JP2016181363A - Method for manufacturing lithium ion secondary battery, and precursor of lithium ion secondary battery - Google Patents

Method for manufacturing lithium ion secondary battery, and precursor of lithium ion secondary battery Download PDF

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JP2016181363A
JP2016181363A JP2015060209A JP2015060209A JP2016181363A JP 2016181363 A JP2016181363 A JP 2016181363A JP 2015060209 A JP2015060209 A JP 2015060209A JP 2015060209 A JP2015060209 A JP 2015060209A JP 2016181363 A JP2016181363 A JP 2016181363A
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lithium
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JP6628485B2 (en
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豊川　卓也
Takuya Toyokawa
卓也 豊川
利絵 寺西
Rie Teranishi
利絵 寺西
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Sekisui Chemical Co Ltd
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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
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Abstract

PROBLEM TO BE SOLVED: To provide: a method for manufacturing a lithium ion secondary battery, by which the predoping of lithium can be performed on an entire precursor rapidly and uniformly; and a precursor of a lithium ion secondary battery.SOLUTION: A method for manufacturing a lithium ion secondary battery comprises: an electrode pair-forming step for forming, as one unit, each electrode pair A arranged by laminating a negative electrode 2 including a negative electrode current collector with through-holes formed therein, and a negative electrode active material layer formed on the negative electrode current collector, a separator 3, and a positive electrode 4 including a positive electrode current collector with through-holes formed therein, and a positive electrode active material layer formed on the positive electrode current collector in this order; a unit lamination step for laminating three or more units of the electrode pairs A, A with a separator interposed between the electrode pairs; a precursor forming step for forming a precursor B of the lithium ion secondary battery 1, which is arranged by laminating a lithium donor 5 on each of ends of the electrode pairs A at two or more locations, including at least on location between the electrode pairs A, A in a laminating direction; and a predoping step for performing the predoping with lithium with an electrolyte disposed between the negative electrode 2 and the positive electrode 4.SELECTED DRAWING: Figure 2

Description

本発明は、リチウムイオン二次電池の製造方法及びリチウムイオン二次電池の前駆体に関する。   The present invention relates to a method for producing a lithium ion secondary battery and a precursor of a lithium ion secondary battery.

リチウムイオン二次電池の放電容量が初期充電後に低下することを防止するために、電池の初期充電工程の前に、負極とリチウム金属とを反応させるリチウムプレドープが従来から行われている（例えば特許文献１）。プレドープを行うと、初期充電工程において、リチウムシリケート等の副生成物が生成されたり、電解液中のリチウムイオンが失われて放電容量が低下したりすることを防止することができる。   In order to prevent the discharge capacity of the lithium ion secondary battery from decreasing after the initial charging, lithium pre-doping for reacting the negative electrode with lithium metal has been conventionally performed before the initial charging process of the battery (for example, Patent Document 1). When pre-doping is performed, it is possible to prevent a by-product such as lithium silicate from being generated in the initial charging step, or loss of lithium ions in the electrolytic solution and a reduction in discharge capacity.

特許第４０１５９９３号公報Japanese Patent No. 4015993

特許文献１のリチウムプレドープは、プレドープに用いられるリチウム金属片を電極積層体の積層方向の両端に配置することにより行う。しかし、この方法によれば、電極積層体のリチウム金属片に近い部分と遠い部分とで、ドープされるリチウムイオンの量及びドープの速度が異なってしまう。したがって、電極積層体の全体に均一にドープするのに長時間を要するという問題があった。   The lithium pre-doping in Patent Document 1 is performed by arranging lithium metal pieces used for pre-doping at both ends in the stacking direction of the electrode stack. However, according to this method, the amount of lithium ions to be doped and the doping speed differ between a portion close to the lithium metal piece and a portion far from the lithium metal piece of the electrode stack. Therefore, there is a problem that it takes a long time to dope the entire electrode laminate uniformly.

本発明は、上記課題に鑑みてなされたものであり、リチウムイオン二次電池の前駆体の全体に速やかかつ略均一にリチウムプレドープを行い得るリチウムイオン二次電池の製造方法及びリチウムイオン二次電池の前駆体を提供する。   The present invention has been made in view of the above problems, and a method for producing a lithium ion secondary battery and a lithium ion secondary battery capable of quickly and substantially uniformly performing lithium pre-doping on the entire precursor of the lithium ion secondary battery A battery precursor is provided.

（１）本発明のリチウムイオン二次電池の製造方法は、貫通孔が形成された負極集電体に負極活物質層が形成された負極と、セパレータと、貫通孔が形成された正極集電体に正極活物質層が形成された正極とをこの順で１ユニットとして積層した電極対を形成する電極対形成工程と、前記電極対間にセパレータを介装させて３ユニット以上積層するユニット積層工程と、少なくとも１カ所の電極対間を含む２カ所以上の電極対の積層方向の端部にリチウム供給体を積層したリチウムイオン二次電池の前駆体を形成する前駆体形成工程と、前記負極と前記正極との間に電解質を配した状態でリチウムプレドープを行うプレドープ工程とを有する。
本発明は、各電極対にリチウムイオンを速やかかつ略均一に拡散させることができる。 (1) A method for producing a lithium ion secondary battery according to the present invention includes a negative electrode in which a negative electrode active material layer is formed on a negative electrode current collector in which through holes are formed, a separator, and a positive electrode current collector in which through holes are formed. An electrode pair forming step for forming an electrode pair in which a positive electrode having a positive electrode active material layer formed on the body is laminated in this order as one unit, and a unit lamination in which three or more units are laminated with a separator interposed between the electrode pairs A precursor forming step of forming a precursor of a lithium ion secondary battery in which a lithium supply body is stacked at an end in a stacking direction of at least two electrode pairs including at least one electrode pair, and the negative electrode And a pre-doping step of performing lithium pre-doping with an electrolyte disposed between the positive electrode and the positive electrode.
According to the present invention, lithium ions can be diffused quickly and substantially uniformly in each electrode pair.

（２）本発明は、前記前駆体形成工程において前記リチウム供給体を１ユニット以上総ユニット数／２以下の整数以下のユニット間隔を設けて前記電極対間に積層してもよい。
本発明は、各電極対にリチウムイオンを特に効率よく拡散させることができる。 (2) According to the present invention, in the precursor forming step, the lithium supply body may be stacked between the electrode pairs by providing unit intervals of 1 unit or more and a total unit number / 2 or less.
The present invention can diffuse lithium ions to each electrode pair particularly efficiently.

（３）本発明の前記負極集電体及び前記正極集電体に形成された前記貫通孔の平均孔径は、０．０８ｍｍ以上０．５ｍｍ以下であるとよい。
本発明は、リチウムイオンをより一層効率よく拡散させることができる。 (3) The average hole diameter of the said through-hole formed in the said negative electrode collector of this invention and the said positive electrode collector is good in it being 0.08 mm or more and 0.5 mm or less.
The present invention can diffuse lithium ions even more efficiently.

（４）本発明は、前記リチウムイオン二次電池の前駆体の最外層に位置する前記正極の外表面側に前記リチウム供給体を積層してもよい。
本発明は、リチウムイオンをより一層均一に拡散させることができる。 (4) In the present invention, the lithium supply body may be laminated on the outer surface side of the positive electrode located in the outermost layer of the precursor of the lithium ion secondary battery.
The present invention can diffuse lithium ions more uniformly.

（５）本発明は、０．０９ｍｍ以上０．２１ｍｍ以下の厚さ寸法を有する前記リチウム供給体を３００μｍ以上１０００μｍ以下の間隔となるように前記電極対間に配してもよい。
本発明は、リチウムイオンを各電極対により効率よく拡散させることができ、またリチウム供給体を容易に積層することができる。 (5) In the present invention, the lithium supply body having a thickness dimension of 0.09 mm or more and 0.21 mm or less may be arranged between the electrode pairs so as to have an interval of 300 μm or more and 1000 μm or less.
In the present invention, lithium ions can be efficiently diffused by each electrode pair, and a lithium supply body can be easily laminated.

