JP5943308B2 - Manufacturing method of battery active material M2Ti2O5S2 - Google Patents
Manufacturing method of battery active material M2Ti2O5S2 Download PDFInfo
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- JP5943308B2 JP5943308B2 JP2012264388A JP2012264388A JP5943308B2 JP 5943308 B2 JP5943308 B2 JP 5943308B2 JP 2012264388 A JP2012264388 A JP 2012264388A JP 2012264388 A JP2012264388 A JP 2012264388A JP 5943308 B2 JP5943308 B2 JP 5943308B2
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- 239000011149 active material Substances 0.000 title claims description 62
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 238000010304 firing Methods 0.000 claims description 28
- 229910052700 potassium Inorganic materials 0.000 claims description 28
- 239000011591 potassium Substances 0.000 claims description 28
- -1 potassium halide Chemical class 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 10
- 239000003586 protic polar solvent Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 description 13
- 239000010453 quartz Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052768 actinide Inorganic materials 0.000 description 2
- 150000001255 actinides Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical group N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
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- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、電池用活物質Ｍ２Ｔｉ２Ｏ５Ｓ２の製造方法に関する。 The present invention relates to a method for producing a battery active material M 2 Ti 2 O 5 S 2 .
リチウムイオン二次電池は、従来の二次電池よりもエネルギー密度が高く、高電圧で作動させることができる。そのため、小型軽量化を図りやすい二次電池として携帯電話等の情報機器に使用されており、近年、電気自動車用やハイブリッド自動車用等、大型の動力用としての需要も高まっている。 Lithium ion secondary batteries have a higher energy density than conventional secondary batteries and can be operated at a high voltage. For this reason, it is used as a secondary battery that can be easily reduced in size and weight in information equipment such as a mobile phone, and in recent years, there is an increasing demand for large motive power such as for electric vehicles and hybrid vehicles.
リチウムイオン二次電池は、正極層及び負極層と、これらの間に配置された電解質層とを有し、電解質層に用いられる電解質としては、例えば非水系の液体状や固体状の物質等が知られている。液体状の電解質（以下において、「電解液」という。）が用いられる場合には、電解液が正極層や負極層の内部へと浸透しやすい。そのため、正極層や負極層に含有されている活物質と電解液との界面が形成されやすく、性能を向上させやすい。ところが、広く用いられている電解液は可燃性であるため、安全性を確保するためのシステムを搭載する必要がある。一方、難燃性である固体状の電解質（以下において、「固体電解質」という。）を用いると、上記システムを簡素化できる。それゆえ、固体電解質を含有する層（以下において、「固体電解質層」という。）が備えられる形態のリチウムイオン二次電池（以下において、「全固体電池」ということがある。）の開発が進められている。 A lithium ion secondary battery has a positive electrode layer and a negative electrode layer, and an electrolyte layer disposed between them. Examples of the electrolyte used for the electrolyte layer include non-aqueous liquid and solid substances. Are known. When a liquid electrolyte (hereinafter referred to as “electrolytic solution”) is used, the electrolytic solution easily penetrates into the positive electrode layer and the negative electrode layer. Therefore, an interface between the active material contained in the positive electrode layer or the negative electrode layer and the electrolytic solution is easily formed, and the performance is easily improved. However, since the widely used electrolyte is flammable, it is necessary to mount a system for ensuring safety. On the other hand, when a solid electrolyte that is flame retardant (hereinafter referred to as “solid electrolyte”) is used, the above system can be simplified. Therefore, development of a lithium ion secondary battery (hereinafter, sometimes referred to as “all-solid battery”) in a form provided with a layer containing a solid electrolyte (hereinafter referred to as “solid electrolyte layer”) proceeds. It has been.
