JP2015064992A - All-solid state battery - Google Patents

All-solid state battery Download PDF

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JP2015064992A
JP2015064992A JP2013197636A JP2013197636A JP2015064992A JP 2015064992 A JP2015064992 A JP 2015064992A JP 2013197636 A JP2013197636 A JP 2013197636A JP 2013197636 A JP2013197636 A JP 2013197636A JP 2015064992 A JP2015064992 A JP 2015064992A
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JP6194719B2 (en
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充 吉岡
Mitsuru Yoshioka
充 吉岡
倍太 尾内
Yasuhiro Onouchi
倍太 尾内
剛司 林
Goji Hayashi
剛司 林
武郎 石倉
Takero Ishikura
武郎 石倉
彰佑 伊藤
Akihiro Ito
彰佑 伊藤
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Murata Manufacturing Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

PROBLEM TO BE SOLVED: To suppress deterioration in a positive electrode active material due to a valence change of V, in an all-solid state battery using, as a positive electrode active material, a lithium-containing vanadium phosphate compound having a Nasicon structure.SOLUTION: An all-solid state battery comprises a solid electrolyte layer 2 and a positive electrode layer 3 and a negative electrode layer 4 which are disposed to sandwich the solid electrolyte layer 2, and includes, as a positive electrode active material, a lithium-containing vanadium phosphate having a Nasicon structure. A part of a site of V in a lithium-containing vanadium phosphate is replaced with an element having hexacoordination same with V. The lithium-containing vanadium phosphate is preferably represented by general formula: LiVM(PO)(where, x: -0.4≤x≤0.2, y: 0.00<y≤0.20, and M: a hexacoordinated element), and more preferably, y satisfies 0.01≤y≤0.05.

Description

この発明は、全固体電池に関するもので、特に、全固体電池における正極活物質に、ナシコン構造を有するリチウム含有リン酸バナジウムを用いた全固体電池に関するものである。   The present invention relates to an all solid state battery, and more particularly to an all solid state battery using lithium-containing vanadium phosphate having a NASICON structure as a positive electrode active material in an all solid state battery.

近年、携帯電話機や携帯用パーソナルコンピュータ等の携帯用電子機器の電源として、電池の需要が大幅に拡大している。このような用途に用いられる電池として、リチウムイオン二次電池がある。リチウムイオン二次電池においては、イオンを移動させるための媒体として、炭酸エステルやエーテル系の有機溶媒等を用い、この有機溶媒等にリチウム塩を溶解した有機電解質（電解液）が従来から用いられている。   In recent years, the demand for batteries as a power source for portable electronic devices such as mobile phones and portable personal computers has greatly increased. As a battery used for such an application, there is a lithium ion secondary battery. In a lithium ion secondary battery, an organic electrolyte (electrolytic solution) in which a lithium salt is dissolved in an organic solvent or the like is conventionally used as a medium for moving ions, such as a carbonate ester or an ether organic solvent. ing.

しかし、上記の構成の電池では、電解液が漏出するという危険性がある。また、電解液に用いられる有機溶媒等は可燃性物質であるという問題がある。そのため、電池の安全性を高めることが求められている。   However, in the battery having the above configuration, there is a risk that the electrolyte solution leaks. Further, there is a problem that an organic solvent or the like used for the electrolytic solution is a combustible substance. Therefore, it is required to increase the safety of the battery.

そこで、リチウムイオン二次電池の安全性を高めるため、電解質として、有機溶媒系電解液に代えて、固体電解質を用いることが提案されている。さらに、電解質として固体電解質を用いるばかりでなく、その他の構成要素も固体で構成されている全固体電池の開発が進められている。   Therefore, in order to increase the safety of the lithium ion secondary battery, it has been proposed to use a solid electrolyte as the electrolyte instead of the organic solvent electrolyte. Furthermore, development of an all-solid battery in which not only a solid electrolyte is used as an electrolyte but also other constituent elements are made of solid is underway.

たとえば、国際公開第２０１２／０６３８７４号パンフレット（特許文献１）には、焼結式全固体電池が記載されている。ここで開示される全固体電池は、正極活物質として、ナシコン構造を有する、たとえばリチウム含有リン酸バナジウム化合物：Ｌｉ3Ｖ2（ＰＯ4）3を用いている。 For example, International Publication No. 2012/063874 pamphlet (Patent Document 1) describes a sintered all solid state battery. The all solid state battery disclosed here uses, for example, a lithium-containing vanadium phosphate compound: Li 3 V 2 (PO 4 ) 3 having a NASICON structure as a positive electrode active material.

国際公開第２０１２／０６３８７４号パンフレットInternational Publication No. 2012/063874 Pamphlet

発明者らが検討した結果、活物質を含めて全体が固体によって構成される全固体電池においては、電池の劣化要因は、充放電に伴う活物質の体積変化にではなく、むしろ活物質の中心金属の価数変化に伴う活物質の劣化が主要因であるらしいことを見出した。   As a result of investigations by the inventors, in an all-solid battery composed entirely of solid including the active material, the deterioration factor of the battery is not the volume change of the active material accompanying charge / discharge, but rather the center of the active material. It was found that the deterioration of the active material due to the valence change of the metal seems to be the main factor.

このような傾向は、剛体となる固体をもって構成された全固体電池、特に焼結体をもって構成された全固体電池において顕著であることもわかった。   It has also been found that such a tendency is remarkable in an all-solid battery configured with a solid body, particularly an all-solid battery configured with a sintered body.

