることが確かめられた。
比較として、結晶質の粉末状の試薬Ｌｉ3ＮをＸＰＳ分析した結果、上記の非晶質のリチウム窒化物の場合とは異なり、結晶質リチウム窒化物では、結合エネルギー３９０．０〜３９６．０ｅＶの範囲において、３９３．５〜３９４ｅＶおよび３９１．５〜３９２．５ｅＶにそれぞれ極大のピークを示した。 The result of the XRD measurement is shown in FIG. As shown in FIG. 3, although the diffraction peak derived from Li was recognized, the other diffraction peak was not recognized. Moreover, the 1s spectrum of N measured by XPS is shown in FIG. In addition, each spectrum in FIG. 4 shows the case of depth 0 (outermost surface), 2, 5, 10, 20, 50, 100, 200, 300, and 500 nm in order from the bottom. As shown in FIG. 4, a peak based on the bond of N and Li is observed, and the 1s spectrum of N has a maximum peak only at 393.5 to 394.5 eV in the range of binding energy 390.0 to 396.0 eV. It was found to have
From the above results, it was found that the brown discoloration part formed at the negative electrode interface part was amorphous lithium nitride. That is, amorphous lithium nitride layers 47 and 47 ′ are formed between the lithium foil 42 and the dry polymer electrolyte layer 41 and between the lithium foil 42 ′ and the dry polymer electrolyte 41, respectively. It was confirmed.
As a comparison, as a result of XPS analysis of the crystalline powdery reagent Li 3 N, the binding energy 390.0 to 396.0 eV is different in the crystalline lithium nitride, unlike the case of the amorphous lithium nitride described above. In this range, maximum peaks were respectively shown at 393.5 to 394 eV and 391.5 to 392.5 eV.

《実施例２》
本実施例では、窒素およびアルゴンの体積比率を変化させることにより、雰囲気中の窒素含有量を０．１〜１０体積％の間で変化させた以外、実施例１と同様の方法によりリチウム対称セルを作製した。
そして、実施例１と同様の方法により、組立て前のリチウム表面の観察、エージング後のリチウム表面の観察、ＸＲＤ測定、およびＸＰＳ分析を行った。その結果を表１に示す。 Example 2
In this example, a lithium symmetric cell was formed in the same manner as in Example 1 except that the nitrogen content in the atmosphere was changed between 0.1 and 10% by volume by changing the volume ratio of nitrogen and argon. Was made.
Then, by the same method as in Example 1, observation of the lithium surface before assembly, observation of the lithium surface after aging, XRD measurement, and XPS analysis were performed. The results are shown in Table 1.

表１に示すように、実施例１と同様の結果が得られ、エージング後の負極界面部には非晶質のリチウム窒化物層が認められた。   As shown in Table 1, the same results as in Example 1 were obtained, and an amorphous lithium nitride layer was observed at the negative electrode interface after aging.

《比較例１》
雰囲気中の窒素含有量を０〜０．０８体積％の間で変化させた以外、実施例１と同様の方法によりリチウム対称セルを作製した。そして、実施例１と同様の方法により、組立て前のリチウム表面の観察、エージング後のリチウム表面の観察、ＸＲＤ測定、およびＸＰＳ分析を行った。その結果を表２に示す。 << Comparative Example 1 >>
A lithium symmetric cell was produced in the same manner as in Example 1 except that the nitrogen content in the atmosphere was changed between 0 and 0.08% by volume. Then, by the same method as in Example 1, observation of the lithium surface before assembly, observation of the lithium surface after aging, XRD measurement, and XPS analysis were performed. The results are shown in Table 2.

エージング後に、リチウム対称セルを分解し、リチウム箔を取り出して、ドライポリマー電解質との接触面を観察したが、リチウム箔表面に変色部は認められなかった。
リチウム表面をＸＲＤ測定およびＸＰＳ分析した。ＸＲＤの結果から、Ｌｉに由来する回折ピークは認められたが、それ以外の回折ピークは認められなかった。また、窒素含有量０％のＸＰＳでリチウムの表面分析を行った結果、図５に示すように、Ｎの１ｓに基づくスペクトルにピークは認められなかった。なお、図５中の各スペクトルは、下から順に、深さ０（最表面）、２、５、１０、２０、５０、１００、２００、３００、および５００ｎｍの場合を示す。
窒素含有量０〜０．０８体積％では、負極界面部にリチウム窒化物層は形成されなかった。 After aging, the lithium symmetrical cell was disassembled, the lithium foil was taken out, and the contact surface with the dry polymer electrolyte was observed, but no discoloration was observed on the lithium foil surface.
The lithium surface was subjected to XRD measurement and XPS analysis. From the XRD results, a diffraction peak derived from Li was observed, but no other diffraction peak was observed. Further, as a result of performing surface analysis of lithium with XPS having a nitrogen content of 0%, no peak was observed in the spectrum based on 1 s of N as shown in FIG. In addition, each spectrum in FIG. 5 shows the case of depth 0 (outermost surface), 2, 5, 10, 20, 50, 100, 200, 300, and 500 nm in order from the bottom.
When the nitrogen content was 0 to 0.08% by volume, no lithium nitride layer was formed at the negative electrode interface.