このようなリチウムイオン二次電池に関する技術として、例えば特許文献１には、Ｙ２Ｏ３、ＴｉＯ２、及び、ＴｉＳ２を混合することにより得た原料組成物を石英管に入れて真空封入した後、石英管を１１００℃で５日間に亘って焼成する過程を有する、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２の製造方法が開示されている。また、特許文献２には、Ｙ２Ｏ３、ＴｉＯ２、及び、ＴｉＳ２を混合することにより得た原料組成物をプレスすることによりペレットを作製し、得られたペレットを石英管に入れて真空封入した後、石英管を１１００℃で９６時間に亘って焼成する過程を有する、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２の製造方法が開示されている。 As a technology relating to such a lithium ion secondary battery, for example, in Patent Document 1, a raw material composition obtained by mixing Y 2 O 3 , TiO 2 , and TiS 2 is placed in a quartz tube and vacuum-sealed. Thereafter, a method for producing a battery active material Y 2 Ti 2 O 5 S 2 is disclosed which has a process of firing a quartz tube at 1100 ° C. for 5 days. Further, Patent Document 2, Y 2 O 3, TiO 2, and the pellet was prepared by pressing a raw material composition obtained by mixing TiS 2, the resulting pellet was placed in a quartz tube A method for producing a battery active material Y 2 Ti 2 O 5 S 2 is disclosed, which includes a process of firing a quartz tube at 1100 ° C. for 96 hours after vacuum sealing.
電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造する際の焼成温度を低温にすると、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２とは異なる副生成物（パイクロア構造のＹ２Ｔｉ２Ｏ７。以下において同じ。）が生成しやすい。特許文献１及び特許文献２に開示されている技術では、１１００℃で焼成しているため、副生成物の生成を抑制しながら、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造することが可能である。ところが、１１００℃もの高温で焼成すると、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造するための製造コストが増大しやすい。そこで、製造コストを低減する観点から、焼成温度を低下させても副生成物の生成を抑制することが可能な、第III族元素であるＭ元素、Ｔｉ元素、Ｏ元素、及び、Ｓ元素を含有し、Ｍ２Ｔｉ２Ｏ５Ｓ２結晶相を含有する電池用活物質Ｍ２Ｔｉ２Ｏ５Ｓ２の製造方法の開発が求められていた。 When the firing temperature in the production of the battery active material Y 2 Ti 2 O 5 S 2 to a low temperature, the active material for battery Y 2 Ti 2 O 5 S 2 different byproducts (the pyrochlore structure of Y 2 Ti 2 O 7 is the same in the following). In the techniques disclosed in Patent Document 1 and Patent Document 2, since the firing is performed at 1100 ° C., the production of the active material for battery Y 2 Ti 2 O 5 S 2 while suppressing the generation of by-products is performed. Is possible. However, when firing at a high temperature as high as 1100 ° C., the production cost for producing the battery active material Y 2 Ti 2 O 5 S 2 tends to increase. Therefore, from the viewpoint of reducing the manufacturing cost, a Group III element, an M element, a Ti element, an O element, and an S element that can suppress the generation of by-products even when the firing temperature is lowered. containing and development of M 2 Ti 2 O 5 S 2 method for producing the active material for battery M 2 Ti 2 O 5 S 2 containing a crystal phase has been demanded.
そこで本発明は、焼成温度を従来よりも低下させても副生成物の生成を抑制することが可能な電池用活物質Ｍ２Ｔｉ２Ｏ５Ｓ２の製造方法を提供することを課題とする。 The present invention aims to provide a battery active material manufacturing method of the M 2 Ti 2 O 5 S 2 capable of firing temperature is lowered than the conventional to suppress the formation of by-products .
本発明者は、鋭意検討の結果、Ｙ２Ｔｉ２Ｏ５Ｓ２の原料にハロゲン化カリウムを添加して焼成することにより、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造するための焼成を従来よりも低温で行っても、副生成物であるＹ２Ｔｉ２Ｏ７の生成を抑制できることを知見した。本発明は、当該知見に基づいて完成させた。 As a result of intensive studies, the inventor has added potassium halide to a raw material of Y 2 Ti 2 O 5 S 2 and baked to produce an active material for a battery Y 2 Ti 2 O 5 S 2. It has been found that the production of Y 2 Ti 2 O 7 as a by-product can be suppressed even when firing is performed at a lower temperature than before. The present invention has been completed based on this finding.
