JPH02204312A - Method for synthesizing metal sulfide-based interlaminar compound - Google Patents
Method for synthesizing metal sulfide-based interlaminar compoundInfo
- Publication number
- JPH02204312A JPH02204312A JP1021696A JP2169689A JPH02204312A JP H02204312 A JPH02204312 A JP H02204312A JP 1021696 A JP1021696 A JP 1021696A JP 2169689 A JP2169689 A JP 2169689A JP H02204312 A JPH02204312 A JP H02204312A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- sulfide
- alkali
- metal sulfide
- reaction
- 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
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 22
- 230000002194 synthesizing effect Effects 0.000 title claims description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 11
- 229910052977 alkali metal sulfide Inorganic materials 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- -1 alkali metal hydrosulfides Chemical class 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 5
- 238000009830 intercalation Methods 0.000 claims description 25
- 230000002687 intercalation Effects 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 19
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003513 alkali Substances 0.000 abstract description 11
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 9
- 150000001768 cations Chemical class 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 8
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 abstract description 4
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 2
- 238000005245 sintering Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007791 liquid phase Substances 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
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DXHPZXWIPWDXHJ-UHFFFAOYSA-N carbon monosulfide Chemical compound [S+]#[C-] DXHPZXWIPWDXHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- QTNDMWXOEPGHBT-UHFFFAOYSA-N dicesium;sulfide Chemical compound [S-2].[Cs+].[Cs+] QTNDMWXOEPGHBT-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- AHKSSQDILPRNLA-UHFFFAOYSA-N rubidium(1+);sulfide Chemical compound [S-2].[Rb+].[Rb+] AHKSSQDILPRNLA-UHFFFAOYSA-N 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
-
- 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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は例えば電池、センサー エレクトロクロミッ
ク素子、電位記憶素子などの電気化学的デバイスに用い
る金属硫化物系層間化合物の合成方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for synthesizing a metal sulfide-based intercalation compound used in electrochemical devices such as batteries, sensors, electrochromic devices, and potential storage devices.
［従来の技術］
従来、金属硫化物系層間化合物は、一般に層状構造を持
つ金属硫化物をホスト物質として、ここにアルカリイオ
ン等のゲスト物質を化学的、電気化学的にドープするこ
とによって得られている。[Prior Art] Conventionally, metal sulfide-based intercalation compounds are generally obtained by doping a metal sulfide with a layered structure as a host material with a guest material such as an alkali ion chemically or electrochemically. ing.
ホスト物質である金属硫化物の合成は例えば刊行物（Ｉ
ｎｏｒｇａｎｉｃ ５ｙｎｔｈｅｓｅｓ、ｖｏｌ、１
２．１．ｐ１５ｇおよびｐ８２（１９７３））に示され
ているように、−殻内に硫化水素または硫化炭素雰囲気
中で金属を加熱したり、金属と硫黄とを密閉容器中で加
熱したり、金属塩化物の蒸気と硫化水素とを加熱するこ
とにより行われている。この様にして得たホスト物質の
電気化学的なドープは、ゲスト物質を溶解した溶媒中で
ホスト物質を電気化学的手法によって酸化または還元す
ることにより行われている。 またゲスト物質を化学的
にドープするには例えば刊行物（Ｊ。The synthesis of metal sulfides as host materials is described, for example, in the publication (I
organic 5 syntheses, vol. 1
2.1. p. 15g and p. 82 (1973)) - heating the metal in a hydrogen sulfide or carbon sulfide atmosphere in the shell, heating the metal and sulfur in a closed container, It is carried out by heating steam and hydrogen sulfide. Electrochemical doping of the host material obtained in this manner is carried out by electrochemically oxidizing or reducing the host material in a solvent in which the guest material is dissolved. In addition, to chemically dope a guest substance, for example, the publication (J.
Ｅｌｅｃｔｏｒｏｃｈｅｍ、Ｓｏｃ、ｖｏＩ １２４．
９．ｐ１３８７〜１９８ｇ（１９７７））に示されてい
るように、ヨウ化リチウムのアセトニトリル溶液を用い
て直接ホスト物質と反応させることにより行われている
。Electrochem, Soc, voI 124.
9. 1387-198g (1977)), this method is carried out by directly reacting a host material with a solution of lithium iodide in acetonitrile.
