JP5511607B2 - Manufacturing method of all-solid-state secondary battery - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 239000007784 solid electrolyte Substances 0.000 claims description 63
- 238000007599 discharging Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- 239000007787 solid Substances 0.000 claims description 20
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 16
- 239000007773 negative electrode material Substances 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 15
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000002180 crystalline carbon material Substances 0.000 claims description 8
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 150000002642 lithium compounds Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 239000012212 insulator Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910018091 Li 2 S Inorganic materials 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Description
本発明は、全固体二次電池の製造方法に関するものである。 The present invention relates to a method for manufacturing an all-solid secondary battery.
近年、携帯電話・ＰＤＡ・ノートパソコンなどの高機能化に伴い、長時間使用が可能であり、且つ小型・軽量で、安全性の高い二次電池が強く要望されている。この要望に応える二次電池として、他の二次電池と比べて高エネルギー密度を有するリチウム二次電池が、従来から多用されている。 In recent years, there has been a strong demand for a secondary battery that can be used for a long time, is small in size and light in weight, and has high safety, with an increase in functionality of a mobile phone, a PDA, a notebook personal computer, and the like. As a secondary battery that meets this demand, lithium secondary batteries having a higher energy density than other secondary batteries have been frequently used.
しかし、通常用いられるリチウム二次電池の多くは、電解液として可燃性の有機溶媒を用いており、過充電時や濫用時に液漏れや発火の危険性がある。そのため、電解液の代わりに固体電解質を用いることで液漏れや発火を防止できる全固体二次電池が鋭意研究されている。 However, many of the lithium secondary batteries that are normally used use a flammable organic solvent as an electrolyte, and there is a risk of liquid leakage or ignition during overcharge or abuse. Therefore, an all-solid secondary battery that can prevent liquid leakage and ignition by using a solid electrolyte instead of an electrolytic solution has been intensively studied.
このような全固体二次電池のエネルギー密度を向上させるため、高容量電極である硫化リチウムを用いることが考えられるが、硫化リチウムは電子伝導性をほとんど有しない。しかし、高圧および高温（６００〜１４００℃）の状態下で炭素材料とともに直流パルス電流を通電することで、この問題を解消し得る全固体二次電池の製造方法が開示されている（例えば、特許文献１）。 In order to improve the energy density of such an all-solid secondary battery, it is conceivable to use lithium sulfide which is a high-capacity electrode, but lithium sulfide has almost no electronic conductivity. However, a method for manufacturing an all-solid-state secondary battery that can solve this problem by applying a DC pulse current together with a carbon material under high pressure and high temperature (600 to 1400 ° C.) is disclosed (for example, patents). Reference 1).
ところで、上記特許文献１における全固体二次電池の充放電容量は、理論容量の１／６程度に過ぎない。これは、全固体二次電池の電極内のイオン伝導パスまたは電子伝導パスが十分に形成されていないためと考えられる。 By the way, the charge / discharge capacity of the all-solid-state secondary battery in Patent Document 1 is only about 1/6 of the theoretical capacity. This is considered because the ion conduction path or the electron conduction path in the electrode of the all-solid-state secondary battery is not sufficiently formed.
そこで、本発明は、電極内のイオン伝導パスまたは電子伝導パスを十分に形成し、充放電容量を向上させた全固体二次電池の製造方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method for producing an all-solid-state secondary battery in which an ion conduction path or an electron conduction path in an electrode is sufficiently formed and charge / discharge capacity is improved.
上記課題を解決するため、本発明の請求項１に係る全固体二次電池の製造方法は、硫化リチウムの正極活物質および無機固体電解質を有する正極合材層と、無機固体電解質からなる固体電解質層と、負極活物質を有する負極層とを具備する全固体二次電池の製造方法であって、
上記固体電解質層を、上記正極合材層と負極層の間に配置して積層部材を成形し、
この積層部材を加圧し且つ４５〜２２０℃の範囲で加熱した状態において、当該積層部材に充放電を少なくとも一回行うものである。
In order to solve the above-mentioned problems, a method for producing an all-solid-state secondary battery according to claim 1 of the present invention is a solid electrolyte comprising a positive electrode mixture layer having a positive electrode active material of lithium sulfide and an inorganic solid electrolyte , and an inorganic solid electrolyte. A method for producing an all-solid-state secondary battery comprising a layer and a negative electrode layer having a negative electrode active material,
The solid electrolyte layer is disposed between the positive electrode mixture layer and the negative electrode layer to form a laminated member,
In the state which pressurized this laminated member and heated in the range of 45-220 degreeC, charging / discharging to the said laminated member is performed at least once.
