JP2013157090A - Lithium ion conductive solid electrolyte - Google Patents
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Abstract
Description
本発明は、リチウムイオン伝導性固体電解質に関する。 The present invention relates to a lithium ion conductive solid electrolyte.
近年、パソコンや携帯電話等の情報通信機器の急速な普及に伴い、その電源である電池の重要性が急速に高まっている。また、最近では環境への配慮、燃費向上の観点からハイブリッド自動車や電気自動車が注目を集めており、それら自動車へ電池が搭載されている。各種の電池がある中で、とりわけエネルギー密度の高いリチウムイオン電池が注目されている。 In recent years, with the rapid spread of information communication devices such as personal computers and mobile phones, the importance of batteries as power sources is rapidly increasing. Recently, hybrid vehicles and electric vehicles have been attracting attention from the viewpoint of environmental considerations and fuel efficiency, and batteries are mounted on these vehicles. Among various types of batteries, lithium ion batteries having a particularly high energy density are attracting attention.
現在、市販されているリチウムイオン電池は電解質の溶媒として可燃性の有機溶剤を用いており、 安全性を確保するため電池に安全装置を付加する必要があり、コストの増加、生産性の低下をもたらしている。また、より高い安全性を確保するため、電池の材料・構造面などでさらなる改善が要求されている。 Currently, commercially available lithium ion batteries use flammable organic solvents as electrolyte solvents, and it is necessary to add a safety device to the batteries to ensure safety, which increases costs and reduces productivity. Has brought. Further, in order to ensure higher safety, further improvements in battery material and structure are required.
これに対し、電解質として固体を用いた全固体電池が提案されている。全固体電池は構成部材に可燃性材料を用いないことから、安全装置の簡素化が図れ、製造コストの低減、生産性の向上が期待されている。このような全固体電池に用いられる固体電解質層としてニオブ酸リチウム（ＬｉＮｂＯ３）が知られている。（特許文献１〜３） On the other hand, an all-solid battery using a solid as an electrolyte has been proposed. Since all solid-state batteries do not use combustible materials as constituent members, the safety device can be simplified, and manufacturing costs can be reduced and productivity can be improved. Lithium niobate (LiNbO 3 ) is known as a solid electrolyte layer used in such an all-solid battery. (Patent Documents 1 to 3)
従来、ＬｉＮｂＯ３固体電解質材料は、リチウムイオン伝導性が低く、上述した全固体電池の固体電解質層としての要求性能を満たすことが出来ないと考えられてきた。ところが、固体電解質そのものではなく、正極材料と固体電解質との界面制御材として用いた場合優れた効果が認められる。例えば、硫化物系固体電解質と正極活物質ＬｉＣｏＯ２とから構成される全固体電池では、固体電解質−正極界面で反応が生じるため電池としての出力密度が充分得られないが、正極活物質表面に数ｎｍのＬｉＮｂＯ３層をコーティングすることにより、出力密度を向上できることが報告されている（非特許文献１）。 Conventionally, LiNbO 3 solid electrolyte material has low lithium ion conductivity, and it has been considered that the required performance as the solid electrolyte layer of the all-solid battery described above cannot be satisfied. However, when used as an interface control material between the positive electrode material and the solid electrolyte instead of the solid electrolyte itself, an excellent effect is recognized. For example, in an all-solid battery composed of a sulfide-based solid electrolyte and a positive electrode active material LiCoO 2 , a reaction occurs at the solid electrolyte-positive electrode interface, so that a sufficient output density as a battery cannot be obtained. It has been reported that the power density can be improved by coating a LiNbO 3 layer of several nm (Non-patent Document 1).
