JP2020021681A - Solid electrolyte layer for all-solid lithium ion battery and all-solid lithium ion battery - Google Patents
Solid electrolyte layer for all-solid lithium ion battery and all-solid lithium ion battery Download PDFInfo
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Abstract
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本発明は、全固体リチウムイオン電池用固体電解質層及び全固体リチウムイオン電池に関する。 The present invention relates to a solid electrolyte layer for an all-solid-state lithium-ion battery and an all-solid-state lithium-ion battery.
近年におけるパソコン、ビデオカメラ、及び携帯電話等の情報関連機器や通信機器等の急速な普及に伴い、その電源として利用される電池の開発が重要視されている。該電池の中でも、エネルギー密度が高いという観点から、リチウム電池が注目を浴びている。また、車載用等の動力源やロードレベリング用といった大型用途におけるリチウム二次電池についても、高エネルギー密度、電池特性向上が求められている。 With the rapid spread of information-related devices and communication devices such as personal computers, video cameras, and mobile phones in recent years, the development of batteries used as power sources for them has been regarded as important. Among these batteries, lithium batteries have attracted attention from the viewpoint of high energy density. In addition, high energy density and improved battery characteristics are also required for lithium secondary batteries for large-scale applications such as power sources for vehicles and load leveling.
ただ、リチウムイオン電池の場合は、電解液は有機化合物が大半であり、たとえ難燃性の化合物を用いたとしても火災に至る危険性が全くなくなるとは言いきれない。こうした液系リチウムイオン電池の代替候補として、電解質を固体とした全固体リチウムイオン電池が近年注目を集めている（特許文献１等）。その中でも、固体電解質としてＬｉ2Ｓ−Ｐ2Ｓ5などのリチウムイオン伝導性の高い硫化物を添加した全固体リチウムイオン電池が主流となりつつある。 However, in the case of a lithium ion battery, most of the electrolyte is an organic compound, and even if a flame-retardant compound is used, it cannot be said that there is no danger of fire. As an alternative candidate for such a liquid lithium-ion battery, an all-solid-state lithium-ion battery having a solid electrolyte has recently attracted attention (Patent Document 1 and the like). Among them, an all-solid-state lithium ion battery to which a sulfide having a high lithium ion conductivity such as Li 2 SP 2 S 5 is added as a solid electrolyte is becoming mainstream.
このような硫化物を添加した全固体リチウムイオン電池の固体電解質として、ＬｉＧｅＰＳ系の固体電解質（ＬＧＰＳ）が知られているが、ＬＧＰＳのＧｅは負極で還元してしまうという問題が生じる。このような問題に対し、特許文献１では固体電解質を２層構造とすることで対応しようとした技術が記載されている。 As a solid electrolyte of such a sulfide-added all solid lithium ion battery, a LiGePS-based solid electrolyte (LGPS) is known. However, there is a problem that Ge of LGPS is reduced at a negative electrode. Patent Literature 1 describes a technique to cope with such a problem by forming the solid electrolyte into a two-layer structure.
特許文献１では固体電解質を、正極側と負極側とで異なる種類の硫化物系電解質からなる２層構造としている。しかしながら、このような構成では、正極合剤と負極合剤の間の電解質のリチウムイオン伝導率が低下し、電池の内部抵抗が増加するという問題が生じるおそれがある。 In Patent Literature 1, the solid electrolyte has a two-layer structure including different types of sulfide-based electrolytes on the positive electrode side and the negative electrode side. However, in such a configuration, there is a possibility that the lithium ion conductivity of the electrolyte between the positive electrode mixture and the negative electrode mixture decreases, and the internal resistance of the battery increases.
本発明の実施形態では、全固体リチウムイオン電池に適用したときに、電池内部抵抗が小さくなり、良好な出力特性及びサイクル特性を有する全固体リチウムイオン電池用固体電解質層を提供することを目的とする。 An object of the embodiments of the present invention is to provide a solid electrolyte layer for an all-solid-state lithium-ion battery having a low internal resistance when applied to an all-solid-state lithium-ion battery and having good output characteristics and cycle characteristics. I do.
本発明者は、種々の検討を行った結果、固体電解質層を正極側に接する電解質層Ａ、負極側に接する電解質層Ｂ、及び、電解質層Ａと電解質層Ｂとの間に設けられた中間電解質層Ｃとで構成し、電解質層Ｂの厚みを制御し、さらに各電解質層の組成を制御することで、上述の課題が解決されることを見出した。 As a result of various studies, the present inventor has found that the solid electrolyte layer has an electrolyte layer A in contact with the positive electrode side, an electrolyte layer B in contact with the negative electrode side, and an intermediate layer provided between the electrolyte layer A and the electrolyte layer B. It has been found that the above-mentioned problems can be solved by forming the electrolyte layer C and the electrolyte layer B, controlling the thickness of the electrolyte layer B, and further controlling the composition of each electrolyte layer.