上記課題を解決するために、本発明は以下の手段をとる。すなわち、
本発明は、第III族元素であるＭ元素、Ｔｉ元素、Ｏ元素、及び、Ｓ元素を含有し、Ｍ２Ｔｉ２Ｏ５Ｓ２結晶相を含有する電池用活物質Ｍ２Ｔｉ２Ｏ５Ｓ２を製造するための原料と、ハロゲン化カリウムとを混合することにより混合物を得る混合工程と、得られた混合物をハロゲン化カリウムの融点以上の温度で焼成する焼成工程と、を有する、電池用活物質Ｍ２Ｔｉ２Ｏ５Ｓ２の製造方法である。
In order to solve the above problems, the present invention takes the following means. That is,
The present invention is, M element is a group III element, Ti element, O element, and contains a S element, M 2 Ti 2 O 5 S 2 battery active material M 2 Ti 2 O 5 containing crystalline phases has a raw material for producing S 2, a mixing step of obtaining a mixture by mixing a potassium halide, a firing step of the resulting mixture is calcined at a temperature above the melting point of potassium halide, a battery Yokatsu is a manufacturing method of the substance M 2 Ti 2 O 5 S 2 .
ここに、本発明において、第III族元素であるＭ元素は、通常、三価の第III族元素であり、Ｓｃ、Ｙ、ランタノイド及びアクチノイドが該当する。また、本発明で使用可能なハロゲン化カリウムとしては、ＫＦ、ＫＣｌ、ＫＢｒ、ＫＩを例示することができる。原料とハロゲン化カリウムとを混合することにより作製した混合物を焼成する過程を経て、電池用活物質Ｍ２Ｔｉ２Ｏ５Ｓ２を製造することにより、焼成温度を従来よりも低下させても、副生成物の生成を防止しながら電池用活物質Ｍ２Ｔｉ２Ｏ５Ｓ２を製造することが可能になる。 Here, in the present invention, the M element which is a Group III element is usually a trivalent Group III element, and corresponds to Sc, Y, lanthanoid and actinoid. Examples of potassium halide that can be used in the present invention include KF, KCl, KBr, and KI. Through the process of firing a mixture prepared by mixing raw materials and potassium halide, by producing the battery active material M 2 Ti 2 O 5 S 2 , even if the firing temperature is lower than conventional, It becomes possible to produce the battery active material M 2 Ti 2 O 5 S 2 while preventing the formation of by-products.
また、上記本発明において、上記Ｍ元素がＹであることが好ましい。かかる形態とすることにより、例えば、焼成温度を従来よりも低い９００℃にしても、副生成物であるＹ２Ｔｉ２Ｏ７の生成を防止しながら、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造することが可能にある。 In the present invention, the M element is preferably Y. By adopting such a form, for example, even when the firing temperature is set to 900 ° C., which is lower than the conventional temperature, the production of the by-product Y 2 Ti 2 O 7 is prevented, and the battery active material Y 2 Ti 2 O 5 is prevented. there can be prepared the S 2.
また、上記本発明において、プロトン性極性溶媒を用いて、上記焼成工程で得られた焼成物からハロゲン化カリウムを除去する除去工程を有することが好ましい。例えば、焼成工程で得られた焼成物をプロトン性極性溶媒に浸漬し、攪拌後にろ過することにより、ハロゲン化カリウムを除去することが可能である。したがって、かかる形態とすることにより、上記効果に加えて、容易にハロゲン化カリウムを除去することが可能になる。 Moreover, in the said invention, it is preferable to have a removal process which removes a potassium halide from the baked product obtained at the said baking process using a protic polar solvent. For example, it is possible to remove potassium halide by immersing the fired product obtained in the firing step in a protic polar solvent and filtering after stirring. Therefore, by adopting such a form, in addition to the above effects, potassium halide can be easily removed.
また、上記本発明において、ハロゲン化カリウムがＫＩであることが好ましい。ＫＩは、最も融点が低いハロゲン化カリウムであるため、ＫＩを用いることにより、焼成温度を低下させやすくなる。 In the present invention, the potassium halide is preferably KI. Since KI is potassium halide having the lowest melting point, the use of KI makes it easy to lower the firing temperature.