［発明が解決しようとする課題］
しかし従来の金属硫化物ホスト物質の製造方法は本質的
に固−気相、ｒＭ−固相、気−気相反応なので均質な物
質が得にくいことに伴うイオン伝導性の不良が生じ易か
った。そのためイオン伝導性の高い金属硫化物ホスト物
質の製造方法が待ち望まれていた。さらにゲスト物質の
電気化学的ドープ法はイオンの泳動等を制御する電流密
度の設定などの操作が複雑すぎて工業化に向かず、また
化学的ドープ法は筒便なドープ法であるが均一な組成の
層間化合物を得にくシまため生成した層間化合物におけ
るゲスト物質のみかけの拡散係数が小さくなるという課
題があった。[Problem to be solved by the invention] However, since the conventional manufacturing method of metal sulfide host materials is essentially a solid-vapor phase, rM-solid phase, and gas-vapor phase reaction, it is difficult to obtain a homogeneous material, and ions are generated. Poor conductivity was likely to occur. Therefore, a method for producing metal sulfide host materials with high ionic conductivity has been awaited. Furthermore, the electrochemical doping method for guest substances is not suitable for industrialization because the operations such as setting the current density to control ion migration are too complicated, and the chemical doping method is a convenient doping method, but it produces a uniform composition. There was a problem that the apparent diffusion coefficient of the guest substance in the generated intercalation compound became small because it was difficult to obtain the intercalation compound.
この発明はかかる課題を解決するためになされたもので
１例えばアルカリイオン等のゲストイオンの拡散係数の
大きな金属硫化物系層間化合物の合成方法を得ることを
目的とする。The present invention has been made to solve the above problems, and an object thereof is to provide a method for synthesizing a metal sulfide-based intercalation compound having a large diffusion coefficient for guest ions such as alkali ions.
［課題を解決するための手段］
この発明の金属硫化物系層間化合物の合成方法は、金属
アルコキシドおよび金属β−ジケトン型有機物の内の少
なくとも一種、アルカリ金属の硫化物およびアルカリ金
属の硫化水素化物の内の少なくとも一種、および酸を混
合して溶液とし反応させ９反応生成物をＨ２Ｓ雰囲気中
で焼成するものである。[Means for Solving the Problems] The method for synthesizing a metal sulfide-based intercalation compound of the present invention comprises at least one of a metal alkoxide and a metal β-diketone type organic substance, an alkali metal sulfide, and an alkali metal hydrogen sulfide. At least one of these and an acid are mixed to form a solution, reacted, and the reaction product is calcined in an H2S atmosphere.
［作用］
この発明における金属アルコキシドおよび金属β−ジケ
トン型有機物の少なくとも一種を出発原料とする反応は
従来の気相反応とは本質的に異なる液相反応の内のゾル
−ゲル法を基本としているので、生成物である金属硫化
物系層間化合物は粒径の揃った微粒子として得られる。[Function] The reaction using at least one of a metal alkoxide and a metal β-diketone type organic substance as a starting material in the present invention is based on a sol-gel method, which is a liquid phase reaction that is essentially different from conventional gas phase reactions. Therefore, the product, a metal sulfide intercalation compound, is obtained as fine particles with uniform particle size.
このことは電子Ｒ微鏡観察によって確認した。従ってア
ルカリカチオンが層間化合物と溶媒との間を行き来する
反応の場である界面の面積が従来のものと比べて飛躍的
に増大させているために、アルカリカチオンの見かけの
拡散係数が大きくなっているものと考えられる。またこ
の発明による金属硫化物系層間化合物は、ホスト物質で
ある金属硫化物を合成すると同時にゲスト物質であるア
ルカリカチオンをドープするのでアルカリカチオンが均
一にドープされた組成になっていると推定される。これ
は従来のいかなる合成方法でも得られなかったものであ
るが、このこともアルカリカチオンの拡散係数を大きく
している主因の１つであると思われる。This was confirmed by electron R microscopic observation. Therefore, the area of the interface, which is the reaction site where alkali cations go back and forth between the intercalation compound and the solvent, has been dramatically increased compared to conventional ones, and the apparent diffusion coefficient of alkali cations has increased. It is thought that there are. In addition, the metal sulfide-based intercalation compound according to the present invention is presumed to have a composition in which alkali cations are uniformly doped because the metal sulfide that is the host material is synthesized and the alkali cation that is the guest material is doped at the same time. . Although this cannot be obtained by any conventional synthesis method, this is also considered to be one of the main reasons for increasing the diffusion coefficient of alkali cations.