上記知見を基礎にして完成した本発明は実施形態において、正極側に接する電解質層Ａ、負極側に接する電解質層Ｂ、及び、前記電解質層Ａと前記電解質層Ｂとの間に設けられた中間電解質層Ｃを有し、前記電解質層Ａは、組成式：Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4（式中、ｘは、０．６＜ｘ＜０．８）で表される固体電解質からなり、前記電解質層Ｂは、組成式：（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5で表される固体電解質からなり、前記中間電解質層Ｃは、Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4（式中、ｘは、０．６＜ｘ＜０．８）で表される固体電解質と組成式：（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5で表される固体電解質とが混合してなり、前記電解質層Ｂの厚みが５０ｎｍ以上であり、前記電解質層Ａと前記中間電解質層Ｃとが接する界面での前記中間電解質層Ｃ側の前記Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰとの総物質量は、前記（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5中のＰの物質量よりも多いか同じであり、前記電解質層Ｂと前記中間電解質層Ｃとが接する界面での前記中間電解質層Ｃ側の前記Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰとの総物質量は、前記（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5中のＰの物質量よりも少ないか同じである全固体リチウムイオン電池用固体電解質層である。 The present invention, which has been completed based on the above findings, in the embodiment, is an electrolyte layer A in contact with the positive electrode side, an electrolyte layer B in contact with the negative electrode side, and an intermediate layer provided between the electrolyte layer A and the electrolyte layer B. It has an electrolyte layer C, and the electrolyte layer A has a composition formula: Li (4-x) Ge (1-x) P x S 4 (where x is 0.6 <x <0.8). made from a solid electrolyte represented, the electrolyte layer B is a composition formula: (70~80) Li 2 S- ( 30~20) made of a solid electrolyte represented by P 2 S 5, the intermediate electrolyte layer C , Li (4-x) Ge (1-x) P x S 4 (where x is 0.6 <x <0.8) and a composition formula: (70-80) Li 2 S- (30~20) P 2 S becomes 5 were mixed and the solid electrolyte represented, the thickness of the electrolyte layer B is not less 50nm or more, the electrolyte layer a and the intermediate electrolyte The total amount of substance of Ge and P of the intermediate electrolyte layer C side the Li (4-x) Ge ( 1-x) in P x S 4 at the interface where the C contact, the (70 to 80) Li 2 S- (30-20) P 2 S 5 The amount of P is greater than or equal to the amount of P, and at the interface where the electrolyte layer B and the intermediate electrolyte layer C are in contact with the intermediate electrolyte layer C side. The total amount of Ge and P in Li (4-x) Ge (1-x) P x S 4 is determined by the amount of P in the (70-80) Li 2 S- (30-20) P 2 S 5. Is a solid electrolyte layer for an all-solid-state lithium-ion battery that is less than or equal to the amount of the substance.
本発明の全固体リチウムイオン電池用固体電解質層は別の実施形態において、前記電解質層Ａと前記中間電解質層Ｃとが接する界面での前記中間電解質層Ｃ側の前記Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰの総物質量と前記（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5中のＰの物質量の比率が３：１〜１：１であり、前記電解質層Ｂと前記中間電解質層Ｃとが接する界面での前記中間電解質層Ｃ側の前記Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰとの総物質量と前記（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5中のＰの物質量の比率が１：１〜１：３である。 In another embodiment, the solid electrolyte layer for an all-solid-state lithium ion battery of the present invention is configured such that the Li (4-x) Ge on the side of the intermediate electrolyte layer C at the interface where the electrolyte layer A and the intermediate electrolyte layer C are in contact with each other. (1-x) P x S wherein Ge and total material amount of P in 4 (70~80) Li 2 S- ( 30~20) P 2 ratio of the amount of substance of P in S 5 3: 1 Ge in the Li (4-x) Ge (1-x) P x S 4 on the side of the intermediate electrolyte layer C at the interface where the electrolyte layer B and the intermediate electrolyte layer C are in contact with each other. the ratio between the total material amount and the (70~80) Li 2 S- (30~20 ) P 2 S material of P out of 5 in the P 1: 1 to 1: 3.
本発明は別の実施形態において、正極層、負極層、及び、本発明の実施形態に係る全固体リチウムイオン電池用固体電解質層を備えた全固体リチウムイオン電池である。 In another embodiment, the present invention is an all-solid lithium-ion battery including a positive electrode layer, a negative electrode layer, and a solid electrolyte layer for an all-solid lithium-ion battery according to the embodiment of the present invention.
本発明によれば、全固体リチウムイオン電池に適用したときに、電池内部抵抗が小さくなり、良好な出力特性及びサイクル特性を有する全固体リチウムイオン電池用固体電解質層を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, when applied to an all-solid-state lithium-ion battery, the internal resistance of a battery becomes small and the solid electrolyte layer for all-solid-state lithium-ion batteries which has favorable output characteristics and cycle characteristics can be provided.
（全固体リチウムイオン電池用固体電解質層）
本発明の実施形態に係る全固体リチウムイオン電池用固体電解質層は、正極側に接する電解質層Ａ、負極側に接する電解質層Ｂ、及び、電解質層Ａと電解質層Ｂとの間に設けられた中間電解質層Ｃを有している。電解質層Ａは、組成式：Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4（式中、ｘは、０．６＜ｘ＜０．８）［以下、ＬＧＰＳとも称する］で表される固体電解質からなる。電解質層Ｂは、組成式：（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5［以下、ＬＰＳとも称する］で表される固体電解質からなる。中間電解質層Ｃは、Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4（式中、ｘは、０．６＜ｘ＜０．８）で表される固体電解質と組成式：（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5で表される固体電解質とが混合してなる。
(Solid electrolyte layer for all solid lithium ion battery)
The solid electrolyte layer for an all solid lithium ion battery according to the embodiment of the present invention is provided with an electrolyte layer A in contact with the positive electrode side, an electrolyte layer B in contact with the negative electrode side, and between the electrolyte layer A and the electrolyte layer B. It has an intermediate electrolyte layer C. The electrolyte layer A is represented by a composition formula: Li (4-x) Ge (1-x) P x S 4 (where x is 0.6 <x <0.8) [hereinafter, also referred to as LGPS]. Consisting of a solid electrolyte. The electrolyte layer B is a composition formula: (70~80) Li 2 S- ( 30~20) P 2 S 5 [ hereinafter, also referred to as LPS] made of a solid electrolyte represented by. The intermediate electrolyte layer C is composed of a solid electrolyte represented by Li (4-x) Ge (1-x) P x S 4 (where x is 0.6 <x <0.8) and a composition formula: ( 70-80) and Li 2 S- (30 to 20) solid electrolyte represented by P 2 S 5 is formed by mixing.