また、本発明の請求項２に係る全固体二次電池の製造方法は、硫化リチウムの正極活物質および無機固体電解質を有する正極合材層と、無機固体電解質からなる固体電解質層と、負極活物質を有する負極層とを具備する全固体二次電池の製造方法であって、
上記固体電解質層を、上記正極合材層と負極層の間に配置して積層部材を成形し、
この積層部材を袋状容器に封入するとともに袋状容器内の空気を吸引して所定の真空状態にし、
この袋状容器を加圧し且つ４５〜２２０℃の範囲で加熱した状態において、当該積層部材に充放電を少なくとも一回行い、
さらに、上記袋状容器を減圧および冷却した状態において、袋状容器内の空気を吸引して所定の真空状態にするとともに、当該積層部材に充放電を行うものである。
According to a second aspect of the present invention, there is provided a method for producing an all solid state secondary battery comprising : a positive electrode mixture layer having a positive electrode active material of lithium sulfide and an inorganic solid electrolyte ; a solid electrolyte layer comprising an inorganic solid electrolyte ; A method for producing an all-solid-state secondary battery comprising a negative electrode layer having a substance,
The solid electrolyte layer is disposed between the positive electrode mixture layer and the negative electrode layer to form a laminated member,
Enclose this laminated member in a bag-like container and suck the air in the bag-like container to a predetermined vacuum state,
In a state where the bag-like container is pressurized and heated in the range of 45 to 220 ° C., the laminated member is charged and discharged at least once,
Further, in a state where the bag-like container is depressurized and cooled, the air in the bag-like container is sucked into a predetermined vacuum state, and the laminated member is charged and discharged.
また、本発明の請求項３に係る全固体二次電池の製造方法は、請求項１または２に記載の全固体二次電池の製造方法において、負極活物質が、結晶性炭素材料に低結晶性炭素材料を被覆した炭素材料であるものである。 According to a third aspect of the present invention, there is provided a method for producing an all solid state secondary battery according to the first or second aspect , wherein the negative electrode active material is a low crystal in a crystalline carbon material. It is a carbon material coated with a functional carbon material.
また、本発明の請求項４に係る全固体二次電池の製造方法は、硫化リチウムの正極活物質および無機固体電解質を有する正極合材層と、無機固体電解質からなる固体電解質層と、リチウムまたはリチウム化合物を有する負極層とを具備する全固体二次電池の製造方法であって、
上記固体電解質層を、上記正極合材層と負極層の間に配置して積層部材を成形し、
この積層部材を加圧し且つ４５〜２２０℃の範囲で加熱した状態において、当該積層部材に充放電を少なくとも一回行うものである。
According to a fourth aspect of the present invention, there is provided a method for producing an all solid state secondary battery comprising : a positive electrode mixture layer having a positive electrode active material of lithium sulfide and an inorganic solid electrolyte ; a solid electrolyte layer comprising an inorganic solid electrolyte; A method for producing an all-solid-state secondary battery comprising a negative electrode layer having a lithium compound,
The solid electrolyte layer is disposed between the positive electrode mixture layer and the negative electrode layer to form a laminated member,
In the state which pressurized this laminated member and heated in the range of 45-220 degreeC, charging / discharging to the said laminated member is performed at least once.
また、本発明の請求項５に係る全固体二次電池の製造方法は、硫化リチウムの正極活物質および無機固体電解質を有する正極合材層と、無機固体電解質からなる固体電解質層と、リチウムまたはリチウム化合物を有する負極層とを具備する全固体二次電池の製造方法であって、
上記固体電解質層を、上記正極合材層と負極層の間に配置して積層部材を成形し、
この積層部材を袋状容器に封入するとともに袋状容器内の空気を吸引して所定の真空状態にし、
この袋状容器を加圧し且つ４５〜２２０℃の範囲で加熱した状態において、当該積層部材に充放電を少なくとも一回行い、
さらに、上記袋状容器を減圧および冷却した状態において、袋状容器内の空気を吸引して所定の真空状態にするとともに、当該積層部材に充放電を行うものである。
According to a fifth aspect of the present invention, there is provided a method for producing an all solid state secondary battery comprising : a positive electrode mixture layer having a positive electrode active material of lithium sulfide and an inorganic solid electrolyte ; a solid electrolyte layer comprising an inorganic solid electrolyte; A method for producing an all-solid-state secondary battery comprising a negative electrode layer having a lithium compound,
The solid electrolyte layer is disposed between the positive electrode mixture layer and the negative electrode layer to form a laminated member,
Enclose this laminated member in a bag-like container and suck the air in the bag-like container to a predetermined vacuum state,
In a state where the bag-like container is pressurized and heated in the range of 45 to 220 ° C., the laminated member is charged and discharged at least once,
Further, in a state where the bag-like container is depressurized and cooled, the air in the bag-like container is sucked into a predetermined vacuum state, and the laminated member is charged and discharged.
さらに、本発明の請求項６に係る全固体二次電池の製造方法は、請求項１乃至５のいずれか一項に記載の全固体二次電池の製造方法において、充放電での電流密度が１．５ｍＡ／ｃｍ２以下であるものである。 Furthermore, the manufacturing method of the all-solid-state secondary battery which concerns on Claim 6 of this invention is the manufacturing method of the all-solid-state secondary battery as described in any one of Claims 1 thru | or 5. It is 1.5 mA / cm 2 or less.
全固体二次電池の上記製造方法によると、イオン伝導パスまたは電子伝導パスを形成して充放電容量を向上させた全固体二次電池を得ることができる。 According to the manufacturing method of an all-solid-state secondary battery, an all-solid-state secondary battery having an improved charge / discharge capacity by forming an ion conduction path or an electron conduction path can be obtained.