（６）本発明のリチウムイオン二次電池の前駆体は、貫通孔が形成された負極集電体に負極活物質層が形成された負極と、セパレータと、貫通孔が形成された正極集電体に正極活物質層が形成された正極とを、この順で１ユニットとして積層した電極対を、前記電極対間にセパレータを介装させつつ３ユニット以上積層するとともに、少なくとも１カ所の電極対間を含む２カ所以上の前記電極対の端部にリチウム供給体を積層させている。 (6) The precursor of the lithium ion secondary battery of the present invention includes a negative electrode current collector in which a through hole is formed, a negative electrode in which a negative electrode active material layer is formed, a separator, and a positive electrode current collector in which through holes are formed. Three or more electrode pairs in which a positive electrode having a positive electrode active material layer formed on the body is laminated in this order as one unit are laminated with a separator interposed between the electrode pairs, and at least one electrode pair Lithium supply bodies are stacked at the ends of the electrode pairs at two or more places including the gap.

（７）本発明のリチウムイオン二次電池の前駆体は、前記リチウム供給体を１ユニット以上総ユニット数／２以下の整数以下のユニット間隔を設けて前記電極対間に積層していてもよい。 (7) In the precursor of the lithium ion secondary battery of the present invention, the lithium supply body may be laminated between the electrode pairs by providing unit intervals of 1 unit or more and a total unit number / 2 or less. .

本発明は、リチウムイオンドープを速やかかつ略均一に行うことができるため、プレドープ工程の所要時間を短縮化することができるという効果を奏する。   According to the present invention, since lithium ion doping can be performed quickly and substantially uniformly, the time required for the pre-doping step can be shortened.

本発明の一実施形態の製造方法で製造されたリチウムイオン二次電池の一ユニットの電極対を示す断面模式図である。It is a cross-sectional schematic diagram which shows the electrode pair of 1 unit of the lithium ion secondary battery manufactured with the manufacturing method of one Embodiment of this invention. 本発明の一実施形態の製造方法で製造されたリチウムイオン二次電池の一例を示す断面模式図である。It is a cross-sectional schematic diagram which shows an example of the lithium ion secondary battery manufactured with the manufacturing method of one Embodiment of this invention. 本発明の一実施形態であるリチウムイオン二次電池の前駆体の他の例を示した模式図である。It is the schematic diagram which showed the other example of the precursor of the lithium ion secondary battery which is one Embodiment of this invention. 本発明の一実施形態であるリチウムイオン二次電池の前駆体の他の例を示した模式図である。It is the schematic diagram which showed the other example of the precursor of the lithium ion secondary battery which is one Embodiment of this invention. 本発明の一実施形態であるリチウムイオン二次電池の前駆体の他の例を示した模式図である。It is the schematic diagram which showed the other example of the precursor of the lithium ion secondary battery which is one Embodiment of this invention.

以下、本発明の実施形態について図を参照して説明する。
図１に示すように、本発明の第一実施形態の製造方法は、負極集電体２ａに負極活物質層２ｂが形成された負極２と、セパレータ３と、正極集電体４ａに正極活物質層４ｂが形成された正極４とを積層させて形成されるリチウムイオン二次電池１の製造方法である。 Embodiments of the present invention will be described below with reference to the drawings.
As shown in FIG. 1, the manufacturing method of 1st embodiment of this invention is the negative electrode 2 by which the negative electrode active material layer 2b was formed in the negative electrode collector 2a, the separator 3, and the positive electrode active material 4a. This is a method for manufacturing the lithium ion secondary battery 1 formed by laminating the positive electrode 4 on which the material layer 4b is formed.

図１又は図２に示すように、本実施形態では、負極２とセパレータ３と正極４とをこの順で１ユニットとして積層した電極対Ａを形成する電極対形成工程と、電極対Ａ，Ａ間にセパレータ３を介装させつつ４ユニット以上積層するユニット積層工程と、２ユニット以上の間隔を空けた２カ所以上の電極対Ａ，Ａ間のそれぞれにリチウム供給体５を積層したリチウムイオン二次電池の前駆体（以下「前駆体」という）Ｂを形成する前駆体形成工程と、負極２と正極４との間に電解質（不図示。以下同様）を配した状態でリチウムプレドープを行うプレドープ工程とを有する。   As shown in FIG. 1 or FIG. 2, in the present embodiment, an electrode pair forming step for forming an electrode pair A in which the negative electrode 2, the separator 3, and the positive electrode 4 are laminated as one unit in this order, and the electrode pairs A, A A unit stacking process in which four or more units are stacked with a separator 3 interposed therebetween, and a lithium ion two in which a lithium supply body 5 is stacked between each of two or more electrode pairs A and A spaced by two or more units. Lithium pre-doping is performed in a state in which a precursor forming step for forming a precursor (hereinafter referred to as “precursor”) B of the secondary battery and an electrolyte (not shown; hereinafter the same) are arranged between the negative electrode 2 and the positive electrode 4. A pre-doping step.

＜電極対形成工程＞
（負極２の作製）
負極２は、導電性を有した板状の集電体（負極集電体２ａ）の表面に負極活物質層２ｂを設けて形成する。負極活物質層２ｂの構成材料（負極材）には、リチウムイオンを吸蔵及び放出可能な負極活物質を含む材料であって、プレドープ工程においてリチウムと不可逆的な反応を起こす負極活物質を含む材料であれば特に制限されず、公知の負極材が適用可能である。 <Electrode pair formation process>
(Preparation of negative electrode 2)
The negative electrode 2 is formed by providing a negative electrode active material layer 2b on the surface of a conductive plate-shaped current collector (negative electrode current collector 2a). The constituent material (negative electrode material) of the negative electrode active material layer 2b is a material containing a negative electrode active material capable of occluding and releasing lithium ions, and a material containing a negative electrode active material that causes an irreversible reaction with lithium in the pre-doping step. If it is, it will not restrict | limit in particular, A well-known negative electrode material is applicable.

負極集電体２ａの材料，面積及び厚さ寸法は特に制限されず、公知のリチウムイオン二次電池の負極集電体２ａと同じ材料，面積及び厚さ寸法のものを適用することができる。負極集電体２ａには、具体的には例えば、銅、チタン、ニッケル、ステンレス鋼等の金属を用いた圧延銅箔や電解銅箔等の金属板を好適に用いることができる。負極集電体２ａの寸法は、例えば面積４ｃｍ×５．５ｃｍ、厚さ寸法５μｍ〜３０μｍとすることができる。   The material, area, and thickness of the negative electrode current collector 2a are not particularly limited, and the same material, area, and thickness as those of the negative electrode current collector 2a of a known lithium ion secondary battery can be used. Specifically, for example, a metal plate such as a rolled copper foil or an electrolytic copper foil using a metal such as copper, titanium, nickel, or stainless steel can be suitably used for the negative electrode current collector 2a. The dimensions of the negative electrode current collector 2a can be, for example, an area of 4 cm × 5.5 cm and a thickness dimension of 5 μm to 30 μm.

本実施形態で使用する負極集電体２ａには、その厚さ方向に電解液が通過することを可能にする貫通孔ｈが複数設けられている。複数の貫通孔ｈの形状、大きさ、個数、相対配置は特に制限されない。貫通孔ｈの平均孔径は、０．０８ｍｍ以上０．５ｍｍ以下であることが好ましい。貫通孔ｈの平均孔径を上記のように設定することでリチウムイオンを可及的速やかに通過させることができるとともに、負極集電体２ａの板面に負極活物質を適切に保持させることができる。
貫通孔ｈは、互いに独立していてもよいし、互いに連結していてもよい。貫通孔ｈの個数が多過ぎたり、貫通孔ｈが大き過ぎたり、偏って配置されたりしていると、負極集電体２ａの表面に負極活物質層２ｂを保持することが難しくなる場合がある。この場合を考慮して、貫通孔ｈの個数や配置等を適宜調整する。 The negative electrode current collector 2a used in the present embodiment is provided with a plurality of through holes h that allow the electrolytic solution to pass through in the thickness direction. The shape, size, number, and relative arrangement of the plurality of through holes h are not particularly limited. The average hole diameter of the through holes h is preferably 0.08 mm or more and 0.5 mm or less. By setting the average hole diameter of the through holes h as described above, lithium ions can be passed as quickly as possible, and the negative electrode active material can be appropriately held on the plate surface of the negative electrode current collector 2a. .
The through holes h may be independent from each other or may be connected to each other. If the number of through holes h is too large, the through holes h are too large, or are biased, it may be difficult to hold the negative electrode active material layer 2b on the surface of the negative electrode current collector 2a. is there. Considering this case, the number and arrangement of the through holes h are appropriately adjusted.