本発明の実施形態に係る全固体リチウムイオン電池用固体電解質層は、電解質層Ａと中間電解質層Ｃとが接する界面での中間電解質層Ｃ側のＬｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰとの総物質量が、（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5中のＰの物質量よりも多いか同じである。すなわち、本発明の実施形態に係る全固体リチウムイオン電池用固体電解質層は、電解質層Ａ側から中間電解質層Ｃ側へ向かって（深さ方向とする）元素分析を進めたとき、ある深さでＬｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰとの総物質量が、（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5中のＰの物質量よりも多いか同じである境界に出会う。当該境界が上記界面の中間電解質層Ｃ側まで元素分析が進んだことを示している。 The solid electrolyte layer for an all-solid-state lithium ion battery according to the embodiment of the present invention includes Li (4-x) Ge (1-x) on the side of the intermediate electrolyte layer C at the interface where the electrolyte layer A and the intermediate electrolyte layer C are in contact with each other. the total amount of substance of the P x S 4 in Ge and P is the same or (70~80) Li 2 S- (30~20 ) P 2 S greater than the amount of substance of P in 5. That is, the solid electrolyte layer for an all-solid-state lithium ion battery according to the embodiment of the present invention has a certain depth when the elemental analysis is performed from the electrolyte layer A side to the intermediate electrolyte layer C side (depth direction). And the total amount of Ge and P in Li (4-x) Ge (1-x) P x S 4 is P (70-80) Li 2 S- (30-20) P 2 S 5 Meet a boundary that is greater than or equal to the amount of material in. The boundary indicates that the elemental analysis has progressed to the intermediate electrolyte layer C side of the interface.
本発明の実施形態に係る全固体リチウムイオン電池用固体電解質層は、電解質層Ｂと中間電解質層Ｃとが接する界面での中間電解質層Ｃ側のＬｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰとの総物質量が、（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5中のＰの物質量よりも少ないか同じである。すなわち、本発明の実施形態に係る全固体リチウムイオン電池用固体電解質層は、電解質層Ｂ側から中間電解質層Ｃ側へ向かって（深さ方向とする）元素分析を進めたとき、ある深さでＬｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰとの総物質量が、（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5中のＰの物質量よりも少ないか同じである境界に出会う。当該境界が上記界面の中間電解質層Ｃ側まで元素分析が進んだことを示している。 The solid electrolyte layer for an all-solid-state lithium ion battery according to the embodiment of the present invention includes Li (4-x) Ge (1-x) on the side of the intermediate electrolyte layer C at the interface where the electrolyte layer B and the intermediate electrolyte layer C are in contact with each other. the total amount of substance of the P x S in 4 Ge and P is the same or less than (70~80) Li 2 S- (30~20 ) substance of P in P 2 S 5. That is, the solid electrolyte layer for an all-solid lithium ion battery according to the embodiment of the present invention has a certain depth when the elemental analysis is performed from the electrolyte layer B side to the intermediate electrolyte layer C side (depth direction). And the total amount of Ge and P in Li (4-x) Ge (1-x) P x S 4 is P (70-80) Li 2 S- (30-20) P 2 S 5 Encounter a boundary that is less than or equal to the amount of material in. The boundary indicates that the elemental analysis has progressed to the intermediate electrolyte layer C side of the interface.
また、ＬＧＰＳはＬＰＳよりもイオン導電率が大きいが、ＬＧＰＳ中に含まれるＧｅは耐還元性が低く、負極活物質に金属Ｌｉやカーボンを使用した場合は、Ｇｅは還元されてしまう。そこで、Ｇｅが負極活物質に接触しないようにするため、負極側に接する電解質層ＢをＬＰＳで表される固体電解質で構成している。 In addition, LGPS has a higher ionic conductivity than LPS, but Ge contained in LGPS has low resistance to reduction. When metal Li or carbon is used as the negative electrode active material, Ge is reduced. Therefore, in order to prevent Ge from contacting the negative electrode active material, the electrolyte layer B in contact with the negative electrode side is formed of a solid electrolyte represented by LPS.
また、電解質層Ｂの厚みは５０ｎｍ以上に制御されている。通常、元素拡散は接触した界面から５０ｎｍの範囲で起きることが多く、負極側に接する電解質層Ｂの厚みを５０ｎｍ以上とすることで、より効果的に負極活物質へのＧｅ等の元素の接触を抑制することができる。 The thickness of the electrolyte layer B is controlled to 50 nm or more. Usually, element diffusion often occurs within a range of 50 nm from the contact interface, and by setting the thickness of the electrolyte layer B in contact with the negative electrode side to 50 nm or more, contact of an element such as Ge with the negative electrode active material can be more effectively performed. Can be suppressed.
種類の異なる電解質層を積層させた場合、その界面は、リチウムイオンが移動するときの律速になる。これは、化学ポテンシャルが異なる電解質層が接しているためである。本発明の実施形態に係る全固体リチウムイオン電池用固体電解質層は、正極側に接する電解質層Ａ、負極側に接する電解質層Ｂ、及び、電解質層Ａと電解質層Ｂとの間に設けられた中間電解質層Ｃを有しており、且つ、各電解質層が互いに異なる種類の電解質層となっている（電解質層Ａ：ＬＧＰＳ、電解質層Ｂ：ＬＰＳ、中間電解質層Ｃ：ＬＧＰＳ及びＬＰＳ）。このように、化学ポテンシャルの変化を緩和することで、固体電解質層におけるリチウムイオンの移動がスムースになり、全固体リチウムイオン電池に適用したときに、電池内部抵抗が小さくなり、良好な出力特性を有する全固体リチウムイオン電池用固体電解質層を提供することができる。また、電解質層Ｂの厚みを５０ｎｍ以上に制御することで、負極活物質へのＧｅ等の元素の接触を抑制することで、良好なサイクル特性を有する全固体リチウムイオン電池用固体電解質層を提供することができる。 When different types of electrolyte layers are stacked, the interface thereof becomes a rate-determining factor when lithium ions move. This is because electrolyte layers having different chemical potentials are in contact with each other. The solid electrolyte layer for an all solid lithium ion battery according to the embodiment of the present invention is provided with an electrolyte layer A in contact with the positive electrode side, an electrolyte layer B in contact with the negative electrode side, and between the electrolyte layer A and the electrolyte layer B. It has an intermediate electrolyte layer C, and each electrolyte layer is a different type of electrolyte layer (electrolyte layer A: LGPS, electrolyte layer B: LPS, intermediate electrolyte layer C: LGPS and LPS). In this way, by mitigating the change in chemical potential, the movement of lithium ions in the solid electrolyte layer becomes smooth, and when applied to an all-solid-state lithium-ion battery, the internal resistance of the battery is reduced and good output characteristics are obtained. A solid electrolyte layer for an all-solid-state lithium-ion battery can be provided. In addition, by controlling the thickness of the electrolyte layer B to 50 nm or more, contact of elements such as Ge with the negative electrode active material is suppressed, thereby providing a solid electrolyte layer for an all-solid-state lithium ion battery having good cycle characteristics. can do.