この場合、ＬｉＮｂＯ３の膜厚は数ｎｍ程度と極めて薄いため、イオン伝導度が低くともＬｉＮｂＯ３層の抵抗増大には至らないが、固体電解質そのものとして用いるにはイオン伝導度が不十分である。非特許文献１より、正極活物質ＬｉＣｏＯ２とイオン伝導体ＬｉＮｂＯ３にて良好な界面が形成できることが示されているため、ＬｉＮｂＯ３を固体電解質層そのものに用いることができれば、大気中で不安定な硫化物系固体電解質を用いることなく、安定な酸化物によって全固体電池が実現できる。そのためには、上述したＬｉＮｂＯ３のリチウムイオン伝導度の低さは、解決すべき重要な課題となっている。 In this case, since the film thickness of LiNbO 3 is as thin as several nm, the resistance of the LiNbO 3 layer does not increase even if the ionic conductivity is low, but the ionic conductivity is insufficient for use as the solid electrolyte itself. . Non-Patent Document 1 shows that a good interface can be formed with the positive electrode active material LiCoO 2 and the ionic conductor LiNbO 3, so if LiNbO 3 can be used for the solid electrolyte layer itself, it is unstable in the atmosphere. An all-solid battery can be realized with a stable oxide without using a sulfide-based solid electrolyte. For this purpose, the low lithium ion conductivity of LiNbO 3 described above is an important issue to be solved.
本発明は、上記に鑑みてなされてものであって、リチウムイオン伝導度の高いリチウムイオン伝導性固体電解質を提供することを目的とする。 The present invention has been made in view of the above, and an object thereof is to provide a lithium ion conductive solid electrolyte having high lithium ion conductivity.
上記目的を達成するため、本発明のリチウムイオン伝導性固体電解質材料はＬｉＮｂＯ３リチウムイオン伝導体とフッ化物とを含有することを特徴とする。 In order to achieve the above object, the lithium ion conductive solid electrolyte material of the present invention is characterized by containing a LiNbO 3 lithium ion conductor and a fluoride.
この構成によれば、ＬｉＮｂＯ３とフッ化物が共存していることで、リチウムイオン伝導性固体電解質材料は高いリチウムイオン伝導度を得ることができる。この効果の原因は必ずしも明らかではないが、ＬｉＮｂＯ３とフッ化物との界面近傍のＬｉＮｂＯ３内にリチウムイオン空孔が誘起され、この空孔がリチウムイオン伝導経路を形成し、リチウムイオンの移動がより活発となるためと考えられる。 According to this configuration, LiNbO 3 and fluoride coexist so that the lithium ion conductive solid electrolyte material can obtain high lithium ion conductivity. The cause of this effect is not necessarily clear, but lithium ion vacancies are induced in LiNbO 3 in the vicinity of the LiNbO 3 and fluoride interface, and these vacancies form a lithium ion conduction path. This is thought to be more active.
さらに、本発明のリチウムイオン伝導性固体電解質材料中のＬｉＦの含有量は１５重量％以上３５重量％以下であることが好ましい。上記範囲とすることで、全固体リチウムイオン二次電池における実用性の目安と考えられている、１ｘ１０−５ Ｓ／ｃｍ以上の高いイオン伝導度を示すリチウムイオン伝導性固体電解質材料を得ることができる。 Furthermore, the content of LiF in the lithium ion conductive solid electrolyte material of the present invention is preferably 15% by weight or more and 35% by weight or less. By setting it as the above range, it is possible to obtain a lithium ion conductive solid electrolyte material exhibiting a high ion conductivity of 1 × 10 −5 S / cm or more, which is considered as a standard of practicality in all solid lithium ion secondary batteries. it can.
フッ化物の含有量が１５重量％未満であった場合、ＬｉＮｂＯ３とフッ化物との界面が充分形成されないため、本発明の効果が充分でない傾向がある。また、フッ化物の含有量が３５重量％を上回る場合、リチウムイオン伝導経路となるべきＬｉＮｂＯ３の絶対量が不足するため、本発明の効果が充分でない傾向がある。 When the content of fluoride is less than 15% by weight, the interface between LiNbO 3 and fluoride is not sufficiently formed, and thus the effect of the present invention tends to be insufficient. When the fluoride content exceeds 35% by weight, the absolute amount of LiNbO 3 to be a lithium ion conduction path is insufficient, and the effect of the present invention tends to be insufficient.