リチウムプレドープを行う際に、負極集電体２ａの片面又は両面に形成された負極活物質層２ｂに対して均一にリチウム金属を拡散させるために、負極活物質層２ｂを形成した負極集電体２ａの領域の全面に亘って均一になるべく多数の貫通孔ｈが配置されていることが好ましい。
負極集電体２ａに設けられた複数の貫通孔ｈの形状や大きさは、互いに同じであってもよいし、異なっていてもよい。 A negative electrode current collector formed with a negative electrode active material layer 2b in order to uniformly diffuse lithium metal to the negative electrode active material layer 2b formed on one or both sides of the negative electrode current collector 2a when performing lithium pre-doping. It is preferable that as many through-holes h as possible be arranged over the entire surface of the body 2a.
The shape and size of the plurality of through holes h provided in the negative electrode current collector 2a may be the same as or different from each other.

負極活物質としては、例えばリチウムと合金化可能なケイ素や酸化ケイ素、スズ、酸化鉄等からなる炭素材料と、ポリフッ化ビニリデン、ポリイミド、ポリアクリル酸、ＳＢＲ、カルボキシメチルセルロースのような結着剤とを溶媒に分散させてなる負極用スラリーを用いて構成されたものが用いられている。   As the negative electrode active material, for example, a carbon material composed of silicon, silicon oxide, tin, iron oxide or the like that can be alloyed with lithium, and a binder such as polyvinylidene fluoride, polyimide, polyacrylic acid, SBR, carboxymethylcellulose, A material composed of a slurry for a negative electrode in which is dispersed in a solvent is used.

負極活物質層２ｂの形成方法は特に限定されず、例えば負極活物質と、バインダーとなる結着剤、必要に応じて加えられた導電助剤を溶媒に分散させてなる負極用スラリーを負極集電体２ａ上に途工し、負極材に含まれる溶媒を乾燥除去して得る方法が挙げられる。負極活物質、バインダー樹脂及び導電助剤の種類及び組み合わせは特に限定されず、公知のリチウムイオン二次電池の負極活物質層２ｂを構成する材料の組み合わせが適用できる。   The formation method of the negative electrode active material layer 2b is not particularly limited. For example, a negative electrode slurry is prepared by dispersing a negative electrode active material, a binder serving as a binder, and a conductive additive added as necessary in a solvent. Examples of the method include a method in which the solvent is prepared on the electric conductor 2a and the solvent contained in the negative electrode material is removed by drying. The types and combinations of the negative electrode active material, the binder resin, and the conductive additive are not particularly limited, and a combination of materials constituting the negative electrode active material layer 2b of a known lithium ion secondary battery can be applied.

（正極４の作製）
正極４は、導電性を有した板状の集電体（正極集電体４ａ）の表面に正極活物質層４ｂを設けて形成される。正極集電体４ａの材料、面積及び厚みは特に制限されず、公知のリチウムイオン二次電池の正極集電体４ａと同じ材料、面積及び厚さ寸法を有する金属板を適用することができる。具体的に正極集電体４ａには、例えば、面積４ｃｍ×５．５ｃｍ、厚さ寸法５μｍ〜３０μｍの圧延アルミニウム箔等を用いることができる。正極集電体４ａには、アルミニウム箔のほか、特に限定されないが、銅、チタン、ニッケル、ステンレス鋼等の金属を用いることができる。なお、正極４と負極２の面積は等しいことが好ましい。 (Preparation of positive electrode 4)
The positive electrode 4 is formed by providing a positive electrode active material layer 4b on the surface of a conductive plate-shaped current collector (positive electrode current collector 4a). The material, area, and thickness of the positive electrode current collector 4a are not particularly limited, and a metal plate having the same material, area, and thickness as the positive electrode current collector 4a of a known lithium ion secondary battery can be applied. Specifically, for example, a rolled aluminum foil having an area of 4 cm × 5.5 cm and a thickness of 5 μm to 30 μm can be used for the positive electrode current collector 4a. In addition to the aluminum foil, the positive electrode current collector 4a is not particularly limited, and metals such as copper, titanium, nickel, and stainless steel can be used. Note that the areas of the positive electrode 4 and the negative electrode 2 are preferably equal.

正極集電体４ａには、その厚さ方向に電解液が通過可能な貫通孔ｈが複数設けられている。複数の貫通孔ｈの形状、大きさ、個数、相対配置の説明は、負極集電体２ａに形成された貫通孔ｈの説明と同様である。   The positive electrode current collector 4a is provided with a plurality of through holes h through which the electrolytic solution can pass in the thickness direction. The description of the shape, size, number, and relative arrangement of the plurality of through holes h is the same as the description of the through holes h formed in the negative electrode current collector 2a.

正極活物質層４ｂの構成材料（正極材）としては、リチウムイオンを吸蔵及び放出可能な正極活物質を含む材料であれば特に限定されず、公知のリチウムイオン二次電池の正極材が適用可能である。   The constituent material (positive electrode material) of the positive electrode active material layer 4b is not particularly limited as long as the material includes a positive electrode active material capable of occluding and releasing lithium ions, and a positive electrode material of a known lithium ion secondary battery can be applied. It is.

正極活物質として、例えば一般式ＬｉＭｘＯｙ（ただし、Ｍは金属であり、ｘ及びｙは金属Ｍと酸素Ｏの組成比である）で表される金属酸リチウム化合物が用いられる。具体的には、金属酸リチウム化合物としては、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム、これらの三元系、リン酸鉄リチウム等が用いられる。   As the positive electrode active material, for example, a metal acid lithium compound represented by the general formula LiMxOy (where M is a metal and x and y are composition ratios of the metal M and oxygen O) is used. Specifically, lithium cobaltate, lithium nickelate, lithium manganate, a ternary system thereof, lithium iron phosphate, or the like is used as the lithium metalate compound.

正極活物質層４ｂの形成方法は特に限定されず、例えば正極活物質と、バインダーとなる結着剤、必要に応じて加えられた導電助剤を溶媒に分散させてなる正極用スラリーを正極集電体４ａ上に途工し、正極材に含まれる溶媒を乾燥除去して得る方法が挙げられる。正極活物質、バインダー樹脂及び導電助剤の種類及び組み合わせは特に限定されず、公知のリチウムイオン二次電池の負極活物質層２ｂを構成する材料の組み合わせが適用できる。   The formation method of the positive electrode active material layer 4b is not particularly limited. For example, a positive electrode slurry obtained by dispersing a positive electrode active material, a binder serving as a binder, and a conductive additive added as necessary in a solvent is collected. There is a method that is obtained by removing the solvent contained in the positive electrode material by drying on the electric body 4a. The types and combinations of the positive electrode active material, the binder resin, and the conductive additive are not particularly limited, and a combination of materials constituting the negative electrode active material layer 2b of a known lithium ion secondary battery can be applied.

負極活物質層２ｂと正極活物質層４ｂとを対向させて負極２と正極４とを配置し、更に両電極の間にセパレータ３を配置して、負極２と、セパレータ３と、正極４とをこの順で１ユニットとして積層した電極対Ａを作製する。   The negative electrode 2 and the positive electrode 4 are disposed so that the negative electrode active material layer 2b and the positive electrode active material layer 4b are opposed to each other, and the separator 3 is disposed between the two electrodes. Are formed as a unit in this order.

＜ユニット積層工程＞
そして、セパレータ３を介装させて電極対Ａを３ユニット以上（本実施形態では４ユニット）積層する。このように電極対Ａを積層することで、負極２、セパレータ３、正極４、セパレータ３・・・がこの順で積層される。 <Unit lamination process>
Then, three or more electrode pairs A (4 units in this embodiment) are stacked with the separator 3 interposed therebetween. By laminating the electrode pair A in this way, the negative electrode 2, the separator 3, the positive electrode 4, the separator 3... Are laminated in this order.

なお、ユニット積層工程は、セパレータ３を１ユニットの電極対Ａごとに介装する限り、１ユニットの電極対形成工程ごとにセパレータ３を介装させて行っても、予め複数ユニットの電極対Ａを用意した上で、電極対Ａごとにセパレータ３を介装させて行っても、どちらでもよい。   In addition, as long as the unit stacking step is performed by interposing the separator 3 for each unit electrode pair forming step as long as the separator 3 is interposed for each unit electrode pair A, a plurality of unit electrode pairs A may be provided in advance. May be performed with the separator 3 interposed for each electrode pair A.