なおこの発明の合成方法が有するこの様な利点は。These advantages of the synthesis method of the present invention are as follows.
この発明がセラミック超微粒子の合成方法として一般に
知られているゾル−ゲル法を基本にしたものであること
に起因すると考えられる。This is believed to be due to the fact that this invention is based on the sol-gel method, which is generally known as a method for synthesizing ultrafine ceramic particles.
［実施例］
この発明の金属硫化物系層間化合物の合成方法に係わる
金属アルコキシドおよび金属β−ジケトン型有機物中の
中心金属としては、一般にその硫化物が層状構造を有す
るとされている元素周期律表中■、族、■族、および■
１族に属する金属原子の内少なくとも一種のものを用い
ることが可能である。[Example] The central metal in the metal alkoxide and metal β-diketone type organic substance related to the method for synthesizing the metal sulfide intercalation compound of the present invention is selected from the periodic system of elements in which the sulfide is generally said to have a layered structure. ■, family, ■family, and ■ in the table
It is possible to use at least one type of metal atoms belonging to Group 1.
また金属アルコキシドの構造としては第１図に示した一
般式のように金属とアルキル基とが酸素を介して結合し
ているものであるが、アルキル基はすべて同じである必
要はない。また第２図に示したような複核構造であって
もよく、その場合、複数の金属原子はそれぞれ異なるも
のであってもよい、図において、Ｒ１−Ｒ６はアルキル
基、Ｍ、Ｍｌ、Ｍ２は金属である。一方金属β−ジケト
ン型有機物は第３図に示すようなβ−ジケトン型の配位
子が中心金属に配位した構造をしており、β位の置換基
Ｒ口〜Ｒ目はアルキル基またはフェニル基であっても良
く、互いに異なるものであっても良い。また金属β−ジ
ケトン型有機物の場合は、例えば化学式（ＣＨｓ ＣＯ
ＣＨＣＯＣＨ３） ２ Ｍ ｏ Ｏ２のように。The structure of a metal alkoxide is such that a metal and an alkyl group are bonded via oxygen, as shown in the general formula shown in FIG. 1, but the alkyl groups do not all have to be the same. It may also have a dinuclear structure as shown in Figure 2, in which case the plurality of metal atoms may be different from each other. In the figure, R1-R6 are alkyl groups, M, Ml, M2 are It is metal. On the other hand, metal β-diketone type organic substances have a structure in which a β-diketone type ligand is coordinated to a central metal as shown in Figure 3, and the substituents R to R at the β position are alkyl groups or It may be a phenyl group or may be different from each other. In the case of metal β-diketone type organic substances, for example, the chemical formula (CHs CO
Like CHCOCH3) 2 M o O2.
一部が酸化物であっても良い。さらに、第４図に示すよ
うに金属アルコキシドと金属β−ジケトン型有機物との
混合体であっても良い。なお、構造式の例には配位数４
の中心金属を示したが、配位数に制限は無い。Part of it may be an oxide. Furthermore, as shown in FIG. 4, it may be a mixture of a metal alkoxide and a metal β-diketone type organic substance. In addition, the example of the structural formula has a coordination number of 4.
Although the central metal is shown, there is no restriction on the number of coordinations.
この発明の金属硫化物系層間化合物の合成方法に係わる
酸としては、いかなる鉱酸や有機酸も用いることができ
、硫化水素などもそ９作用から考えて酸として用いるこ
とができる。Any mineral acid or organic acid can be used as the acid involved in the method of synthesizing the metal sulfide intercalation compound of the present invention, and hydrogen sulfide can also be used as the acid in view of its effects.
この発明の金属硫化物系層間化合物の合成方法に係わる
アルカリ金属の硫イピ物およびアルカリ金属の硫化水素
化物としては、例えば硫化ナトリウム、硫化水素ナトリ
ウム、硫化す、チウム、硫化カリウム、硫化ルビジウム
、硫化セシウムなど全てのアルカリ金属の硫化物及び硫
化水素化物の内から選ばれた少なくとも一種を用いるこ
とができる。Examples of the alkali metal sulfide and alkali metal hydrogen sulfide used in the method for synthesizing metal sulfide-based intercalation compounds of the present invention include sodium sulfide, sodium hydrogen sulfide, sulphur sulfide, thium, potassium sulfide, rubidium sulfide, At least one selected from sulfides and hydrogen sulfides of all alkali metals such as cesium sulfide can be used.
