JPH0412057A - Electroconductive complex sintered material of lithium ion - Google Patents
Electroconductive complex sintered material of lithium ionInfo
- Publication number
- JPH0412057A JPH0412057A JP2110887A JP11088790A JPH0412057A JP H0412057 A JPH0412057 A JP H0412057A JP 2110887 A JP2110887 A JP 2110887A JP 11088790 A JP11088790 A JP 11088790A JP H0412057 A JPH0412057 A JP H0412057A
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- lithium ion
- lithium
- li2o
- conductivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002131 composite material Substances 0.000 claims description 7
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 16
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 239000010416 ion conductor Substances 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 241000894007 species Species 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100481408 Danio rerio tie2 gene Proteins 0.000 description 1
- 229910011763 Li2 O Inorganic materials 0.000 description 1
- 101100481410 Mus musculus Tek gene Proteins 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005372 isotope separation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Primary Cells (AREA)
- Secondary Cells (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Conductive Materials (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、リチウムの同位体の分離などに使用できる固
体電解質、または固体電池やイオンセンサーの材料とな
る物質に関する、
［従来の技術１
従来、リチウムイオン導電体としては、リチウム電池の
固体電解質としてヨウ化リチウムが用いられており、チ
ッ化リチウム系のものについての提案もある（特開昭５
６−１２８５８０号）。しかし、これらは常温ではある
程度のリチウム導電性を示すが、分解温度が低いので、
高温で使用することはできない、リチウム同位体の分離
には３（）０°Ｃ以上の高温での使用に耐えるものでな
ければならず、セラミックス系でリチウム導電性を有す
るらのが期待されており、一部提案もなされている（特
開昭５６−１６４０１５号、５７−２Ｏ０２２２号）。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a solid electrolyte that can be used for the separation of lithium isotopes, or a material that is a material for solid batteries and ion sensors. As a lithium ion conductor, lithium iodide is used as a solid electrolyte in lithium batteries, and there are also proposals for lithium nitride-based materials (Japanese Patent Application Laid-Open No.
No. 6-128580). However, although these exhibit some degree of lithium conductivity at room temperature, their decomposition temperature is low, so
For the separation of lithium isotopes, which cannot be used at high temperatures, it must be able to withstand use at high temperatures of 3 ()0°C or higher, and ceramic-based materials with lithium conductivity are expected. Some proposals have also been made (Japanese Unexamined Patent Publication Nos. 56-164015 and 57-2O0222).
［発明が解決しようとする課題］
従来のリチウム導電体は、常温ではリチウム導電性を示
しても高温においては使用できなかったり、またセラミ
ックス系のものでも強度において不十分であって、現実
には高温で使用できるリチウム導電体が供給されていな
いのが実状である。[Problems to be solved by the invention] Although conventional lithium conductors exhibit lithium conductivity at room temperature, they cannot be used at high temperatures, and even ceramic-based materials are insufficient in strength and cannot be used in reality. The reality is that lithium conductors that can be used at high temperatures are not available.
本発明は、従来のリチウムイオン導電体の欠点を解消し
、高温においても安定で、導電率が高く、しかも十分な
強度を有し、材料の信頼性の上でも優れたリチウムイオ
ン導電性セラミックス焼結体を提供することを目的とし
てなされたものである。The present invention eliminates the drawbacks of conventional lithium ion conductors, and creates a lithium ion conductive ceramic sintered material that is stable even at high temperatures, has high conductivity, has sufficient strength, and has excellent material reliability. This was done for the purpose of providing unity.
［課題を解決するための手段］
ＬｉｚＯを含むリチウムイオン導電体としては、Ｌｉ２
Ｏ・３ＴｉＣｈ（ラムスプライト型構造）や２Ｌｉｚ０
・５ Ｔ ｉｏ ２の組成のものが知られているが、こ
れらは強度が者しく小さいために実用に供することがで
きない。[Means for solving the problem] As a lithium ion conductor containing LizO, Li2
O・3TiCh (ram sprite type structure) and 2Liz0
・Those having a composition of 5 T io 2 are known, but these cannot be put to practical use because their strength is extremely low.