＜前駆体形成工程＞
２ユニット以上の間隔を空けた２カ所以上の電極対Ａ，Ａ間（すなわち電極対Ａの積層方向の端部）のそれぞれに、リチウム供給体５を積層して前駆体Ｂを得る。本実施形態では、具体的には、４ユニットの電極対Ａの真ん中（２ユニットの電極対Ａ，Ａと２ユニットの電極対Ａ，Ａに挟まれる電極対Ａの積層方向の端部）にリチウム供給体５を配した前駆体Ｂを１セットとして、４セットの前駆体Ｂを積層する。すなわち、積層方向の一端側から２ユニットの位置でリチウム供給体５を積層した後、４ユニット毎に間隔を空けて３カ所にリチウム供給体５を配し、積層方向の他端側に２ユニットの電極対Ａを積層している。 <Precursor formation step>
A precursor B is obtained by laminating a lithium supply body 5 between each of two or more electrode pairs A and A (that is, the end of the electrode pair A in the stacking direction) spaced by two units or more. In the present embodiment, specifically, in the middle of the electrode pair A of 4 units (the end in the stacking direction of the electrode pair A sandwiched between the 2 unit electrode pairs A and A and the 2 unit electrode pairs A and A). Four sets of precursors B are stacked with one set of precursors B on which the lithium supplier 5 is arranged. That is, after the lithium supply body 5 is stacked at a position of 2 units from one end side in the stacking direction, the lithium supply body 5 is arranged at three positions at intervals of 4 units, and 2 units are disposed on the other end side in the stacking direction. Electrode pairs A are stacked.

なお、前駆体形成工程は、電極対形成工程及びユニット積層工程と同時に行っても、分けて行ってもよい。前駆体形成工程を電極対形成工程及びユニット積層工程と同時に行う場合は、負極２−セパレータ３−正極４−セパレータ３を積層する間（すなわち電極対形成工程及びユニット積層工程を繰り返す際に）にリチウム供給体５を配していく。一方、前駆体形成工程を電極対形成工程及びユニット積層工程と分けて行う場合は、予め電極対Ａを複数作成しておき、セパレータ３を介装させつつ電極対Ａを複数ユニット重ねる度にリチウム供給体５を配する。このように電極対形成工程及びユニット積層工程とリチウム供給体５の介装工程とを分けて行うと、前駆体Ｂの作製を効率的に行うことができる。
積層前又は積層後に負極２及び正極４をプレスして、各電極を構成する電極活物質層の体積密度を調整してもよい。 The precursor forming step may be performed simultaneously with the electrode pair forming step and the unit stacking step or separately. When the precursor forming step is performed simultaneously with the electrode pair forming step and the unit stacking step, the negative electrode 2-separator 3-positive electrode 4-separator 3 is stacked (that is, when the electrode pair forming step and the unit stacking step are repeated). The lithium supply body 5 is arranged. On the other hand, when the precursor forming step is performed separately from the electrode pair forming step and the unit stacking step, a plurality of electrode pairs A are prepared in advance, and each time a plurality of electrode pairs A are stacked while the separator 3 is interposed, lithium is added. A supply body 5 is arranged. Thus, when the electrode pair forming step, the unit stacking step, and the interposing step of the lithium supply body 5 are performed separately, the precursor B can be efficiently manufactured.
You may press the negative electrode 2 and the positive electrode 4 before or after lamination | stacking, and may adjust the volume density of the electrode active material layer which comprises each electrode.

セパレータ３は絶縁性を有し、電解液を保持又は通過させることが可能なものであれば特に限定されず、公知のリチウムイオン二次電池で使用されるセパレータ３が適用可能である。セパレータ３の具体例としては、不織布、オレフィン系樹脂からなる多孔質膜、絶縁性粒子からなる多孔性絶縁膜等が挙げられる。セパレータ３の厚みは、絶縁性が保たれる厚みであれば特に限定されず、例えば５〜５０μｍ程度の厚みが挙げられる。   The separator 3 is not particularly limited as long as it has insulating properties and can hold or pass the electrolytic solution, and a separator 3 used in a known lithium ion secondary battery is applicable. Specific examples of the separator 3 include a nonwoven fabric, a porous film made of an olefin resin, a porous insulating film made of insulating particles, and the like. The thickness of the separator 3 will not be specifically limited if it is the thickness by which insulation is maintained, For example, the thickness of about 5-50 micrometers is mentioned.

リチウム供給体５を構成する材料は、接触した電解液にリチウム金属又はリチウムイオンが溶出する材料であれば特に限定されず、公知のリチウムプレドープに使用されるリチウム金属含有材料が適用できる。例えば、リチウム金属又はリチウム合金からなる金属箔、リチウム金属又はリチウム合金を含む多孔性樹脂材料、リチウム金属又はリチウム合金を含む多孔性無機材料等、が挙げられる。リチウム供給体５がリチウム金属箔であると、リチウムプレドープの進行とともにリチウム金属箔が溶解して無くなる。   The material which comprises the lithium supply body 5 will not be specifically limited if lithium metal or a lithium ion elutes into the electrolyte solution which contacted, The lithium metal containing material used for well-known lithium pre dope is applicable. Examples thereof include a metal foil made of lithium metal or a lithium alloy, a porous resin material containing lithium metal or a lithium alloy, a porous inorganic material containing lithium metal or a lithium alloy, and the like. When the lithium supply body 5 is a lithium metal foil, the lithium metal foil dissolves and disappears with the progress of lithium pre-doping.

リチウム供給体５の形状は、電極対Ａの表面すなわち負極２又は正極４の平板面に対向して載置することができる平面を有する板状であればよい。具体的に、板状のリチウム供給体５としては、薄く延した箔、線材のリチウム金属で編まれた平面状の布材、導電板の表面上に形成されたリチウム金属の膜等の形状を含む。なお、リチウム供給体５の負極２又は正極４に対向させる平板面の面積は、短絡防止の観点から負極２又は正極４の板面よりもわずかに小さく形成されていることが望ましい。   The shape of the lithium supply body 5 may be a plate shape having a flat surface that can be placed opposite to the surface of the electrode pair A, that is, the flat surface of the negative electrode 2 or the positive electrode 4. Specifically, the plate-like lithium supply body 5 has a shape such as a thinly stretched foil, a planar cloth material knitted with lithium metal as a wire, and a lithium metal film formed on the surface of a conductive plate. Including. Note that the area of the flat plate surface facing the negative electrode 2 or the positive electrode 4 of the lithium supply body 5 is desirably slightly smaller than the plate surface of the negative electrode 2 or the positive electrode 4 from the viewpoint of preventing a short circuit.

リチウム供給体５の厚さは特に限定されず、負極２の不可逆容量を担保する量のリチウム金属を供給可能な厚さを適宜設定すればよいが、溶け残りが発生するのは好ましくない。したがって、リチウム供給体５の厚さ寸法は、例えば、９０μｍ以上２１０μｍ以下であることが好ましく、１００μｍ〜２００μｍの範囲であればより好ましい。
また、リチウム供給体５の配置間隔は、３００μｍ以上１０００μｍ以下であることが好ましく、４００μｍ以上９００μｍ以下であることがより好ましい。このような厚さ寸法にすることにより、皺等を生じさせずにリチウム供給体５を容易に積層することが可能となる。 The thickness of the lithium supply body 5 is not particularly limited, and a thickness capable of supplying an amount of lithium metal that secures the irreversible capacity of the negative electrode 2 may be set as appropriate, but it is not preferable that unmelted residue is generated. Therefore, it is preferable that the thickness dimension of the lithium supply body 5 is 90 micrometers or more and 210 micrometers or less, for example, and it is more preferable if it is the range of 100 micrometers-200 micrometers.
Moreover, the arrangement interval of the lithium supply body 5 is preferably 300 μm or more and 1000 μm or less, and more preferably 400 μm or more and 900 μm or less. By setting it to such a thickness dimension, it becomes possible to laminate | stack the lithium supply body 5 easily, without producing a wrinkle etc.

このようにリチウム供給体５を少なくとも１か所の電極対Ａ，Ａ同士の間を含む単数又は複数ユニットの電極対Ａの端部に１ユニット以上総ユニット数／２以下の整数以下のユニット間隔を設けて配することによって、リチウム金属又はリチウムイオンの拡散を電極対Ａの積層方向に双方向に速やかに拡散させてリチウムドープを速やかに行うことが可能となる。   In this way, the unit interval of 1 unit or more and the total number of units / 2 or less of the lithium supply body 5 at the end of the single or plural unit electrode pair A including at least one of the electrode pairs A and A. By providing and arranging, lithium metal or lithium ions can be diffused quickly in both directions in the direction of lamination of the electrode pair A, so that lithium doping can be performed quickly.