この発明の金属硫化物系＃間化合物の合成方法に係わる
溶媒としては、無機系及び有機系の内の少なくとも一種
のものを広く用いることができる。As the solvent involved in the method of synthesizing the metal sulfide intermetallic compound of the present invention, at least one type of inorganic and organic solvents can be widely used.
この発明の金属硫化物系層間化合物の合成方法に係わる
合成反応は、溶媒中でアルカリ金属の硫化物や硫化水素
化物を酸と反応させることによって上記溶媒中に硫化水
素とアルカリカチオンとを同時に発生せしめ、これらと
上記溶媒中に共存せしめた金属アルコキシドおよび金属
β−ジケトン型有機物の内の少なくとも一種との液層反
応によって、アルカリカチオンが均一にドープされた金
属硫化物系層間化合物をただ一回の反応によって合成す
るものである。The synthesis reaction related to the method for synthesizing metal sulfide-based intercalation compounds of the present invention involves simultaneously generating hydrogen sulfide and alkali cations in the solvent by reacting an alkali metal sulfide or hydrogen sulfide with an acid in the solvent. Then, a metal sulfide-based intercalation compound uniformly doped with alkali cations is formed by a liquid phase reaction between these and at least one of a metal alkoxide and a metal β-diketone type organic substance coexisting in the above solvent. It is synthesized by the reaction of
なお、この発明の実施例の金属硫化物系層間化合物の合
成方法において、金属アルコキシドおよび金属β−ジケ
トン型有機物の内の少なくとも一種の溶液に、アルカリ
金属の硫化物およびアルカリ金属の硫化水素化物の内の
少なくとも一種を混合した後、Ｍを混合するか、金属ア
ルコキシドおよび金属β−ジケトン型有機物の内の少な
くとも一種の溶液に、アルカリ金属の硫化物およびアル
カリ金属の硫化水素化物の内の少なくとも一種のものの
酸溶液を混合しても良い。In the method for synthesizing a metal sulfide-based intercalation compound according to an embodiment of the present invention, an alkali metal sulfide and an alkali metal hydrogen sulfide are added to a solution of at least one of a metal alkoxide and a metal β-diketone type organic substance. After mixing at least one of them, M is mixed, or at least one of an alkali metal sulfide and an alkali metal hydrogen sulfide is added to a solution of at least one of a metal alkoxide and a metal β-diketone type organic substance. You may also mix acid solutions.
以下、この発明を実施例により具体的に説明する。Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例１
金属アルコキシドとしてチタンテトライソプロポキシド
２８．５６．を、溶媒である無水チオフェン５０ｃｌ１
３に溶解した。ここにアルカリ金属の硫化物として硫化
リチウム２．７７４ｇを溶解した後、ａとして硫化水素
を流量２ｃｍ３／ｓｉｎで１時間添加した。これをろ過
してチオフェンで洗った後真空乾燥してこの発明の一実
施例の金属硫化物系層間化合物の合成方法による金属硫
化物系層間化合物のＬｉｌ］、ａＴｉＳ２を得た。得ら
れた生成物をペレット状に成形して作用電極とし、リチ
ウムフォイルを対極と参照極。Example 1 Titanium tetraisopropoxide as metal alkoxide 28.56. and 50 cl1 of anhydrous thiophene as a solvent.
It was dissolved in 3. After 2.774 g of lithium sulfide was dissolved therein as an alkali metal sulfide, hydrogen sulfide was added as a at a flow rate of 2 cm 3 /sin for 1 hour. This was filtered, washed with thiophene, and then dried in vacuum to obtain a metal sulfide intercalation compound, aTiS2, obtained by the method for synthesizing a metal sulfide intercalation compound according to an embodiment of the present invention. The resulting product was formed into a pellet to serve as the working electrode, and lithium foil was used as the counter and reference electrode.
ＬｉＣｌ０ｍのＩＮプロピレンカーボネート溶液を電解
液として測定セルを組んだ。このセルを用いてリチウム
の見かけの拡散係数をカレントパルス法によって測定し
結果を表に示す。A measurement cell was assembled using an IN propylene carbonate solution containing 0 m of LiCl as an electrolyte. Using this cell, the apparent diffusion coefficient of lithium was measured by the current pulse method, and the results are shown in the table.