《比較例２》
雰囲気中の窒素含有量を１５〜１００体積％の間で変化させた以外、実施例１と同様の方法によりリチウム対称セルを作製した。そして、実施例１と同様の方法により、組立て前のリチウム表面の観察、エージング後のリチウム表面の観察、ＸＲＤ測定、およびＸＰＳ分析を行った。その結果を表３に示す。 << Comparative Example 2 >>
A lithium symmetric cell was produced in the same manner as in Example 1 except that the nitrogen content in the atmosphere was changed between 15 and 100% by volume. Then, by the same method as in Example 1, observation of the lithium surface before assembly, observation of the lithium surface after aging, XRD measurement, and XPS analysis were performed. The results are shown in Table 3.

雰囲気中の窒素含有量が１５体積％以上である場合、セル組立て前にリチウム表面に褐色の変色部が認められた。その変色部をＸＲＤ測定した結果、Ｌｉ3Ｎに基づく結晶性の回折ピークが認められた。このことから、雰囲気中の窒素含有量が１５体積％以上である場合、結晶性のＬｉ3Ｎが生成することがわかった。なお、窒素含有量１００体積％の純窒素雰囲気でリチウム対称セルを作製した場合に認められた変色部をＸＲＤ測定した結果を図６に示す。 When the nitrogen content in the atmosphere was 15% by volume or more, a brown discoloration was observed on the lithium surface before cell assembly. As a result of XRD measurement of the discolored portion, a crystalline diffraction peak based on Li 3 N was observed. From this, it was found that when the nitrogen content in the atmosphere is 15% by volume or more, crystalline Li 3 N is generated. In addition, the result of having performed the XRD measurement of the discoloration part recognized when producing a lithium symmetrical cell in the pure nitrogen atmosphere of nitrogen content 100 volume% is shown in FIG.

その変色部をＸＰＳ分析した結果、結晶質の粉末状の試薬Ｌｉ3ＮをＸＰＳ分析した結果と同様に、Ｎの１ｓスペクトルの結合エネルギー３９０〜３９６ｅＶの範囲において、３９３．５〜３９４ｅＶおよび３９１．５〜３９２．５ｅＶにそれぞれ極大ピークを示すことが確かめられた。なお、窒素含有量１００体積％の純窒素雰囲気でリチウム対称セルを作製した場合に認められた変色部をＸＰＳ分析した結果を図７に示す。なお、図７中の各スペクトルは、下から順に、深さ０（最表面）、２、５、１０、２０、５０、１００、２００、３００、および５００ｎｍの場合を示す。
エージングした後に、リチウム対称セルを分解し、リチウム箔を取り出して、電解質層との接触面を観察した結果、組立て前のリチウム箔を分析した場合と同様の結果が得られた。
以上のことから、雰囲気中の窒素含有量が１５〜１００体積％の場合、負極界面部に結晶性のＬｉ3Ｎ層が生成することが確かめられた。 As a result of XPS analysis of the discolored portion, 393.5 to 394 eV and 391.N in the range of binding energy 390 to 396 eV of the 1s spectrum of N in the same manner as the result of XPS analysis of the crystalline powdery reagent Li 3 N. It was confirmed that a maximum peak was observed at 5 to 392.5 eV. FIG. 7 shows the result of XPS analysis of the discolored portion observed when a lithium symmetric cell was produced in a pure nitrogen atmosphere with a nitrogen content of 100% by volume. In addition, each spectrum in FIG. 7 shows the case of depth 0 (outermost surface), 2, 5, 10, 20, 50, 100, 200, 300, and 500 nm in order from the bottom.
After aging, the lithium symmetric cell was disassembled, the lithium foil was taken out, and the contact surface with the electrolyte layer was observed. As a result, the same result as that obtained when the lithium foil before assembly was analyzed was obtained.
From the above, it was confirmed that when the nitrogen content in the atmosphere is 15 to 100% by volume, a crystalline Li 3 N layer is formed at the negative electrode interface.

実施例１および２、ならびに比較例１および２の結果から、雰囲気中の窒素含有量が０．１〜１０体積％であると、抵抗の小さい非晶質のリチウム窒化物が生成することがわかった。雰囲気中の窒素含有量が１０体積％を超えると、結晶質のリチウム窒化物が負極界面部に生成し、雰囲気中の窒素含有量が０．１体積％未満であると、負極界面部にリチウム窒化物層が生成しにくいことがわかった。
実施例１および２において、エージング後にリチウム箔表面にリチウム窒化物層が生成した理由は以下の２つが考えられる。１つは、窒素含有雰囲気で電解質層を作製した際、電解質層内に窒素が溶存し、電解質層内の窒素が電解質層と接触するリチウム系活物質と反応して生成したと考えられる。もう１つは、雰囲気中の窒素がリチウム系活物質に直接反応して生成したことが考えられる。 From the results of Examples 1 and 2 and Comparative Examples 1 and 2, it can be seen that amorphous lithium nitride having low resistance is formed when the nitrogen content in the atmosphere is 0.1 to 10% by volume. It was. When the nitrogen content in the atmosphere exceeds 10% by volume, crystalline lithium nitride is generated at the negative electrode interface, and when the nitrogen content in the atmosphere is less than 0.1% by volume, lithium is present at the negative electrode interface. It was found that a nitride layer was difficult to form.
In Examples 1 and 2, there are two possible reasons why the lithium nitride layer was formed on the surface of the lithium foil after aging. One is considered that when an electrolyte layer was produced in a nitrogen-containing atmosphere, nitrogen was dissolved in the electrolyte layer, and the nitrogen in the electrolyte layer was produced by reacting with a lithium-based active material in contact with the electrolyte layer. The other is considered to be that nitrogen in the atmosphere was generated by directly reacting with the lithium-based active material.