また、リチウム供給体５の厚さを９０μｍ以上２１０μｍ以下、より好ましくは１０μｍ以上２００μｍ以下の範囲に設定することで、リチウム供給体５を電極対Ａ，Ａ間に配する際にリチウム供給体５（例えばリチウム金属箔）に皺がよることを低減することができる。これにより、電極対Ａに対してリチウム供給体５が密着する部分と密着しない部分が発生する場合に生じるドープむらが発生することを抑制して、電極対Ａに速やかかつ均一にリチウムドープを行うことが可能となる。   Further, by setting the thickness of the lithium supply body 5 in the range of 90 μm or more and 210 μm or less, more preferably in the range of 10 μm or more and 200 μm or less, the lithium supply body 5 is disposed when the lithium supply body 5 is disposed between the electrode pairs A and A. It is possible to reduce wrinkling due to (for example, lithium metal foil). This suppresses the occurrence of uneven doping when the portion where the lithium supply body 5 is in close contact with the electrode pair A and the portion where it is not in close contact with the electrode pair A, so that the electrode pair A is quickly and uniformly doped with lithium. It becomes possible.

＜外装体６への封入＞
前駆体Ｂを１セット以上形成した後、前駆体Ｂを外装体６で仮封止する。外装体６の種類は特に限定されず、公知のリチウムイオン二次電池に使用される金属製又は樹脂製の外装体６を採用することができる。本実施形態においては、外装体６として樹脂フィルムを用いて、前駆体Ｂをラミネートしたシート型のセルを得る。セルの仮封止にあたっては、負極集電体２ａ及び正極集電体４ａにそれぞれ電気的に接続させたリードタブ７を外装体６の外部に突出させる。 <Encapsulation in exterior body 6>
After forming one or more sets of the precursors B, the precursors B are temporarily sealed with the exterior body 6. The kind of the exterior body 6 is not specifically limited, The metal or resin exterior body 6 used for a well-known lithium ion secondary battery is employable. In this embodiment, a resin film is used as the exterior body 6 to obtain a sheet-type cell in which the precursor B is laminated. In the temporary sealing of the cell, the lead tab 7 electrically connected to the negative electrode current collector 2 a and the positive electrode current collector 4 a is protruded to the outside of the exterior body 6.

ラミネートセルは、仮封止を部分的に解いて、電解質を注入した後に完全に封止する。電解質は、ゲル状又は液状であることが好ましく、液状の電解液であることがより好ましい。ゲル状又は液状であると、リチウム供給体５から溶出したリチウム金属又はリチウムイオンの電解質内における拡散効率が高まり、リチウムプレドープの処理効率が向上する。   The laminate cell is completely sealed after partially releasing the temporary sealing and injecting the electrolyte. The electrolyte is preferably in the form of a gel or liquid, and more preferably a liquid electrolyte. When it is in a gel or liquid state, the diffusion efficiency of lithium metal or lithium ions eluted from the lithium supply body 5 in the electrolyte is increased, and the processing efficiency of lithium pre-doping is improved.

（電解液について）
本実施形態においては、リチウム供給体５にリチウム金属が含まれるので、電解質としては、水分が実質的に含まれない非水系電解液が好ましい。非水系電解液としては、例えば、非水系溶媒にリチウム塩が溶解された公知の非水系電解液が挙げられる。非水溶媒は、γ−ブチロラクトン等のラクトン化合物；エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート等の炭酸エステル化合物；ギ酸メチル、酢酸メチル、プロピオン酸メチル等のカルボン酸エステル化合物；テトラヒドロフラン、ジメトキシエタン等のエーテル化合物；テトラヒドロフラン、ジメトキシエタン等のエーテル化合物；アセトニトリル等のニトリル化合物；スルホラン等のスルホン化合物、ジメチルホルムアミド等のアミド化合物等、単独または２種類以上を混合して調製される。電解質塩としては、リチウムイオン二次電池において通常用いられるものであれば特に限定されず、例えば、六フッ化リン酸リチウム、過塩素酸リチウム、四フッ化ホウ酸リチウム等のリチウム塩等が挙げられる。電解液のリチウム塩濃度は特に限定されず、例えば、０．５〜２ｍｏｌ／Ｌ程度が挙げられる。 (About electrolyte)
In this embodiment, since lithium metal is contained in the lithium supply body 5, the electrolyte is preferably a non-aqueous electrolyte solution that does not substantially contain moisture. Examples of the non-aqueous electrolyte include known non-aqueous electrolytes in which a lithium salt is dissolved in a non-aqueous solvent. The non-aqueous solvent is a lactone compound such as γ-butyrolactone; a carbonic acid ester compound such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, or methyl ethyl carbonate; a carboxylic acid ester compound such as methyl formate, methyl acetate, or methyl propionate; Ether compounds such as tetrahydrofuran and dimethoxyethane; ether compounds such as tetrahydrofuran and dimethoxyethane; nitrile compounds such as acetonitrile; sulfone compounds such as sulfolane; amide compounds such as dimethylformamide; . The electrolyte salt is not particularly limited as long as it is usually used in a lithium ion secondary battery. Examples thereof include lithium salts such as lithium hexafluorophosphate, lithium perchlorate, and lithium tetrafluoroborate. It is done. The lithium salt concentration of the electrolytic solution is not particularly limited, and examples thereof include about 0.5 to 2 mol / L.

＜プレドープ工程＞
封止したラミネートセルを所定温度で静置することによって、リチウムプレドープを自然に進行させることができる。この際、ラミネートセルを加圧することにより、リチウムプレドープを更に促進することができる。リチウム供給体５から電解液に溶出したリチウム金属又はリチウムイオンは、負極集電体２ａの貫通孔ｈ及び正極集電体４ａの貫通孔ｈを通過して、各負極活物質層２ｂに拡散及び浸透する。 <Pre-doping process>
Lithium pre-doping can be allowed to proceed naturally by allowing the sealed laminate cell to stand at a predetermined temperature. At this time, the lithium pre-dope can be further promoted by pressurizing the laminate cell. Lithium metal or lithium ions eluted from the lithium supply body 5 into the electrolytic solution pass through the through holes h of the negative electrode current collector 2a and the through holes h of the positive electrode current collector 4a, and diffuse into the negative electrode active material layers 2b. To penetrate.

仮に、リチウム供給体５を前駆体Ｂの両端（最外層）のみに配するか、前駆体Ｂの中心に単数配するだけでは、リチウム金属箔の拡散が行われにくい箇所が発生しやすく、リチウムイオンのドープが不均一となる。その結果、リチウムイオン二次電池１の充放電時に反応が先行して進む部分はリチウムが結合することにより物理的に膨張するが、反応し難い部分は膨張しない。このため、不均一な反応は、負極活物質の不均一な膨張によるうねり又は歪みを引き起こし、負極活物質の部分的な剥がれ（ピール）が生じて電池のサイクル特性を低下させることとなる。   If the lithium supply body 5 is disposed only at both ends (outermost layer) of the precursor B or is disposed singly at the center of the precursor B, a portion where the lithium metal foil is difficult to diffuse easily occurs. Ion doping becomes uneven. As a result, the portion where the reaction proceeds first during charging / discharging of the lithium ion secondary battery 1 physically expands due to the bonding of lithium, but the portion which does not easily react does not expand. For this reason, the non-uniform reaction causes undulation or distortion due to non-uniform expansion of the negative electrode active material, causing partial peeling (peeling) of the negative electrode active material and degrading the cycle characteristics of the battery.

一方、本実施形態の製造方法によれば、リチウム金属又はリチウムイオンを各負極活物質層２ｂに速やかにドープさせることができるため、リチウムイオン二次電池１の初期充電時にリチウム金属又はリチウムイオンが略均一にドープされた状態にすることができる。そのため、本実施形態の製造方法は、リチウムイオン二次電池１の充放電による負極活物質の膨張収縮が均一に行われ易く、サイクル後の負極２のピール強度も均一となり、結果としてサイクル特性を向上させることができるという効果を奏する。   On the other hand, according to the manufacturing method of the present embodiment, lithium metal or lithium ions can be quickly doped into each negative electrode active material layer 2b. A substantially uniformly doped state can be obtained. Therefore, in the manufacturing method of the present embodiment, the expansion and contraction of the negative electrode active material due to charging / discharging of the lithium ion secondary battery 1 is easily performed, and the peel strength of the negative electrode 2 after cycling becomes uniform, resulting in cycle characteristics. There is an effect that it can be improved.