そこで、この発明の目的は、正極活物質として、ナシコン構造を有するリチウム含有リン酸バナジウム化合物を用いる全固体電池において、Ｖの価数変化に伴う正極活物質の劣化を抑制しようとすることである。   Accordingly, an object of the present invention is to suppress deterioration of the positive electrode active material due to a change in the valence of V in an all solid state battery using a lithium-containing vanadium phosphate compound having a NASICON structure as the positive electrode active material. .

この発明は、固体電解質層と、固体電解質層を挟んで配置された正極層および負極層と、を備え、正極活物質として、ナシコン構造を有するリチウム含有リン酸バナジウムを含む、全固体電池に向けられるものであって、上述した技術的課題を解決するため、リチウム含有リン酸バナジウムにおいて、Ｖのサイトの一部を、Ｖと同じ６配位を有する元素で置換することを特徴としている。   The present invention is directed to an all solid state battery comprising a solid electrolyte layer, and a positive electrode layer and a negative electrode layer disposed with the solid electrolyte layer interposed therebetween, and including lithium-containing vanadium phosphate having a NASICON structure as a positive electrode active material. In order to solve the above-described technical problem, the lithium-containing vanadium phosphate is characterized in that a part of the V site is replaced with an element having the same 6-coordination as V.

上述の置換する元素は、好ましくは、Ｍｇ、Ｃａ、Ｓｒ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｚｎ、Ｃｄ、Ｉｎ、Ｔｌ、Ｓｎ、Ｐｂ、ＳｂおよびＢｉからなる群から選ばれる少なくとも１種の元素であり、より好ましくは、Ｍｇ、Ｃａ、Ｓｒ、Ｓｃ、Ｙ、Ｚｒ、Ｈｆ、Ｚｎ、Ｃｄ、Ｉｎ、ＳｎおよびＰｂからなる群から選ばれる少なくとも１種の元素である。   The element to be substituted is preferably a group consisting of Mg, Ca, Sr, Sc, Y, Ti, Zr, Hf, Nb, Ta, Mo, Zn, Cd, In, Tl, Sn, Pb, Sb and Bi. And at least one element selected from the group consisting of Mg, Ca, Sr, Sc, Y, Zr, Hf, Zn, Cd, In, Sn, and Pb. is there.

好ましくは、リチウム含有リン酸バナジウムは、一般式：Ｌｉ3+xＶ2-yＭy（ＰＯ4）3（ただし、ｘ：−０．４≦ｘ≦０．２、ｙ：０．００＜ｙ≦０．２０、Ｍ：６配位を有する元素）で表されるものであり、より好ましくは、ｙは、０．０１≦ｙ≦０．０５である。 Preferably, the lithium-containing vanadium phosphate has the general formula: Li 3 + x V 2- y My (PO 4 ) 3 (where x: −0.4 ≦ x ≦ 0.2, y: 0.00 < y ≦ 0.20, M: element having 6 coordination), and more preferably, y is 0.01 ≦ y ≦ 0.05.

この発明は、少なくとも正極層と固体電解質層とが焼結によって接合されている、全固体電池に対して有利に適用される。   The present invention is advantageously applied to an all solid state battery in which at least a positive electrode layer and a solid electrolyte layer are joined by sintering.

この発明によれば、Ｖの価数変化に伴う正極活物質の劣化を抑制することができる。原因は、正確には不明であるが、充放電に伴うリチウム含有リン酸バナジウムからの酸素脱離が抑制されるためであると推測される。   According to the present invention, it is possible to suppress the deterioration of the positive electrode active material accompanying the change in the valence of V. Although the cause is not exactly known, it is presumed that oxygen desorption from the lithium-containing vanadium phosphate accompanying charge / discharge is suppressed.

この発明の一実施形態による全固体電池に備える電池積層体１を模式的に示す断面図である。It is sectional drawing which shows typically the battery laminated body 1 with which the all-solid-state battery by one Embodiment of this invention is equipped.

まず、この発明の一実施形態による全固体電池について説明する。全固体電池は、図１に示すような電池積層体１をもって構成される。電池積層体１は、固体電解質を含む固体電解質層２と、固体電解質層２を挟んで互いに対向するように配置された正極層３および負極層４と、を備えている。   First, an all solid state battery according to an embodiment of the present invention will be described. The all-solid battery is configured with a battery stack 1 as shown in FIG. The battery stack 1 includes a solid electrolyte layer 2 including a solid electrolyte, and a positive electrode layer 3 and a negative electrode layer 4 disposed so as to face each other with the solid electrolyte layer 2 interposed therebetween.

正極層３に含まれる正極活物質は、ナシコン構造を有するリチウム含有リン酸バナジウムを含み、リチウム含有リン酸バナジウムは、Ｖのサイトの一部を、６配位を有する元素で置換したものである。このように、リチウム含有リン酸バナジウムにおけるＶのサイトの一部を、６配位を有する元素で置換すれば、Ｖの価数変化に伴う正極活物質の劣化を抑制でき、充放電の繰返しによる劣化を抑制できるとが、後述する実験からわかった。原因は、正確には不明であるが、充放電に伴うリチウム含有リン酸バナジウムからの酸素脱離が抑制されるためであると推測される。   The positive electrode active material contained in the positive electrode layer 3 includes lithium-containing vanadium phosphate having a NASICON structure, and the lithium-containing vanadium phosphate is obtained by substituting a part of the V site with an element having 6-coordination. . As described above, if a part of the V site in the lithium-containing vanadium phosphate is replaced with an element having 6-coordination, the deterioration of the positive electrode active material due to the change in the valence of V can be suppressed. It was found from experiments described later that the deterioration can be suppressed. Although the cause is not exactly known, it is presumed that oxygen desorption from the lithium-containing vanadium phosphate accompanying charge / discharge is suppressed.