電解質層Ａと中間電解質層Ｃとが接する界面での中間電解質層Ｃ側のＬｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰの総物質量とＬＰＳ（（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5）中のＰの物質量の比率が３：１〜１：１であり、電解質層Ｂと中間電解質層Ｃとが接する界面での中間電解質層Ｃ側のＬｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰとの総物質量とＬＰＳ（（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5）中のＰの物質量の比率が１：１〜１：３であるのが好ましい。このような構成によれば、化学ポテンシャル変化がより緩和され、リチウムイオン伝導率がより高くなるという効果が得られる。 The total amount of Ge and P in Li (4-x) Ge (1-x) P x S 4 on the intermediate electrolyte layer C side at the interface where the electrolyte layer A and the intermediate electrolyte layer C are in contact with LPS ((70 ~80) Li 2 S- (30~20) the ratio of P 2 S 5) the amount of substance of P in 3: 1 to 1: 1, at the interface of the electrolyte layer B and the intermediate electrolyte layer C is in contact The total amount of Ge and P in Li (4-x) Ge (1-x) P x S 4 on the side of the intermediate electrolyte layer C and LPS ((70-80) Li 2 S- (30-20) P It is preferable that the ratio of the substance amount of P in 2 S 5 ) is 1: 1 to 1: 3. According to such a configuration, it is possible to obtain the effect that the change in chemical potential is further reduced and the lithium ion conductivity is further increased.
（リチウムイオン電池）
本発明の実施形態に係る全固体リチウムイオン電池用固体電解質層と、正極層及び負極層とを用いて全固体リチウムイオン電池を作製することができる。
(Lithium ion battery)
An all-solid-state lithium-ion battery can be manufactured using the solid electrolyte layer for an all-solid-state lithium-ion battery according to the embodiment of the present invention, and the positive electrode layer and the negative electrode layer.
（全固体リチウムイオン電池用固体電解質層の製造方法）
次に、本発明の実施形態に係る全固体リチウムイオン電池用固体電解質層の製造方法について詳細に説明する。
（１）電解質層Ａ材料：ＬＧＰＳの製造工程
出発原料として、硫化リチウム（Ｌｉ2Ｓ）と、五硫化二リン（Ｐ2Ｓ5）と、硫化ゲルマニウム（ＧｅＳ2）とを用いる。これらの粉末をアルゴン雰囲気下のグローブボックス内で、Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4（式中、ｘは、０．６＜ｘ＜０．８）の組成となるように秤量、混合し、原料組成物を得る。次に、原料組成物を、ジルコニアボールとともに、ジルコニア製のポットに入れ、ポットを完全に密閉する。このポットを遊星型ボールミル機に取り付け、メカニカルミリングを行う。これにより非晶質化したイオン伝導性材料を得る。
次に、得られたイオン伝導性材料をペレット状に成型し、得られたペレットを、カーボンコートした石英管に入れ真空封入する。次に、石英管を焼成炉に設置し、６時間かけて室温から５５０℃まで昇温し、５５０℃を８時間維持し、その後室温まで徐冷する。これにより、Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4（式中、ｘは、０．６＜ｘ＜０．８）の組成を有する結晶質の硫化物固体電解質材料を得る。
(Method of manufacturing solid electrolyte layer for all solid lithium ion battery)
Next, a method for producing a solid electrolyte layer for an all-solid lithium-ion battery according to an embodiment of the present invention will be described in detail.
(1) Electrolyte layer A material: LGPS manufacturing process As starting materials, lithium sulfide (Li 2 S), diphosphorus pentasulfide (P 2 S 5 ), and germanium sulfide (GeS 2 ) are used. These powders have a composition of Li (4-x) Ge (1-x) P x S 4 (where x is 0.6 <x <0.8) in a glove box under an argon atmosphere. And weighing to obtain a raw material composition. Next, the raw material composition is put into a zirconia pot together with zirconia balls, and the pot is completely sealed. This pot is attached to a planetary ball mill, and mechanical milling is performed. Thus, an amorphous ion-conductive material is obtained.
Next, the obtained ion-conductive material is molded into a pellet shape, and the obtained pellet is placed in a carbon-coated quartz tube and vacuum-sealed. Next, the quartz tube is placed in a firing furnace, and the temperature is raised from room temperature to 550 ° C. over 6 hours, maintained at 550 ° C. for 8 hours, and then gradually cooled to room temperature. Thereby, a crystalline sulfide solid electrolyte material having a composition of Li (4-x) Ge (1-x) P x S 4 (where x is 0.6 <x <0.8) is obtained. .