本発明によれば、焼成温度を従来よりも低下させても副生成物の生成を抑制することが可能な電池用活物質Ｍ２Ｔｉ２Ｏ５Ｓ２の製造方法を提供することができる。 According to the present invention, it is possible to provide a battery active material manufacturing method of the M 2 Ti 2 O 5 S 2 capable of firing temperature is lowered than the conventional to suppress the formation of by-products.
以下、図面を参照しつつ、本発明について説明する。なお、以下の説明では、電池用活物質Ｍ２Ｔｉ２Ｏ５Ｓ２の一形態である電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造する形態を主に例示するが、本発明は当該形態に限定されない。 The present invention will be described below with reference to the drawings. In the following description, mainly illustrating a configuration for manufacturing the active material for battery Y 2 Ti 2 O 5 S 2 which is an embodiment of a battery active material M 2 Ti 2 O 5 S 2 , the present invention is It is not limited to the said form.
図１は、本発明の電池用活物質Ｍ２Ｔｉ２Ｏ５Ｓ２の製造方法（以下において、「本発明の製造方法」ということがある。）を説明する図である。図１に示した本発明の製造方法は、混合工程（Ｓ１）と、焼成工程（Ｓ２）と、除去工程（Ｓ３）と、を有している。 FIG. 1 is a diagram for explaining a method for producing a battery active material M 2 Ti 2 O 5 S 2 of the present invention (hereinafter sometimes referred to as “the production method of the present invention”). The manufacturing method of the present invention shown in FIG. 1 includes a mixing step (S1), a firing step (S2), and a removing step (S3).
混合工程（以下において、「Ｓ１」ということがある。）は、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造するための原料（以下において、「ＹＴＯＳ用原料」ということがある。）と、ハロゲン化カリウムとを混合することにより混合物を得る工程である。ＹＴＯＳ用原料は、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造可能であれば、その種類及び組合せは特に限定されない。Ｓ１で使用可能なＹＴＯＳ用原料としては、Ｔｉ、Ｓ、ＴｉＯ２、及び、Ｙ２Ｏ３の組合せや、ＴｉＳ２、ＴｉＯ２、及び、Ｙ２Ｏ３の組合せ等を例示することができる。また、Ｓ１で使用可能なハロゲン化カリウムとしては、ＫＦ、ＫＣｌ、ＫＢｒ、ＫＩ等を例示することができる。 The mixing step (hereinafter sometimes referred to as “S1”) is a raw material for producing the battery active material Y 2 Ti 2 O 5 S 2 (hereinafter sometimes referred to as “YTOS raw material”). And potassium halide are mixed to obtain a mixture. As long as the YTOS raw material can produce the battery active material Y 2 Ti 2 O 5 S 2 , the type and combination thereof are not particularly limited. Examples of raw materials for YTOS that can be used in S1 include combinations of Ti, S, TiO 2 , and Y 2 O 3 , combinations of TiS 2 , TiO 2 , and Y 2 O 3 . Examples of potassium halide that can be used in S1 include KF, KCl, KBr, and KI.
Ｓ１で混合される、ＹＴＯＳ用原料とハロゲン化カリウムとの混合比率は、副生成物の生成を抑制しつつ電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造するための焼成温度を低下させる効果を奏する範囲内で、適宜変更することができる。当該効果を奏しやすくする観点から、Ｓ１で混合されるＹＴＯＳ用原料とハロゲン化カリウムとの総重量に占めるハロゲン化カリウムの重量の比率Ｘは、Ｘ≧１／３以上とすることが好ましい。 The mixing ratio of the YTOS raw material and potassium halide mixed in S1 lowers the firing temperature for producing the battery active material Y 2 Ti 2 O 5 S 2 while suppressing the formation of by-products. It can be changed as appropriate within the range where the effect is achieved. From the viewpoint of facilitating the effect, it is preferable that the ratio X of the weight of potassium halide to the total weight of the YTOS raw material and potassium halide mixed in S1 is X ≧ 1/3 or more.
