JPH03246868A - Lithium ion conductive solid electrolyte material - Google Patents
Lithium ion conductive solid electrolyte materialInfo
- Publication number
- JPH03246868A JPH03246868A JP2042646A JP4264690A JPH03246868A JP H03246868 A JPH03246868 A JP H03246868A JP 2042646 A JP2042646 A JP 2042646A JP 4264690 A JP4264690 A JP 4264690A JP H03246868 A JPH03246868 A JP H03246868A
- Authority
- JP
- Japan
- Prior art keywords
- lithium ion
- solid electrolyte
- conductance
- ion conductive
- conductive solid
- 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.)
- Pending
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 229910052745 lead Inorganic materials 0.000 abstract description 3
- 229910012666 LiTi2P3O12 Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002228 NASICON Substances 0.000 description 2
- 244000299461 Theobroma cacao Species 0.000 description 2
- 235000005764 Theobroma cacao ssp. cacao Nutrition 0.000 description 2
- 235000005767 Theobroma cacao ssp. sphaerocarpum Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 235000001046 cacaotero Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910008102 Li3 N Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/185—Cells with non-aqueous electrolyte with solid electrolyte with oxides, hydroxides or oxysalts as solid electrolytes
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Conductive Materials (AREA)
- Primary Cells (AREA)
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の産業上利用分野）
本発明はリチウムイオン導電性固体電解質材料、特にコ
ンダクタンスが大きく、化学的に安定な材料にに関する
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field of the Invention) The present invention relates to a lithium ion conductive solid electrolyte material, particularly a material having high conductance and being chemically stable.
（発明の従来技術および問題点）
リチウムを負極活物質として用い、電解質としてリチウ
ムイオン導電性の固体電解質を用いた固体電池は、高エ
ネルギー密度であり、液漏れがなく、小型薄型にできる
等の点で、非常に利点が多い。(Prior art and problems of the invention) A solid-state battery using lithium as a negative electrode active material and a lithium ion conductive solid electrolyte as an electrolyte has high energy density, no leakage, and can be made small and thin. There are many advantages in this respect.
このような固体電池への応用を目的としてリチウムイオ
ン導電性固体電解質材料の開発が注目されている。しか
し、現在のところ、リチウムイオン導電性固体電解質材
料は得られておらず、僅かに、４０ｍｏ１％のＡｌ２Ｏ
３を添加したＬｉＩのみがリチウム固体電池に応用され
、実用されているにすぎない。The development of lithium ion conductive solid electrolyte materials is attracting attention for application to such solid-state batteries. However, at present, no lithium ion conductive solid electrolyte material has been obtained, and only 40 mo1% Al2O
Only LiI to which 3 is added has been applied to lithium solid-state batteries and is in practical use.
リチウムイオン導電性の固体電解質材料として、Ｌｉ３
Ｎ、ＬｉＡｌ５ｉ０４等が知られているが、Ｌｉ３Ｎは
導電率は大きいが、分解電圧が低いこと、ＬｉＡｌ５ｉ
０４は室温での導電率が１Ｏ−９Ｓ ／ ｃ ｍ以下と
小さく、いずれも固体電池への適用はなされていない。As a lithium ion conductive solid electrolyte material, Li3
N, LiAl5i04, etc. are known, but Li3N has high conductivity but low decomposition voltage, and LiAl5i
04 has a low conductivity at room temperature of 1O-9S/cm or less, and none of them have been applied to solid-state batteries.
近年、ナトリウムイオン導電性の固体電解質材料として
知られているＮＡＳＩＣＯＮ系材料（Ｎａｌ＋ＸＺｒ２
５ｉＸＰ３−ｘＯ１２）と同様の結晶構造（Ｒ２Ｏ）を
有するＬｉＴｉ２Ｐ３０１２が、室温で４Ｘ１０−７Ｓ
／ｃｍと比較的高いリチウムイオン導電性を示すことが
知られているが、固体電池に必要な導電率を充分満足し
ているとは言い難い状況である。このようなわけで、こ
れらの欠点を除去した固体電解質材料、特に導電率が大
きく、化学的に安定な材料の開発が求められている。In recent years, NASICON-based materials (Nal+XZr2), which are known as sodium ion conductive solid electrolyte materials, have been
LiTi2P3012, which has a similar crystal structure (R2O) to 4X10-7S at room temperature
Although it is known to exhibit a relatively high lithium ion conductivity of /cm, it is difficult to say that it sufficiently satisfies the conductivity required for solid-state batteries. Therefore, there is a need for the development of solid electrolyte materials that eliminate these drawbacks, especially materials that have high electrical conductivity and are chemically stable.