（２）電解質層Ｂ材料：ＬＰＳ（（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5）の製造工程
アルゴン雰囲気下のグローブボックス内で、Ｌｉ2ＳとＰ2Ｓ5とを（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5の組成比となるよう秤量し、乳鉢で混合、粉砕する。この後、ＺｒＯ2ボールとともにＺｒＯ2ポットに入れ、遊星型ボールミルで１０〜２０時間メカニカルミリング処理することでガラス状の固体電解質を得る。
(2) electrolyte layer B material: with LPS ((70~80) Li 2 S- (30~20) P 2 S 5) of the manufacturing process in a glove box under argon atmosphere, and Li 2 S and P 2 S 5 the (70-80) were weighed Li 2 S- (30 to 20) so that the composition ratio of P 2 S 5, mixed in a mortar and ground. Then, placed in a ZrO 2 pot with ZrO 2 balls, obtaining a glassy solid electrolyte by 10-20 hours mechanical milling with a planetary ball mill.
（３）中間電解質層Ｃ材料１、２の製造工程
中間電解質層Ｃ材料を形成するために、ＬＧＰＳ中のＧｅとＰとの総物質量とＬＰＳ中のＰの物質量の比率、および、ＬＧＰＳ中のＧｅとＰとの総物質量とＬＰＳ中のＰの物質量の比率を所定値となるようにＬＧＰＳ、ＬＰＳをそれぞれ秤量、混合し、２種類のＬＧＰＳ中のＧｅとＰとの総物質量とＬＰＳ中のＰの物質量の比率を有する中間電解質層Ｃ材料１、２を作製する。
(3) Manufacturing Process of Intermediate Electrolyte Layer C Materials 1 and 2 In order to form the intermediate electrolyte layer C material, the ratio of the total amount of Ge and P in LGPS to the amount of P in LPS, and LGPS LGPS and LPS were weighed and mixed so that the ratio of the total amount of Ge and P in the substance to the substance amount of P in the LPS became a predetermined value, and the total substance of Ge and P in the two types of LGPS The intermediate electrolyte layer C materials 1 and 2 having the ratio of the amount of P to the amount of P in LPS are prepared.
（４）全固体リチウムイオン電池用固体電解質層の製造工程
次に、電解質層Ａ材料、中間電解質層Ｃ材料１、２をこの順に金型に入れてプレスし、電解質層Ａ／中間電解質層Ｃ材料１／中間電解質層Ｃ材料２の構成の電解質層ペレットを作製する。
次に、電解質層Ｂ材料のターゲットを準備し、例えば、気相法の一つであるパルスレーザー堆積法を用いて、真空チャンバ内で電解質層ペレットの中間電解質層Ｃ材料２側に電解質層Ｂの厚みが５０ｎｍ以上となるように、製膜処理を行う。これにより、全固体リチウムイオン電池用固体電解質層が得られる。
(4) Manufacturing Process of Solid Electrolyte Layer for All-Solid-State Lithium-Ion Battery Next, the electrolyte layer A material and the intermediate electrolyte layer C materials 1 and 2 are placed in a mold in this order and pressed, and the electrolyte layer A / intermediate electrolyte layer C An electrolyte layer pellet having a configuration of material 1 / intermediate electrolyte layer C material 2 is prepared.
Next, a target of the electrolyte layer B material is prepared, and for example, a pulse laser deposition method, which is one of the gas phase methods, is used to place the electrolyte layer B on the intermediate electrolyte layer C material 2 side of the electrolyte layer pellet in a vacuum chamber. Is performed so that the thickness of the film becomes 50 nm or more. Thereby, a solid electrolyte layer for an all-solid-state lithium ion battery is obtained.
以下、本発明及びその利点をより良く理解するための実施例を提供するが、本発明はこれらの実施例に限られるものではない。
（実施例１）
中間電解質層Ｃを形成するために、ＬＧＰＳ（Ｌｉ3.25Ｇｅ0.25Ｐ0.75Ｓ4）中のＧｅとＰとの総物質量とＬＰＳ（７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5）中のＰの物質量の比率が３：１、および、ＬＧＰＳ（Ｌｉ3.25Ｇｅ0.25Ｐ0.75Ｓ4）中のＧｅとＰとの総物質量とＬＰＳ（７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5）中のＰの物質量の比率が１：３となるようにＬＧＰＳ、ＬＰＳをそれぞれ秤量、混合し、それぞれ中間電解質層Ｃ（３：１）材料、中間電解質層Ｃ（１：３）材料とした。
次に、ＬＧＰＳ（Ｌｉ3.25Ｇｅ0.25Ｐ0.75Ｓ4）、中間電解質層Ｃ（３：１）材料、中間電解質層Ｃ（１：３）材料を内径１０ｍｍの金型を用いてプレスをして、電解質層Ａ／中間電解質層Ｃ（３：１）／中間電解質層Ｃ（１：３）の構成の電解質層ペレットを作製した。
次に、ＬＰＳ（７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5）のターゲットを準備し、気相法の一つであるパルスレーザー堆積法を用いて、真空チャンバ内で前記電解質層ペレットの中間電解質層Ｃ（１：３）側にＬＰＳの厚みが１０００ｎｍとなるように、製膜処理を行った。
以上のようにして、正極側に接する電解質層の固体電解質をＬＧＰＳ（Ｌｉ3.25Ｇｅ0.25Ｐ0.75Ｓ4）、負極側に接する電解質層の電解質を７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5、中間層をＬＧＰＳと７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5の混合品とし、正極側に接する電解質層と中間電解質層と接する界面での中間電解質層側のＬＧＰＳ中のＧｅとＰとの総物質量と７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5中のＰの物質量の比率を３：１、負極側に接する電解質層と中間電解質層と接する界面での中間電解質層側のＬＧＰＳ中のＧｅとＰとの総物質量と７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5中のＰの物質量の比率を１：３、負極側に接する電解質ＬＰＳの厚みを１０００ｎｍとして全固体リチウムイオン電池用固体電解質層を作製した。
Hereinafter, examples for better understanding of the present invention and its advantages will be provided, but the present invention is not limited to these examples.