以下、本発明の実施の形態に係る全固体二次電池の製造方法を図面に基づいて説明する。なお、本実施の形態では、全固体二次電池の一例として、全固体リチウムイオン二次電池について説明する。 Hereinafter, a method for producing an all-solid-state secondary battery according to an embodiment of the present invention will be described with reference to the drawings. Note that in this embodiment, an all-solid lithium ion secondary battery will be described as an example of an all-solid secondary battery.
まず、全固体リチウムイオン二次電池の基本的構成について説明する。
この全固体リチウムイオン二次電池は、図示しないが、正極合材層と負極層との間に固体電解質層が配置（積層）され、正極合材層の固体電解質層とは反対側の表面に正極集電体が、また負極層の固体電解質層とは反対側の表面に負極集電体が、負極層の外周に絶縁体フィルムがそれぞれ配置されたものである。
First, the basic configuration of the all solid lithium ion secondary battery will be described.
Although not shown in the figure, this all solid lithium ion secondary battery has a solid electrolyte layer disposed (laminated) between the positive electrode mixture layer and the negative electrode layer, and is on the surface of the positive electrode mixture layer opposite to the solid electrolyte layer. The positive electrode current collector, the negative electrode current collector on the surface of the negative electrode layer opposite to the solid electrolyte layer, and the insulator film on the outer periphery of the negative electrode layer, respectively.
上記正極合材層は、硫黄を成分とする正極活物質と固体電解質と導電助剤との混合物からなり、これらの重量比は、硫黄を成分とする正極活物質２５％、固体電解質５０％、導電助剤２５％である。また固体電解質層は、固体電解質からなる。さらに上記負極層は、負極活物質と固体電解質との混合物からなり、これらの重量比は、負極活物質６０％、固体電解質４０％である。なお、各層の原料としては、いずれも粉末状のものが用いられている。 The positive electrode mixture layer is composed of a mixture of a positive electrode active material containing sulfur as a component, a solid electrolyte, and a conductive additive. These weight ratios are 25% for a positive electrode active material containing sulfur as a component, 50% for a solid electrolyte, The conductivity aid is 25%. The solid electrolyte layer is made of a solid electrolyte. Furthermore, the negative electrode layer is composed of a mixture of a negative electrode active material and a solid electrolyte, and the weight ratio thereof is 60% for the negative electrode active material and 40% for the solid electrolyte. In addition, as a raw material for each layer, a powdery material is used.
上記正極活物質には、硫黄を成分とするので例えば硫化リチウム（Ｌｉ２Ｓ）が用いられ、正極合材層の固体電解質には、例えばリチウムイオン伝導性固体電解質［Ｌｉ２Ｓ（７０mol％）−Ｐ２Ｓ5（３０mol％）］が用いられ、導電助剤には、アセチレンガスを熱分解して得られる炭素微粒子であるアセチレンブラックが用いられる。 Since the positive electrode active material contains sulfur as a component, for example, lithium sulfide (Li 2 S) is used. For the solid electrolyte of the positive electrode mixture layer, for example, lithium ion conductive solid electrolyte [Li 2 S (70 mol%) —P 2 S 5 (30 mol%)] is used, and acetylene black, which is carbon fine particles obtained by thermally decomposing acetylene gas, is used as the conductive assistant.
また、固体電解質層の固体電解質には、例えば正極合材層の固体電解質と同一のリチウムイオン伝導性固体電解質［Ｌｉ２Ｓ（７０mol％）−Ｐ２Ｓ5（３０mol％）］が用いられる。 For example, the same lithium ion conductive solid electrolyte [Li 2 S (70 mol%)-P 2 S 5 (30 mol%)] as the solid electrolyte of the positive electrode mixture layer is used as the solid electrolyte of the solid electrolyte layer.
さらに、上記負極活物質には、例えば結晶性炭素材料である黒鉛に低結晶性炭素材料を被覆し且つ重量あたりの実効容量が０．３５Ａｈ／ｇ以上の炭素材料が用いられる。なお、負極活物質が結晶性炭素材料のみであれば、容量は大きいものの、充放電時の負極活物質におけるリチウムイオンの挿入脱離は一方向だけで行われることになる。したがって、任意の方向で負極活物質におけるリチウムイオンの挿入脱離を可能にすることで充放電時の負極におけるリチウムイオンの挿入脱離をスムーズにするためにも、結晶性炭素材料に低結晶性炭素材料を被覆したものを負極活物質として用いる。一方、負極層の固体電解質には、例えば正極合材層や固体電解質層の固体電解質と同一のリチウムイオン伝導性固体電解質が用いられる。 Furthermore, as the negative electrode active material, for example, a carbon material in which graphite, which is a crystalline carbon material, is coated with a low crystalline carbon material and an effective capacity per weight is 0.35 Ah / g or more is used. Note that if the negative electrode active material is only a crystalline carbon material, the capacity is large, but insertion / extraction of lithium ions in the negative electrode active material during charge / discharge is performed in only one direction. Therefore, the crystalline carbon material has low crystallinity in order to facilitate the insertion and desorption of lithium ions in the negative electrode during charge and discharge by enabling the insertion and desorption of lithium ions in the negative electrode active material in any direction. A material coated with a carbon material is used as the negative electrode active material. On the other hand, for the solid electrolyte of the negative electrode layer, for example, the same lithium ion conductive solid electrolyte as the solid electrolyte of the positive electrode mixture layer or the solid electrolyte layer is used.