本発明者は、Ｌ ｉ２Ｏを含む各種の組成物を検討した
結果、Ｌｉ２Ｏ−ＡＲ２Ｏ３−ＴｉＯ２の系において、
Ｌ ｉ２Ｏ Ａ １２Ｏ３・４ Ｔ ｉｏ ｚトル＋
ル（Ｔ ｉｏ ２）の２相の結晶相を含む焼結体がリ
チウムイオン導電性と強度を合わせ持つことを見出し、
本発明に到達したものである。As a result of studying various compositions containing Li2O, the present inventor found that in the Li2O-AR2O3-TiO2 system,
L i2O A 12O3・4 T io ztor+
discovered that a sintered body containing two crystal phases of T io 2 has both lithium ion conductivity and strength,
This has led to the present invention.
スナワチ本発明ハ、Ｌｉ２Ｏ’Ａｌ２Ｏｉ’４Ｔｉｅ。The present invention is Li2O'Al2Oi'4Tie.
とルチル（ＴｉＯ２）の２相の結晶相を含むことを特徴
とするリチウムイオン導電性複合焼結体に関する。The present invention relates to a lithium ion conductive composite sintered body characterized by containing two crystal phases of rutile (TiO2) and rutile (TiO2).
本発明者の研究によれば、１１００℃以上での焼結晶で
は、一般式Ｌ １２ＡＬ工Ｔｉ、ｏ ｔｌ＋ｖｘ＋２ｙ
、で示されるＬｉ２ＯとＡｌ２Ｏ，とＴｉＯ２からなる
結晶構造のものは、Ｌｉ２Ａ１２Ｔｉ、０１２（上記一
般式において、ｘ＝ｌ、ｙ＝４）のもの、すなわち、Ｌ
ｉ２Ｏ−Ａｌ２Ｏ，・４ＴｉＣｈＬＪ’存在しないよう
でアル。Ｌ：２ＯａＡｌ２Ｏ３・４ＴｉＯ２の結晶にラ
イては、その構造が具体的にどのようなものかは明確で
ないが、この結晶相については文献による報告もあり（
Ｊ ｏｕｒｎａｌ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ
ＣｅｒａｍｉｃＳｏｃｉｅｔｙ Ｖｏｌ、４３． Ｎｏ
、１２． ＰＰ、６１１−６１４（＋９６０））、また
Ｘ線回折で同定することができる。According to the research of the present inventor, in a fired crystal at 1100°C or higher, the general formula L 12AL Ti, o tl + vx + 2y
The crystal structure consisting of Li2O, Al2O, and TiO2 shown in
i2O-Al2O, 4TiChLJ' does not seem to exist. Regarding the L:2OaAl2O3/4TiO2 crystal, it is not clear what its structure is, but there are reports in the literature regarding this crystalline phase (
Journal of the American
Ceramic Society Vol. 43. No
, 12. PP, 611-614 (+960)), and can also be identified by X-ray diffraction.
Ｌ ｉ２Ｏ ’Ａ １２Ｏ 、・４ＴｉＯ２とルチル（
Ｔ ｉｏ 、）の２相の結晶からなる焼結体は、Ｌ ｉ
２Ｏ ：Ａ １２Ｏ 、：Ｔ ｉ Ｏ２の比が１：１：
４よりＴｉＯ２を多く含むように配合した原料を、１１
００℃以上の温度で緻密に焼結することにより作製する
ことができる。例えば、アルミナ（Ａ［２Ｏ，）粉体と
チタニア（Ｔ１０□）粉体を混合し、これにリチウム塩
（硝酸リチウム、塩化リチウム、炭酸リチウム、水酸化
リチウムなど）を添加して、チタン酸アルミニウムを生
成しない１３００℃以下の温度で、かつ十分に緻密化が
進行する１１００℃以上の温度で焼成することにより製
造することができる。L i2O 'A 12O , 4TiO2 and rutile (
A sintered body consisting of two-phase crystals of L i
The ratio of 2O:A 12O,:T i O2 is 1:1:
11 contains raw materials containing more TiO2 than 4.
It can be produced by densely sintering at a temperature of 00°C or higher. For example, by mixing alumina (A[2O,) powder and titania (T10□) powder and adding lithium salts (lithium nitrate, lithium chloride, lithium carbonate, lithium hydroxide, etc.) to this, aluminum titanate is produced. It can be produced by firing at a temperature of 1,300° C. or lower, which does not produce any carbon, and at a temperature of 1,100° C. or higher, where densification sufficiently progresses.