実施例２
金属β−ジケトン型有機物として、ＷＩ化チタン（■）
アセチルアセトナート２０．９７ｇを溶媒である無水ア
セトニトリル５０ｃ１１３に溶解した。ここにアルカリ
金属の硫化物として硫化リチウム２．２１０ｇを溶解し
た後に酸として硫１’ｉｌ ５８．８６ｇを添加した。Example 2 Titanium WI (■) as a metal β-diketone type organic substance
20.97 g of acetylacetonate was dissolved in anhydrous acetonitrile 50c113 as a solvent. After dissolving 2.210 g of lithium sulfide as an alkali metal sulfide, 58.86 g of 1'il sulfur was added as an acid.
ここから反応生成物を分別＃ｊｉ濃縮乾燥し、これを硫
化水素雰囲気中１０００℃で６時間焼成してこの発明の
他の実施例の金属硫化物系層間化合物の合成方法による
金属硫化物系層間化合物のＬｉｓ、ｅＴｉＳ＋を得た。The reaction product is separated, concentrated and dried, and then calcined for 6 hours at 1000°C in a hydrogen sulfide atmosphere to form a metal sulfide intercalation compound according to the method for synthesizing a metal sulfide intercalation compound according to another embodiment of the present invention. The compounds Lis and eTiS+ were obtained.
これについて、実施例１と同様にしてリチウムイオンの
見かけの拡散係数を測定し結果を表に示す。Regarding this, the apparent diffusion coefficient of lithium ions was measured in the same manner as in Example 1, and the results are shown in the table.
比較例
二硫化チタン（６津製薬！１１） １５．６８１にｎ−
ブチルリチウムのヘキサン溶液（ＭＥＲＣＫ）を添加し
アルゴン気流中に室温で２０時間放置してＬｉ、ｉ＋、
ａＴｉＳ２を調整した後、リチウムイオンの見かけの拡
散係数を実施例１と同様に測定し結果を表に示す。Comparative example Titanium disulfide (6tsu Pharmaceutical! 11) 15.681 n-
A hexane solution of butyl lithium (MERCK) was added and left at room temperature in an argon stream for 20 hours to form Li, i+,
After adjusting aTiS2, the apparent diffusion coefficient of lithium ions was measured in the same manner as in Example 1, and the results are shown in the table.
表から明かのように、この発明の実施例の金属硫化物系
ｊ［化合物の合成方法による金属硫化物系層間化合物は
従来のものと比較してリチウムの見かけの拡散係数が２
桁近く高くなることが明かとなった。As is clear from the table, the metal sulfide intercalation compound produced by the metal sulfide compound synthesis method of the embodiment of the present invention has an apparent diffusion coefficient of lithium of 2 compared to the conventional compound.
It became clear that the price would be nearly an order of magnitude higher.
［発明の効果］
以上説明したとおり、この発明は金属アルコキシドおよ
び金属β−ジケトン型有機物の内の少なくとも一種、ア
ルカリ金属の硫化物およびアルカリ金属の硫化水素化物
の内の少なくとも一種、および酸を混合して溶液とし反
応させ、反応生成物をＨ２Ｓ雰囲気中で焼成することに
より、ゲストイオンの拡散係数の大きな金属硫化物系層
間化合物の合成方法を得ることができる。[Effects of the Invention] As explained above, the present invention provides a mixture of at least one of a metal alkoxide and a metal β-diketone type organic substance, at least one of an alkali metal sulfide and an alkali metal hydrogen sulfide, and an acid. A method for synthesizing a metal sulfide-based intercalation compound having a large guest ion diffusion coefficient can be obtained by reacting in a solution and firing the reaction product in an H2S atmosphere.