ところで、正極集電体には例えば錫（Ｓｎ）の箔が用いられ、負極集電体には例えば銅（Ｃｕ）の箔が用いられる。
以下に、図２〜図４に基づき上記全固体リチウムイオン二次電池の製造方法について説明する。
By the way, for example, a tin (Sn) foil is used for the positive electrode current collector, and for example, a copper (Cu) foil is used for the negative electrode current collector.
Below, the manufacturing method of the said all-solid-state lithium ion secondary battery is demonstrated based on FIGS.
まず、固体電解質層を成形する。具体的には、図２（ａ）に示すように、冷間ダイス鋼（ＳＤＫ）など超硬性の鋼材で製造された内径１０ｍｍの円筒形状の型（以下、単に円筒金型Ｍという）に、固体電解質層３の原料であるリチウムイオン伝導性固体電解質５０ｍｇを秤量して入れ、１８８ＭＰａで１回加圧して固体電解質層３を成形する。
First, a solid electrolyte layer is formed. Specifically, as shown in FIG. 2 (a), a cylindrical mold having an inner diameter of 10 mm (hereinafter simply referred to as a cylindrical mold M) manufactured from superhard steel such as cold die steel (SDK). 50 mg of lithium ion conductive solid electrolyte which is a raw material of the
次に、負極層を成形する。具体的には、図示しないが黒鉛に低結晶性炭素材料を被覆したもの６０ｍｇとリチウムイオン伝導性固体電解質４０ｍｇとを秤量して乳鉢に入れ、十分混合する。そして、この混合物３０ｍｇを秤量し、図２（ｂ）に示すように、円筒金型Ｍに固体電解質層３の上から入れ、それぞれ１８８ＭＰａで３回加圧して負極層４を成形する。
Next, the negative electrode layer is formed. Specifically, although not shown, 60 mg of graphite coated with a low crystalline carbon material and 40 mg of lithium ion conductive solid electrolyte are weighed and placed in a mortar and mixed thoroughly. Then, 30 mg of this mixture is weighed, and, as shown in FIG. 2 (b), the
その後、正極合材層を成形する。具体的には、図示しないがボールミル用でステンレス製のボールおよびポットを準備し、このボールを入れたポットに、硫化リチウム５０ｍｇと、リチウムイオン伝導性固体電解質１００ｍｇと、アセチレンブラック５０ｍｇとを秤量して入れ、３０分間ボールミル混合を行う。そして、この混合物２０ｍｇを秤量し、図２（ｃ）に示すように、円筒金型Ｍの固体電解質層３の上（負極層４とは反対側）から入れ、順次３７６ＭＰａ、７５２ＭＰａ、１０５０ＭＰａで加圧して正極合材層２を成形する。
Thereafter, a positive electrode mixture layer is formed. Specifically, although not shown, a ball and a pot made of stainless steel are prepared for a ball mill, and 50 mg of lithium sulfide, 100 mg of lithium ion conductive solid electrolyte, and 50 mg of acetylene black are weighed into the pot containing the ball. And ball mill mixing for 30 minutes. Then, 20 mg of this mixture was weighed, and placed from above the
次に、この正極合材層２、固体電解質層３および負極層４からなる積層部材７を円筒金型Ｍから取り出す。次に、図示しないが、内径１１ｍｍの円環形状の絶縁体フィルムを、この絶縁体フィルムと同じ外径の円形状の銅箔である負極集電体の上に配置する。そして、上記積層部材７の負極層４が負極集電体に接するように、積層部材７（外径１０ｍｍ）を絶縁体フィルムの環内（内径１１ｍｍ）に入れる。その後、積層部材７の正極合材層２の上に錫箔の正極集電体を配置して、図１に示す構成とする。
Next, the
そして、この積層部材７、正極集電体、負極集電体および絶縁体フィルムからなる部材を、図１に示す正極リード１３および負極リード１４を有する袋状容器であるラミネートセル（ラミネートフィルムともいう）Ｌに封入し、このラミネートセルＬから空気を吸引して所定の真空度を維持することで、ラミネートセルＬ内の空気が含んでいる水分の影響を上記部材（積層部材７、正極集電体、負極集電体および絶縁体フィルムからなる部材）が受けないようにし、さらに後述する予備充放電の際の圧力がラミネートセルＬに均一に負荷するようにする。なお以下では、積層部材７、正極集電体、負極集電体および絶縁体フィルムからなる部材をラミネートセルＬに封入して所定の真空度に維持したものを、単にラミネートセルＬという。
And the member which consists of this
次に、図３に示すように上記ラミネートセルＬを恒温槽Ｈ内に配置して、６０ＭＰａまで加圧するとともに、この恒温槽Ｈによる温度制御でラミネートセルＬを４５〜２２０℃のいずれかの温度まで加熱し、この状態を８時間維持した後、充電終止電圧が３．５Ｖ、放電終止電圧が０．５Ｖおよび充放電の電流密度が０．１ｍＡ／ｃｍ２となる条件で、定電流による予備充放電をラミネートセルＬに行う。 Next, as shown in FIG. 3, the laminate cell L is placed in a constant temperature bath H and pressurized to 60 MPa, and the temperature of the laminate cell L is controlled at any temperature of 45 to 220 ° C. by the constant temperature bath H. Until the charge end voltage is 3.5 V, the discharge end voltage is 0.5 V, and the charge / discharge current density is 0.1 mA / cm 2. Charging / discharging is performed on the laminate cell L.