焼成工程（以下において、「Ｓ２」ということがある。）は、Ｓ１で得られた混合物を焼成することにより、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造する工程である。Ｓ２の焼成温度は、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造可能であれば、特に限定されないが、製造コストを低減しやすい形態にする観点からは、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造可能な範囲内で可能な限り低温にすることが好ましい。例えば、Ｓ１でハロゲン化カリウムとしてＫＩを使用する場合、Ｓ２の焼結温度は、ＫＩの融点である６８０℃以上にすることが好ましい。 The firing step (hereinafter sometimes referred to as “S2”) is a step of producing the battery active material Y 2 Ti 2 O 5 S 2 by firing the mixture obtained in S1. The firing temperature of S2 is not particularly limited as long as the battery active material Y 2 Ti 2 O 5 S 2 can be produced, but from the viewpoint of easily reducing the production cost, the battery active material Y 2 Ti It is preferable to make 2 O 5 S 2 as low as possible within the range that can be produced. For example, when KI is used as potassium halide in S1, the sintering temperature of S2 is preferably 680 ° C. or higher, which is the melting point of KI.
除去工程（以下において、「Ｓ３」ということがある。）は、プロトン性極性溶媒を用いて、Ｓ２で得られた焼成物からハロゲン化カリウムを除去する工程である。ハロゲン化カリウムは電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２とは反応しない。また、ハロゲン化カリウムはプロトン性極性溶媒に易溶のイオン性物質である。それゆえ、Ｓ２で得られた焼成物をプロトン性極性溶媒に浸漬し、例えば攪拌後に濾過することにより、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｏ２とハロゲン化カリウムとを容易に分離することができる。
Ｓ３で使用可能なプロトン性極性溶媒としては、水やエタノール等を例示することができる。
The removal step (hereinafter sometimes referred to as “S3”) is a step of removing potassium halide from the fired product obtained in S2 using a protic polar solvent. Potassium halide does not react with the battery active material Y 2 Ti 2 O 5 S 2 . In addition, potassium halide is an ionic substance that is easily soluble in a protic polar solvent. Therefore, the active material for battery Y 2 Ti 2 O 5 O 2 and potassium halide can be easily separated by immersing the fired product obtained in S2 in a protic polar solvent and filtering, for example, after stirring. Can do.
Examples of protic polar solvents that can be used in S3 include water and ethanol.
Ｓ２を有する本発明の製造方法では、ハロゲン化カリウムを用いることにより、従来よりも低温で焼成しても、副生成物の生成を抑制することができる。したがって、本発明によれば、焼成温度を従来よりも低下させても副生成物の生成を抑制することが可能な電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２の製造方法を提供することができる。さらに、ハロゲン化カリウムはプロトン性極性溶媒に易溶のイオン性物質であるため、プロトン性極性溶媒を用いてハロゲン化カリウムを除去するＳ３を有する形態とすることにより、製造した電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を容易に分離することが可能になる。 In the production method of the present invention having S2, by using potassium halide, it is possible to suppress the formation of by-products even when firing at a lower temperature than before. Therefore, according to the present invention, it is possible to provide a method for producing a battery active material Y 2 Ti 2 O 5 S 2 that can suppress the formation of by-products even when the firing temperature is lowered than before. it can. Furthermore, since potassium halide is an ionic substance that is readily soluble in a protic polar solvent, the battery active material Y produced by adopting a form having S3 that removes potassium halide using a protic polar solvent. 2 Ti 2 O 5 S 2 can be easily separated.