（発明の目的）
本発明は上述の現状に鑑みなされたもので、コンダクタ
ンスが大きく、かつ化学的に安定なリチウムイオン導電
性固体電解質材料を提供することを目的とする。(Object of the Invention) The present invention was made in view of the above-mentioned current situation, and an object of the present invention is to provide a lithium ion conductive solid electrolyte material that has high conductance and is chemically stable.
（問題点を解決するための手段）
したがって、本発明によるリチウムイオン導電性固体電
解質材料は、
一般式
％式％
（ただし、ＭはＣａ、Ｐｂ、Ｎｉ、Ｃｕ、Ｚｎ、Ｃｏ等
の２価元素、Ｏ＜ｘ＜０．６）で示される組成物よりな
ることを特徴とするものである。(Means for solving the problem) Therefore, the lithium ion conductive solid electrolyte material according to the present invention has the general formula % (where M is a divalent element such as Ca, Pb, Ni, Cu, Zn, Co, etc.). , O<x<0.6).
本発明によるリチウムイオン導電性固体電解質材料によ
れば、比較的高いリチウムイオン導電性を示すと共に、
分解電圧も高く、熱的に安定であり、また、水分に対し
ても、他のリチウムイオン導電体に比較して安定である
という利点があり、このためリチウムイオン導電性固体
電解質材料をリチウム固体電池の電解質材料に適用する
ことにより、固体電池の特性改善が達成しえるという利
点がある。According to the lithium ion conductive solid electrolyte material according to the present invention, it exhibits relatively high lithium ion conductivity and
It has the advantage of having a high decomposition voltage, being thermally stable, and being more stable against moisture than other lithium ion conductors. By applying it to battery electrolyte materials, there is an advantage that the characteristics of solid-state batteries can be improved.
（発明の詳細な説明） 本発明をさらに詳しく説明する。(Detailed description of the invention) The present invention will be explained in more detail.
一般式
％式％
（ただし、Ｍは２価の金属元素、０＜ｘ＜０．６）で示
される組成物は、リチウムイオン導電率の高い材料を作
ることを目的に、その結晶構造に着目して作製したもの
である。The composition shown by the general formula % formula % (where M is a divalent metal element, 0<x<0.6) is created by focusing on its crystal structure with the aim of creating a material with high lithium ion conductivity. It was made by
リチウムイオン導電性固体電解質材料、上記−最大のｘ
＝ＯのＬｉＴｉ２Ｐ３０１２は、ＮＡＳ ＩＣ０Ｎ系材
料と同様の構造を有するものである。Lithium ion conductive solid electrolyte material, above - maximum x
=O LiTi2P3012 has a structure similar to that of NAS ICON-based materials.
すなわち、この構造は三次元の網目構造をしており、Ｌ
ｉイオンの移動が容易なトンネルが多数存在すると考え
られている。In other words, this structure has a three-dimensional network structure, and L
It is believed that there are many tunnels through which i-ions can easily move.
したがって、このＬｉＴｉ２Ｐ３０１２の４価のＴｉイ
オンを低原子価の陽イオンで置換し、Ｌｉイオンの濃度
を増加させ、このトンネル内に存在するＬｉイオンの数
を増やすことによって、リチウムイオン導電性を向上さ
せることができると考えられることから、本発明による
リチウムイオン導電性固体電解質；
Ｌｉ１＋２ＸＴｉ２−ＸＭＸＰ３０１２の系に着目した
のである（ただしＭは二価の金属元素、Ｏ＜ｘ＜０．６
）。Therefore, by replacing the tetravalent Ti ions of LiTi2P3012 with low-valent cations, increasing the concentration of Li ions, and increasing the number of Li ions existing in this tunnel, lithium ion conductivity can be improved. Therefore, we focused on the lithium ion conductive solid electrolyte according to the present invention; Li1+2XTi2-XMXP3012 system (where M is a divalent metal element and O<x<0.6
).
このような２価の金属元素としては、たとえばＣａ、Ｐ
ｂ、Ｎｉ、Ｃｕ、Ｚｎ、Ｃｏなどの一種以上を例として
あげることができる。Such divalent metal elements include, for example, Ca, P
Examples include one or more of Ni, Cu, Zn, and Co.