《実施例３》
純窒素雰囲気において基材となるＰＥＴフィルム上に、実施例１と同じドライポリマー電解質の溶液をキャストし、その後溶媒を室温で４８時間真空乾燥し、溶媒成分であるアセトニトリルとＤＭＥを除去した。このようにして、電解質層を作製した。その後、作製したドライポリマー電解質を純アルゴン雰囲気に移動させて、実施例１と同様の方法によりリチウム対称セルを組立てた。 Example 3
A solution of the same dry polymer electrolyte as in Example 1 was cast on a PET film serving as a substrate in a pure nitrogen atmosphere, and then the solvent was vacuum dried at room temperature for 48 hours to remove the solvent components acetonitrile and DME. In this way, an electrolyte layer was produced. Thereafter, the produced dry polymer electrolyte was moved to a pure argon atmosphere, and a lithium symmetric cell was assembled in the same manner as in Example 1.

そして、リチウム対称セルを６０℃の恒温槽で３日間エージングした後に、リチウム対称セルを分解し、リチウム箔を取り出して電解質層との接触面を観察した結果、褐色の変色部が認められた。リチウム対称セル組立ての前には、このような変色部は認められなかった。
また、この変色部についてＸＲＤ測定およびＸＰＳ分析した。その結果、実施例１と同様の結果が得られたことから、負極界面部には非晶質のリチウム窒化物層が生成していることがわかった。
エージングした後にリチウム箔表面にリチウム窒化物層が生成した理由は、電解質層を純窒素雰囲気にて作製した際、電解質層に窒素が溶存し、その後、この窒素が電解質層と接触するリチウム系活物質と反応して生成したと考えられる。 And after aging a lithium symmetrical cell for 3 days with a 60 degreeC thermostat, the lithium symmetrical cell was decomposed | disassembled, the lithium foil was taken out and the contact surface with an electrolyte layer was observed, As a result, the brown discoloration part was recognized. Such discoloration was not observed before the lithium symmetrical cell assembly.
The discolored portion was subjected to XRD measurement and XPS analysis. As a result, the same results as in Example 1 were obtained, and it was found that an amorphous lithium nitride layer was formed at the negative electrode interface.
The reason why the lithium nitride layer was formed on the surface of the lithium foil after aging was that when the electrolyte layer was produced in a pure nitrogen atmosphere, nitrogen was dissolved in the electrolyte layer, and then this lithium was contacted with the electrolyte layer. Probably produced by reacting with the substance.

ソーラトロン社製の１２５５ＷＢ型電気化学測定システムを用いて、上記で作製した各リチウム対称セルについて交流インピーダンス測定を行った。測定した結果、周波数０．０１Ｈｚ〜１ＭＨｚの範囲でのＮｙｑｕｉｓｔプロットにおいて円弧が確認された。そして、この円弧の高周波側の実軸切片を電解質抵抗として考え、低周波側の実軸切片を電解質抵抗と界面抵抗との合計として考え、これらの切片の値から界面抵抗値を算出した。
実施例１、３、および４（窒素含有量３．５体積％）、ならびに比較例１および２（窒素含有量１００体積％）のエージング前のリチウム対称セルを６０℃で保存し、３０℃での界面抵抗の経時変化を測定した。これらの測定結果を図８に示す。 Using a 1255WB electrochemical measurement system manufactured by Solartron, AC impedance measurement was performed on each lithium symmetric cell produced above. As a result of the measurement, an arc was confirmed in the Nyquist plot in the frequency range of 0.01 Hz to 1 MHz. The real axis intercept on the high frequency side of the arc was considered as the electrolyte resistance, the real axis intercept on the low frequency side was considered as the sum of the electrolyte resistance and the interface resistance, and the interface resistance value was calculated from the values of these intercepts.
The lithium symmetric cells before aging of Examples 1, 3, and 4 (nitrogen content 3.5% by volume) and Comparative Examples 1 and 2 (nitrogen content 100% by volume) were stored at 60 ° C. and 30 ° C. The change over time in the interfacial resistance was measured. The measurement results are shown in FIG.

実施例１、３、および４のリチウム対称セルでは、初期において界面抵抗がわずかに増大したが、すぐに界面抵抗の増大は認められなくなり、安定した値が得られた。これは負極界面部に非晶質のリチウム窒化物層が形成され、この層がドライポリマー電解質の分解を抑制する保護被膜として機能したためと考えられる。
一方、比較例１および２のリチウム対称セルでは、界面抵抗が大きく増大した。比較例１のリチウム対称セルでは、保護膜となるリチウム窒化物層が十分に存在しないため、負極界面部に絶縁性の被膜が生成し、界面抵抗が大きくなったと考えられる。また、比較例２のリチウム対称セルでは、リチウム窒化物層が結晶質であったため、負極界面部でのリチウムイオンの移動が難しくなり、また負極界面部の接合が不十分となったため、界面抵抗が大きくなったと考えられる。 In the lithium symmetric cells of Examples 1, 3, and 4, the interfacial resistance increased slightly in the initial stage, but immediately no increase in interfacial resistance was observed, and a stable value was obtained. This is presumably because an amorphous lithium nitride layer was formed at the negative electrode interface, and this layer functioned as a protective film that suppressed the decomposition of the dry polymer electrolyte.
On the other hand, in the lithium symmetric cells of Comparative Examples 1 and 2, the interface resistance was greatly increased. In the lithium symmetric cell of Comparative Example 1, since the lithium nitride layer serving as a protective film does not exist sufficiently, it is considered that an insulating film was formed at the negative electrode interface and the interface resistance was increased. Further, in the lithium symmetric cell of Comparative Example 2, since the lithium nitride layer was crystalline, it was difficult to move lithium ions at the negative electrode interface, and the junction at the negative electrode interface was insufficient, so that the interface resistance Seems to have grown.