本発明者の研究によれば、例えｊＩ、原料として、Ａ
１２Ｏ ’ｓとＴｉＯ２とＬｉＮ０１をＬ ｉ２Ｏ ：
Ａ １２Ｏ３：ＴｉＯ２の比がｌ：１：４．１：’）も
Ｔｉｏ２が多いｍ成となるように配合して焼結した場合
には、６００℃までに窒素酸化物が飛び、８００ ’Ｃ
で２Ｌｉ２Ｏ・５ Ｔ ｉ Ｏ２とこれに加えてアナタ
ーゼ（ＴｉＯ２）が生成し、アナターゼの一部はルチル
（Ｔ ｉ Ｏ２）となる。According to the research of the present inventor, even if jI, as a raw material, A
12O's, TiO2 and LiN01:
A: If the ratio of 12O3:TiO2 is 1:1:4.1:'), nitrogen oxides will fly off by 600°C, and the temperature will increase at 800'C.
In addition to 2Li2O.5T i O2, anatase (TiO2) is generated, and a part of the anatase becomes rutile (T i O2).
１０００°Ｃでは、Ｌ ｉ、ｏ・３ＴｉＯ，とルチルの
２相構造となるが、１１００°Ｃ以上では、Ｌｉ２Ｏ・
Ｌｉ２Ｏ．・４ＴｉＯ２の他にＴ ｉｏ ２（ルチル）
が含まれる２相構造となる。At 1000°C, it becomes a two-phase structure of Li,o・3TiO, and rutile, but at 1100°C or higher, Li2O・
Li2O.・In addition to 4TiO2, T io 2 (rutile)
It has a two-phase structure containing.
実験によれば、Ｌｉ２Ｏ：、’Ｍ’２Ｏ．：ＴｉＯ２の
配合比が１ ：１ ：４よりもＴ ｉ Ｏ２のみ多い組
成物の１１００〜１３００℃での焼結晶は、上記２相楕
遣以外はとらない。このものはリチウムイオン導電性に
加えて優れた強度を有する焼結体となる。According to experiments, Li2O:, 'M'2O. :The composition in which only TiO2 is more than 1:1:4 has a sintered crystal at 1100 to 1300[deg.] C. except for the above-mentioned two-phase ellipse. This material becomes a sintered body that has excellent strength in addition to lithium ion conductivity.
リチウムイオン電導を可能としているのは、Ｌ１２Ｏ・
Ａｌｘ０ｚ・４ Ｔ ｉ Ｏ２であり、ＴｉＯ２の量が
あまり多くなると、電子電導の割合が多くなってしまう
ので、実用上十分なリチウムイオン電導のためには、Ｌ
ｉ２Ｏ’ＡｆＶ２Ｏ．・４ Ｔ ＋ ０２結晶１モルに
対してルチルが４モルよりより少なく、すなわち焼結体
全体の重量に対するＬ ｉ ２Ｏ−Ａ ｌ ２Ｏ３・４
Ｔｉｅ２結晶の含有量が５８重量％以上となるようにす
るのが望ましい。また、ＴｉＯ２は強度に寄与している
と考えられ、十分な強度を得るためには、Ｌ１２Ｏ・Ａ
ｌ２Ｏ，・４ Ｔ ＋ ０２結晶１モルに対してルチル
が０．６モルより多く、すなわち、焼結体全体の重量に
対するＬ ｉ２Ｏ ’Ａ ｎ２Ｏ３・４ Ｔ ｉ Ｏ２
結晶の含有量か９０重量％以下となるようにするのが望
ましい。What makes lithium ion conduction possible is L12O.
Alx0z・4T i O2, and if the amount of TiO2 is too large, the proportion of electronic conduction will increase, so for practically sufficient lithium ion conduction, L
i2O'AfV2O.・4 Rutile is less than 4 moles per mole of T + 02 crystals, i.e. L i 2O-A l 2O3.4 with respect to the weight of the entire sintered body
It is desirable that the content of Tie2 crystals is 58% by weight or more. In addition, TiO2 is thought to contribute to strength, and in order to obtain sufficient strength, L12O・A
l2O,・4 T + 02 Rutile is more than 0.6 mole per mole of crystal, that is, L i2O 'A n2O3・4 T i O2 with respect to the weight of the entire sintered body
It is desirable that the crystal content be 90% by weight or less.