前述の一般式において、Ｏ＜ｘ＜０．６にある本発明に
よるリチウムイオン導電性固体電解質材料はＮＡＳＩＣ
ＯＮ系材料と同様の構造を採り、いずれもリチウムイオ
ン導電性を示す。In the above general formula, the lithium ion conductive solid electrolyte material according to the present invention in which O<x<0.6 is NASIC
They have the same structure as ON-based materials, and both exhibit lithium ion conductivity.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
（実施例１）
市販特級試薬のＬ ｉ ２ＣＯ３、ＴｉＯ２、ＣａＯ１
及びＮＨ４Ｈ２ＰＯ４を原料とし、これらの原料をＬｉ
１＋２ＸＴｉ２−ＸＭＸＰ３０１２なる秤量式に基づき
、所定量を秤量し、充分混合した。(Example 1) Commercially available special grade reagents L i 2CO3, TiO2, CaO1
and NH4H2PO4 as raw materials, and these raw materials are used as Li
Based on the weighing formula 1+2XTi2-XMXP3012, a predetermined amount was weighed and thoroughly mixed.
その後、これらをアルミするつぼに移して、仮焼成する
。仮焼成は、８００℃の温度で２４時間、大気中にて行
なう。焼成後、生成物を電気炉より取り出し、粉砕した
後、１〜１．５ｔ／ｃｍ２の圧力で成形し、成形体とす
る。この成形体を、さらに１１００℃の温度で、４時間
焼成を行なう。Then, they are transferred to an aluminum pot and calcined. Temporary firing is performed in the air at a temperature of 800° C. for 24 hours. After firing, the product is taken out of the electric furnace, pulverized, and then molded at a pressure of 1 to 1.5 t/cm2 to form a molded body. This molded body is further fired at a temperature of 1100° C. for 4 hours.
このようにして製造された焼結体から、円盤状試料を切
り出し、その両面にＡｇ電極を付け、コンダクタンスは
交流法を用い、複素アドミッタンス法により求めた。ま
た電子輸率は、直流法を用い、電子伝導性によるコンダ
クタンスを求め、全コンダクタンスとの比より求めた。A disk-shaped sample was cut out from the sintered body thus produced, Ag electrodes were attached to both sides, and the conductance was determined by the complex admittance method using the alternating current method. Further, the electron transfer number was determined by calculating the conductance due to electron conductivity using the direct current method and calculating the ratio to the total conductance.
さらに分解電圧は、直流法を用い、電流−電位曲線より
求めた。Further, the decomposition voltage was determined from a current-potential curve using a direct current method.
測定に用いた試料の形状は全て同じである。The shapes of the samples used for measurements were all the same.
Ｍ＝Ｃａとした場合の、
Ｌｉ １．２Ｔｉ １．９ｃａｏ、ＩＰ３０１２（−最
大のＸ＝０．１の場合）
Ｌｉ１．４Ｔｉ １．５Ｃａｏ、２Ｐ３０１２（Ｘ−〇
、２の場合）
Ｌｉ２゜ｏＴｉｌ、ｃａｃａｏ、５Ｐ３０１２（Ｘ＝０
．５の場合）
のコンダクタンスの温度依存性を第１図に示す。When M=Ca, Li 1.2Ti 1.9cao, IP3012 (-maximum X=0.1) Li1.4Ti 1.5Cao, 2P3012 (X-〇, 2) Li2゜oTil, cacao, 5P3012 (X=0
．． Figure 1 shows the temperature dependence of the conductance in case 5).
図中の、（１）は、
Ｌｉ １．２Ｔｉ １．９ｃａｏ、ＩＰ３０１２試料、
（２）は、
Ｌｉ１．４Ｔｉ１．５Ｃａｏ、２Ｐ３０１２試料、（３
）は、
Ｌｉ２．ｏ’ｒｉ１．５Ｃａｏ、５Ｐ３０１２試料につ
いての結果を占めずグラフであり、全ての試料において
優れたコンダクタンスを有している。In the figure, (1) is Li 1.2Ti 1.9cao, IP3012 sample,
(2) is Li1.4Ti1.5Cao, 2P3012 sample, (3
) is Li2. The graph shows the results for the o'ri1.5Cao and 5P3012 samples, and all samples have excellent conductance.