その後、ラミネートセルＬを恒温槽Ｈ内から取り出して加圧から開放（減圧）するとともに常温に戻す（冷却する）。そして、再びラミネートセルＬから空気を吸引して所定の真空度を維持することで、予備充放電で発生したガスを抜くとともに、大気圧をラミネートセルＬに封入した部材（積層部材７、正極集電体、負極集電体および絶縁体フィルム）に均一に負荷させて固体／固体界面の接触状態を改善する。
Thereafter, the laminate cell L is taken out from the thermostat H and released from the pressurization (reduced pressure) and returned to room temperature (cooled). Then, by sucking air from the laminate cell L again to maintain a predetermined degree of vacuum, the gas generated by the preliminary charge / discharge is removed, and a member (
次に、図４に示すように再びラミネートセルＬを恒温槽Ｈに戻して、温度制御により３０℃の状態で約８時間維持した後、充電終止電圧が３．５Ｖ、放電終止電圧が０．５Ｖおよび充放電の電流密度が０．１ｍＡ／ｃｍ２となる条件で、定電流による本充放電をラミネートセルＬに行う。 Next, as shown in FIG. 4, the laminate cell L is returned to the thermostat H again and maintained at 30 ° C. for about 8 hours by temperature control, and then the charge end voltage is 3.5 V and the discharge end voltage is 0. The main charge / discharge with a constant current is performed on the laminate cell L under the condition that the current density of 5 V and the charge / discharge is 0.1 mA / cm 2 .
この本充放電を終えたラミネートセルＬが、本発明に係る製造方法で製造された全固体リチウムイオン二次電池となる。
以下、本発明の具体的な実施例および比較例について説明する。これら実施例および比較例における予備充放電を行う温度と本充放電での初期充放電容量との関係を、表１に示す。なお、以下の実施例において、特に条件の明記がないものは、上記実施の形態で説明した条件（例えば、予備充放電での圧力は６０ＭＰａ）を用いる。
The laminate cell L that has completed this main charge / discharge is an all solid lithium ion secondary battery manufactured by the manufacturing method according to the present invention.
Hereinafter, specific examples and comparative examples of the present invention will be described. Table 1 shows the relationship between the temperature at which preliminary charge / discharge is performed in these Examples and Comparative Examples and the initial charge / discharge capacity in the main charge / discharge. In the following examples, unless otherwise specified, the conditions described in the above embodiment (for example, the pressure during pre-charging / discharging is 60 MPa) are used.
予備充放電を行う温度を６０℃とした。この場合、図５での破線で示すように、予備充放電での初期充電容量は５４５ｍＡｈ／ｇ、初期放電容量は５２０ｍＡｈ／ｇであった。また、図５での一点鎖線で示すように、本充放電での初期充電容量は５０５ｍＡｈ／ｇ、初期放電容量は４６０ｍＡｈ／ｇであった。 The temperature at which pre-charging / discharging was performed was 60 ° C. In this case, as indicated by a broken line in FIG. 5, the initial charge capacity in the preliminary charge / discharge was 545 mAh / g, and the initial discharge capacity was 520 mAh / g. Moreover, as shown by the one-dot chain line in FIG. 5, the initial charge capacity in the main charge / discharge was 505 mAh / g, and the initial discharge capacity was 460 mAh / g.
予備充放電を行う温度を４５℃とした。この場合、本充放電での初期充電容量は３７５ｍＡｈ／ｇ、初期放電容量は３４０ｍＡｈ／ｇであった。 The temperature at which pre-charging / discharging was performed was 45 ° C. In this case, the initial charge capacity in the main charge / discharge was 375 mAh / g, and the initial discharge capacity was 340 mAh / g.
予備充放電を行う温度を１００℃とした。この場合、本充放電での初期充電容量は８１５ｍＡｈ／ｇ、初期放電容量は７２５ｍＡｈ／ｇであった。 The temperature at which pre-charging / discharging was performed was set to 100 ° C. In this case, the initial charge capacity in the main charge / discharge was 815 mAh / g, and the initial discharge capacity was 725 mAh / g.
予備充放電を行う温度を１５０℃とした。この場合、本充放電での初期充電容量は９７０ｍＡｈ／ｇ、初期放電容量は８５０ｍＡｈ／ｇであった。 The temperature at which pre-charging / discharging was performed was set to 150 ° C. In this case, the initial charge capacity in the main charge / discharge was 970 mAh / g, and the initial discharge capacity was 850 mAh / g.