ＡＩ、Ｏ，の配合比も２Ｏ％程度の範囲内での変動は可
能であり、従って、原料の配合は、焼結後にＬｉ２Ｏ：
／Ｍ２Ｏ．：ＴｉＯ２がモル比で１：０．８〜１．２：
４．６〜８となるように行う。この比率の範囲において
八１２Ｏ．のモル比が１より大きい場合には、α相ある
いはγ相アルミナがわずかに形成される可能性があり、
また、Ａｌ２Ｏ３のモル比が１より小さい場合には、Ｌ
ｉ２Ｏが過剰となり、わずかに別の結晶のものが形成さ
れる可能性がある。このような別の結晶の存在は微量で
あれば、焼結体の性能に与える影響は少ないが、好まし
いものではないので、原料の配合は、焼結体中、Ｌｉ２
Ｏ：Ａ １！２Ｏ ｓ：Ｔ ｉｏ ２のモル比が１ ：
１ ：４．６〜８となるようにするのが望ましく、特に
望ましくは、１：１：６付近である。The blending ratio of AI and O can also be varied within a range of about 20%, so the blending of raw materials should be Li2O:
/M2O. :TiO2 molar ratio: 1:0.8 to 1.2:
4. Do this so that the ratio is 6 to 8. In this ratio range, 812O. If the molar ratio of
Furthermore, when the molar ratio of Al2O3 is less than 1, L
There may be an excess of i2O and the formation of slightly different crystals. If the presence of such other crystals is in a small amount, it will have little effect on the performance of the sintered body, but it is not preferable.
The molar ratio of O:A1!2Os:Tio2 is 1:
It is desirable that the ratio be 1:4.6 to 8, and particularly preferably around 1:1:6.
１：１：４よりもＴｉＯ□が多く、かつＬｉ２Ｏがかな
り過剰な組成のもの、例えばＬｉ２Ｏ：Ａｌ２Ｏ３：Ｔ
ｉＯ２のモル比が２：１：６の配合比のものは、１１０
０℃以上の焼結ニオイテ、Ｌ １ｚｏ−Ａ （１２ｏ
ｚ、４ Ｔ ｉ Ｏ２の他にＬ ｌ ２Ｏ・３Ｔ１０２
＜ラムスプライト型）を含む構造となる。この２相構遺
では、リチウム導電体を示すが、強度がないので、リチ
ウム導電体として実用性がない。A composition with more TiO□ than 1:1:4 and a considerable excess of Li2O, such as Li2O:Al2O3:T
The one with a molar ratio of iO2 of 2:1:6 is 110
Sintered nitrite at 0°C or higher, L 1zo-A (12o
z, 4 In addition to T i O2, L l 2O・3T102
<Ram sprite type). Although this two-phase structure represents a lithium conductor, it lacks strength and is therefore not practical as a lithium conductor.
上記よりもさらにＬ ｉ ２Ｏのモル比が多（なると、
Ｌ ｉ２Ｏ４’ ｉｏ ７．２Ｌｉ２Ｏ・５ Ｔ ＋
０２．２Ｌｉ、Ｏ・Ａ １２Ｏ３などが形成されるよう
になり、Ｌ１□Ｏ・Ａｌ２Ｏ３・４ＴｉＯ２結晶は形成
されない。The molar ratio of Li 2O is even higher than the above (if
L i2O4' io 7.2Li2O・5 T +
02.2Li, O·A 12O3, etc. are formed, and L1□O·Al2O3·4TiO2 crystals are not formed.
影緩良勉１１
本発明において焼結体のイオン電導度はインピーダンス
アナライザーを用いて、測定温度、周波数を変化させて
、交流イオン電導度を測定することにより行った。他の
データは以下のようにして確認あるいは測定した。Tsutomu Kageyuru 11 In the present invention, the ionic conductivity of the sintered body was measured by measuring alternating current ionic conductivity using an impedance analyzer while changing the measurement temperature and frequency. Other data were confirmed or measured as follows.