上述の置換する元素として、Ｍｇ、Ｃａ、Ｓｒ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｚｎ、Ｃｄ、Ｉｎ、Ｔｌ、Ｓｎ、Ｐｂ、ＳｂおよびＢｉからなる群から選ばれる少なくとも１種の元素が用いられると、全固体電池の出力をより高めることができる。これは、Ｖ（３価、４価、５価元素）よりも大きなイオン半径を有する元素で置換することで、Ｌｉ3Ｖ2（ＰＯ4）3の結晶構造内のＬｉイオンパスが広がるためであると推測される。 The element to be replaced is selected from the group consisting of Mg, Ca, Sr, Sc, Y, Ti, Zr, Hf, Nb, Ta, Mo, Zn, Cd, In, Tl, Sn, Pb, Sb, and Bi. When at least one element is used, the output of the all solid state battery can be further increased. This is because the Li ion path in the crystal structure of Li 3 V 2 (PO 4 ) 3 is expanded by substituting with an element having an ionic radius larger than V (trivalent, tetravalent, pentavalent element). It is guessed.

上述の置換する元素として、より限定的に、Ｍｇ、Ｃａ、Ｓｒ、Ｓｃ、Ｙ、Ｚｒ、Ｈｆ、Ｚｎ、Ｃｄ、Ｉｎ、ＳｎおよびＰｂからなる群から選ばれる少なくとも１種の元素が用いられると、全固体電池の出力をより高めることができるばかりでなく、Ｌｉ3Ｖ2（ＰＯ4）3のＶの６配位サイトにて、取り得る価数がひとつに限られているので、置換した元素自体が価数変化することがなく、正極活物質の劣化をより抑制することができる。 More preferably, at least one element selected from the group consisting of Mg, Ca, Sr, Sc, Y, Zr, Hf, Zn, Cd, In, Sn, and Pb is used as the element to be replaced. Not only can the output of the all-solid-state battery be further increased, but the substitution can be made at the six-coordinate site of Li 3 V 2 (PO 4 ) 3 because the valence is limited to one. The element itself does not change in valence, and deterioration of the positive electrode active material can be further suppressed.

この発明による正極活物質に含まれるナシコン構造を有するリチウム含有リン酸バナジウムは、一般式：Ｌｉ3+xＶ2-yＭy（ＰＯ4）3で表わされる。ここで、Ｖのサイトでの元素置換量ｙを、０．００＜ｙ≦０．２０の範囲に選ぶことにより、異相の生成による、充放電容量の低下が抑制される。さらに、元素置換量ｙを、０．０１≦ｙ≦０．０５の範囲に選ぶことにより、より高い効果を得ることができる。なお、Ｌｉの量は、置換元素量とその価数により、価数補償する範囲で変動する。上記一般式におけるＬｉの量である「３＋ｘ」は、２．６〜３．２の範囲で変動し、「ｘ」で表わせば、−０．４≦ｘ≦０．２の範囲で変動する。 The lithium-containing vanadium phosphate having a NASICON structure contained in the positive electrode active material according to the present invention is represented by the general formula: Li 3 + x V 2- y My (PO 4 ) 3 . Here, by selecting the element substitution amount y at the site of V in the range of 0.00 <y ≦ 0.20, the reduction of the charge / discharge capacity due to the generation of the heterogeneous phase is suppressed. Furthermore, a higher effect can be obtained by selecting the element substitution amount y in the range of 0.01 ≦ y ≦ 0.05. The amount of Li varies within the range for valence compensation depending on the amount of substitution element and its valence. “3 + x”, which is the amount of Li in the above general formula, varies in the range of 2.6 to 3.2. If expressed by “x”, it varies in the range of −0.4 ≦ x ≦ 0.2.

少なくとも正極層３は、固体電解質層２と焼結によって接合されている。上述したような効果は、少なくとも正極層３と固体電解質層２とがこのような焼結体によって構成された場合において、より顕著に奏される。   At least the positive electrode layer 3 is joined to the solid electrolyte layer 2 by sintering. The effects as described above are more prominent when at least the positive electrode layer 3 and the solid electrolyte layer 2 are formed of such a sintered body.

前述の固体電解質には、たとえば、イオン伝導性を有し、電子伝導性が無視できるほど小さい材料を用いることができる。このような材料の例としては、ハロゲン化リチウム、窒化リチウム、リチウム酸素酸塩、およびこれらの誘導体が挙げられる。また、リン酸リチウム（Ｌｉ３ＰＯ４）等のＬｉ−Ｐ−Ｏ系化合物、リン酸リチウムに窒素を混ぜたＬＩＰＯＮ（ＬｉＰＯ4-xＮｘ）、Ｌｉ４ＳｉＯ４等のＬｉ−Ｓｉ−Ｏ系化合物、Ｌｉ−Ｐ−Ｓｉ−Ｏ系化合物、Ｌｉ−Ｖ−Ｓｉ−Ｏ系化合物、Ｌａ0.51Ｌｉ0.35ＴｉＯ2.94、Ｌａ0.55Ｌｉ0.35ＴｉＯ３、Ｌｉ3xＬａ2/3-xＴｉＯ３等のぺロブスカイト型構造を有する化合物、Ｌｉ７Ｌａ３Ｚｒ２Ｏ12等のＬｉ、Ｌａ、Ｚｒを有するガーネット型構造を有する化合物、等を挙げることができる。Ｌｉ−Ｐ−Ｓ系、Ｌｉ−Ｇｅ−Ｐ−Ｓ系等の硫化物材料を用いてもよい。 For the above-mentioned solid electrolyte, for example, a material having ion conductivity and small enough to have negligible electronic conductivity can be used. Examples of such materials include lithium halide, lithium nitride, lithium oxyacid salt, and derivatives thereof. In addition, Li—PO system compounds such as lithium phosphate (Li 3 PO 4 ), LiPON (LiPO 4−x N x ) in which nitrogen is mixed with lithium phosphate, Li—Si—O such as Li 4 SiO 4 Compounds such as La-based compounds, Li-P-Si-O based compounds, Li-V-Si-O based compounds, La 0.51 Li 0.35 TiO 2.94 , La 0.55 Li 0.35 TiO 3 , Li 3x La 2 / 3-x TiO 3 A compound having a lobskite structure, a compound having a garnet structure having Li, La, and Zr such as Li 7 La 3 Zr 2 O 12 can be given. You may use sulfide materials, such as a Li-PS-system and a Li-Ge-PS system.