実施例１のリチウム対称セルは、実施例３のリチウム対称セルと比べて低い界面抵抗が得られた。これは、実施例１では、リチウム窒化物層を確認できなかったが、窒素含有雰囲気でリチウムを取り扱っていたため、組立て前のリチウム箔表面には、検出できないレベルであるがリチウム窒化物が生成したと考えられる。そして、リチウム対称セルの組立て時において、この層の存在により電解質層とリチウム箔との接触が抑制され、界面抵抗が減少したと推測される。   The lithium symmetric cell of Example 1 had a lower interface resistance than the lithium symmetric cell of Example 3. In Example 1, the lithium nitride layer could not be confirmed. However, since lithium was handled in a nitrogen-containing atmosphere, lithium nitride was generated on the surface of the lithium foil before assembly, although it was an undetectable level. it is conceivable that. Then, when the lithium symmetric cell is assembled, it is assumed that the contact between the electrolyte layer and the lithium foil is suppressed by the presence of this layer, and the interface resistance is reduced.

《実施例４》
以下の手順により、図９と同じ扁平型の全固体型ポリマー電池を作製した。本実施例では、電解質層の作製および電解質層を用いた全固体型ポリマー電池の組立ては、窒素３．５体積％およびアルゴン９６．５体積％の雰囲気であるグローブボックス中にて行った。 Example 4
The same flat all solid-state polymer battery as in FIG. 9 was produced by the following procedure. In this example, the production of the electrolyte layer and the assembly of the all-solid-state polymer battery using the electrolyte layer were performed in a glove box having an atmosphere of 3.5% by volume of nitrogen and 96.5% by volume of argon.

（１）中間積層体の作製
リチウム箔（直径１０ｍｍ、厚さ１００μｍ）からなる負極層２を、銅箔（直径１４ｍｍ、厚み１０μｍ）からなる負極集電層４上に圧着して円板状の負極積層体１１を得た。このとき、リチウム箔と銅箔とは、同じ位置に中心を有するように配された。したがって、負極積層体１１において負極層２の周縁部は、負極集電層４が露出した。
実施例１と同じドライポリマー電解質の溶液を、負極積層体１１の負極層２上にキャストした。そして、室温で４８時間真空乾燥し、溶媒成分であるアセトニトリルおよびＤＭＥを除去して、負極積層体１１における負極層２上にドライポリマー電解質層１を形成した。このようにして、負極積層体１１および電解質層１の中間積層体を得た。このとき、電解質層１の厚みは１００μｍであった。また、負極層２と電解質層１とは、中心が同じ位置であり同径であった。したがって、負極積層体１１のドライポリマー電解質層１を形成した側の表面の周縁部には、ドライポリマー電解質層１は形成されず、負極集電層４が露出した。 (1) Production of Intermediate Laminate Negative electrode layer 2 made of lithium foil (diameter 10 mm, thickness 100 μm) is pressure-bonded onto negative electrode current collecting layer 4 made of copper foil (diameter 14 mm, thickness 10 μm) to form a disc shape A negative electrode laminate 11 was obtained. At this time, the lithium foil and the copper foil were arranged so as to have the center at the same position. Therefore, the negative electrode current collecting layer 4 was exposed at the peripheral edge of the negative electrode layer 2 in the negative electrode laminate 11.
The same dry polymer electrolyte solution as in Example 1 was cast on the negative electrode layer 2 of the negative electrode laminate 11. Then, it was vacuum-dried at room temperature for 48 hours to remove acetonitrile and DME as solvent components, and the dry polymer electrolyte layer 1 was formed on the negative electrode layer 2 in the negative electrode laminate 11. In this way, an intermediate laminate of the negative electrode laminate 11 and the electrolyte layer 1 was obtained. At this time, the thickness of the electrolyte layer 1 was 100 μm. Moreover, the negative electrode layer 2 and the electrolyte layer 1 had the same center and the same diameter. Therefore, the dry polymer electrolyte layer 1 was not formed in the peripheral portion of the surface of the negative electrode laminate 11 on the side where the dry polymer electrolyte layer 1 was formed, and the negative electrode current collecting layer 4 was exposed.