なお、前駆体Ｂの最外層に位置する負極２及び正極４の外表面側にセパレータ３を介してリチウム供給体５を積層するとなおよい。リチウム供給体５をこのように配することで、電極対Ａに対してリチウムイオンを積層方向の双方から拡散させ、より速やかにドープを行うことができる。   In addition, it is more preferable that the lithium supply body 5 is laminated on the outer surface side of the negative electrode 2 and the positive electrode 4 positioned in the outermost layer of the precursor B via the separator 3. By arranging the lithium supply body 5 in this manner, lithium ions can be diffused from both sides of the electrode pair A in the stacking direction, and doping can be performed more quickly.

以下、実施例を示して本発明についてさらに詳しく説明する。ただし、本発明は以下に示す実施例に何ら限定されない。   Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

（１）使用した原料
本実施例で使用した原料を以下に示す。
［実施例１］
（負極２の作製）
厚さ１０μｍのパンチング銅箔（厚さ１０μｍ，穴径０．３５ｍｍ，空孔率１６．７％、福田金属箔粉工業(株)社製）の両面に、片面塗工厚み３０μｍで負極材を塗布し負極２を得た。得られた負極２は、負極活物質層２ｂ部分が４０ｍｍ×５５ｍｍであった。 (1) Used raw materials The raw materials used in this example are shown below.
[Example 1]
(Preparation of negative electrode 2)
A negative electrode material with a single-side coating thickness of 30 μm on both sides of a 10 μm-thick punched copper foil (thickness 10 μm, hole diameter 0.35 mm, porosity 16.7%, manufactured by Fukuda Metal Foil Powder Co., Ltd.) The negative electrode 2 was obtained by coating. As for the obtained negative electrode 2, the negative electrode active material layer 2b part was 40 mm x 55 mm.

（正極４の作製）
負極２の製造工程と同様に、厚さ１５μｍのパンチングＡｌ箔（穴径０．３５ｍｍ、空孔率１６．７％、福田金属箔粉工業(株)社製）の両面に、上記で得られた正極材を片面厚さ４２．５μｍ塗布した。得られた正極４は、正極活物質層４ｂ部分が４０ｍｍ×５５ｍｍであった。 (Preparation of positive electrode 4)
Similar to the manufacturing process of the negative electrode 2, it is obtained on both sides of a 15 μm-thick punching Al foil (hole diameter 0.35 mm, porosity 16.7%, manufactured by Fukuda Metal Foil Powder Co., Ltd.). The positive electrode material was applied with a thickness of 42.5 μm on one side. The obtained positive electrode 4 had a positive electrode active material layer 4b portion of 40 mm × 55 mm.

（電解液の作製）
有機溶媒として、ＥＣ及びＰＣの混合溶媒（ＥＣ：ＰＣ＝３０：７０（体積比））をポリ容器に量り取り、ここにシュウ酸リチウム−三フッ化ホウ素錯体を加えて、シュウ酸リチウム−三フッ化ホウ素錯体中のリチウム原子の濃度が１．０モル／ｋｇとなるようにし、２３℃で混合することにより、電解液を得た。 (Preparation of electrolyte)
As an organic solvent, a mixed solvent of EC and PC (EC: PC = 30: 70 (volume ratio)) is weighed into a plastic container, to which a lithium oxalate-boron trifluoride complex is added, and lithium oxalate-3 The concentration of lithium atoms in the boron fluoride complex was adjusted to 1.0 mol / kg and mixed at 23 ° C. to obtain an electrolytic solution.

（リチウムイオン二次電池１の製造）
上記で得られた負極２及び正極４の間に厚さ２５μｍ、表面積４２ｃｍ×５７ｃｍのセパレータ３（積水化学工業(株)社製）を、負極２−セパレータ３−正極４を１ユニットとして、各ユニット間にセパレータ３を介装させつつ４ユニットの電極対Ａを積層した。４ユニットの電極対Ａの積層方向中央（すなわち電極対Ａを２ユニットずつに分けた箇所）に表面積４０ｍｍ×５５ｍｍ，厚さ０．１ｍｍのリチウム箔を配して１セットの前駆体Ｂとし、４セットを積層させた。この場合、リチウム箔の設置枚数は計４枚で、設置間隔は８８０μｍであった。そして４セットの前駆体Ｂの積層方向の一端側に配された正極４にセパレータ３を介装させて更に負極２を積層した前駆体Ｂを作製した（図１参照）。 (Manufacture of lithium ion secondary battery 1)
A separator 3 (manufactured by Sekisui Chemical Co., Ltd.) having a thickness of 25 μm and a surface area of 42 cm × 57 cm between the negative electrode 2 and the positive electrode 4 obtained above, Four units of electrode pairs A were stacked with the separator 3 interposed between the units. A set of precursors B is formed by arranging a lithium foil having a surface area of 40 mm × 55 mm and a thickness of 0.1 mm at the center in the stacking direction of 4 units of the electrode pair A (that is, where the electrode pair A is divided into 2 units). Four sets were laminated. In this case, the total number of lithium foils installed was 4, and the installation interval was 880 μm. And the precursor B which laminated | stacked the negative electrode 2 by interposing the separator 3 in the positive electrode 4 distribute | arranged to the one end side of the lamination direction of the 4 sets of precursor B was produced (refer FIG. 1).

（リチウムドープ工程）
前駆体Ｂの各負極２及び各正極４からリードタブ７を突出させた状態で、前駆体Ｂをアルミニウムラミネート外装体６で仮封止し、外装体６内部に電解液を注液した上で、前駆体Ｂを真空封止してリチウムイオン二次電池１のセルを得た。その後、得られたセルを加圧治具により加圧及び固定し、４５℃の恒温槽中にて５時間静置することによりリチウムプレドープ処理を行った。 (Lithium doping process)
In a state where the lead tab 7 protrudes from each negative electrode 2 and each positive electrode 4 of the precursor B, the precursor B is temporarily sealed with an aluminum laminate exterior body 6, and an electrolyte is injected into the exterior body 6. The precursor B was vacuum sealed to obtain a cell of the lithium ion secondary battery 1. Thereafter, the obtained cell was pressurized and fixed with a pressure jig, and left in a 45 ° C. constant temperature bath for 5 hours to perform a lithium pre-doping treatment.

［実施例２］
厚さ寸法が実施例１の半分である０．０５ｍｍのリチウム箔を、図３に示すように実施例１の半分の間隔である２ユニット間隔で計８枚配し、その際の設置間隔を４４０μｍとした以外は、実施例１と同条件でリチウムイオン二次電池を作製した。 [Example 2]
As shown in FIG. 3, a total of 8 lithium foils having a thickness of half that of Example 1 are arranged at intervals of 2 units, which is a half interval of Example 1, and the installation interval at that time is set as follows. A lithium ion secondary battery was produced under the same conditions as in Example 1 except that the thickness was 440 μm.

［実施例３］
厚さ寸法が実施例１の１／４である０．０２５ｍｍのリチウム箔を、図４に示すように実施例１の約１／４倍の間隔である１ユニット間隔で計１６枚配し、その際の設置間隔を２２０μｍとした以外は、実施例１と同条件でリチウムイオン二次電池１を作製した。 [Example 3]
A total of 16 pieces of 0.025 mm lithium foil having a thickness dimension of 1/4 of Example 1 are arranged at intervals of 1 unit, which is about 1/4 times that of Example 1, as shown in FIG. A lithium ion secondary battery 1 was produced under the same conditions as in Example 1 except that the installation interval at that time was 220 μm.

［実施例４］
厚さ寸法が実施例１の１．６７倍ある０．１６７ｍｍのリチウム箔を、図５に示すように８ユニット間隔で計３枚配し、その際の設置間隔を実施例１の２倍の１７６０μｍとした以外は、実施例１と同条件でリチウムイオン二次電池を作製した。 [Example 4]
As shown in FIG. 5, a total of three lithium foils having a thickness of 1.67 mm, which is 1.67 times that of Example 1, are arranged at intervals of 8 units, and the installation interval at that time is twice that of Example 1. A lithium ion secondary battery was produced under the same conditions as in Example 1 except that the thickness was 1760 μm.