また、固体電解質は、特に、ナシコン構造を有する化合物を含んでいることが好ましい。ナシコン構造を有する化合物の組成は、ＬｉｘＡｙ（ＰＯ４）３（１≦ｘ≦２、１≦ｙ≦２、Ａは、Ｔｉ、Ｇｅ、Ａｌ、ＧａおよびＺｒの少なくとも１種）で表わされ、Ｐの一部がＢ、Ｓｉ等で置換されていてもよい。ナシコン構造を有する化合物の例としては、Ｌｉ1.5Ａｌ0.5Ｇｅ1.5（ＰＯ４）３やＬｉ1.5Ａｌ0.5Ｔｉ1.5（ＰＯ４）３等が挙げられる。 The solid electrolyte particularly preferably contains a compound having a NASICON structure. The composition of the compound having a NASICON structure is represented by Li x A y (PO 4 ) 3 (1 ≦ x ≦ 2, 1 ≦ y ≦ 2, A is at least one of Ti, Ge, Al, Ga and Zr). In addition, a part of P may be substituted with B, Si or the like. Examples of the compound having a NASICON structure include Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 and Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 .

負極層４に含まれる負極活物質としては、前述した本発明による正極活物質が含まれてもよく、それ以外に、黒鉛−リチウム化合物、Ｌｉ−Ａｌ等のリチウム合金、Ｌｉ３Ｖ２（ＰＯ４）３やＬｉ３Ｆｅ２（ＰＯ４）３等のナシコン型のリチウム含有リン酸化合物、Ｌｉ４Ｔｉ５Ｏ12、Ｔｉ、Ｓｉ、Ｓｎ、Ｃｒ、ＦｅおよびＭｏからなる群より選ばれる少なくとも１種の元素の酸化物等が用いられる。具体的には、酸化チタン、酸化シリコン、酸化ニオブ、酸化錫、酸化クロム、酸化鉄および酸化モリブデンからなる群より選ばれる少なくとも１種の酸化物を含んでいることが好ましい。このような酸化物は、重量あたりの容量が大きく、Ｌｉに対する電位が低い。そのため、全固定電池において、容量密度が大きく、電池電圧が高くなり、エネルギー密度を高くすることができる。 The negative electrode active material contained in the negative electrode layer 4 may include the above-described positive electrode active material according to the present invention. In addition, a graphite-lithium compound, a lithium alloy such as Li—Al, Li 3 V 2 (PO 4 ) at least one selected from the group consisting of NASICON type lithium-containing phosphate compounds such as 3 and Li 3 Fe 2 (PO 4 ) 3 , Li 4 Ti 5 O 12 , Ti, Si, Sn, Cr, Fe and Mo An oxide of a seed element or the like is used. Specifically, it preferably contains at least one oxide selected from the group consisting of titanium oxide, silicon oxide, niobium oxide, tin oxide, chromium oxide, iron oxide and molybdenum oxide. Such an oxide has a large capacity per weight and a low potential with respect to Li. Therefore, in the all fixed batteries, the capacity density is large, the battery voltage is increased, and the energy density can be increased.

図１では図示しないが、正極層３および負極層４の、固体電解質層２側とは反対側の面には、集電体層が配置されてもよい。集電体層の材料としては、たとえば、炭素、金属、酸化物等の電子伝導性材料が用いられる。集電体層は融着ガラス等、焼成することで電子伝導性材料を焼結する材料を含んでもよいし、熱硬化性樹脂等、１００〜２００℃程度のアニール処理で電子伝導性材料を固定できる材料を含んでもよい。接着剤等、熱処理をせずに電子伝導性材料を固定できる材料を含んでもよい。なお、集電体層に固体電解質材料等のイオン伝導する材料が含まれると、集電体層を介して電池積層体１が内部短絡する恐れがあるため、好ましくない。   Although not shown in FIG. 1, a current collector layer may be disposed on the surface of the positive electrode layer 3 and the negative electrode layer 4 opposite to the solid electrolyte layer 2 side. As a material for the current collector layer, for example, an electron conductive material such as carbon, metal, oxide, or the like is used. The current collector layer may include a material that sinters the electron conductive material by firing, such as fused glass, or the electron conductive material is fixed by annealing at about 100 to 200 ° C., such as a thermosetting resin. Materials that can be included may be included. A material such as an adhesive that can fix the electron conductive material without heat treatment may be included. In addition, it is not preferable that the current collector layer contains an ion-conducting material such as a solid electrolyte material because the battery stack 1 may be internally short-circuited through the current collector layer.