（２）正極積層体の作製
正極活物質として４００℃で熱処理した電解二酸化マンガン、導電材としてアセチレンブラック、結着剤として粘度平均分子量１００，０００のポリエチレンオキサイド、およびＬｉ塩であるＬｉＮ（ＣＦ3ＳＯ2）2に、アセトニトリル、ＤＭＥ、およびＮＭＰを加えて、混合し、ペースト状の正極合剤を得た。このとき、二酸化マンガン：アセチレンブラック：ドライポリマー電解質の重量比は、７０：２０：１０とした。なお、ドライポリマー電解質は、固形分の質量で計算した。
得られたペースト状の正極合剤をアルミニウム箔（厚み１５μｍ）からなる正極集電層５の片面に塗布し、８５℃で４８時間乾燥した後、圧延して正極集電層５上に正極層３を形成し、フィルム状電極を得た。得られたフィルム状電極を直径１４ｍｍの円形に切り抜いた後、正極層３が直径１０ｍｍとなるように剥離処理し、正極層３の周縁部において正極集電層５が露出した正極積層体を得た。このとき、正極層３の厚みは２０μｍであった。 (2) Production of positive electrode laminate Electrolytic manganese dioxide heat-treated at 400 ° C. as a positive electrode active material, acetylene black as a conductive material, polyethylene oxide having a viscosity average molecular weight of 100,000 as a binder, and LiN (CF 3 To SO 2 ) 2 , acetonitrile, DME, and NMP were added and mixed to obtain a paste-like positive electrode mixture. At this time, the weight ratio of manganese dioxide: acetylene black: dry polymer electrolyte was 70:20:10. In addition, the dry polymer electrolyte was calculated with the mass of solid content.
The obtained paste-like positive electrode mixture was applied to one surface of a positive electrode current collecting layer 5 made of an aluminum foil (thickness 15 μm), dried at 85 ° C. for 48 hours, and then rolled to form a positive electrode layer on the positive electrode current collecting layer 5 3 was formed to obtain a film-like electrode. The obtained film-like electrode was cut out into a circle having a diameter of 14 mm, and then peeled off so that the positive electrode layer 3 had a diameter of 10 mm. Thus, a positive electrode laminate in which the positive electrode current collecting layer 5 was exposed at the peripheral edge of the positive electrode layer 3 was obtained. It was. At this time, the thickness of the positive electrode layer 3 was 20 μm.

（３）全固体型ポリマー電池の組立て
そして、上記で得られた中間積層体と、正極積層体とを、ドライポリマー電解質層１と正極層３とが対向するように重ね合わせて電極複合体を得た。さらに窓枠状の絶縁樹脂フィルムからなるシール材６を、電極複合体の周縁部（正極集電層５の周縁部と、負極集電層４の周縁部との間）に配した後、シール材６を溶着させて電極複合体を密封し、６０℃の恒温槽で３日間エージングした。このようにして、図９に示す扁平型の全固体型ポリマー電池を作製した。 (3) Assembly of all-solid-state polymer battery Then, the intermediate laminate obtained above and the positive electrode laminate are overlapped so that the dry polymer electrolyte layer 1 and the positive electrode layer 3 face each other to form an electrode composite. Obtained. Further, a sealing material 6 made of a window frame-shaped insulating resin film is disposed on the peripheral edge of the electrode composite (between the peripheral edge of the positive current collecting layer 5 and the peripheral edge of the negative current collecting layer 4), and then sealed. The electrode 6 was sealed by welding the material 6, and aged for 3 days in a constant temperature bath at 60 ° C. In this way, a flat type all solid-state polymer battery shown in FIG. 9 was produced.

なお、全固体型ポリマー電池を分解し、リチウム箔（負極層）を取り出して、電解質層との接触面を観察した。その結果、リチウム箔表面に褐色に変色した部分が確認できた。この変色部は実施例１の結果からリチウム窒化物層と考えられる。この変色部は全固体型ポリマー電池組立ての際には認められていなかった。
次に、電池を６０℃で３０日間保存した後、環境温度：３０℃、電流密度：２５μＡ／ｃｍ2、および終止電圧：１．８Ｖの条件で放電させ、電池容量を測定した。その結果、正極活物質１ｇあたりの放電容量は２５５ｍＡｈ／ｇであった。二酸化マンガンの理論反応を一電子反応と仮定すると、理論容量は３０８ｍＡｈ／ｇとなる。このことから、上記の放電試験において、正極活物質の理論容量の８０％以上の電池容量が得られたことがわかった。 The all solid-state polymer battery was disassembled, the lithium foil (negative electrode layer) was taken out, and the contact surface with the electrolyte layer was observed. As a result, a brownish colored portion was confirmed on the lithium foil surface. This discolored portion is considered to be a lithium nitride layer from the results of Example 1. This discoloration was not recognized during the assembly of the all-solid-state polymer battery.
Next, after storing the battery at 60 ° C. for 30 days, the battery was discharged under the conditions of environmental temperature: 30 ° C., current density: 25 μA / cm 2 , and final voltage: 1.8 V, and the battery capacity was measured. As a result, the discharge capacity per 1 g of the positive electrode active material was 255 mAh / g. Assuming that the theoretical reaction of manganese dioxide is a one-electron reaction, the theoretical capacity is 308 mAh / g. From this, it was found that a battery capacity of 80% or more of the theoretical capacity of the positive electrode active material was obtained in the above discharge test.