予備充放電を行う温度を２００℃とした。この場合、本充放電での初期充電容量は１０９５ｍＡｈ／ｇ、初期放電容量は９３０ｍＡｈ／ｇであった。 The temperature at which pre-charging / discharging was performed was 200 ° C. In this case, the initial charge capacity in the main charge / discharge was 1095 mAh / g, and the initial discharge capacity was 930 mAh / g.
予備充放電を行う温度を２２０℃とした。この場合、本充放電での初期充電容量は９９０ｍＡｈ／ｇ、初期放電容量は７９０ｍＡｈ／ｇであった。
［比較例１］
The temperature at which pre-charging / discharging was performed was 220 ° C. In this case, the initial charge capacity in the main charge / discharge was 990 mAh / g, and the initial discharge capacity was 790 mAh / g.
[Comparative Example 1]
予備充放電を行う温度を３０℃（加熱なし）とし、加圧は行わなかった。この場合、図５での実線で示すように、本充放電での初期充電容量は２２５ｍＡｈ／ｇ、初期放電容量は２２０ｍＡｈ／ｇであった。
［比較例２］
The temperature at which pre-charging / discharging was performed was 30 ° C. (no heating), and no pressure was applied. In this case, as indicated by a solid line in FIG. 5, the initial charge capacity in the main charge / discharge was 225 mAh / g, and the initial discharge capacity was 220 mAh / g.
[Comparative Example 2]
予備充放電を行う温度を６０℃とし、加圧は行わなかった。この場合、本充放電での初期充電容量は２３５ｍＡｈ／ｇ、初期放電容量は２２５ｍＡｈ／ｇであった。 The temperature for pre-charging / discharging was set to 60 ° C., and no pressure was applied. In this case, the initial charge capacity in the main charge / discharge was 235 mAh / g, and the initial discharge capacity was 225 mAh / g.
また、加熱のみをして予備充放電を行った比較例２では、加圧および加熱をして予備充放電を行った実施例１ほどの本充放電容量の向上が見られなかった。
さらに、実施例３〜６のように、加圧し且つ１００〜２２０℃の範囲で加熱をして予備充放電を行った場合には、本充放電容量の顕著な向上が見られた。
Further, in Comparative Example 2 in which preliminary charging / discharging was performed only by heating, the improvement in the main charging / discharging capacity as in Example 1 in which preliminary charging / discharging was performed by pressurization and heating was not observed.
Furthermore, when pre-charging / discharging was performed by pressurizing and heating in the range of 100-220 ° C. as in Examples 3-6, a significant improvement in the main charge / discharge capacity was observed.
したがって、ラミネートセルＬを加圧し且つ４５〜２２０℃の範囲で加熱した状態において、積層部材７に充放電を少なくとも一回行うことにより、イオン伝導パスまたは電子伝導パスを形成して固体／固体界面の接触状態を改善し、充放電容量の向上を図ることができる。
Therefore, in a state where the laminate cell L is pressurized and heated in the range of 45 to 220 ° C., the
また、予備充放電の後にラミネートセルＬを加圧から開放（減圧）するとともに常温に戻し、このラミネートセルＬから空気を吸引して所定の真空度を維持するので、予備充放電で発生したガスを抜くとともに、大気圧をラミネートセルＬに封入した部材（積層部材７、正極集電体、負極集電体および絶縁体フィルム）に均一に負荷させて固体／固体界面の接触状態を一層改善し、さらに充放電容量の向上を図ることができる。
Further, after the preliminary charge / discharge, the laminate cell L is released from pressure (reduced pressure) and returned to room temperature, and air is sucked from the laminate cell L to maintain a predetermined degree of vacuum. In addition, the contact state of the solid / solid interface is further improved by uniformly loading the member (
ところで、上記では予備充放電の回数を１回として説明したが、複数回であっても良い。
また、予備充放電を行う圧力を、上記では６０ＭＰａとして説明したが、この値に限定されるものではなく、少なくとも０．５ＭＰａ以上とするのが好ましい。０．５ＭＰａ未満であれば、粒子の接触状態が十分維持されず、十分なイオン伝導パスまたは電子伝導パスが形成されないからである。
By the way, although the number of times of preliminary charging / discharging has been described above as one time, it may be a plurality of times.
Moreover, although the pressure which performs preliminary charging / discharging was demonstrated as 60 Mpa above, it is not limited to this value, It is preferable to set it as at least 0.5 Mpa or more. If it is less than 0.5 MPa, the contact state of the particles is not sufficiently maintained, and a sufficient ion conduction path or electron conduction path is not formed.
さらに、硫黄を成分とする正極活物質として硫化リチウムについて説明したが、これに限定されるものではない。具体的に説明すると、負極活物質がリチウムを含まない場合では、正極活物質はリチウムを含む硫化物であればよく、負極活物質がリチウムを含む場合では、正極活物質は硫黄、リチウムを含む硫化物、またはリチウムを含まない硫化物であればよい。 Furthermore, although lithium sulfide was demonstrated as a positive electrode active material which uses sulfur as a component, it is not limited to this. Specifically, when the negative electrode active material does not contain lithium, the positive electrode active material may be a sulfide containing lithium. When the negative electrode active material contains lithium, the positive electrode active material contains sulfur and lithium. Any sulfide or sulfide containing no lithium may be used.