第１図および第２図は、それぞれこの発明の実施例の金
属硫化物系層間化合物の合成方法に係わる金属アルコキ
シドの構造式を示す構造図、第３図はこの発明の実施例
の金属硫化物系層間化合物の合成方法に係わる金属β−
ジケトン型有機物の構造式を示す構造図、第４図はこの
発明の実施例の金属硫化物系層間化合物の合成方法に係
わる金属アルコキシドと金属β−ジケトン型有機物の混
合体の’ＦＲＲ式を示すａ造園である。
図において、Ｒ＋”Ｒａはアルキル基、Ｍ、Ｍ＋。
Ｍ２は金属、Ｒ口〜Ｒ目はアルキル基またはフェニル基
である。
なお、各図中同一符号は同一または相当部分を示す。
第１図
第２図
Ｒ，〜６：アルキル基
Ｍ、Ｍｔ、Ｍ２ ：金属1 and 2 are structural diagrams showing the structural formulas of metal alkoxides related to the method for synthesizing metal sulfide-based intercalation compounds according to embodiments of the present invention, and FIG. 3 is structural diagrams showing the structural formulas of metal alkoxides according to embodiments of the invention. Metal β- related to the synthesis method of intercalation compound
Structural diagram showing the structural formula of a diketone type organic substance. FIG. 4 shows the 'FRR formula of a mixture of a metal alkoxide and a metal β-diketone type organic substance related to the method for synthesizing a metal sulfide intercalation compound according to an embodiment of the present invention. a. Landscaping. In the figures, R+"Ra is an alkyl group, M, M+. M2 is a metal, and R-th to R-th are an alkyl group or a phenyl group. In each figure, the same reference numerals indicate the same or corresponding parts. FIG. Figure 2 R, ~6: Alkyl group M, Mt, M2: Metal
Claims (1)
の少なくとも一種、アルカリ金属の硫化物およびアルカ
リ金属の硫化水素化物の内の少なくとも一種、および酸
を混合して溶液とし反応させ、反応生成物をＨ＿２Ｓ雰
囲気中で焼成する金属硫化物系層間化合物の合成方法。At least one of a metal alkoxide and a metal β-diketone type organic substance, at least one of an alkali metal sulfide and an alkali metal hydrogen sulfide, and an acid are mixed and reacted as a solution, and the reaction product is placed in an H_2S atmosphere. A method for synthesizing metal sulfide-based intercalation compounds by firing in a medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1021696A JPH02204312A (en) | 1989-01-31 | 1989-01-31 | Method for synthesizing metal sulfide-based interlaminar compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1021696A JPH02204312A (en) | 1989-01-31 | 1989-01-31 | Method for synthesizing metal sulfide-based interlaminar compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02204312A true JPH02204312A (en) | 1990-08-14 |
Family
ID=12062233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1021696A Pending JPH02204312A (en) | 1989-01-31 | 1989-01-31 | Method for synthesizing metal sulfide-based interlaminar compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02204312A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009155197A (en) * | 2007-12-26 | 2009-07-16 | Samsung Electro Mech Co Ltd | Method for production of lamella-structure nanoparticle |
| WO2014148432A1 (en) * | 2013-03-18 | 2014-09-25 | 独立行政法人産業技術総合研究所 | Lithium titanium sulfide, lithium niobium sulfide, and lithium titanium niobium sulfide |
| WO2020213340A1 (en) * | 2019-04-19 | 2020-10-22 | 三井金属鉱業株式会社 | Method for producing sulfide solid electrolyte |
-
1989
- 1989-01-31 JP JP1021696A patent/JPH02204312A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009155197A (en) * | 2007-12-26 | 2009-07-16 | Samsung Electro Mech Co Ltd | Method for production of lamella-structure nanoparticle |
| WO2014148432A1 (en) * | 2013-03-18 | 2014-09-25 | 独立行政法人産業技術総合研究所 | Lithium titanium sulfide, lithium niobium sulfide, and lithium titanium niobium sulfide |
| JP6011989B2 (en) * | 2013-03-18 | 2016-10-25 | 国立研究開発法人産業技術総合研究所 | Lithium titanium sulfide, lithium niobium sulfide and lithium titanium niobium sulfide |
| US10090524B2 (en) | 2013-03-18 | 2018-10-02 | National Institute Of Advanced Industrial Science And Technology | Lithium titanium sulfide, lithium niobium sulfide, and lithium titanium niobium sulfide |
| WO2020213340A1 (en) * | 2019-04-19 | 2020-10-22 | 三井金属鉱業株式会社 | Method for producing sulfide solid electrolyte |
| JPWO2020213340A1 (en) * | 2019-04-19 | 2021-09-13 | 三井金属鉱業株式会社 | Method for producing sulfide solid electrolyte |
| KR20210120126A (en) * | 2019-04-19 | 2021-10-06 | 미쓰이금속광업주식회사 | Method for preparing sulfide solid electrolyte |
| CN113631507A (en) * | 2019-04-19 | 2021-11-09 | 三井金属矿业株式会社 | Method for producing sulfide solid electrolyte |
| US11618678B2 (en) | 2019-04-19 | 2023-04-04 | Mitsui Mining & Smelting Co., Ltd. | Method for producing sulfide solid electrolyte |
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