以下、この発明の効果を確認するために実施した実験例について説明する。   Hereinafter, experimental examples carried out to confirm the effects of the present invention will be described.

〈正極活物質の作製〉
原料として、炭酸リチウム（Ｌｉ２ＣＯ３）、五酸化バナジウム（Ｖ２Ｏ５）、リン酸二水素アンモニウム（ＮＨ４Ｈ２ＰＯ４）、酸化二オブ（Ｎｂ２Ｏ５）、酸化イットリウム（Ｙ２Ｏ３）、酸化アルミニウム（Ａｌ２Ｏ３）を用意した。これらの原料からわかるように、この実験例では、置換元素として、Ｎｂ、ＹおよびＡｌを用いた。 <Preparation of positive electrode active material>
As raw materials, lithium carbonate (Li 2 CO 3 ), vanadium pentoxide (V 2 O 5 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), niobium oxide (Nb 2 O 5 ), yttrium oxide (Y 2 O 3 ) and aluminum oxide (Al 2 O 3 ) were prepared. As can be seen from these raw materials, Nb, Y and Al were used as substitution elements in this experimental example.

次に、上記原料を、Ｌｉ3+xＶ2-yＭy（ＰＯ4）3において、Ｖサイトの一部を置換するＭとして、表１の「置換元素Ｍ」の欄に示した元素を選び、これを「置換量ｙ」の欄に示した量で置換して、「正極活物質の組成」の欄に示す組成が得られるように秤量した。 Next, the raw material, the Li 3 + x V 2-y M y (PO 4) 3, as M to replace a portion of the V-site, an element shown in the column of "substitution elements M" in Table 1 This was replaced with the amount shown in the column “Substitution amount y”, and weighed so as to obtain the composition shown in the column “Positive electrode active material composition”.

次に、秤量した原料を混合し、空気雰囲気下、６００℃の温度で２時間焼成し、揮発成分を除去した後、ポリエチレン製容器に入れ、水を加え、直径５ｍｍの玉石とともにポット架上で１５０rpmの回転数で、４８時間回転することにより、焼成粉末を粉砕した。   Next, the weighed raw materials are mixed, baked for 2 hours at a temperature of 600 ° C. in an air atmosphere, and after removing volatile components, put into a polyethylene container, add water, and cobblestone with a diameter of 5 mm on a pot rack. The fired powder was pulverized by rotating for 48 hours at a rotation speed of 150 rpm.

次に、１２０℃の温度に加熱されたホットプレート上で、上記粉砕された焼成粉末から水分を除去した後、この焼成粉末を、導電助剤としてのアセチレンブラックと混合し、窒素雰囲気下、９３０℃の温度で２０時間焼成し、表１の「正極活物質の組成」の欄に示す組成を有する試料１〜７に係る正極活物質：Ｌｉ3+xＶ2-yＭy（ＰＯ4）3を得た。なお、アセチレンブラックの担持量は、正極活物質としてのリチウム含有リン酸バナジウム１００重量部に対して、１０重量部とした。 Next, after removing moisture from the pulverized baked powder on a hot plate heated to a temperature of 120 ° C., the baked powder is mixed with acetylene black as a conductive auxiliary agent, and 930 in a nitrogen atmosphere. Positive electrode active material according to Samples 1 to 7 having a composition shown in the column of “Composition of positive electrode active material” in Table 1 at a temperature of 20 ° C .: Li 3 + x V 2− y My (PO 4 ) Got 3 . The amount of acetylene black supported was 10 parts by weight with respect to 100 parts by weight of lithium-containing vanadium phosphate as the positive electrode active material.

Figure 2015064992
Figure 2015064992

表１には、「置換元素のイオン半径」が示されている。なお、参考のため、Ｖのイオン半径は０．５４〜０．６４Åである。   Table 1 shows the “ion radius of the substitution element”. For reference, the ionic radius of V is 0.54 to 0.64cm.

〈正極活物質の結晶構造解析〉
試料１〜７の各々に係る正極活物質の結晶構造を解析するため、４．０°／分のスキャン速度、測角範囲１０°〜６０°でＸＲＤ（Ｘ線回折装置）による測定を実施した。 <Crystal structure analysis of positive electrode active material>
In order to analyze the crystal structure of the positive electrode active material according to each of Samples 1 to 7, measurement was performed by an XRD (X-ray diffractometer) at a scan speed of 4.0 ° / min and an angle measurement range of 10 ° to 60 °. .

その結果、試料４に係る正極活物質を除き、ナシコン型のリチウム含有リン酸化合物であるＬｉ３Ｆｅ２（ＰＯ４）３のＪＣＰＤＳ（Joint Committee on Powder Diffraction Standards）カード（カード番号７８−１１０６）のパターンとよく一致し、ナシコン構造を有するリチウム含有化合物であることが確認され、かつ異相の生成は確認されなかった。 As a result, a JCPDS (Joint Committee on Powder Diffraction Standards) card (card number 78-1106) of Li 3 Fe 2 (PO 4 ) 3 which is a NASICON type lithium-containing phosphate compound, excluding the positive electrode active material according to sample 4 It was confirmed that it was a lithium-containing compound having a NASICON structure, and formation of a heterogeneous phase was not confirmed.

他方、試料４に係る正極活物質は、上記のナシコン型の結晶相に加えて、異相としてＮｂ２Ｏ５が混在していることが確認された。 On the other hand, the positive electrode active material according to Sample 4 was confirmed to contain Nb 2 O 5 as a heterogeneous phase in addition to the NASICON crystal phase.