(Example 1)
In order to form the intermediate electrolyte layer C, the total amount of Ge and P in LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ) and the amount of P in LPS (75Li 2 S-25P 2 S 5 ) were determined. The ratio is 3: 1, and the ratio of the total amount of Ge and P in LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ) to the amount of P in LPS (75Li 2 S-25P 2 S 5 ) is LGPS and LPS were weighed and mixed so as to be 1: 3, respectively, to obtain an intermediate electrolyte layer C (3: 1) material and an intermediate electrolyte layer C (1: 3) material, respectively.
Next, LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ), the intermediate electrolyte layer C (3: 1) material, and the intermediate electrolyte layer C (1: 3) material were pressed using a mold having an inner diameter of 10 mm, An electrolyte layer pellet having a structure of electrolyte layer A / intermediate electrolyte layer C (3: 1) / intermediate electrolyte layer C (1: 3) was produced.
Next, a target of LPS (75Li 2 S-25P 2 S 5 ) is prepared, and the intermediate electrolyte layer C (of the electrolyte layer pellets) is prepared in a vacuum chamber by using a pulse laser deposition method, which is one of the gas phase methods. A film forming process was performed so that the thickness of the LPS on the 1: 3) side was 1000 nm.
As described above, the solid electrolyte of the electrolyte layer in contact with the positive electrode side is LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ), the electrolyte of the electrolyte layer in contact with the negative electrode side is 75 Li 2 S-25P 2 S 5 , and the intermediate layer is LGPS. And 75Li 2 S-25P 2 S 5 , the total amount of Ge and P in LGPS on the intermediate electrolyte layer side at the interface between the electrolyte layer in contact with the positive electrode side and the intermediate electrolyte layer, and 75Li 2 S- The ratio of the amount of P in 25P 2 S 5 is 3: 1, the total amount of Ge and P in the LGPS on the intermediate electrolyte layer side at the interface between the electrolyte layer in contact with the negative electrode side and the intermediate electrolyte layer is 75Li. A solid electrolyte layer for an all-solid-state lithium-ion battery was prepared by setting the ratio of the amount of P in 2 S-25P 2 S 5 to 1: 3 and the thickness of the electrolyte LPS in contact with the negative electrode side to 1000 nm.
（実施例２）
中間電解質層Ｃを形成するために、ＬＧＰＳ（Ｌｉ3.25Ｇｅ0.25Ｐ0.75Ｓ4）中のＧｅとＰとの総物質量とＬＰＳ（７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5）中のＰの物質量の比率が１：１となるようにＬＧＰＳ、ＬＰＳをそれぞれ秤量、混合し、中間電解質層Ｃ（１：１）材料とした。次に、ＬＧＰＳ、中間電解質層Ｃ（１：１）材料を内径１０ｍｍの金型を用いてプレスをして、電解質層Ａ／中間電解質層Ｃ（１：１）の構成の電解質層ペレットを作製した。
次に、ＬＰＳ（７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5）のターゲットを準備し、気相法の一つであるパルスレーザー堆積法を用いて、真空チャンバ内で前記電解質層ペレットの中間電解質層Ｃ（１：１）側にＬＰＳの厚みが１０００ｎｍとなるように、製膜処理を行った。
以上のようにして、正極側に接する電解質層と中間電解質層と接する界面での中間電解質層側のＬＧＰＳ（Ｌｉ3.25Ｇｅ0.25Ｐ0.75Ｓ4）中のＧｅとＰとの総物質量と７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5中のＰの物質量の比率を１：１、負極側に接する電解質層と中間電解質層と接する界面での中間電解質層側のＬＧＰＳ中のＧｅとＰとの総物質量と７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5中のＰの物質量の比率を１：１として全固体リチウムイオン電池用固体電解質層を作製した。
(Example 2)
In order to form the intermediate electrolyte layer C, the total amount of Ge and P in LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ) and the amount of P in LPS (75Li 2 S-25P 2 S 5 ) were determined. LGPS and LPS were weighed and mixed so that the ratio became 1: 1 to obtain a material for the intermediate electrolyte layer C (1: 1). Next, an LGPS and an intermediate electrolyte layer C (1: 1) material are pressed using a mold having an inner diameter of 10 mm to produce an electrolyte layer pellet having a configuration of electrolyte layer A / intermediate electrolyte layer C (1: 1). did.
Next, a target of LPS (75Li 2 S-25P 2 S 5 ) is prepared, and the intermediate electrolyte layer C (of the electrolyte layer pellets) is prepared in a vacuum chamber by using a pulse laser deposition method, which is one of the gas phase methods. A film forming process was performed so that the thickness of the LPS on the 1: 1) side was 1000 nm.
As described above, the total amount of Ge and P in the LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ) on the intermediate electrolyte layer side at the interface between the electrolyte layer in contact with the positive electrode side and the intermediate electrolyte layer is 75 Li 2 The ratio of the amount of P in S-25P 2 S 5 is 1: 1, and the total amount of Ge and P in the LGPS on the intermediate electrolyte layer side at the interface between the electrolyte layer in contact with the negative electrode and the intermediate electrolyte layer the a 75Li 2 S-25P 2 ratio of the amount of substance of P in S 5 1: to prepare a solid electrolyte layer for all-solid-state lithium-ion batteries as one.
（実施例３）
実施例１において、負極側に接する電解質ＬＰＳ（７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5）の厚みを５０ｎｍとして全固体リチウムイオン電池用固体電解質層を作製した。
(Example 3)
In Example 1, to prepare a solid electrolyte layer for all-solid-state lithium-ion batteries the thickness of the electrolyte LPS (75Li 2 S-25P 2 S 5) in contact with the negative electrode side as 50nm.