（リチウムイオン導電種の確認）
イオン導電種がリチウムイオンであることの確認は次の
ようにして行った。リチウムイオンは白金と反応してＬ
＋ ２Ｐ ｔ Ｏ３という化合物を作ることが知られ
ている。電極として白金を用いて、両電極間に直流電圧
を印加して分極を起こさせた場合、負極側にＬ ｌ ２
Ｐ ｔ Ｏ：ｌが生成していれば、リチウムイオンが
導電種として働いていると確認できるので、直流電圧を
印加して一定時間経過後の正負の電極についてＸ線構造
解析を行うことによりイテっだ。(Confirmation of lithium ion conductive species) Confirmation that the ion conductive species was lithium ions was performed as follows. Lithium ions react with platinum to form L
+ 2P t O3 is known to be produced. When platinum is used as an electrode and a DC voltage is applied between both electrodes to cause polarization, L l 2 on the negative electrode side.
If P t O:l is generated, it can be confirmed that lithium ions are working as a conductive species. Therefore, it is possible to determine whether it is possible by applying a DC voltage and performing X-ray structural analysis on the positive and negative electrodes after a certain period of time. Yes.
（輸率の計算）
輸率とは全型導度（イオン電導度十電子電導度）に対す
るイオン電導度の比であり、従ってイオン電導度のみで
あれば輸率は１となる。イオン電導と電子電導の混合電
子体であれば輸率は１より小さくなる。そして、混合電
子体の場合、交流回路で測定した電導度は、イオン電導
度σｉと電子電導層σｅとの混合電導度σｔ＝σｉ十σ
ｅである。直流回路を用いると分極を生じるので、イオ
ン電導度σ１は時間がたつにつれて０に近付き、理論的
には時間がωのときの電導度がσｅとなる。本発明の系
では、３０分程度経過すると電導度が一定ｌこなったの
で、この時の電導度の値をσｅとして、以下の式で輸率
を計算した。(Calculation of transport number) The transport number is the ratio of the ionic conductivity to the total type conductivity (ion conductivity and ten-electron conductivity). Therefore, if there is only the ionic conductivity, the transport number is 1. If it is a mixed electron body with ionic conduction and electronic conduction, the transference number will be smaller than 1. In the case of a mixed electronic body, the conductivity measured in an AC circuit is the mixed conductivity of the ionic conductivity σi and the electronic conductive layer σe = σi + σ
It is e. Since polarization occurs when a DC circuit is used, the ionic conductivity σ1 approaches 0 as time passes, and theoretically, the conductivity when the time is ω becomes σe. In the system of the present invention, the conductivity reached a constant value after about 30 minutes, so the transference number was calculated using the following formula, using the value of conductivity at this time as σe.
輸率［＝σｉ／（σｉ十σｅ）＝（σＥ−σｅ）／σｔ
＝１−Ｒｔ／Ｒｅ ・−＝ （１）ここで、ＲＬ
は、インピーダンスアナライザーで測定した交流回路抵
抗値であり、Ｒｅは、直流回路につなぎ３０分経過後一
定となった時の抵抗値である。Transference number [=σi/(σi + σe)=(σE−σe)/σt
=1-Rt/Re ・-= (1) Here, RL
is the AC circuit resistance value measured with an impedance analyzer, and Re is the resistance value when it becomes constant after 30 minutes have passed since it was connected to the DC circuit.
［作用１
本発明の複合焼結体は、Ｌｉ２Ｏ’Ａｌ２Ｏ，・４Ｔｉ
Ｏ２の結晶とルチルの結晶の２相からなり、優れたリチ
ウムイオン導電性と強度を示すものである。これは、Ｌ
ｉ２Ｏ ’Ａ １２Ｏ３・４ＴｉＯ２結晶がその内部
において、結晶中のリチウムイオンの移動を可能として
おり、これによりリチウムイオン導電性を示すものと解
される。[Effect 1 The composite sintered body of the present invention is made of Li2O'Al2O,.4Ti
It consists of two phases: O2 crystals and rutile crystals, and exhibits excellent lithium ion conductivity and strength. This is L
It is understood that the i2O'A 12O3.4TiO2 crystal allows lithium ions to move within the crystal, thereby exhibiting lithium ion conductivity.