〈固体電解質の準備〉
固体電解質として、Ｌｉ1.5Ａｌ0.5Ｇｅ1.5（ＰＯ４）３の組成を有するリチウム含有リン酸ゲルマニウムガラスを用意した。このリチウム含有リン酸ゲルマニウムガラスは、熱処理により、Ｌｉ1.5Ａｌ0.5Ｇｅ1.5（ＰＯ４）３で表わされるナシコン型の結晶相を析出するものである。 <Preparation of solid electrolyte>
A lithium-containing germanium phosphate glass having a composition of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 was prepared as a solid electrolyte. This lithium-containing germanium phosphate glass precipitates a NASICON type crystal phase represented by Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 by heat treatment.

〈正極スラリーおよび固体電解質スラリーの作製〉
ポリビニルアルコール樹脂を、エタノールを含む有機溶剤に溶解した後、これに、試料１〜７の各々に係る正極活物質を加えて、ポット架上で１５０rpmの回転数で、２４時間回転することによって、正極活物質スラリーを作製した。ここで、正極活物質とポリビニルアルコール樹脂との重量比は８０：２０とした。 <Preparation of positive electrode slurry and solid electrolyte slurry>
After dissolving the polyvinyl alcohol resin in an organic solvent containing ethanol, the positive electrode active material according to each of samples 1 to 7 is added thereto, and the mixture is rotated on a pot rack at a rotation speed of 150 rpm for 24 hours. A positive electrode active material slurry was prepared. Here, the weight ratio of the positive electrode active material to the polyvinyl alcohol resin was 80:20.

上述した固体電解質のガラス粉末を用い、正極活物質スラリーの場合と同様の操作を経て、固体電解質スラリーを作製した。このようにして得られた固体電解質スラリーの一部は、以下のように、正極スラリーを得るために用いた。   Using the solid electrolyte glass powder described above, a solid electrolyte slurry was prepared through the same operation as that of the positive electrode active material slurry. A part of the solid electrolyte slurry thus obtained was used to obtain a positive electrode slurry as follows.

上述した正極活物質スラリーと固体電解質スラリーとを５０：５０の重量比で混合し、試料１〜７の各々に係る正極スラリーを得た。   The positive electrode active material slurry and the solid electrolyte slurry described above were mixed at a weight ratio of 50:50 to obtain a positive electrode slurry according to each of samples 1 to 7.

〈グリーンシートの作製〉
試料１〜７の各々に係る正極スラリーを、コンマコータを用いて、厚み５０μｍの正極グリーンシートに成形した。 <Production of green sheet>
The positive electrode slurry according to each of Samples 1 to 7 was formed into a positive electrode green sheet having a thickness of 50 μm using a comma coater.

他方、前述のように作製した固体電解質スラリーの残部についても、コンマコータを用いて、厚み１００μｍの固体電解質グリーンシートに成形した。   On the other hand, the remaining part of the solid electrolyte slurry produced as described above was also formed into a solid electrolyte green sheet having a thickness of 100 μm using a comma coater.

〈試料電池の作製〉
上記の試料１〜７の各々に係る正極グリーンシートおよび固体電解質グリーンシートを組合せて、次のように試料電池を作製した。なお、試料電池は、あくまでも、正極活物質の評価用の電池であり、正確に言うと、一部において電解液を用いている点で全固体電池ではない。 <Production of sample battery>
A sample battery was prepared as follows by combining the positive electrode green sheet and the solid electrolyte green sheet according to each of the above samples 1 to 7. Note that the sample battery is merely a battery for evaluating the positive electrode active material, and to be exact, it is not an all-solid battery in that an electrolyte is used in part.

正極グリーンシートおよび固体電解質グリーンシートを直径１２ｍｍの円形に打ち抜いた後、正極グリーンシートの上に固体電解質グリーンシートを積層し、８０℃の温度で１トンの荷重をかけて熱圧着して積層体を得た。なお、正極活物質の重量は２．５ｍｇ前後となった。   After the positive electrode green sheet and the solid electrolyte green sheet are punched into a circle having a diameter of 12 mm, the solid electrolyte green sheet is laminated on the positive electrode green sheet, and is thermocompression-bonded at a temperature of 80 ° C. with a load of 1 ton. Got. The weight of the positive electrode active material was about 2.5 mg.

次に、積層体を２枚のアルミナ製のセラミック板で挟み込み、酸素をわずかに含む窒素雰囲気下で、５００℃の温度で焼成し、有機物の除去を行なった後、窒素雰囲気下で、６００℃で再び焼成し、焼結体を得た。   Next, the laminate was sandwiched between two alumina ceramic plates, fired at a temperature of 500 ° C. in a nitrogen atmosphere containing a slight amount of oxygen to remove organic substances, and then at 600 ° C. in a nitrogen atmosphere. And fired again to obtain a sintered body.

得られた焼結体を、１００℃の温度で乾燥し、水分を除去した後、電解液を含浸したＰＭＭＡゲル電解質を介して、負極となる金属Ｌｉ板を、この焼結体上に積層し、２０３２型のコインセルで封止して、試料１〜７の各々に係る試料電池を得た。   The obtained sintered body was dried at a temperature of 100 ° C. to remove moisture, and then a metal Li plate serving as a negative electrode was laminated on the sintered body through a PMMA gel electrolyte impregnated with an electrolytic solution. And a 2032 type coin cell to obtain a sample battery according to each of samples 1 to 7.