（実施例４）
中間電解質層Ｃを形成するために、ＬＧＰＳ（Ｌｉ3.25Ｇｅ0.25Ｐ0.75Ｓ4）中のＧｅとＰとの総物質量とＬＰＳ（７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5）中のＰの物質量の比率が３：１、および、ＬＧＰＳ中のＧｅとＰとの総物質量とＬＰＳ中のＰの物質量の比率が１：３となるようにＬＧＰＳ、ＬＰＳをそれぞれ秤量、混合し、それぞれ中間電解質層Ｃ（３：１）材料、中間電解質層Ｃ（１：３）材料とした。
次に、ＬＧＰＳ（Ｌｉ3.25Ｇｅ0.25Ｐ0.75Ｓ4）、中間電解質層Ｃ（３：１）材料、中間電解質層Ｃ（１：３）材料、ＬＰＳ（７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5）を内径１０ｍｍの金型を用いてプレスをして、電解質層Ａ／中間電解質層Ｃ（３：１）／中間電解質層Ｃ（１：３）／電解質層Ｂの構成の電解質層ペレットを作製した。
以上のようにして、負極側に接する電解質ＬＰＳ（７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5）の厚みを１００００ｎｍとして全固体リチウムイオン電池用固体電解質層を作製した。
(Example 4)
In order to form the intermediate electrolyte layer C, the total amount of Ge and P in LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ) and the amount of P in LPS (75Li 2 S-25P 2 S 5 ) were determined. LGPS and LPS were weighed and mixed so that the ratio was 3: 1, and the ratio of the total amount of Ge and P in LGPS to the amount of P in LPS was 1: 3, and the intermediate electrolytes were mixed. The layer C (3: 1) material and the intermediate electrolyte layer C (1: 3) material were used.
Next, LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ), intermediate electrolyte layer C (3: 1) material, intermediate electrolyte layer C (1: 3) material, and LPS (75Li 2 S-25P 2 S 5 ) Pressing was performed using a 10 mm mold to prepare an electrolyte layer pellet having a structure of electrolyte layer A / intermediate electrolyte layer C (3: 1) / intermediate electrolyte layer C (1: 3) / electrolyte layer B.
As described above, the thickness of the electrolyte LPS (75Li 2 S-25P 2 S 5 ) in contact with the negative electrode side was set to 10000 nm to prepare a solid electrolyte layer for an all-solid lithium ion battery.
（比較例１）
実施例１において、電解質の中間層を設けず、全固体リチウムイオン電池用固体電解質層を作製した。
(Comparative Example 1)
In Example 1, a solid electrolyte layer for an all-solid lithium-ion battery was produced without providing an electrolyte intermediate layer.
（比較例２）
実施例１において、パルスレーザー堆積法でのＬＰＳ製膜を実施せず、負極側に接する電解質ＬＰＳの厚みを０として、全固体リチウムイオン電池用固体電解質層を作製した。
(Comparative Example 2)
In Example 1, an LPS film was not formed by the pulsed laser deposition method, and the thickness of the electrolyte LPS in contact with the negative electrode side was set to 0 to produce a solid electrolyte layer for an all-solid-state lithium ion battery.
（比較例３）
実施例１において、正極側に接する電解質層と中間電解質層と接する界面での中間電解質層側のＬＧＰＳ（Ｌｉ3.25Ｇｅ0.25Ｐ0.75Ｓ4）中のＧｅとＰとの総物質量と７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5中のＰの物質量の比率を１：３、負極側に接する電解質層と中間電解質層と接する界面での中間電解質層側のＬＧＰＳ中のＧｅとＰとの総物質量と７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5中のＰの物質量の比率を３：１として、全固体リチウムイオン電池用固体電解質層を作製した。
(Comparative Example 3)
In Example 1, the total amount of Ge and P in LGPS (Li 3.25 Ge 0.25 P 0.75 S 4 ) on the intermediate electrolyte layer side at the interface between the electrolyte layer in contact with the positive electrode side and the intermediate electrolyte layer and 75Li 2 S The ratio of the amount of P in -25P 2 S 5 is 1: 3, and the total amount of Ge and P in the LGPS on the intermediate electrolyte layer side at the interface between the electrolyte layer in contact with the negative electrode side and the intermediate electrolyte layer is the ratio of 75Li 2 S-25P 2 S material of P in 3: as 1, to prepare a solid electrolyte layer for all-solid-state lithium-ion batteries.
（比較例４）
実施例１において、電解質層を全てＬＰＳ（７５Ｌｉ2Ｓ−２５Ｐ2Ｓ5）として、全固体リチウムイオン電池用固体電解質層を作製した。
(Comparative Example 4)
In Example 1, the electrolyte layer as all LPS (75Li 2 S-25P 2 S 5), to prepare a solid electrolyte layer for all-solid-state lithium-ion batteries.
（評価）
こうしてできた各実施例及び比較例のサンプルを用いて下記の条件にて各評価を実施した。
−電池特性の評価（全固体リチウムイオン電池）−
得られた電解質層を使用し、正極活物質としてニオブ酸リチウムで表面処理を行ったＬｉＮｉ0.82Ｃｏ0.15Ｍｎ0.03Ｏ2を使用し、正極活物質：ＬＧＰＳ＝７：３を混合し、正極層とし、負極にＬｉ金属を使用して、内径１０ｍｍの金型中に正極層、電解質層、Ｌｉを充填し、５００ＭＰａでプレスした。このプレス後の成形体を、金属製治具を用いて１００ＭＰａで拘束することにより、全固体リチウムイオン電池を作製した。
次に、当該電池について、電池内部抵抗として、1ｋＨｚ交流インピーダンスを測定した。次に、充放電レート０．０５Ｃで得られた初期容量（２５℃、充電上限電圧：３．７Ｖ、放電下限電圧：２．５Ｖ）を測定して放電容量１とした。次に充放電レート１Ｃで充放電を１０回繰り返した（２５℃、充電上限電圧：３．７Ｖ、放電下限電圧：２．５Ｖ）。充放電レート１Ｃでの１回目の放電で得られた容量を放電容量２とし、（放電容量２）／（放電容量１）の比を百分率として出力特性（％）とした。また、充放電レート１Ｃでの１０回目の放電で得られた容量を放電容量３とし、（放電容量３）／（放電容量２）の比を百分率としてサイクル特性（％）とした。
評価条件及び結果を表１に示す。
(Evaluation)
Each evaluation was carried out under the following conditions using the samples of the examples and comparative examples thus obtained.