また、強度に関しては、本発明の複合焼結体は」−記Ｌ
ｉｚＯ’ＡＬＯ，・４ＴｉＯ，とルチルとの組み合わせ
が強度を与えている。これに対して、Ｌｉ２Ｏ’Ａｌ２
Ｏ，・４ＴｉＯ２結晶を含むものであっても、Ｌｉ２Ｏ
−ＡＮ２Ｏｓ・４ＴｉＯ２結晶単独のもの或いはこれと
ルチル以外の結晶、例えば！、、、ｉ２Ｏ・３ Ｔ ｉ
Ｏ２との組み合わせのものは本発明品に比べると強度
が１７１０以下程度と者しく小さい。In addition, regarding strength, the composite sintered body of the present invention is
The combination of izO'ALO, 4TiO, and rutile provides strength. On the other hand, Li2O'Al2
Even if it contains O, 4TiO2 crystal, Li2O
-AN2Os・4TiO2 crystal alone or crystals other than rutile, for example! ,,,i2O・3 T i
The strength of the combination with O2 is about 1710 or less, which is significantly lower than the product of the present invention.
本発明にかかる複合焼結体は、Ｌｉ２Ｏ’Ａ（２Ｏ゜・
４ＴｉＯ２結晶とルチル結晶との組み合わせにより、高
温での使用に耐えるリチウムイオン導電体が提供される
。The composite sintered body according to the present invention has Li2O'A (2O°・
The combination of 4TiO2 and rutile crystals provides a lithium ion conductor that can withstand use at high temperatures.
［実施例１］
原料として、それぞれ９９．９％以上の純度のチタニア
（ＴｉＯ２）、アルミナ（１２Ｏ，）及び硝酸リチウム
（ＬｉＮ○、）を、焼結体におけるＬｉ、Ｏ：Ａｌ２Ｏ
５： Ｔ ｉ Ｏ２のモル比が１：１：６となるように
配合し、水に溶解した。これをボールミルで十分混合し
たのち、乾燥器（１２Ｏ℃）で乾燥させた。[Example 1] As raw materials, titania (TiO2), alumina (12O,) and lithium nitrate (LiN○,) each with a purity of 99.9% or more were used as raw materials in a sintered body with Li, O:Al2O
5: T i O2 was blended in a molar ratio of 1:1:6 and dissolved in water. After thoroughly mixing this with a ball mill, it was dried in a drier (120° C.).
次に８００℃で１時間仮焼し、粉砕、成形の後、１２Ｏ
０℃で２時間焼成してｍ密な焼結体を得た。Next, it was calcined at 800℃ for 1 hour, crushed and shaped, and then 12O
A dense sintered body was obtained by firing at 0° C. for 2 hours.
この焼結体の結晶構造をＸ線回折により調べたところ、
第１図のような回折図となり、△で示したＬ ｉ ２Ａ
１２Ｔ ｉ 、Ｏ１２（Ｌ ｉ ２Ｏ−Ａ （１２Ｏ
ｖ・４ＴｉＯ２）のピークと、○で示したＴｉＯ□（ル
チル）のピークにより、これらの２相からなる複合焼結
体となっていることが確認された。When the crystal structure of this sintered body was investigated by X-ray diffraction, it was found that
The diffraction diagram is as shown in Figure 1, and L i 2A is indicated by △.
12T i , O12(L i 2O−A (12O
It was confirmed by the peak of v·4TiO2) and the peak of TiO□ (rutile) indicated by ◯ that it was a composite sintered body consisting of these two phases.
インビーグンスアナライザー（Ｗｉ河ヒューレソトバッ
カード社製、ＬＦ−４１９２Ａ）を用いて、上記の焼結
体の交流イオン電導度を測定した。なお、測定試料とし
ては、直径２Ｏｍｍ、厚さＩＩのベレットを用い、電極
は白金ペーストを用い９００℃で２Ｏ分焼成しその上に
白金の網をかぶせ再焼成し、それに白金線をからませて
その線を測定装置まで延ばした。The alternating current ionic conductivity of the above sintered body was measured using an Invigorance Analyzer (LF-4192A, manufactured by Wire Sotobackard). The measurement sample used was a pellet with a diameter of 20 mm and a thickness of II. The electrode was made of platinum paste, fired at 900°C for 20 minutes, covered with a platinum mesh, fired again, and entwined with a platinum wire. The line was extended to the measuring device.