図中の破線は比較のためにＬｉＴｉ２Ｐ３０１２のコン
ダクタンスを示した。The broken line in the figure indicates the conductance of LiTi2P3012 for comparison.
第２図に室温におけるコンダクタンスの組成依存性を示
す、第２図より明らかなように、組成がＬｉ１．４Ｔｉ
１．５Ｃａｏ、２Ｐ３０１２ （ＸＯ１２）の付近で
コンダクタンスは最大になり、０＜ｘ＜０．６において
試料は、高いコンダクタンスを有している。ｘ＞０．６
においては、結晶構造がＮＡＳＩＣＯＮ型の構造から別
の相へ転移するため、コンダクタンスＬｉＴｉ２Ｐ３０
１２よりも著しく低下した。Figure 2 shows the composition dependence of conductance at room temperature.As is clear from Figure 2, the composition is Li1.4Ti.
The conductance is maximum near 1.5Cao, 2P3012 (XO12), and the sample has high conductance at 0<x<0.6. x>0.6
In , the conductance LiTi2P30 changes because the crystal structure transitions from the NASICON type structure to another phase.
It was significantly lower than 12.
直流法によるコンダクタンスは、室温において、約１０
”−９３であり、電子輸率はいずれも約１×１０−５で
あり、本発明によるリチウムイオン導電性固体電解質材
料はいずれも電子電導性は無視できるほど小さいことが
わかる。The conductance measured by the DC method is approximately 10 at room temperature.
''-93, and the electron transport numbers are about 1 x 10-5, indicating that all the lithium ion conductive solid electrolyte materials according to the present invention have negligibly small electron conductivity.
また、電流−電位曲線は、１２０℃において、全試料と
も印加電圧が１５Ｖ付近まで、比例関係が成り立ってお
り、分解による電流の急増は見られなかった。したがっ
て分解電圧は１５Ｖ以上であることがわかる。Further, the current-potential curves maintained a proportional relationship at 120° C. up to an applied voltage of around 15 V for all samples, and no rapid increase in current due to decomposition was observed. Therefore, it can be seen that the decomposition voltage is 15V or more.
（実施例２）
実施例１と同様にＣａＯをＰｂＯに置き換えることによ
り、
Ｌｉ １．４Ｔｉ １．５Ｐｂｏ、２Ｐ３０１２（−最
大のＭ＝Ｐｂ、Ｘ＝０．２の場合）を作製した。コンダ
クタンスの測定方法ならびに試料の形状は実施例１と同
じである。第３図にこの試料のコンダクタンスの温度依
存性を示す。こ（７）Ｌｉ１．４Ｔｉ１．５Ｐｂｏ、２
Ｐ３０１２試料も高いコンダクタンスを有している。図
中の破線は比較のためにＬｉＴｉ２Ｐ３０１２のコンダ
クタンスを示した。また、この系の場合も室温における
コンダクタンスはＯ＜ｘ＜０．６の範囲において、Ｌｉ
Ｔｉ２Ｐ３０１２よりも高い値を示した。(Example 2) Li 1.4Ti 1.5Pbo, 2P3012 (-maximum M=Pb, X=0.2) was produced by replacing CaO with PbO in the same manner as in Example 1. The method for measuring conductance and the shape of the sample were the same as in Example 1. Figure 3 shows the temperature dependence of the conductance of this sample. (7) Li1.4Ti1.5Pbo, 2
The P3012 sample also has high conductance. The broken line in the figure indicates the conductance of LiTi2P3012 for comparison. Also, in the case of this system, the conductance at room temperature is in the range O<x<0.6, Li
It showed a higher value than Ti2P3012.
（実施例３）
実施例１と同様にＣａＯをＮｉＯに置き換えることによ
り、
Ｌ ｉ １．４Ｔ ｉ １．ｓＮ ｉ ０．２Ｐ３０１
２（−最大のＭ＝Ｎｉ、Ｘ＝０．２の場合）を作製した
。コンダクタンスの測定方法ならびに試料の形状は実施
例１と同じである。第４図にこの試料のコンダクタンス
の温度依存性を示す、このＬｉ１．４Ｔｉ １．ａＮｉ
ｏ、２Ｐ３０１２試料も高いコンダクタンスを有してい
る０図中の破線は比較のためにＬｉＴｉ２Ｐ３０１２の
コンダクタンスを示した。また、この系の場合も室温に
おけるコンダクタンスはＯ＜ｘ＜０．６の範囲において
、ＬｉＴｉ２Ｐ３０１２よりも高い値を示した。(Example 3) By replacing CaO with NiO as in Example 1, L i 1.4T i 1. sN i 0.2P301
2 (-maximum M=Ni, X=0.2) was produced. The method for measuring conductance and the shape of the sample were the same as in Example 1. Figure 4 shows the temperature dependence of the conductance of this sample. aNi
o, 2P3012 sample also has high conductance. The dashed line in the figure shows the conductance of LiTi2P3012 for comparison. Also, in the case of this system, the conductance at room temperature showed a value higher than that of LiTi2P3012 in the range of O<x<0.6.