本発明によれば、従来のＬｉＮｂＯ３のみを固体電解質として用いる場合に比べて、より高いリチウムイオン伝導度を有するリチウムイオン伝導性固体電解質材料を提供することできる。 According to the present invention, it is possible to provide a lithium ion conductive solid electrolyte material having higher lithium ion conductivity than when only conventional LiNbO 3 is used as a solid electrolyte.
本実施形態のリチウムイオン伝導性固体電解質材料は、ＬｉＮｂＯ３とフッ化物との混合物からなる固体電解質であることを特徴とする。ＬｉＮｂＯ３とフッ化物とが混合されることにより、リチウムイオン伝導性固体電解質材料のリチウムイオン伝導度は向上する。具体的には、ＬｉＮｂＯ３を主成分とするリチウムイオン伝導性固体電解質であって、さらにフッ化物を含有する。ここで、「ＬｉＮｂＯ３を主成分として含む」とは、リチウムイオン伝導性固体電解質におけるＬｉＮｂＯ３含有量が５０重量％以上であることをいう。 The lithium ion conductive solid electrolyte material of this embodiment is a solid electrolyte made of a mixture of LiNbO 3 and fluoride. By mixing LiNbO 3 and fluoride, the lithium ion conductivity of the lithium ion conductive solid electrolyte material is improved. Specifically, it is a lithium ion conductive solid electrolyte mainly composed of LiNbO 3 and further contains a fluoride. Here, “comprising LiNbO 3 as a main component” means that the LiNbO 3 content in the lithium ion conductive solid electrolyte is 50% by weight or more.
リチウムイオンは、リチウムイオン空孔を介して化合物中をイオン伝導するが、ＬｉＮｂＯ３のみの場合はリチウムイオン空孔の量が十分ではない。ＬｉＮｂＯ３とフッ化物とを混合することにより、ＬｉＮｂＯ３のリチウムイオンはＬｉＮｂＯ３の界面近傍でフッ化物中のフッ素の方に引き寄せられる。これにより、ＬｉＮｂＯ３中にリチウムイオン空孔が誘起され、それを介してリチウムイオンが伝導すると考えられる。これによりリチウムイオン伝導性固体電解質材料のリチウムイオン伝導度が向上すると推察される。 Lithium ions conduct ions in the compound through lithium ion vacancies, but the amount of lithium ion vacancies is not sufficient when only LiNbO 3 is used. By mixing the LiNbO 3 and fluoride, lithium ions LiNbO 3 is attracted toward the fluorine in the fluoride in the vicinity of the interface LiNbO 3. Thereby, it is considered that lithium ion vacancies are induced in LiNbO 3 and lithium ions are conducted through the vacancies. This is presumed to improve the lithium ion conductivity of the lithium ion conductive solid electrolyte material.
本実施形態のリチウムイオン伝導性固体電解質材料に含まれるフッ化物はフッ化リチウム（ＬｉＦ）、フッ化ナトリウム（ＮａＦ）、フッ化カルシウム（ＣａＦ２）、フッ化ストロンチウム（ＳｒＦ２）、フッ化バリウム（ＢａＦ２）等を適宜用いることができるが、特にＬｉＦであることが好ましい。ＬｉＦ中のＬｉはＬｉＮｂＯ３の構成元素でもあるため、ＬｉＮｂＯ３とフッ化物との界面にイオン伝導を妨げる不純物相が生成しがたく、リチウムイオン伝導度の向上が顕著となる。 The fluoride contained in the lithium ion conductive solid electrolyte material of the present embodiment is lithium fluoride (LiF), sodium fluoride (NaF), calcium fluoride (CaF 2 ), strontium fluoride (SrF 2 ), barium fluoride. (BaF 2 ) or the like can be used as appropriate, but LiF is particularly preferable. Since Li in LiF is also a constituent element of LiNbO 3 , it is difficult to generate an impurity phase that hinders ion conduction at the interface between LiNbO 3 and fluoride, and the improvement in lithium ion conductivity is remarkable.