〈試料電池の評価〉
試料１〜７の各々に係る試料電池について、電圧３．０〜４．７Ｖの範囲で５０μＡの電流で定電流定電圧充放電測定を１００サイクル行なった。 <Evaluation of sample battery>
About the sample battery which concerns on each of the samples 1-7, the constant current constant voltage charge / discharge measurement was performed 100 cycles with the electric current of 50 microamperes in the range of voltage 3.0-4.7V.

表２の「１サイクル目」および「１００サイクル目」の各欄には、それぞれ、上記定電流定電圧充放電測定により求められた１サイクル目および１０サイクル目の各放電容量が示されている。なお、放電容量は正極活物質の重量あたりに換算してある。また、表２の「１００サイクル目／１サイクル目」の欄には、１サイクル目の放電容量に対する１００サイクル目の放電容量の比率［％］が示されている。   In each column of “1st cycle” and “100th cycle” in Table 2, the respective discharge capacities of the first cycle and the 10th cycle obtained by the constant current / constant voltage charge / discharge measurement are shown. . The discharge capacity is converted per weight of the positive electrode active material. In the column of “100th cycle / 1st cycle” in Table 2, the ratio [%] of the discharge capacity at the 100th cycle to the discharge capacity at the 1st cycle is shown.

Figure 2015064992
Figure 2015064992

リチウム含有リン酸バナジウムにおいて、Ｖサイトの一部を他の元素で置換しなかった試料７を除いて、試料１〜６のすべてにおいて、「１００サイクル目／１サイクル目」の値が高く、優れたサイクル安定性を持つことを確認できた。   In the lithium-containing vanadium phosphate, the value of “100th cycle / 1st cycle” is high and excellent in all of Samples 1 to 6 except Sample 7 in which part of the V site was not substituted with another element. It was confirmed that it had cycle stability.

特に、「置換量ｙ」が０．０１〜０．２の範囲にある試料１〜３、５および６では、サイクル安定性がより高く、また、「置換量ｙ」が０．０１〜０．０５といった、より限定的な範囲にある試料１、２、５および６では、サイクル安定性がさらに高くなった。   In particular, Samples 1 to 3, 5, and 6 in which the “substitution amount y” is in the range of 0.01 to 0.2 have higher cycle stability, and the “substitution amount y” is 0.01 to 0.2. Samples 1, 2, 5 and 6 in a more limited range, such as 05, had even higher cycle stability.

これらに対して、「置換量ｙ」が０．２５と最も高く、前述したように、ＸＲＤで異相が見られた正極活物質を用いて構成された試料４では、サイクル安定性は、試料７より優れるものの、試料１〜３、５および６より低い結果となった。   On the other hand, the “substitution amount y” is the highest at 0.25, and as described above, in the sample 4 configured using the positive electrode active material in which a heterogeneous phase was observed by XRD, the cycle stability was 7 Although better, results were lower than Samples 1-3, 5 and 6.

なお、「置換量ｙ」が増加するに応じて、１サイクル目の放電容量が低下する傾向があるが、これは充放電反応（価数変化）に直接関与しない置換元素の割合が増加したためであると推測される。   As the “substitution amount y” increases, the discharge capacity at the first cycle tends to decrease. This is because the ratio of substitution elements not directly involved in the charge / discharge reaction (valence change) increases. Presumed to be.

次に、上記試料２、５、６および７の各々に係る試料電池について、電圧３．０〜４．７Ｖの範囲で５００μＡの電流で定電流定電圧充放電測定を行ない、上記の場合と同様の方法にて、放電容量を求めた。その結果が表３の「５００μＡ」の欄に示されている。表３の「５０μＡ」の欄には、前述のようにして求めた表２の「１サイクル目」の数値がそのまま転記されている。   Next, with respect to the sample batteries according to each of the samples 2, 5, 6 and 7, the constant current and constant voltage charge / discharge measurement was performed at a current of 500 μA in the voltage range of 3.0 to 4.7 V, and the same as in the above case. The discharge capacity was determined by the method. The result is shown in the column of “500 μA” in Table 3. In the column of “50 μA” in Table 3, the value of “First cycle” in Table 2 obtained as described above is directly transferred.

Figure 2015064992
Figure 2015064992

表３からわかるように、Ｖに比べてイオン半径の大きなＮｂおよびＹでそれぞれ置換したリチウム含有リン酸バナジウムを用いて構成された試料２および５では、５００μＡといった高い電流でも放電容量が高く、出力特性が、置換しなかった試料７に比べて高くなった。   As can be seen from Table 3, Samples 2 and 5 constituted by using lithium-containing vanadium phosphate each substituted with Nb and Y having a larger ionic radius than V had a high discharge capacity even at a high current of 500 μA, and the output The characteristics were higher compared to sample 7 which was not substituted.

他方、Ｖに比べてイオン半径の小さなＡｌで置換したリチウム含有リン酸バナジウムを用いて構成された試料６では、出力特性は、置換しなかった試料７と同程度であった。   On the other hand, the sample 6 constituted by using lithium-containing vanadium phosphate substituted with Al having a smaller ion radius than V had the same output characteristics as the sample 7 not substituted.

以上のことから、Ｌｉ３Ｖ２（ＰＯ４）３のＶのサイトの一部を、特にＶより大きなイオン半径を有する６配位元素で置換することで、サイクル安定性を向上させる効果に加えて、固体電池の出力を高めることができることが明らかになった。なお、この効果は、置換元素がＮｂおよびＹの場合に限られることはなく、Ｖと同じ６配位を有する元素で、Ｖよりイオン半径が大きければ、他の元素を用いても同様の効果が得られることが容易に推測できる。 From the above, in addition to the effect of improving cycle stability by replacing a part of the V site of Li 3 V 2 (PO 4 ) 3 with a hexacoordinate element having an ionic radius larger than V in particular. It has become clear that the output of the solid state battery can be increased. This effect is not limited to the case where the substituting elements are Nb and Y. The same effect can be obtained by using other elements as long as the element has the same 6-coordinate as V and has an ionic radius larger than V. Can be easily estimated.