本発明において、Ｍ２Ｔｉ２Ｏ５Ｓ２結晶相の存在は、Ｘ線回折（ＸＲＤ）等により確認することができる。また、Ｍ２Ｔｉ２Ｏ５Ｓ２結晶相は、欠陥型Ruddlesden-Popper構造の結晶相に該当するものと考えられる。一般的に、Ruddlesden-Popper構造は、一般式Ａｎ＋１ＢｎＣ３ｎ＋１（ｎは整数）で表される組成を有し、ペロブスカイト構造と、岩塩構造とが交互に重なった層状構造を有する。ここで、ｎ＝２とした場合、上記の一般式はＡ３Ｂ２Ｃ７で表すことができる。このＡ３Ｂ２Ｃ７と、本発明におけるＭ２Ｔｉ２Ｏ５Ｓ２とを比較すると、ＡサイトにはＭが位置し、ＢサイトにはＴｉが位置し、ＣサイトにはＯ及びＳが位置することになる。さらに、Ａサイトにおいて、Ｍが３原子位置すると、完全なRuddlesden-Popper構造に該当するが、本発明においてはＭが２原子しか位置していない。そのため、このＡサイトに欠陥が生じ、この欠陥部位に金属イオン（例えばＬｉイオン）が挿入脱離し、活物質としての機能が顕著に発現すると考えられる。また、Ｍ２Ｔｉ２Ｏ５Ｓ２結晶相と、金属イオン（例えばＬｉイオン）との反応は、以下の通りであると考えられ、Ｍ２Ｔｉ２Ｏ５Ｓ２結晶相は、いわゆる挿入脱離型の活物質として機能すると考えられる。
Ｍ２Ｔｉ２Ｏ５Ｓ２＋ｘＬｉ＋＋ｘｅ−⇔ＬｉｘＭ２Ｔｉ２Ｏ５Ｓ２
In the present invention, the presence of the M 2 Ti 2 O 5 S 2 crystal phase can be confirmed by X-ray diffraction (XRD) or the like. Further, the M 2 Ti 2 O 5 S 2 crystal phase is considered to correspond to a crystal phase having a defective Ruddlesden-Popper structure. In general, the Ruddlesden-Popper structure has a composition represented by the general formula A n + 1 B n C 3n + 1 (n is an integer), and has a layered structure in which perovskite structures and rock salt structures are alternately stacked. Here, when n = 2, the above general formula can be expressed as A 3 B 2 C 7 . When this A 3 B 2 C 7 is compared with M 2 Ti 2 O 5 S 2 in the present invention, M is located at the A site, Ti is located at the B site, and O and S are located at the C site. Will be located. Further, when M is located at 3 atoms in the A site, it corresponds to a complete Ruddlesden-Popper structure, but in the present invention, M is located at only 2 atoms. Therefore, it is considered that a defect is generated at the A site, and a metal ion (for example, Li ion) is inserted and desorbed at the defect site, so that the function as an active material is remarkably exhibited. In addition, the reaction between the M 2 Ti 2 O 5 S 2 crystal phase and metal ions (for example, Li ions) is considered to be as follows, and the M 2 Ti 2 O 5 S 2 crystal phase is a so-called insertion desorption. It is thought to function as a release active material.
M 2 Ti 2 O 5 S 2 + xLi + + xe - ⇔Li x M 2 Ti 2 O 5 S 2
本発明におけるＭ元素は、通常、三価の第III族元素であり、Ｓｃ、Ｙ、ランタノイド、及び、アクチノイドが該当する。中でも、Ｍ元素は、Ｙ、Ｎｄ、Ｓｃ、Ｐｒ、Ｓｍ、Ｇｄ、Ｔｂ、Ｄｙ、Ｅｒからなる群から選択される少なくとも一種以上であることが好ましく、Ｙ、Ｎｄ、Ｓｃからなる群から選択される少なくとも一種以上であることがより好ましい。 The M element in the present invention is usually a trivalent group III element, and corresponds to Sc, Y, lanthanoid, and actinoid. Among them, the M element is preferably at least one selected from the group consisting of Y, Nd, Sc, Pr, Sm, Gd, Tb, Dy, and Er, and is selected from the group consisting of Y, Nd, and Sc. More preferably, it is at least one or more.