実施形態のリチウムイオン伝導性固体電解質材料中に含まれるフッ化物の含有量は１５重量％以上３５重量％以下であることが好ましい。フッ化物の添加によりリチウムイオン伝導性が向上するのは、ＬｉＮｂＯ３とフッ化物、例えばＬｉＦとの界面の効果によると推察されるが、添加量が１５重量％未満である場合、形成する界面が少なくリチウムイオン伝導度の大きな向上が見られない。一方、フッ化物の含有量が３５重量％より多くなるとリチウムイオン伝導度が低下する傾向が見られ、過剰すぎる添加は逆効果となる。これはリチウムイオン伝導を担うＬｉＮｂＯ３の体積が少なくなり、リチウムイオン伝導経路そのものが減少することに起因する。 The content of fluoride contained in the lithium ion conductive solid electrolyte material of the embodiment is preferably 15% by weight or more and 35% by weight or less. It is assumed that the lithium ion conductivity is improved by the addition of the fluoride due to the effect of the interface between LiNbO 3 and the fluoride, for example, LiF, but when the addition amount is less than 15% by weight, the interface to be formed There is little increase in lithium ion conductivity. On the other hand, when the content of fluoride exceeds 35% by weight, the lithium ion conductivity tends to decrease, and excessive addition has an adverse effect. This is because the volume of LiNbO 3 responsible for lithium ion conduction decreases, and the lithium ion conduction path itself decreases.
本実施形態のリチウムイオン伝導性固体電解質材料は、例えば、ＬｉＮｂＯ３とフッ化物との複合体からなる化合物を用いた固相反応法により製造することができる。リチウム源としては炭酸リチウムや水酸化リチウム、硝酸リチウム等を、ニオブ源としては酸化ニオブを用いることができる。例えば、炭酸リチウムと酸化ニオブを原料として用いた場合は、それぞれ所定量に秤量された各原料をボールミルにて混合し、混合粉体を１１００℃で焼成することでＬｉＮｂＯ３の粉体を得ることができる。係る粉体とＬｉＦ、ＮａＦ、ＣａＦ２等のフッ化物のいずれかの粉体とを上述の重量割合で十分に混合し、成形した後、焼成することで所望の混合物を得ることができる。 The lithium ion conductive solid electrolyte material of the present embodiment can be manufactured by, for example, a solid phase reaction method using a compound made of a complex of LiNbO 3 and fluoride. Lithium carbonate, lithium hydroxide, lithium nitrate or the like can be used as the lithium source, and niobium oxide can be used as the niobium source. For example, when lithium carbonate and niobium oxide are used as raw materials, each raw material weighed in a predetermined amount is mixed in a ball mill, and the mixed powder is fired at 1100 ° C. to obtain a LiNbO 3 powder. Can do. A desired mixture can be obtained by sufficiently mixing the powder and any powder of a fluoride such as LiF, NaF, and CaF 2 in the above-described weight ratio, molding, and firing.