また、負極活物質についても上記した内容に限定されるものではない。具体的に説明すると、正極活物質がリチウムを含む場合では、負極活物質は錫、ケイ素、合金系負極、リチウム箔など他の物質であってもよい。 Further, the negative electrode active material is not limited to the contents described above. Specifically, when the positive electrode active material contains lithium, the negative electrode active material may be other materials such as tin, silicon, an alloy-based negative electrode, and a lithium foil.
また、予備充放電および本充放電での電流密度を０．１ｍＡ／ｃｍ２として説明したが、この値に限定されるものではなく、電流の速さに電池反応が追随できる電流密度であればよい。具体的には、１．５ｍＡ／ｃｍ２以下の範囲であり、この範囲内であれば、電流の速さに電池反応が追随できるため、十分なイオン伝導パスまたは電子伝導パスが形成される。 Moreover, although the current density in preliminary charging / discharging and main charging / discharging was described as 0.1 mA / cm 2 , the current density is not limited to this value. Good. Specifically, it is in a range of 1.5 mA / cm 2 or less, and if it is within this range, the battery reaction can follow the speed of the current, so that a sufficient ion conduction path or electron conduction path is formed.
２ 正極合材層
３ 固体電解質層
４ 負極層
７ 積層部材
１３ 正極リード
１４ 負極リード
Ｈ 恒温槽
Ｌ ラミネートセル
Ｍ 円筒金型
2 Positive
Claims (6)
上記固体電解質層を、上記正極合材層と負極層の間に配置して積層部材を成形し、
この積層部材を加圧し且つ４５〜２２０℃の範囲で加熱した状態において、当該積層部材に充放電を少なくとも一回行うことを特徴とした全固体二次電池の製造方法。 A method for producing an all-solid-state secondary battery comprising a positive electrode mixture layer having a positive electrode active material of lithium sulfide and an inorganic solid electrolyte , a solid electrolyte layer comprising an inorganic solid electrolyte , and a negative electrode layer having a negative electrode active material. ,
The solid electrolyte layer is disposed between the positive electrode mixture layer and the negative electrode layer to form a laminated member,
In the state which pressurized this laminated member and heated in the range of 45-220 degreeC, charging / discharging to the said laminated member is performed at least once, The manufacturing method of the all-solid-state secondary battery characterized by the above-mentioned.
上記固体電解質層を、上記正極合材層と負極層の間に配置して積層部材を成形し、
この積層部材を袋状容器に封入するとともに袋状容器内の空気を吸引して所定の真空状態にし、
この袋状容器を加圧し且つ４５〜２２０℃の範囲で加熱した状態において、当該積層部材に充放電を少なくとも一回行い、
さらに、上記袋状容器を減圧および冷却した状態において、袋状容器内の空気を吸引して所定の真空状態にするとともに、当該積層部材に充放電を行うことを特徴とした全固体二次電池の製造方法。 A method for producing an all-solid-state secondary battery comprising a positive electrode mixture layer having a positive electrode active material of lithium sulfide and an inorganic solid electrolyte , a solid electrolyte layer comprising an inorganic solid electrolyte , and a negative electrode layer having a negative electrode active material. ,
The solid electrolyte layer is disposed between the positive electrode mixture layer and the negative electrode layer to form a laminated member,
Enclose this laminated member in a bag-like container and suck the air in the bag-like container to a predetermined vacuum state,
In a state where the bag-like container is pressurized and heated in the range of 45 to 220 ° C., the laminated member is charged and discharged at least once,
Furthermore, in a state where the bag-like container is decompressed and cooled, the air in the bag-like container is sucked into a predetermined vacuum state, and the laminated member is charged and discharged. Manufacturing method.
上記固体電解質層を、上記正極合材層と負極層の間に配置して積層部材を成形し、
この積層部材を加圧し且つ４５〜２２０℃の範囲で加熱した状態において、当該積層部材に充放電を少なくとも一回行うことを特徴とした全固体二次電池の製造方法。 A method for producing an all-solid-state secondary battery comprising a positive electrode mixture layer having a positive electrode active material of lithium sulfide and an inorganic solid electrolyte , a solid electrolyte layer made of an inorganic solid electrolyte , and a negative electrode layer having lithium or a lithium compound. And
The solid electrolyte layer is disposed between the positive electrode mixture layer and the negative electrode layer to form a laminated member,
In the state which pressurized this laminated member and heated in the range of 45-220 degreeC, charging / discharging to the said laminated member is performed at least once, The manufacturing method of the all-solid-state secondary battery characterized by the above-mentioned.