まず、２Ｏ℃から８００℃まで上げ下げを繰り返し安定
性について評価したところ、はとんど劣化が見られず、
温度の上下に対して安定であった。First, when we repeatedly raised and lowered the temperature from 20°C to 800°C and evaluated its stability, we found that there was almost no deterioration.
It was stable against temperature fluctuations.
また、ｘｉ回折により、正極に変化は見られず、負極に
はＬｉ２ＰｔＯｓのピークが表れたのでリチウムイオン
が導電種であると確認された。Moreover, no change was observed in the positive electrode by xi diffraction, and a peak of Li2PtOs appeared in the negative electrode, so it was confirmed that lithium ions were the conductive species.
測定周波数範囲は１（１２ｋＨｚから１０’ｋＨｚ、測
定温度範囲は２Ｏ〜６００℃とした。この焼結体の導電
率を示すグラフを第２図に示した。１２図から、導電率
は熱活性化型の温度依存性を示し、温度が高い程導電率
が大きい。また、測定周波数については周波数依存性を
示しているが、温度が高い程周波数依存性は小さく、こ
のことは、イオンと電子の混合電子体であることを示し
ている。The measurement frequency range was 1 (12 kHz to 10' kHz, and the measurement temperature range was 20 to 600°C. A graph showing the electrical conductivity of this sintered body is shown in Figure 2. From Figure 12, the electrical conductivity is determined by thermal activation. The higher the temperature, the greater the conductivity.Also, the measurement frequency shows frequency dependence, but the higher the temperature, the smaller the frequency dependence. This shows that it is a mixed electron body.
輸率に計算についての上記（１）式に基づき、イオンの
輸率は０．９９８と計算され、イオン電導が大きく支配
していると結論することができる。Based on the above formula (1) for calculating the transference number, the transference number of the ion is calculated to be 0.998, and it can be concluded that ion conduction is largely dominant.
」二記焼結体の強度を、曲げ試験機（インストロン社製
、１１８５）を用いて、４．２ｍ＋ａＸ３．２ｍｍＸ２
４．７ｍＬａの大きさの測定試料について、支点間鉗離
１６１、クロスヘツド速度０．５ｍｍ／ｍｉｎで３点曲
げ試験により測定したところ１３．２ｋＦＩ／ｎ＋＋ａ
２（１２９，４ＭＰ＆）であった。The strength of the sintered body was measured using a bending tester (manufactured by Instron, 1185) at 4.2 m + a x 3.2 mm x 2.
A measurement sample with a size of 4.7 mLa was measured by a 3-point bending test with a fulcrum separation of 161 and a crosshead speed of 0.5 mm/min, and the result was 13.2 kFI/n++a.
2 (129,4MP&).
［比較例１］
焼結体中のＬ ＋ ２Ｏ ： Ａ ｅ ２Ｏ 、’、
Ｔ ｉ Ｏ２のモル比が２：１：６となるように原料を
配合した他は実施例１と同様にして焼結体を作製した。[Comparative Example 1] L + 2O in the sintered body: A e 2O,',
A sintered body was produced in the same manner as in Example 1, except that the raw materials were mixed so that the molar ratio of T i O2 was 2:1:6.
この焼結体の結晶構造をＸ＃！回折で調べたところ、第
３図のような＠Ｊ ｔｆｒ ｍとなり、△で示すＬｉ２
Ａｆ２Ｔｉ、０．２（Ｌｉ２Ｏ−／Ｍ２Ｏｆｆ、４Ｔｉ
０２）のビー１と、×テ示すＬ ｉ、Ｔ ｉ、０７（Ｌ
ｉ２Ｏ・３ＴｉＯ２）のピークにより、これら２相か
らなっていることが確認された。導電率は実施例１の場
合とは１！′同様な傾向を示し、イオンの輸率は０．９
９８と計算された。しかし、この焼結体は実施例１と同
様にして強度を測定したところ、０．６６ｋｇ／ｍｍ２
（６，４７ＭＰａ）と非常に低く、？ｒ種の用途に用い
ることができないものであった。The crystal structure of this sintered body is X#! When examined by diffraction, the result is @J tfr m as shown in Figure 3, and Li2 is shown by △.