以上の実施例では、ＭとしてＣａ、Ｐｂ、Ｎｉについて
示したが、これら２価の元素に限定されるものではなく
、Ｃｕ、Ｚｎ、Ｃｏ等他の２価元素の場合も同様の効果
を生ずる。In the above embodiments, Ca, Pb, and Ni are shown as M, but the M is not limited to these divalent elements, and similar effects can be produced in the case of other divalent elements such as Cu, Zn, and Co. .
（発明の効果）
以上説明したように、本発明による、
Ｌｉｌ＋２ｘＴｉ２−ｘＭｘＰ３０ｔ２（但し、Ｍは２
価の金属元素、Ｏ＜ｘ＜Ｏ。(Effect of the invention) As explained above, according to the present invention, Lil+2xTi2-xMxP30t2 (where M is 2
Valence metal element, O<x<O.
６）
なる組成物は、全て優れたコンダクタンスを有している
。また、このリチウムイオン導電性固体電解質材料は分
解電圧も高く、熱的及び水分に対しても安定であり、リ
チウム固体電池の電解質材料に用いることにより固体電
池の特性改善が達成できる利点がある。6) All of the compositions have excellent conductance. Furthermore, this lithium ion conductive solid electrolyte material has a high decomposition voltage and is stable against heat and moisture, and has the advantage of being able to improve the characteristics of solid-state batteries by using it as an electrolyte material for lithium solid-state batteries.
第１図は本発明のリチウムイオン導電性固体電解質材料
Ｌｉｘ＋２ｘＴｉ２−ｘＣａｘＰ３０１：ｚのコンダク
タンスの温度依存性を示す図である。
図中試料（１）は、
Ｌｉ１．２Ｔｉ１．９ｃａｏ、ＩＰ３０１２、試料（２
）は、
Ｌｉ１．４Ｔｉ１．５Ｃａｏ、２Ｐ３０１２、試料（３
）は、
Ｌｉ２．ｏＴｉ １．ｃａｃａｏ、５Ｐ３０１２を表し
、図中の破線はＬｉＴｉ２Ｐ３０１２のコンダクタンス
を示している。
第２図は本発明のリチウムイオン導電性固体電解質材料
Ｌｉ１＋２ＸＴｉ ２−ｘｃａｘＰ３０１２の室温にお
けるコンダクタンスの組成依存性を示す図である。
第３図は本発明のリチウムイオン導電性固体電解質材料
のＬｉ １．４Ｔｉ１．５Ｐｂｏ、２Ｐ３０１２のコン
ダクタンスの温度依存性を示す図である。
第４図は本発明のリチウムイオン導電性固体電解質材料
Ｌｉ１．４Ｔｉ １．５Ｎｉ０．２Ｐ３０１２のコンダ
クタンスの温度依存性を示す図であり、図中の破線はＬ
ｉＴｉ２Ｐ３０１２のコンダクタンスを示している。FIG. 1 is a diagram showing the temperature dependence of the conductance of the lithium ion conductive solid electrolyte material Lix+2xTi2-xCaxP301:z of the present invention. Sample (1) in the figure is Li1.2Ti1.9cao, IP3012, sample (2
) is Li1.4Ti1.5Cao, 2P3012, sample (3
) is Li2. oTi 1. cacao, 5P3012, and the broken line in the figure indicates the conductance of LiTi2P3012. FIG. 2 is a diagram showing the composition dependence of conductance at room temperature of the lithium ion conductive solid electrolyte material Li1+2XTi 2-xcaxP3012 of the present invention. FIG. 3 is a diagram showing the temperature dependence of the conductance of Li 1.4Ti1.5Pbo, 2P3012, which is the lithium ion conductive solid electrolyte material of the present invention. FIG. 4 is a diagram showing the temperature dependence of the conductance of the lithium ion conductive solid electrolyte material Li1.4Ti 1.5Ni0.2P3012 of the present invention, and the broken line in the diagram is L
The conductance of iTi2P3012 is shown.