［比較例１］
セパレータ３を介装させつつ１６ユニットの電極対Ａを連続して積層し、積層方向の一端の正極４にセパレータ３を挟んで負極２を積層し、積層方向の両端に（設置間隔は３５２０μｍ）、厚さ０．２ｍｍのリチウム箔を配したこと以外は実施例１と同条件でリチウムイオン二次電池セルを作製した。 [Comparative Example 1]
16 units of electrode pairs A are continuously stacked with the separator 3 interposed therebetween, and the negative electrode 2 is stacked with the separator 3 sandwiched between the positive electrode 4 at one end in the stacking direction and the both ends in the stacking direction (setting interval is 3520 μm). A lithium ion secondary battery cell was produced under the same conditions as in Example 1 except that a 0.2 mm thick lithium foil was provided.

［比較例２］
正極４に孔無しの正極集電体４ａを用い、負極２に孔無しの負極集電体２ａを用いたこと以外は、実施例１と同条件でリチウムイオン二次電池を作製した。 [Comparative Example 2]
A lithium ion secondary battery was produced under the same conditions as in Example 1 except that the positive electrode current collector 4a without holes was used for the positive electrode 4 and the negative electrode current collector 2a without holes was used for the negative electrode 2.

＜評価方法＞
（リチウムイオン二次電池の充放電特性の評価）
実施例１−４及び比較例１，２で得られたリチウムイオン二次電池について、２５℃において０．２Ｃの定電流定電圧充電を、上限電圧４．２Ｖとして電流値が０．１Ｃに収束するまで行った後、０．２Ｃの定電流放電を２．５Ｖまで行った。次いで、充放電電流を０．２Ｃとして同様の方法で、充放電サイクルを３回繰り返し行い、リチウムイオン二次電池の状態を安定させた。次いで、充放電電流を０．２Ｃとして同様の方法で、充放電を行い、容量発現率（｛［１サイクル目の放電容量（ｍＡｈ）］／［定格容量（ｍＡｈ）］｝×１００）（％）、充放電電流を１Ｃとして同様の方法で、充放電サイクルを繰り返し行い、１００サイクルでの容量維持率（｛［１００サイクル目の放電容量（ｍＡｈ）］／［１サイクル目の放電容量（ｍＡｈ）］｝×１００）（％）を算出した。 <Evaluation method>
(Evaluation of charge / discharge characteristics of lithium ion secondary battery)
About the lithium ion secondary battery obtained in Example 1-4 and Comparative Examples 1 and 2, constant current constant voltage charge of 0.2 C at 25 ° C. was converged to 0.1 C with an upper limit voltage of 4.2 V. Then, 0.2 C constant current discharge was performed up to 2.5V. Subsequently, the charge / discharge current was set to 0.2 C, and the charge / discharge cycle was repeated three times in the same manner to stabilize the state of the lithium ion secondary battery. Next, charging / discharging was performed in the same manner with a charging / discharging current of 0.2 C, and a capacity expression rate ({[discharge capacity (mAh) of the first cycle) / [rated capacity (mAh)]} × 100) (% ), The charge / discharge current is set to 1 C in the same manner, the charge / discharge cycle is repeated, and the capacity retention rate at 100 cycles ({[discharge capacity at the 100th cycle (mAh)] / [discharge capacity at the first cycle (mAh) )]} × 100) (%).

（リチウムイオン二次電池１の負極２の剥離強度）
負極２へのリチウムドープのムラ（バラつき）は、リチウムドープ後に充放電された負極２の最大の剥離強度と最小の剥離強度との差（すなわち剥離強度の差異の最大値）を測定することで行った。 (Peeling strength of the negative electrode 2 of the lithium ion secondary battery 1)
The unevenness (variation) of lithium doping to the negative electrode 2 is determined by measuring the difference between the maximum peel strength and the minimum peel strength of the negative electrode 2 charged and discharged after lithium doping (that is, the maximum difference in peel strength). went.

すなわち、負極２へのリチウムドープのムラ（バラつき）が大きいと、充放電によりバルクとしては、リチウムの吸蔵量（ドープ量）が均一になっていたとしても、充放電による電極体積の膨張収縮による歪にて電極が劣化し、その負極２の剥離強度の差として現れる。そこで、負極２へのリチウムドープのムラ（バラつき）は次のように測定した。   That is, if the unevenness (variation) of lithium dope in the negative electrode 2 is large, even if the occlusion amount (dope amount) of lithium is uniform as a result of charge / discharge, the expansion / contraction of the electrode volume due to charge / discharge The electrode deteriorates due to strain and appears as a difference in peel strength of the negative electrode 2. Therefore, the unevenness (variation) of lithium dope in the negative electrode 2 was measured as follows.

充放電後のリチウムイオン二次電池の負極２（出荷時に０．２Ｃにて３サイクル充放電後と規定）を、９０度剥離試験機（ＴＥ−３００１：テスター産業(株)製）にて、剥離強度を測定した。
試験機の測定部であるアルミ板の基台に巾１９ｍｍの両面テープ（ＳＰＧ−１９：スリーエム ジャパン（株）製）を貼り付け、その上に負極２を貼り付ける。負極２の端部を挟み、引っ張る動作を一度行った。測定は、各層の負極２の周辺部と中央部とを分け、負極２の剥離強度の差を測定した。 The negative electrode 2 of the lithium ion secondary battery after charging / discharging (defined as after 3 cycles of charging / discharging at 0.2 C at the time of shipment) was subjected to a 90-degree peel tester (TE-3001: manufactured by Tester Sangyo Co., Ltd.) The peel strength was measured.
A 19 mm wide double-sided tape (SPG-19: manufactured by 3M Japan Co., Ltd.) is affixed to the base of an aluminum plate, which is a measurement unit of the testing machine, and the negative electrode 2 is affixed thereon. The end of the negative electrode 2 was sandwiched and pulled once. In the measurement, the peripheral part and the central part of the negative electrode 2 of each layer were separated, and the difference in peel strength of the negative electrode 2 was measured.

周辺部は、例えば、負極２の端縁から内側に約１／３までの領域とし、残りの約１／３の領域を中央部とすることが出来る。具体的に、本実施例では、巾１９ｍｍのテープを負極２の端縁に合わせて貼着し、剥離して周辺部の測定を行った。また、負極２の一辺及びこれに交叉する辺の中心点に両面テープの幅方向の中心が合うようにしてテープを貼着し、剥離して中央部の測定を行った。剥離速度は、３０ｍｍ／分とし、剥離角度は９０度とし、剥離時の剥離強度を測定した。なお、圧着は金属のローラーで行った。   The peripheral portion can be, for example, a region extending about 1/3 from the edge of the negative electrode 2 to the inside, and the remaining approximately 1/3 region can be the central portion. Specifically, in this example, a tape having a width of 19 mm was attached to the edge of the negative electrode 2 and peeled to measure the peripheral portion. Moreover, the tape was stuck so that the center of the width direction of the double-sided tape was aligned with the center point of one side of the negative electrode 2 and the side intersecting with this, and the center portion was measured by peeling. The peeling speed was 30 mm / min, the peeling angle was 90 degrees, and the peeling strength at the time of peeling was measured. The crimping was performed with a metal roller.

上記各実施例１−４および比較例１，２のリチウムドープの完了までに要した時間，１００サイクル時の容量維持率及び負極２の最大剥離強度差の評価結果は表１に示すとおりである。   Table 1 shows the evaluation results of the time required for completion of lithium doping in each of the above Examples 1-4 and Comparative Examples 1 and 2, the capacity retention ratio at 100 cycles, and the maximum peel strength difference of the negative electrode 2. .

Figure 2016181363
Figure 2016181363

上記の結果から、実施例１−４のリチウムプレドープ方法によれば、ドープの完了までを８時間以内と比較的短時間とすることができた。また、実施例１−４のリチウムプレドープ方法によれば、負極活物質層２ｂの剥離強度の差異を０．０４０Ｎ／ｍｍ以下（すなわち略一定）とし、均質で優れた構造的強度の電極が得られることが分かった。また、実施例１−４のリチウムプレドープ方法によれば、容量維持率８０％以上と高度にすることができることが分かった。   From the above results, according to the lithium pre-doping method of Example 1-4, the completion of the doping could be made within a relatively short time of 8 hours or less. Moreover, according to the lithium pre-doping method of Example 1-4, the difference in peel strength of the negative electrode active material layer 2b is 0.040 N / mm or less (that is, substantially constant), and an electrode having a uniform and excellent structural strength is obtained. It turns out that it is obtained. Moreover, according to the lithium pre dope method of Example 1-4, it turned out that a capacity | capacitance maintenance factor can be made high with 80% or more.