《実施例５》
電解質層作製時および全固体型ポリマー電池の組立て時における雰囲気中の窒素含有量を０．１〜１０％の間で変化させて、実施例４と同様の方法により全固体型ポリマー電池を作製した。
保存試験として、電池を６０℃で３０日間保存した後、電池を解体し、リチウム箔のドライポリマー電解質層との接触面を観察した。また、放電試験として、電池を６０℃で３０日間保存した後、環境温度：３０℃、電流密度：２５μＡ／ｃｍ2、および終止電圧：１．８Ｖの条件で放電させ、電池容量を測定した。その結果を表４に示す。 Example 5
The all-solid-state polymer battery was produced in the same manner as in Example 4 by changing the nitrogen content in the atmosphere during the preparation of the electrolyte layer and during the assembly of the all-solid-state polymer battery between 0.1 and 10%. .
As a storage test, after storing the battery at 60 ° C. for 30 days, the battery was disassembled and the contact surface of the lithium foil with the dry polymer electrolyte layer was observed. In addition, as a discharge test, the battery was stored at 60 ° C. for 30 days, and then discharged under the conditions of environmental temperature: 30 ° C., current density: 25 μA / cm 2 , and final voltage: 1.8 V, and the battery capacity was measured. The results are shown in Table 4.

いずれの条件で作製した場合も、放電容量は約２５５ｍＡ／ｇであり、理論容量の８０％以上の電池が得られた。   When manufactured under any conditions, the discharge capacity was about 255 mA / g, and a battery with 80% or more of the theoretical capacity was obtained.

《比較例３》
電解質層作製時および全固体型ポリマー電池の組立て時における雰囲気中の窒素含有量を０〜０．０８体積％の範囲で変えて、実施例４と同様の方法により全固体型ポリマー電池を作製した。 << Comparative Example 3 >>
An all-solid-state polymer battery was produced in the same manner as in Example 4 except that the nitrogen content in the atmosphere during the preparation of the electrolyte layer and during the assembly of the all-solid-state polymer battery was changed in the range of 0 to 0.08% by volume. .

６０℃で３日間エージングした後の全固体型ポリマー電池を分解し、リチウム箔を取り出し、電解質層との接触面を観察した結果、リチウム箔表面に変色部は認められなかった。
次に、実施例５と同様の条件で保存試験および放電試験を行った。その結果を表５に示す。 The all solid-state polymer battery after aging at 60 ° C. for 3 days was disassembled, the lithium foil was taken out, and the contact surface with the electrolyte layer was observed. As a result, no discoloration was found on the lithium foil surface.
Next, a storage test and a discharge test were performed under the same conditions as in Example 5. The results are shown in Table 5.

いずれの条件で作製した場合でも、電池の放電容量は約１５０ｍＡｈ／ｇであり、理論容量の５０％以下であった。これは、負極界面部に保護膜となるリチウム窒化物層が存在しないため、保存試験時に負極界面部に絶縁性の被膜が生成し、界面抵抗が増大したためと考えられる。   In any case, the discharge capacity of the battery was about 150 mAh / g, which was 50% or less of the theoretical capacity. This is presumably because the lithium nitride layer serving as a protective film does not exist at the negative electrode interface, and thus an insulating film was formed at the negative electrode interface during the storage test, resulting in an increase in interface resistance.

《比較例４》
電解質層作製および全固体型ポリマー電池の組立てを、窒素含有量１００体積％の純窒素雰囲気にて行った以外、実施例４と同様の方法により全固体型ポリマー電池を作製した。このとき、組立て前のリチウム箔表面に褐色の変色部が認められた。
６０℃で３日間エージングした後の全固体型ポリマー電池を分解し、リチウム箔を取り出し、電解質層との接触面を観察した結果、リチウム箔表面に変色部が認められた。 << Comparative Example 4 >>
An all-solid polymer battery was produced in the same manner as in Example 4 except that the electrolyte layer production and the assembly of the all-solid polymer battery were performed in a pure nitrogen atmosphere having a nitrogen content of 100% by volume. At this time, the brown discoloration part was recognized by the lithium foil surface before an assembly.
As a result of disassembling the all-solid-state polymer battery after aging at 60 ° C. for 3 days, taking out the lithium foil, and observing the contact surface with the electrolyte layer, a discolored portion was observed on the surface of the lithium foil.

次に、実施例５と同様の条件で保存試験および放電試験を行った。その結果、電池の放電容量は約１００ｍＡｈ／ｇであり、理論容量の３５％以下であることがわかった。これは、負極界面部に結晶質のリチウム窒化物層が存在することにより、負極界面部でのリチウムの移動が難しくなり、また負極界面部の接合が不十分となり、放電容量が低下したためと考えられる。   Next, a storage test and a discharge test were performed under the same conditions as in Example 5. As a result, it was found that the discharge capacity of the battery was about 100 mAh / g, which was 35% or less of the theoretical capacity. This is thought to be because the lithium lithium layer at the negative electrode interface becomes difficult due to the presence of the crystalline lithium nitride layer at the negative electrode interface, and the discharge capacity is reduced due to insufficient bonding at the negative electrode interface. It is done.