Claims (1)
＿２（ただし、Ｍは２価の金属元素、０＜ｘ＜０．６）
で示される組成物よりなることを特徴とするリチウムイ
オン導電性固体電解質材料。(1) General formula Li_1_+_2xTi_2_-_xMxP_3O_1
_2 (However, M is a divalent metal element, 0<x<0.6)
A lithium ion conductive solid electrolyte material comprising a composition represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2042646A JPH03246868A (en) | 1990-02-26 | 1990-02-26 | Lithium ion conductive solid electrolyte material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2042646A JPH03246868A (en) | 1990-02-26 | 1990-02-26 | Lithium ion conductive solid electrolyte material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03246868A true JPH03246868A (en) | 1991-11-05 |
Family
ID=12641779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2042646A Pending JPH03246868A (en) | 1990-02-26 | 1990-02-26 | Lithium ion conductive solid electrolyte material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03246868A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004093236A1 (en) * | 2003-04-18 | 2004-10-28 | Matsushita Electric Industrial Co., Ltd. | Solid electrolyte and all-solid cell containing same |
| DE102006018233A1 (en) * | 2005-07-14 | 2007-10-25 | Elsper, Rüdiger, Dr. | Manufacture of inorganic solid state cation conductor involves removing low valent heavy metal portion from dispersion of starting material of metal mixed oxide or salt in presence of monovalent cations and/or disproportionated |
| DE102006025663A1 (en) * | 2005-07-14 | 2007-12-06 | Elsper, Rüdiger, Dr. | Manufacture of inorganic solid state cation conductor involves removing low valent heavy metal portion from dispersion of starting material of metal mixed oxide or salt in presence of monovalent cations and/or disproportionated |
| US7939201B2 (en) | 2005-08-08 | 2011-05-10 | A123 Systems, Inc. | Nanoscale ion storage materials including co-existing phases or solid solutions |
| US8158090B2 (en) | 2005-08-08 | 2012-04-17 | A123 Systems, Inc. | Amorphous and partially amorphous nanoscale ion storage materials |
| US8323832B2 (en) | 2005-08-08 | 2012-12-04 | A123 Systems, Inc. | Nanoscale ion storage materials |
-
1990
- 1990-02-26 JP JP2042646A patent/JPH03246868A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004093236A1 (en) * | 2003-04-18 | 2004-10-28 | Matsushita Electric Industrial Co., Ltd. | Solid electrolyte and all-solid cell containing same |
| JP2004335455A (en) * | 2003-04-18 | 2004-11-25 | Matsushita Electric Ind Co Ltd | Solid electrolyte and all-solid battery containing it |
| US7514181B2 (en) | 2003-04-18 | 2009-04-07 | Panasonic Corporation | Solid electrolyte and all solid state battery containing same |
| DE102006018233A1 (en) * | 2005-07-14 | 2007-10-25 | Elsper, Rüdiger, Dr. | Manufacture of inorganic solid state cation conductor involves removing low valent heavy metal portion from dispersion of starting material of metal mixed oxide or salt in presence of monovalent cations and/or disproportionated |
| DE102006025663A1 (en) * | 2005-07-14 | 2007-12-06 | Elsper, Rüdiger, Dr. | Manufacture of inorganic solid state cation conductor involves removing low valent heavy metal portion from dispersion of starting material of metal mixed oxide or salt in presence of monovalent cations and/or disproportionated |
| US7939201B2 (en) | 2005-08-08 | 2011-05-10 | A123 Systems, Inc. | Nanoscale ion storage materials including co-existing phases or solid solutions |
| US8057936B2 (en) | 2005-08-08 | 2011-11-15 | A123 Systems, Inc. | Nanoscale ion storage materials including co-existing phases or solid solutions |
| US8158090B2 (en) | 2005-08-08 | 2012-04-17 | A123 Systems, Inc. | Amorphous and partially amorphous nanoscale ion storage materials |
| US8323832B2 (en) | 2005-08-08 | 2012-12-04 | A123 Systems, Inc. | Nanoscale ion storage materials |
| US8617430B2 (en) | 2005-08-08 | 2013-12-31 | A123 Systems Llc | Amorphous and partially amorphous nanoscale ion storage materials |
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