Af2Ti, 0.2(Li2O-/M2Off, 4Ti
02) Be 1, ×T indicates L i, T i, 07 (L
The peak of i2O.3TiO2) confirmed that it consisted of these two phases. The conductivity is 1 compared to Example 1! 'Showing a similar tendency, the transference number of the ion is 0.9
It was calculated as 98. However, when the strength of this sintered body was measured in the same manner as in Example 1, it was found to be 0.66 kg/mm2.
(6.47MPa), which is very low. It could not be used for r types of applications.
［比較例２］
焼結体中ノＬ Ｉ ２Ｏ ： Ａ １２Ｏ３ ： Ｔ
ｉ Ｏ２（１’） モル比７！ｌ’１ ：１ ：４とな
るように原料を配合した他は、実施例１と同様にして焼
結体を作製した。この焼結体ノｕ 晶Ｍ 造ハＸ ｔｌ
Ａ 回折ノ結果、Ｌ ｉ２Ｏ−Ａ １２Ｏ、−４Ｔｉｅ
、のピークを示した。導電率は実施例１と同様な傾向で
、実施例１よりもやや高い値を示した。[Comparative Example 2] L I 2O : A 12O3 : T in the sintered body
i O2(1') molar ratio 7! A sintered body was produced in the same manner as in Example 1, except that the raw materials were mixed in a ratio of l'1:1:4. This sintered body crystal M
A Diffraction results, Li2O-A 12O, -4Tie
, showed a peak of . The electrical conductivity had the same tendency as Example 1, and showed a slightly higher value than Example 1.
しかし、この焼結体は実施例１と同様にして強度を測定
したところ、１．６２ｋｙ／ｌＩＩ＋１２（１５，９Ｍ
Ｐａ＞と非常に低く、実際の使用には耐えないもので
あった。However, when the strength of this sintered body was measured in the same manner as in Example 1, it was found to be 1.62ky/lII+12 (15.9M
Pa>, which was extremely low and could not withstand actual use.
［発明の効果］
本発明にかかるリチウムイオン導電性複合焼結体は、優
れたリチウムイオン導電性に加えて、高い強度を有する
ので、信頼性のある材料として、固体電解質等に用いる
ことができる。さらに緻密に焼結されたセラミックスで
あるため、高温でのリチウムの同位体分離や高温センサ
ー等の分野において用いるのに好適である。[Effects of the Invention] The lithium ion conductive composite sintered body according to the present invention has high strength in addition to excellent lithium ion conductivity, so it can be used as a reliable material for solid electrolytes, etc. . Furthermore, since it is a densely sintered ceramic, it is suitable for use in fields such as lithium isotope separation and high-temperature sensors.
第１図は、実施例１の焼結体のＸ線回折図であり、第２
メは、その焼結体の導電率を示すグラフである。
第３図は、比較例１の焼結体のＸ線回折図である。
第
図
回杭−亀皮
第
図
肩友教［ｋ Ｈｚ〕FIG. 1 is an X-ray diffraction diagram of the sintered body of Example 1, and FIG.
Figure 4 is a graph showing the electrical conductivity of the sintered body. FIG. 3 is an X-ray diffraction diagram of the sintered body of Comparative Example 1. Diagram times pile - turtle skin diagram Shoulder Yukyo [k Hz]
Claims (1)
（ＴｉＯ＿２）の２相の結晶相を含むことを特徴とする
リチウムイオン導電性複合焼結体。A lithium ion conductive composite sintered body characterized by containing two crystal phases: Li_2O.Al_2O_3.4TiO_2 and rutile (TiO_2).
Priority Applications (1)
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|---|---|---|---|
| JP2110887A JP2944142B2 (en) | 1990-04-26 | 1990-04-26 | Lithium ion conductive composite sintered body |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2110887A JP2944142B2 (en) | 1990-04-26 | 1990-04-26 | Lithium ion conductive composite sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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| JP2944142B2 JP2944142B2 (en) | 1999-08-30 |
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ID=14547212
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7224307B2 (en) | 2000-12-25 | 2007-05-29 | Sony Corporation | Electronic device |
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|---|---|
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