《実施例６》
中間積層体の作製を純窒素雰囲気にて行い、正極積層体の作製および全固体型電池の組立てを純アルゴン雰囲気にて行った以外、実施例４と同様の条件で全固体型ポリマー電池を作製した。
６０℃で３日間エージングした後、全固体型ポリマー電池を分解し、リチウム箔を取り出し、電解質層との接触面を観察した結果、リチウム箔表面に変色部が認められた。
次に、実施例５と同様の条件で放電試験した結果、電池の放電容量は２４７ｍＡｈ／ｇであり、理論容量の８０％以上であることがわかった。 Example 6
An all-solid polymer battery was produced under the same conditions as in Example 4, except that the intermediate laminate was produced in a pure nitrogen atmosphere, and the positive electrode laminate and the all-solid battery were assembled in a pure argon atmosphere. did.
After aging at 60 ° C. for 3 days, the all solid-state polymer battery was disassembled, the lithium foil was taken out, and the contact surface with the electrolyte layer was observed. As a result, a discolored portion was observed on the lithium foil surface.
Next, as a result of a discharge test under the same conditions as in Example 5, it was found that the discharge capacity of the battery was 247 mAh / g, which was 80% or more of the theoretical capacity.

本発明の全固体型電池は、薄型化が可能であり、保存後の高率放電特性および信頼性に優れ、携帯情報端末、携帯電子機器、および医療用機器などの薄型で高信頼性が要求されるデバイスの電源として好適に用いられる。   The all-solid-state battery of the present invention can be thinned, has excellent high-rate discharge characteristics and reliability after storage, and is required to be thin and highly reliable, such as personal digital assistants, portable electronic devices, and medical devices. It is suitably used as a power source for a device to be used.

本発明の実施例１の評価用リチウム対称セルの概略縦断面図である。It is a schematic longitudinal cross-sectional view of the lithium symmetrical cell for evaluation of Example 1 of this invention. 本発明の実施例１のリチウム対称セルにおけるリチウム箔表面の写真である。It is a photograph of the lithium foil surface in the lithium symmetrical cell of Example 1 of this invention. 本発明の実施例１のリチウム対称セルにおけるリチウム箔表面のＸＲＤチャートである。It is an XRD chart of the lithium foil surface in the lithium symmetrical cell of Example 1 of this invention. 本発明の実施例１のリチウム対称セルにおけるリチウム箔表面のＸＰＳチャートである。It is an XPS chart of the lithium foil surface in the lithium symmetrical cell of Example 1 of the present invention. 従来の比較例１のリチウム対称セルにおけるリチウム箔表面のＸＰＳチャートである。7 is an XPS chart of a lithium foil surface in a lithium symmetric cell of Comparative Example 1 of the related art. 従来の比較例２のリチウム対称セルにおけるリチウム箔表面のＸＲＤチャートである。It is an XRD chart of the lithium foil surface in the lithium symmetrical cell of the conventional comparative example 2. 従来の比較例２のリチウム対称セルにおけるリチウム箔表面のＸＰＳチャートである。10 is an XPS chart of a lithium foil surface in a lithium symmetric cell of a conventional comparative example 2. 本発明の実施例１および３ならびに従来の比較例１および２のリチウム対称セルにおける６０℃保存期間と負極界面抵抗との関係を示す図である。It is a figure which shows the relationship between the 60 degreeC preservation | save period and negative electrode interface resistance in the lithium symmetrical cell of Example 1 and 3 of this invention, and the conventional comparative examples 1 and 2. FIG. 本発明の一実施の形態の全固体型ポリマー電池の概略縦断面図である。It is a schematic longitudinal cross-sectional view of the all-solid-state polymer battery of one embodiment of this invention.

符号の説明Explanation of symbols

１、４１ ドライポリマー電解質層
２ 負極層
３ 正極層
４ 負極集電層
５ 正極集電層
６ シール材
７、４７、４７´ リチウム窒化物層
１１ 負極積層体
１２ 正極積層体
２１ 全固体型ポリマー電池
３０ リチウム対称セル
３１ 封口板
３２ ケース
３３ ガスケット
３４ スペーサー
３５ 皿バネ
４２、４２´ リチウム箔 DESCRIPTION OF SYMBOLS 1, 41 Dry polymer electrolyte layer 2 Negative electrode layer 3 Positive electrode layer 4 Negative electrode current collection layer 5 Positive electrode current collection layer 6 Sealing material 7, 47, 47 'Lithium nitride layer 11 Negative electrode laminated body 12 Positive electrode laminated body 21 All solid-state polymer battery 30 Lithium symmetrical cell 31 Sealing plate 32 Case 33 Gasket 34 Spacer 35 Belleville spring 42, 42 'Lithium foil

Claims (4)