また、リチウムイオン伝導性固体電解質材料の製造方法は固相反応法に限定されることはなく、スパッタリング法、パルスレーザーデポジッション（ＰＬＤ）法等の薄膜作製方法を用いてもよい。例えば、固相反応法と同様の方法でＬｉＮｂＯ３とＬｉＦとからなるターゲットを作製し、上記の方法で成膜することでＬｉＮｂＯ３とＬｉＦとの混合体からなるリチウムイオン伝導性固体電解質材料を作製することができる。あるいは、ＬｉＮｂＯ３からなるターゲットと、ＬｉＦとからなるターゲットとを組み合わせた複合ターゲットとして成膜してもよい。また、フッ化物はＬｉＦに限らずＮａＦ、ＣａＦ２等のフッ化物でも同様に成膜することができる。 Moreover, the manufacturing method of a lithium ion conductive solid electrolyte material is not limited to a solid-phase reaction method, You may use thin film preparation methods, such as sputtering method and a pulse laser deposition (PLD) method. For example, a target made of LiNbO 3 and LiF is prepared by the same method as the solid phase reaction method, and a lithium ion conductive solid electrolyte material made of a mixture of LiNbO 3 and LiF is formed by the above method. Can be produced. Alternatively, a target made of LiNbO 3, may be formed as a composite target of a combination of a target consisting of a LiF. Further, the fluoride film is not limited to LiF, and a film such as NaF or CaF 2 can be formed in the same manner.
本実施形態のリチウムイオン伝導性固体電解質材料は、例えば、全固体リチウムイオン二次電池の固体電解質層および固体電解質層の一部として用いることができる。この場合、固体電解質以外の構成部材、例えば、正極、負極、端子部材、外装ケースなどは、リチウムイオン二次電池の分野において公知の部材を広く用いることができる。例えば、正極としてＬｉＣｏＯ２を、負極として金属リチウムを用い、正極／本実施形態のリチウムイオン伝導性固体電解質材料／負極の順に積層することによって、容易に全固体電池の電極素体を得ることができる。この電池素体は、端子部材を設けた上でラミネートケースや金属缶などに収容し、リチウムイオン二次電池としてもよく、ポリイミドなどの樹脂材料によって被覆してリチウムイオン二次電池としてもよい。 The lithium ion conductive solid electrolyte material of the present embodiment can be used, for example, as a part of the solid electrolyte layer and the solid electrolyte layer of the all solid lithium ion secondary battery. In this case, members known in the field of lithium ion secondary batteries can be widely used as constituent members other than the solid electrolyte, for example, the positive electrode, the negative electrode, the terminal member, and the outer case. For example, by using LiCoO 2 as the positive electrode and metallic lithium as the negative electrode, and stacking in the order of positive electrode / lithium ion conductive solid electrolyte material / negative electrode of the present embodiment, an electrode body of an all-solid battery can be easily obtained. it can. The battery body may be accommodated in a laminate case or a metal can with a terminal member and may be a lithium ion secondary battery, or may be covered with a resin material such as polyimide to be a lithium ion secondary battery.
なお、本発明は上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。加えて、ＬｉＮｂＯ３以外の酸化物リチウムイオン伝導体に対するフッ化物の混合は、本発明と同様の効果が期待できる場合がある。例えば、Ｌｉ１４ＺｎＧｅ４Ｏ１６、Ｌｉ１．３Ｔｉ１．７Ａｌ０．３（ＰＯ４）４、Ｌａ０．６６７−ｘＬｉ３ｘＴｉＯ３（０＜ｘ＜０．１６）、Ｌｉ３−ｘＰＯ４−ｘＮｘ、（０＜ｘ＜１）、Ｌｉ９ＡｌＳｉＯ８、Ｌｉ７Ｌａ３Ｚｒ２Ｏ１２等でもフッ化物と混合することでリチウムイオン伝導度の向上が期待できる。 The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope. In addition, the mixing of fluoride with oxide lithium ion conductors other than LiNbO 3 may be expected to have the same effect as the present invention. For example, Li 14 ZnGe 4 O 16 , Li 1.3 Ti 1.7 Al 0.3 (PO 4 ) 4 , La 0.667-x Li 3x TiO 3 (0 <x <0.16), Li 3− x PO 4−x N x , (0 <x <1), Li 9 AlSiO 8 , Li 7 La 3 Zr 2 O 12, etc. can be expected to improve lithium ion conductivity by mixing with fluoride.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。
（実施例１）
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.