１．電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２の製造
＜実施例１＞
Ｔｉ（株式会社高純度化学研究所製）及びＳ（株式会社高純度化学研究所製）をモル比でＴｉ：Ｓ＝１：２で混合することにより得た混合物を石英管に入れ、真空封入した。その後、石英管を６００℃に加熱し、６００℃の状態を２４時間に亘って維持することにより、ＴｉＳ２を合成した。
合成したＴｉＳ２と、ＴｉＯ２（株式会社高純度化学研究所製）と、Ｙ２Ｏ３（株式会社高純度化学研究所製）とを、モル比でＴｉＳ２：ＴｉＯ２：Ｙ２Ｏ３＝１：１：１で混合することにより、混合されたＹＴＯＳ用原料を得た。次いで、このＹＴＯＳ用原料とＫＩ（株式会社高純度化学研究所製）とを、質量比でＹＴＯＳ用原料：ＫＩ＝１：１で混合することにより混合物を得、この混合物を石英管に入れて真空封入した。その後、石英管を９００℃に加熱し、９００℃の状態を７２時間に亘って維持することにより、実施例１の電池用活物質を合成した。
1. Production of Battery Active Material Y 2 Ti 2 O 5 S 2 <Example 1>
A mixture obtained by mixing Ti (manufactured by Kojundo Chemical Laboratory Co., Ltd.) and S (manufactured by Kojundo Chemical Laboratory Co., Ltd.) at a molar ratio of Ti: S = 1: 2 is placed in a quartz tube and vacuum sealed. did. Thereafter, the quartz tube was heated to 600 ° C., by maintaining over the state of 600 ° C. for 24 hours to synthesize TiS 2.
The synthesized TiS 2 , TiO 2 (manufactured by Kojundo Chemical Laboratory Co., Ltd.), and Y 2 O 3 (manufactured by Kojundo Chemical Laboratories Co., Ltd.) in a molar ratio of TiS 2 : TiO 2 : Y 2 O 3 By mixing at 1: 1: 1, a mixed YTOS raw material was obtained. Next, this YTOS raw material and KI (manufactured by Kojundo Chemical Laboratory Co., Ltd.) are mixed at a mass ratio of YTOS raw material: KI = 1: 1 to obtain a mixture, and this mixture is put in a quartz tube. Vacuum sealed. Thereafter, the quartz tube was heated to 900 ° C., and the state of 900 ° C. was maintained for 72 hours, thereby synthesizing the battery active material of Example 1.
＜実施例２＞
得られた実施例１の電池用活物質を水に浸して攪拌した後、ろ過することにより、ＫＩを除去した。このようにして、ＫＩが除去された電池用活物質（実施例２の電池用活物質）を得た。
<Example 2>
The obtained battery active material of Example 1 was immersed in water and stirred, and then filtered to remove KI. Thus, the battery active material from which KI was removed (battery active material of Example 2) was obtained.
２．Ｘ線回折測定
実施例１の電池用活物質、及び、実施例２の電池用活物質を粉砕し、粉末用の活物質を得た。この粉末状の活物質に対して、Ｘ線回折（ＸＲＤ）測定を行った。実施例１の電池用活物質及び実施例２の電池用活物質の結果を、ＫＩのピーク位置とともに、図２に示す。
図２より、実施例１の電池用活物質及び実施例２の電池用活物質は、何れもＹ２Ｔｉ２Ｏ５Ｓ２結晶相を示すピークが確認され、Ｙ２Ｔｉ２Ｏ７結晶相を示すピークは確認されなかった。また、実施例１の電池用活物質ではＫＩのピークが確認されたが、実施例２の電池用活物質ではＫＩのピークが確認されなかった。すなわち、実施例２の電池用活物質にはＫＩが含まれていないことが確認された。なお、Ｙ２Ｔｉ２Ｏ５Ｓ２結晶相を示すピークは、２θ＝１５．５°、２６．３°、３３．５°、３６．４°、４２．９°、４８．２°に現れた。
以上より、本発明によれば、副生成物の生成を防止するために従来は１１００℃程度にする必要があった焼成温度を９００℃へと低下させても、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２を製造可能であり、且つ、従来よりも低温の９００℃で焼成しても、副生成物の生成を防止することが可能であることが確認された。このように、本発明によれば焼成温度を従来よりも低下させることが可能なので、電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２の製造コストを低減することも可能になる。
2. X-ray diffraction measurement The active material for a battery of Example 1 and the active material for a battery of Example 2 were pulverized to obtain an active material for powder. X-ray diffraction (XRD) measurement was performed on the powdery active material. The results of the battery active material of Example 1 and the battery active material of Example 2 are shown in FIG. 2 together with the peak position of KI.