正極層、リチウムを含む負極層、および前記正極層と前記負極層との間に配されたドライポリマー電解質層を備えた全固体型ポリマー電池であって、
前記負極層と前記電解質層との間に非晶質のリチウム窒化物層が設けられていることを特徴とする全固体型ポリマー電池。 An all-solid-state polymer battery comprising a positive electrode layer, a negative electrode layer containing lithium, and a dry polymer electrolyte layer disposed between the positive electrode layer and the negative electrode layer,
An all-solid-state polymer battery, wherein an amorphous lithium nitride layer is provided between the negative electrode layer and the electrolyte layer. 前記リチウム窒化物層の表面をＸＰＳ分析した際に得られるＮの１ｓスペクトルが、結合エネルギー３９０．０〜３９６．０ｅＶの範囲において、３９３．５〜３９４．５ｅＶのみに極大ピークを有する請求項１に記載の全固体型ポリマー電池。   2. The 1s spectrum of N obtained when XPS analysis of the surface of the lithium nitride layer has a maximum peak only at 393.5 to 394.5 eV in a binding energy range of 390.0 to 396.0 eV. All-solid-state polymer battery described in 1. （１）正極集電層の片面に正極層を配置し、正極積層体を得る工程、
（２）負極集電層の片面にリチウムを含む負極層を配置し、負極積層体を得る工程、
（３）前記負極積層体における前記負極層上に、ドライポリマー電解質の溶液を塗布した後、乾燥させて溶媒を除去し、前記負極層上にドライポリマー電解質層を形成し、中間積層体を得る工程、
（４）前記正極層と前記電解質層が対向するように、前記正極積層体と前記中間積層体とを重ね合わせ、電極複合体を得る工程、および
（５）前記電極複合体を密封する工程を含み、
前記工程（２）〜（５）を、窒素含有量０．１〜１０体積％の雰囲気下で実施することにより、前記電解質層と前記負極層との間に非晶質のリチウム窒化物層を形成することを特徴とする全固体型ポリマー電池の製造方法。 (1) A step of arranging a positive electrode layer on one side of the positive electrode current collecting layer to obtain a positive electrode laminate,
(2) Disposing a negative electrode layer containing lithium on one surface of the negative electrode current collecting layer to obtain a negative electrode laminate,
(3) After applying a solution of a dry polymer electrolyte on the negative electrode layer in the negative electrode laminate, the solvent is removed by drying, and a dry polymer electrolyte layer is formed on the negative electrode layer to obtain an intermediate laminate. Process,
(4) a step of superimposing the positive electrode laminate and the intermediate laminate so that the positive electrode layer and the electrolyte layer face each other to obtain an electrode composite; and (5) a step of sealing the electrode composite. Including
An amorphous lithium nitride layer is formed between the electrolyte layer and the negative electrode layer by performing the steps (2) to (5) in an atmosphere having a nitrogen content of 0.1 to 10% by volume. A method for producing an all solid-state polymer battery. （Ａ）基材上にドライポリマー電解質の溶液を塗布した後、乾燥させて溶媒を除去し、基材上にドライポリマー電解質層を形成する工程、
（Ｂ）正極集電層の片面に正極層を配置し、正極積層体を得る工程、
（Ｃ）負極集電層の片面にリチウムを含む負極層を配置し、負極積層体を得る工程、
（Ｄ）前記基材からドライポリマー電解質層を剥離し、前記負極積層体における前記負極層上にドライポリマー電解質層を配置して中間積層体を得る工程、
（Ｅ）前記正極層と前記電解質層が対向するように、前記正極積層体と前記中間積層体とを重ね合わせ、電極複合体を得る工程、および
（Ｆ）前記電極複合体を密封する工程を含み、
前記工程（Ａ）を純窒素雰囲気下で実施し、前記工程（Ｃ）〜（Ｆ）を窒素含有量１０体積％以下の雰囲気下で実施することにより、前記電解質層と前記負極層との間に非晶質のリチウム窒化物層を形成することを特徴とする全固体型ポリマー電池の製造方法。 (A) A step of applying a dry polymer electrolyte solution on a substrate and then drying to remove the solvent to form a dry polymer electrolyte layer on the substrate;
(B) A step of arranging a positive electrode layer on one side of the positive electrode current collecting layer to obtain a positive electrode laminate,
(C) a step of disposing a negative electrode layer containing lithium on one side of the negative electrode current collecting layer to obtain a negative electrode laminate,
(D) peeling the dry polymer electrolyte layer from the substrate and disposing the dry polymer electrolyte layer on the negative electrode layer in the negative electrode laminate to obtain an intermediate laminate;
(E) a step of superposing the positive electrode laminate and the intermediate laminate so that the positive electrode layer and the electrolyte layer face each other to obtain an electrode composite; and (F) a step of sealing the electrode composite. Including
By performing the step (A) in a pure nitrogen atmosphere and performing the steps (C) to (F) in an atmosphere having a nitrogen content of 10% by volume or less, the electrolyte layer and the negative electrode layer An amorphous lithium nitride layer is formed on the all-solid-state polymer battery.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112038590A (en) * 2019-06-04 2020-12-04 中国科学院物理研究所 Novel solid-state battery and positive electrode material thereof
WO2023042640A1 (en) * 2021-09-14 2023-03-23 マクセル株式会社 Battery and usage method for same, and battery system

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63298980A (en) * 1987-05-28 1988-12-06 Yuasa Battery Co Ltd Solid electrolyte battery
JPH10144349A (en) * 1996-11-11 1998-05-29 Sanyo Electric Co Ltd Solid electrolytic battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63298980A (en) * 1987-05-28 1988-12-06 Yuasa Battery Co Ltd Solid electrolyte battery
JPH10144349A (en) * 1996-11-11 1998-05-29 Sanyo Electric Co Ltd Solid electrolytic battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112038590A (en) * 2019-06-04 2020-12-04 中国科学院物理研究所 Novel solid-state battery and positive electrode material thereof
CN112038590B (en) * 2019-06-04 2023-05-02 中国科学院物理研究所 Novel solid-state battery and positive electrode material thereof
WO2023042640A1 (en) * 2021-09-14 2023-03-23 マクセル株式会社 Battery and usage method for same, and battery system

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