また、Ｖよりイオン半径の小さな元素で置換した場合は、出力特性の向上は大きく見込めないことが明らかになった。   Further, it has been clarified that when the element having a smaller ion radius than V is substituted, the output characteristics cannot be greatly improved.

なお、上記実験例では、固体電解質としてのＬｉ1.5Ａｌ0.5Ｇｅ1.5（ＰＯ４）３の原料粉末は非晶質体であったが、この原料粉末は非晶質体に限られることなく、結晶体であっても同様の効果が得られる。 In the above experimental example, the raw material powder of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 as the solid electrolyte was an amorphous body, but the raw material powder is not limited to an amorphous body, The same effect can be obtained even with the body.

また、この実験例では、スラリー作製時に既にリチウム含有リン酸バナジウムの結晶構造を有するものを用いたが、積層体の焼結時にリチウム含有リン酸バナジウムの結晶構造に変化する前駆体を用いてもよい。   Further, in this experimental example, the one having the crystal structure of lithium-containing vanadium phosphate was used at the time of slurry preparation, but a precursor that changes to the crystal structure of lithium-containing vanadium phosphate at the time of sintering the laminate was also used. Good.

また、実験例においては、リチウム含有リン酸バナジウムの焼成時に加える炭素粉末として、アセチレンブラックを用いたが、炭素粉末としては、焼成時にそのすべてが焼失せずに残存し、焼成後に電子伝導性を有するものなら何を用いてもよい。したがって、たとえば、焼成により電子伝導性を発現する有機化合物を炭素粉末の代わりに用いてもよい。   In the experimental examples, acetylene black was used as the carbon powder to be added at the time of firing lithium-containing vanadium phosphate. However, as the carbon powder, all of the carbon powder remained without being burned off during firing, and the electron conductivity after firing was reduced. Whatever you have can be used. Therefore, for example, an organic compound that exhibits electronic conductivity by firing may be used in place of the carbon powder.

１ 電池積層体
２ 固体電解質層
３ 正極層
４ 負極層 DESCRIPTION OF SYMBOLS 1 Battery laminated body 2 Solid electrolyte layer 3 Positive electrode layer 4 Negative electrode layer

Claims (6)

固体電解質層と、前記固体電解質層を挟んで配置された正極層および負極層と、を備え、
正極活物質として、ナシコン構造を有するリチウム含有リン酸バナジウムを含み、リチウム含有リン酸バナジウムは、Ｖのサイトの一部を、６配位を有する元素で置換したものである、
全固体電池。 A solid electrolyte layer, and a positive electrode layer and a negative electrode layer disposed across the solid electrolyte layer,
As the positive electrode active material, lithium-containing vanadium phosphate having a NASICON structure is included, and the lithium-containing vanadium phosphate is obtained by substituting a part of the V site with an element having 6-coordination.
All solid battery. 置換する前記元素は、Ｍｇ、Ｃａ、Ｓｒ、Ｓｃ、Ｙ、Ｔｉ、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｚｎ、Ｃｄ、Ｉｎ、Ｔｌ、Ｓｎ、Ｐｂ、ＳｂおよびＢｉからなる群から選ばれる少なくとも１種の元素である、請求項１に記載の全固体電池。   The element to be substituted is at least selected from the group consisting of Mg, Ca, Sr, Sc, Y, Ti, Zr, Hf, Nb, Ta, Mo, Zn, Cd, In, Tl, Sn, Pb, Sb, and Bi. The all-solid-state battery of Claim 1 which is 1 type of elements. 置換する前記元素は、Ｍｇ、Ｃａ、Ｓｒ、Ｓｃ、Ｙ、Ｚｒ、Ｈｆ、Ｚｎ、Ｃｄ、Ｉｎ、ＳｎおよびＰｂからなる群から選ばれる少なくとも１種の元素である、請求項１に記載の全固体電池。   2. The whole element according to claim 1, wherein the element to be substituted is at least one element selected from the group consisting of Mg, Ca, Sr, Sc, Y, Zr, Hf, Zn, Cd, In, Sn, and Pb. Solid battery. 前記リチウム含有リン酸バナジウムは、一般式：Ｌｉ3+xＶ2-yＭy（ＰＯ4）3（ただし、ｘ：−０．４≦ｘ≦０．２、ｙ：０．００＜ｙ≦０．２０、Ｍ：６配位を有する元素）で表されるものである、請求項１ないし３のいずれかに記載の全固体電池。 The lithium-containing vanadium phosphate has a general formula: Li 3 + x V 2- y My (PO 4 ) 3 (where x: −0.4 ≦ x ≦ 0.2, y: 0.00 <y ≦ The all-solid-state battery in any one of Claims 1 thru | or 3 which is represented by 0.20, M: 6 element. 前記ｙは、０．０１≦ｙ≦０．０５である、請求項４に記載の全固体電池。   The all-solid-state battery according to claim 4, wherein y is 0.01 ≦ y ≦ 0.05. 少なくとも前記正極層と前記固体電解質層とが焼結によって接合されている、請求項１ないし５のいずれかに記載の全固体電池。   6. The all solid state battery according to claim 1, wherein at least the positive electrode layer and the solid electrolyte layer are joined by sintering.
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