Example 1
原料としてＬｉ２ＣＯ３ならびにＮｂ２Ｏ５の各粉体をエタノール溶媒とともにボールミルで混合し、スラリーを得た。スラリーから溶媒を乾燥させて得られた混合粉を１１００℃で５時間焼成することにより、ＬｉＮｂＯ３化合物を得た。係るＬｉＮｂＯ３を乳鉢により粗粉砕し、その粉体をエタノール溶媒とともにボールミルにて微粉砕した。 Each powder of Li 2 CO 3 and Nb 2 O 5 as raw materials was mixed with an ethanol solvent by a ball mill to obtain a slurry. The mixed powder obtained by drying the solvent from the slurry was fired at 1100 ° C. for 5 hours to obtain a LiNbO 3 compound. Such LiNbO 3 was coarsely pulverized with a mortar, and the powder was finely pulverized with an ethanol solvent by a ball mill.
上記ＬｉＮｂＯ３微粉末とＬｉＦとを、ＬｉＦ混合量が原料粉体全体に対して１０重量％の混合比になるよう秤量し、再びボールミルにてエタノール溶媒とともによく混合した。溶媒を乾燥させて得た混合粉体を直径１２ｍｍのダイスを用いて成形した後、９００℃で焼成し、実施例１のリチウムイオン伝導性固体電解質材料を得た。
（実施例２〜７）
The LiNbO 3 fine powder and LiF were weighed so that the amount of LiF mixed was 10% by weight with respect to the whole raw material powder, and again mixed well with an ethanol solvent in a ball mill. The mixed powder obtained by drying the solvent was molded using a die having a diameter of 12 mm, and then fired at 900 ° C. to obtain a lithium ion conductive solid electrolyte material of Example 1.
(Examples 2 to 7)
ＬｉＦ混合量を、それぞれ１５重量％、２０重量％、２５重量％、３０重量％、３５重量％、４０重量％とした以外は実施例１と同様の作製方法により実施例２〜７のリチウムイオン伝導性固体電解質材料を得た。
（実施例８〜１０）
The lithium ions of Examples 2 to 7 were prepared in the same manner as in Example 1 except that the amount of LiF mixed was 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, and 40% by weight, respectively. A conductive solid electrolyte material was obtained.
(Examples 8 to 10)
ＬｉＦに代えてＮａＦを、２０重量％、２５重量％、３０重量％それぞれ添加した以外は実施例１と同様の作製方法により実施例８〜１０のリチウムイオン伝導性固体電解質材料を得た。
（実施例１１〜１３）
Lithium ion conductive solid electrolyte materials of Examples 8 to 10 were obtained in the same manner as in Example 1 except that 20% by weight, 25% by weight, and 30% by weight of NaF were added in place of LiF.
(Examples 11 to 13)
ＬｉＦに代えてＣａＦ２を、２０重量％、２５重量％、３０重量％それぞれ添加した以外は実施例１と同様の作製方法により実施例１１〜１３のリチウムイオン伝導性固体電解質材料を得た。
（比較例１）
Lithium ion conductive solid electrolyte materials of Examples 11 to 13 were obtained by the same production method as Example 1 except that CaF 2 was added in an amount of 20% by weight, 25% by weight, and 30% by weight in place of LiF.
(Comparative Example 1)
フッ化物を混合していない以外は実施例１と同様の作製方法により比較例１のリチウムイオン伝導性固体電解質材料を得た。
（実施例１〜１３、比較例１の評価）
A lithium ion conductive solid electrolyte material of Comparative Example 1 was obtained by the same production method as in Example 1 except that no fluoride was mixed.