一方、比較例１，２のリチウムプレドープ方法では、リチウムが完全に溶け切らず、負極活物質層２ｂの剥離強度の最大の差異が０．０５０以上と大きく、更に中央部の方が周辺部よりも剥離強度が小さかったことから、リチウムプレドープが不均一となっていることが分かった。また、容量維持率が５０％以下と低く、リチウムプレドープによる負極活物質層２ｂの損傷が生じていることが分かった。   On the other hand, in the lithium pre-doping methods of Comparative Examples 1 and 2, lithium is not completely melted, the maximum difference in peel strength of the negative electrode active material layer 2b is as large as 0.050 or more, and the central part is the peripheral part. Since the peel strength was lower than that, it was found that the lithium pre-dope was non-uniform. In addition, it was found that the capacity retention rate was as low as 50% or less, and the negative electrode active material layer 2b was damaged by lithium pre-doping.

以上本発明の実施形態について、リチウム供給体５を４ユニットごとの電極対Ａの間隔を空けて配した場合を例として説明したが、リチウム供給体５は、１ユニット以上総ユニット数／２以下の整数以下のユニット間隔を設けて配されていればよい。   As described above, the embodiment of the present invention has been described by taking as an example the case where the lithium supply body 5 is arranged with an interval between the electrode pairs A every 4 units. However, the lithium supply body 5 is 1 unit or more and the total number of units / 2 or less. It suffices if they are arranged with a unit interval equal to or less than the integer.

具体的には、リチウム供給体５は、例えば電極対Ａの総ユニットが３ユニットである場合は、３／２が１．５であるため、１ユニット毎に配されていればよく、電極対Ａの総ユニットが４ユニットから５ユニットである場合は、１ユニット間隔以上２ユニット間隔以下でリチウム箔がリチウムイオンの拡散が均質に行われる位置に配されていればよい。また、例えば電極対Ａの総ユニットが１８ユニットの場合、１ユニット間隔以上９ユニット間隔以下でリチウム箔が配されていればよい。
このようにリチウム供給体５を配することで、リチウムイオンの移動距離を最長でも前駆体Ｂ全体の積層長さの半分以下に抑え、リチウムドープを速やかかつ効率的に行うことができる。 Specifically, for example, when the total unit of the electrode pair A is 3 units, the lithium supply body 5 has only to be arranged for each unit because 3/2 is 1.5. When the total unit of A is from 4 units to 5 units, it is only necessary that the lithium foil is disposed at a position where the lithium ions are uniformly diffused at intervals of 1 unit or more and 2 units or less. Further, for example, when the total number of electrode pairs A is 18 units, it is sufficient that the lithium foil is arranged at intervals of 1 unit or more and 9 units or less.
By arranging the lithium supply body 5 in this way, lithium ion can be rapidly and efficiently performed by suppressing the movement distance of lithium ions to half or less of the total lamination length of the precursor B at the longest.

１…リチウムイオン二次電池、２…負極、２ａ…負極集電体、２ｂ…負極活物質層、３…セパレータ、４正極、４ａ…正極種電体、４ｂ…正極活物質層、５…リチウム供給体、Ａ…電極対、Ｂ…前駆体 DESCRIPTION OF SYMBOLS 1 ... Lithium ion secondary battery, 2 ... Negative electrode, 2a ... Negative electrode collector, 2b ... Negative electrode active material layer, 3 ... Separator, 4 positive electrode, 4a ... Positive electrode seed | species collector, 4b ... Positive electrode active material layer, 5 ... Lithium Supply body, A ... electrode pair, B ... precursor

Claims (7)

貫通孔が形成された負極集電体に負極活物質層が形成された負極と、セパレータと、貫通孔が形成された正極集電体に正極活物質層が形成された正極とをこの順で１ユニットとして積層した電極対を形成する電極対形成工程と、
前記電極対間にセパレータを介装させて３ユニット以上積層するユニット積層工程と、
少なくとも１カ所の電極対間を含む２カ所以上の電極対の積層方向の端部にリチウム供給体を積層したリチウムイオン二次電池の前駆体を形成する前駆体形成工程と、
前記負極と前記正極との間に電解質を配した状態でリチウムプレドープを行うプレドープ工程とを有するリチウムイオン二次電池の製造方法。 A negative electrode in which a negative electrode active material layer is formed on a negative electrode current collector in which through holes are formed, a separator, and a positive electrode in which a positive electrode active material layer is formed on a positive electrode current collector in which through holes are formed. An electrode pair forming step of forming electrode pairs stacked as one unit;
A unit stacking step of stacking three or more units with a separator interposed between the electrode pairs;
A precursor forming step of forming a precursor of a lithium ion secondary battery in which a lithium supply body is stacked at an end in a stacking direction of two or more electrode pairs including at least one electrode pair;
The manufacturing method of a lithium ion secondary battery which has a pre dope process which performs lithium pre dope in the state which arranged electrolyte between the said negative electrode and the said positive electrode. 前記前駆体形成工程において前記リチウム供給体を１ユニット以上総ユニット数／２以下の整数以下のユニット間隔を設けて前記電極対間に積層する請求項１に記載のリチウムイオン二次電池の製造方法。   2. The method of manufacturing a lithium ion secondary battery according to claim 1, wherein, in the precursor forming step, the lithium supplier is stacked between the electrode pairs with a unit interval of 1 unit or more and a total unit number of 2 or less. . 前記負極集電体及び前記正極集電体に形成された前記貫通孔の平均孔径が０．０８ｍｍ以上０．５ｍｍ以下である請求項１又は２に記載のリチウムイオン二次電池の製造方法。   The method for producing a lithium ion secondary battery according to claim 1 or 2, wherein an average hole diameter of the through holes formed in the negative electrode current collector and the positive electrode current collector is 0.08 mm or more and 0.5 mm or less. 前記リチウムイオン二次電池の前駆体の最外層に位置する前記正極の外表面側に前記リチウム供給体を積層する請求項１から３のいずれか１項に記載のリチウムイオン二次電池の製造方法。   The method for producing a lithium ion secondary battery according to any one of claims 1 to 3, wherein the lithium supply body is laminated on an outer surface side of the positive electrode located in an outermost layer of a precursor of the lithium ion secondary battery. . ０．０９ｍｍ以上０．２１ｍｍ以下の厚さ寸法を有する前記リチウム供給体を３００μｍ以上１０００μｍ以下の間隔となるように前記電極対間に配する請求項１から４のいずれか一項に記載のリチウムイオン二次電池の製造方法。   5. The lithium according to claim 1, wherein the lithium supply body having a thickness dimension of 0.09 mm or more and 0.21 mm or less is arranged between the electrode pairs so as to have an interval of 300 μm or more and 1000 μm or less. A method for manufacturing an ion secondary battery. 貫通孔が形成された負極集電体に負極活物質層が形成された負極と、
セパレータと、
貫通孔が形成された正極集電体に正極活物質層が形成された正極とを、
この順で１ユニットとして積層した電極対を、
前記電極対間にセパレータを介装させつつ３ユニット以上積層するとともに、
少なくとも１カ所の電極対間を含む２カ所以上の電極対の端部にリチウム供給体を積層させたリチウムイオン二次電池の前駆体。 A negative electrode in which a negative electrode active material layer is formed on a negative electrode current collector having a through-hole formed therein;
A separator;
A positive electrode in which a positive electrode active material layer is formed on a positive electrode current collector in which a through hole is formed;
The electrode pairs stacked as one unit in this order
While laminating three or more units with a separator interposed between the electrode pairs,
A precursor of a lithium ion secondary battery in which a lithium supply body is laminated on the ends of two or more electrode pairs including at least one electrode pair. 前記リチウム供給体を１ユニット以上総ユニット数／２以下の整数以下のユニット間隔を設けて前記電極対間に積層した請求項６に記載のリチウムイオン二次電池の前駆体。

The precursor of the lithium ion secondary battery according to claim 6, wherein the lithium supplier is stacked between the electrode pairs with a unit interval of 1 unit or more and a total unit number of 2 or less.

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WO2000007255A1 (en) * 1998-07-27 2000-02-10 Kanebo, Limited Organic electrolytic cell
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