-Evaluation of battery characteristics (All-solid-state lithium-ion battery)-
Using the obtained electrolyte layer, LiNi 0.82 Co 0.15 Mn 0.03 O 2 surface-treated with lithium niobate was used as a positive electrode active material, and a positive electrode active material: LGPS = 7: 3 was mixed to form a positive electrode layer. Using a Li metal for the negative electrode, a positive electrode layer, an electrolyte layer, and Li were filled in a mold having an inner diameter of 10 mm and pressed at 500 MPa. The pressed compact was restrained at 100 MPa using a metal jig to produce an all-solid lithium-ion battery.
Next, 1 kHz AC impedance was measured as the internal resistance of the battery. Next, the initial capacity (25 ° C., charge upper limit voltage: 3.7 V, discharge lower limit voltage: 2.5 V) obtained at a charge / discharge rate of 0.05 C was measured and set as discharge capacity 1. Next, charge / discharge was repeated 10 times at a charge / discharge rate of 1 C (25 ° C., charge upper limit voltage: 3.7 V, discharge lower limit voltage: 2.5 V). The capacity obtained by the first discharge at a charge / discharge rate of 1 C was defined as discharge capacity 2, and the ratio of (discharge capacity 2) / (discharge capacity 1) was defined as a percentage and output characteristics (%). The capacity obtained by the 10th discharge at a charge / discharge rate of 1 C was defined as a discharge capacity 3, and the ratio of (discharge capacity 3) / (discharge capacity 2) was defined as a percentage and defined as cycle characteristics (%).
Table 1 shows the evaluation conditions and results.
Claims (3)
前記電解質層Ａは、組成式：Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4（式中、ｘは、０．６＜ｘ＜０．８）で表される固体電解質からなり、
前記電解質層Ｂは、組成式：（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5で表される固体電解質からなり、
前記中間電解質層Ｃは、Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4（式中、ｘは、０．６＜ｘ＜０．８）で表される固体電解質と組成式：（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5で表される固体電解質とが混合してなり、
前記電解質層Ｂの厚みが５０ｎｍ以上であり、
前記電解質層Ａと前記中間電解質層Ｃとが接する界面での前記中間電解質層Ｃ側の前記Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰとの総物質量は、前記（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5中のＰの物質量よりも多いか同じであり、
前記電解質層Ｂと前記中間電解質層Ｃとが接する界面での前記中間電解質層Ｃ側の前記Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰとの総物質量は、前記（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5中のＰの物質量よりも少ないか同じである全固体リチウムイオン電池用固体電解質層。 An electrolyte layer A in contact with the positive electrode side, an electrolyte layer B in contact with the negative electrode side, and an intermediate electrolyte layer C provided between the electrolyte layer A and the electrolyte layer B,
The electrolyte layer A is composed of a solid electrolyte represented by a composition formula: Li (4-x) Ge (1-x) P x S 4 (where x is 0.6 <x <0.8). ,
The electrolyte layer B is a composition formula: (70-80) consists of Li 2 S- (30 to 20) solid electrolyte represented by P 2 S 5,
The intermediate electrolyte layer C is composed of a solid electrolyte represented by Li (4-x) Ge (1-x) P x S 4 (where x is 0.6 <x <0.8) and a composition formula: (70-80) Li 2 S- (30-20) P 2 S 5 and a solid electrolyte mixed,
The thickness of the electrolyte layer B is 50 nm or more,
The total amount of Ge and P in the Li (4-x) Ge (1-x) P x S 4 on the intermediate electrolyte layer C side at the interface where the electrolyte layer A and the intermediate electrolyte layer C are in contact with each other. , the (70~80) Li 2 S- (30~20 ) are the same or P 2 S greater than the amount of substance of P in 5,
The total amount of Ge and P in the Li (4-x) Ge (1-x) P x S 4 on the side of the intermediate electrolyte layer C at the interface where the electrolyte layer B and the intermediate electrolyte layer C are in contact with each other. , the (70~80) Li 2 S- (30~20 ) P 2 S all-solid-state lithium-ion batteries for a solid electrolyte layer is the same or less than the amount of substance of P in 5.
前記電解質層Ｂと前記中間電解質層Ｃとが接する界面での前記中間電解質層Ｃ側の前記Ｌｉ(4-x)Ｇｅ(1-x)ＰxＳ4中のＧｅとＰとの総物質量と前記（７０〜８０）Ｌｉ2Ｓ−（３０〜２０）Ｐ2Ｓ5中のＰの物質量の比率が１：１〜１：３である請求項１に記載の全固体リチウムイオン電池用固体電解質層。 The total amount of Ge and P in the Li (4-x) Ge (1-x) P x S 4 on the intermediate electrolyte layer C side at the interface where the electrolyte layer A and the intermediate electrolyte layer C are in contact with each other; wherein (70~80) Li 2 S- (30~20 ) P 2 ratio of the amount of substance of P in S 5 3: 1 to 1: 1,
The total amount of Ge and P in the Li (4-x) Ge (1-x) P x S 4 on the side of the intermediate electrolyte layer C at the interface where the electrolyte layer B and the intermediate electrolyte layer C are in contact with each other. ratio of the (70~80) Li 2 S- (30~20 ) P 2 S material of P in 5 and 1: 1 to 1: for all-solid-state lithium-ion battery according to claim 1 which is 3 Solid electrolyte layer.
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