(Evaluation of Examples 1 to 13 and Comparative Example 1)
実施例１〜１３、比較例１で得られたリチウムイオン伝導性固体電解質材料を厚み１ｍｍのペレットに加工した後、そのペレットの両面にＡｕスパッタを施すことにより、金電極を形成した試料を得た。これら試料のインピーダンス測定結果からリチウムイオン伝導度を算出した。結果を表１に示す。 After processing the lithium ion conductive solid electrolyte materials obtained in Examples 1 to 13 and Comparative Example 1 into pellets having a thickness of 1 mm, Au sputtering was performed on both sides of the pellets to obtain a sample on which gold electrodes were formed. It was. Lithium ion conductivity was calculated from the impedance measurement results of these samples. The results are shown in Table 1.
表１に示すように、フッ化物を添加したリチウムイオン伝導性固体電解質材料は、ＬｉＮｂＯ３単体の固体電解質材料よりもリチウムイオン伝導度が向上していた。特に、フッ化物がＬｉＦであって、ＬｉＦの混合量が固体電解質全体の１５重量％から３５重量％の場合に１ｘ１０−５ Ｓ／ｃｍ以上という実用性の高いリチウムイオン伝導度が得られた。 As shown in Table 1, the lithium ion conductive solid electrolyte material to which fluoride was added had improved lithium ion conductivity than the solid electrolyte material of LiNbO 3 alone. In particular, when the fluoride was LiF and the mixed amount of LiF was 15 wt% to 35 wt% of the entire solid electrolyte, a highly practical lithium ion conductivity of 1 × 10 −5 S / cm or more was obtained.
ＬｉＦはＬｉとＦの結合が強固であり、ＬｉはＬｉＦ中を容易に伝導できないため、ＬｉＮｂＯ３とＬｉＦとの界面近傍でリチウムイオン伝導が向上したと推察される。ＬｉＦの混合量が１５重量％より少ないと界面の生成が十分ではなく、リチウムイオン伝導が十分に得られない。また、３５重量％より多くなるとリチウムイオン伝導を担うＬｉＮｂＯ３の量が低くなり過ぎ、リチウムイオン伝導の低下が見られると推察される。表１からも明らかなように、ＬｉＦ混合量は１５重量％〜３５重量％とすることで、顕著なリチウムイオン伝導の向上が見られる。 Since LiF has a strong bond between Li and F and Li cannot easily conduct in LiF, it is presumed that lithium ion conduction is improved in the vicinity of the interface between LiNbO 3 and LiF. When the amount of LiF is less than 15% by weight, the interface is not sufficiently generated, and lithium ion conduction cannot be sufficiently obtained. Also, is more than 35 wt%, the too low amount of LiNbO 3 carrying lithium ion conductivity, it is presumed that reduction in lithium ion conductivity is observed. As is clear from Table 1, when the LiF mixing amount is 15% by weight to 35% by weight, significant improvement in lithium ion conduction is observed.
本発明のリチウムイオン伝導性固体電解質材料は高いリチウムイオン伝導性を有するため充放電特性に優れている。そのため、安全性の高いリチウムイオン電池の電解質層として好適に利用することができる。 Since the lithium ion conductive solid electrolyte material of the present invention has high lithium ion conductivity, it has excellent charge / discharge characteristics. Therefore, it can be suitably used as an electrolyte layer of a highly safe lithium ion battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017091788A (en) * | 2015-11-10 | 2017-05-25 | 日本特殊陶業株式会社 | Ion conductor, lithium battery, and method of producing ion conductor |
| WO2022230426A1 (en) | 2021-04-28 | 2022-11-03 | 昭和電工株式会社 | Lithium ion conducting oxide and all solid battery |