上記固体電解質層を、上記正極合材層と負極層の間に配置して積層部材を成形し、
この積層部材を袋状容器に封入するとともに袋状容器内の空気を吸引して所定の真空状態にし、
この袋状容器を加圧し且つ４５〜２２０℃の範囲で加熱した状態において、当該積層部材に充放電を少なくとも一回行い、
さらに、上記袋状容器を減圧および冷却した状態において、袋状容器内の空気を吸引して所定の真空状態にするとともに、当該積層部材に充放電を行うことを特徴とした全固体二次電池の製造方法。 A method for producing an all-solid-state secondary battery comprising a positive electrode mixture layer having a positive electrode active material of lithium sulfide and an inorganic solid electrolyte , a solid electrolyte layer made of an inorganic solid electrolyte , and a negative electrode layer having lithium or a lithium compound. And
The solid electrolyte layer is disposed between the positive electrode mixture layer and the negative electrode layer to form a laminated member,
Enclose this laminated member in a bag-like container and suck the air in the bag-like container to a predetermined vacuum state,
In a state where the bag-like container is pressurized and heated in the range of 45 to 220 ° C., the laminated member is charged and discharged at least once,
Furthermore, in a state where the bag-like container is decompressed and cooled, the air in the bag-like container is sucked into a predetermined vacuum state, and the laminated member is charged and discharged. Manufacturing method.
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| JP2013222501A (en) * | 2012-04-12 | 2013-10-28 | Osaka Prefecture Univ | Positive electrode for all-solid-state lithium secondary battery and manufacturing method therefor |
| JP2014035987A (en) * | 2012-08-10 | 2014-02-24 | Toyota Motor Corp | METHOD FOR MANUFACTURING Si-CONTAINING ACTIVE MATERIAL LAYER, METHOD FOR MANUFACTURING SOLID-STATE BATTERY, Si-CONTAINING ACTIVE MATERIAL LAYER, AND SOLID-STATE BATTERY |
| JP5880409B2 (en) * | 2012-11-28 | 2016-03-09 | トヨタ自動車株式会社 | Manufacturing method of all-solid lithium secondary battery |
| WO2014141962A1 (en) * | 2013-03-11 | 2014-09-18 | 株式会社村田製作所 | All-solid-state battery |
| EP3012887B1 (en) * | 2013-06-21 | 2017-10-18 | Nagase ChemteX Corporation | Positive electrode mixture and all-solid-state lithium sulfur cell |
| JP6380883B2 (en) | 2013-10-16 | 2018-08-29 | ナガセケムテックス株式会社 | Positive electrode mixture, method for producing the same, and all solid-state lithium-sulfur battery |
| JP6828240B2 (en) * | 2016-01-12 | 2021-02-10 | トヨタ自動車株式会社 | Manufacturing method of all-solid-state battery |
| US11437612B2 (en) | 2017-08-09 | 2022-09-06 | Toyota Jidosha Kabushiki Kaisha | Cathode mixture and method for producing the same |
| US11271243B2 (en) | 2017-12-18 | 2022-03-08 | Samsung Electronics Co., Ltd. | All-solid secondary battery |
| JP7156157B2 (en) * | 2018-06-01 | 2022-10-19 | トヨタ自動車株式会社 | Positive electrode mixture, all-solid battery, method for producing positive electrode mixture, and method for producing all-solid battery |
| CN112385069A (en) * | 2018-07-13 | 2021-02-19 | 日立造船株式会社 | Manufacturing equipment of all-solid-state secondary battery |
| JP2020013732A (en) * | 2018-07-19 | 2020-01-23 | ブラザー工業株式会社 | Lithium sulfur battery |
| JP7035984B2 (en) | 2018-11-27 | 2022-03-15 | トヨタ自動車株式会社 | Manufacturing method of positive electrode mixture, all-solid-state battery and positive electrode mixture |
| JPWO2022172612A1 (en) * | 2021-02-12 | 2022-08-18 | ||
| JP7400765B2 (en) * | 2021-04-01 | 2023-12-19 | トヨタ自動車株式会社 | All-solid-state battery manufacturing method |
| WO2024195089A1 (en) * | 2023-03-23 | 2024-09-26 | 日産自動車株式会社 | Reacted all-solid-state battery and method for manufacturing same |
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| JP3803866B2 (en) * | 1995-11-14 | 2006-08-02 | 大阪瓦斯株式会社 | Double-layer carbon material for secondary battery and lithium secondary battery using the same |
| JP2008097940A (en) * | 2006-10-10 | 2008-04-24 | Nissan Motor Co Ltd | Bipolar type secondary battery |
| JP2008103284A (en) * | 2006-10-20 | 2008-05-01 | Idemitsu Kosan Co Ltd | All-solid battery |
| JP2009295289A (en) * | 2008-06-02 | 2009-12-17 | Panasonic Corp | Lithium-ion secondary battery and method of manufacturing the same |
| JP5559989B2 (en) * | 2008-07-30 | 2014-07-23 | 出光興産株式会社 | All-solid secondary battery and device comprising the same |
| JP2010033937A (en) * | 2008-07-30 | 2010-02-12 | Idemitsu Kosan Co Ltd | Lithium-ion battery |
| WO2010035602A1 (en) * | 2008-09-24 | 2010-04-01 | 独立行政法人産業技術総合研究所 | Lithium sulfide-carbon complex, process for producing the complex, and lithium ion secondary battery utilizing the complex |
| JP2010113968A (en) * | 2008-11-06 | 2010-05-20 | Sumitomo Electric Ind Ltd | Method of manufacturing nonaqueous electrolyte battery |
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