| KR20230037137A (en) * | 2021-09-09 | 2023-03-16 | 울산대학교 산학협력단 | Sulfide-based solid electrolyte, manufacturing method thereof, and all-solid lithium battery manufactured therefrom |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5971264A (en) * | 1982-10-15 | 1984-04-21 | Sanyo Electric Co Ltd | Solid electrolyte battery |
| JPS59189566A (en) * | 1983-04-11 | 1984-10-27 | Canon Inc | Thin film solid electrolyte and its manufacture |
| JP2008243736A (en) * | 2007-03-28 | 2008-10-09 | Arisawa Mfg Co Ltd | Lithium ion secondary battery and its manufacturing method |
| JP2009218124A (en) * | 2008-03-11 | 2009-09-24 | Sumitomo Electric Ind Ltd | Li ion-conductive solid electrolyte |
| JP2010244847A (en) * | 2009-04-06 | 2010-10-28 | Toyota Motor Corp | Solid electrolyte material |
| JP2011081934A (en) * | 2009-10-05 | 2011-04-21 | Konica Minolta Holdings Inc | Solid electrolyte and secondary battery |
-
2012
- 2012-01-26 JP JP2012014552A patent/JP5910112B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5971264A (en) * | 1982-10-15 | 1984-04-21 | Sanyo Electric Co Ltd | Solid electrolyte battery |
| JPS59189566A (en) * | 1983-04-11 | 1984-10-27 | Canon Inc | Thin film solid electrolyte and its manufacture |
| JP2008243736A (en) * | 2007-03-28 | 2008-10-09 | Arisawa Mfg Co Ltd | Lithium ion secondary battery and its manufacturing method |
| JP2009218124A (en) * | 2008-03-11 | 2009-09-24 | Sumitomo Electric Ind Ltd | Li ion-conductive solid electrolyte |
| JP2010244847A (en) * | 2009-04-06 | 2010-10-28 | Toyota Motor Corp | Solid electrolyte material |
| JP2011081934A (en) * | 2009-10-05 | 2011-04-21 | Konica Minolta Holdings Inc | Solid electrolyte and secondary battery |
Non-Patent Citations (1)
| Title |
|---|
| JPN6015023407; ＳＵＮ Ｈ Ｙ， ＴＡＫＥＤＡ Ｙ， ＩＭＡＮＩＳＨＩ Ｎ ， ＹＡＭＡＭＯＴＯ Ｏ: 'Ｆｅｒｒｏｅｌｅｃｔｒｉｃ Ｍａｔｅｒｉａｌｓ ａｓ ａ Ｃｅｒａｍｉｃ Ｆｉｌｌｅｒ ｉｎ Ｓｏｌｉｄ Ｃｏｍｐｏｓｉｔｅ Ｐｏｌｙｅｔｈｙｌｅｎｅ Ｏｘｉｄｅ-Ｂａｓｅｄ Ｅｌｅｃｔｒｏｌｙｔｅｓ' Ｊ Ｅｌｅｃｔｒｏｃｈｅｍ Ｓｏｃ Ｖｏｌ．１４７／Ｎｏ．７, 200007, Ｐａｇｅ．２４６２-２４６７ * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017091788A (en) * | 2015-11-10 | 2017-05-25 | 日本特殊陶業株式会社 | Ion conductor, lithium battery, and method of producing ion conductor |
| WO2022230426A1 (en) | 2021-04-28 | 2022-11-03 | 昭和電工株式会社 | Lithium ion conducting oxide and all solid battery |
| KR20230156423A (en) | 2021-04-28 | 2023-11-14 | 가부시끼가이샤 레조낙 | Lithium-ion conductive oxide and all-solid-state batteries |
| KR20230037137A (en) * | 2021-09-09 | 2023-03-16 | 울산대학교 산학협력단 | Sulfide-based solid electrolyte, manufacturing method thereof, and all-solid lithium battery manufactured therefrom |
| WO2023038371A1 (en) * | 2021-09-09 | 2023-03-16 | 울산대학교 산학협력단 | Sulfide-based solid electrolyte, preparation method thereof, and all-solid-state battery prepared therefrom |
| KR102613606B1 (en) | 2021-09-09 | 2023-12-14 | 울산대학교 산학협력단 | Sulfide-based solid electrolyte, manufacturing method thereof, and all-solid lithium battery manufactured therefrom |
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