As shown in FIG. 2, the battery active material of Example 1 and the battery active material of Example 2 were confirmed to have peaks indicating the Y 2 Ti 2 O 5 S 2 crystal phase, and the Y 2 Ti 2 O 7 crystal phase was confirmed. The peak which shows was not confirmed. Moreover, although the KI peak was confirmed in the battery active material of Example 1, the KI peak was not confirmed in the battery active material of Example 2. That is, it was confirmed that the battery active material of Example 2 did not contain KI. The peaks indicating the Y 2 Ti 2 O 5 S 2 crystal phase appear at 2θ = 15.5 °, 26.3 °, 33.5 °, 36.4 °, 42.9 °, 48.2 °. It was.
As described above, according to the present invention, even if the firing temperature, which conventionally has been required to be about 1100 ° C. in order to prevent the formation of by-products, is reduced to 900 ° C., the active material for batteries Y 2 Ti 2 It was confirmed that O 5 S 2 can be produced and that by-product formation can be prevented even when firing at 900 ° C., which is lower than in the past. As described above, according to the present invention, the firing temperature can be lowered as compared with the prior art, so that the manufacturing cost of the battery active material Y 2 Ti 2 O 5 S 2 can be reduced.
３．電池の作製
実施例２の電池用活物質を石英管に入れて真空封入した後、石英管を１２０℃に加熱し、１２０℃の状態を１２時間に亘って維持することにより、実施例２の電池用活物質を乾燥した。次いで、乾燥した実施例２の電池用活物質をプレスすることによりペレット状に成型した。
成型された電池用活物質とともに、対極としてＬｉ金属を用い、且つ、ＥＣ（エチレンカーボネート）及びＤＥＣ（ジエチルカーボネート）を混合した溶媒にＬｉＰＦ６を濃度１ｍｏｌ／Ｌで溶解させた電解液を用いて、ＣＲ２０２３型の評価用電池（実施例の評価用電池）を作製した。
3. Production of Battery After putting the battery active material of Example 2 into a quartz tube and vacuum-sealing it, the quartz tube was heated to 120 ° C. and maintained at 120 ° C. for 12 hours. The battery active material was dried. Next, the dried battery active material of Example 2 was pressed into a pellet.
Along with the molded battery active material, using Li metal as a counter electrode, and using an electrolytic solution in which LiPF 6 is dissolved at a concentration of 1 mol / L in a solvent in which EC (ethylene carbonate) and DEC (diethyl carbonate) are mixed A CR2023 type evaluation battery (evaluation battery of Examples) was produced.
４．充放電試験
作製した実施例の評価用電池を２５℃の恒温槽に設置し、定電流充放電（０．２ｍＡ）、充放電範囲０．０５Ｖ以上３．０Ｖ以下の条件で、充放電を行った。ＫＩを用いることなく１１００℃で焼結させる過程を経て作製した電池用電解質Ｙ２Ｔｉ２Ｏ５Ｓ２を用いるほかは実施例の評価用電池と同様に作製した比較例の電池の結果とともに、図３に充放電試験結果を示す。図３において、点線が実施例の評価用電池の結果であり、実線が比較例の電池の結果である。
図３に示したように、実施例の評価用電池は、比較例の電池と同等の性質を示した。したがって、本発明の製造方法で製造した電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２は、ハロゲン化カリウムを用いない従来法で作製された電池用活物質Ｙ２Ｔｉ２Ｏ５Ｓ２と同等の性能を有することが確認された。
4). Charging / discharging test The battery for evaluation of the produced Example was installed in a thermostat at 25 ° C., and charging / discharging was performed under conditions of constant current charging / discharging (0.2 mA) and a charging / discharging range of 0.05 V to 3.0 V. It was. Along with the result of the battery of the comparative example produced in the same manner as the evaluation battery of the example except that the battery electrolyte Y 2 Ti 2 O 5 S 2 produced through the process of sintering at 1100 ° C. without using KI is used, FIG. 3 shows the charge / discharge test results. In FIG. 3, the dotted line is the result of the battery for evaluation of the example, and the solid line is the result of the battery of the comparative example.
As shown in FIG. 3, the evaluation battery of the example showed the same properties as the battery of the comparative example. Therefore, the battery active material Y 2 Ti 2 O 5 S 2 produced by the production method of the present invention is equivalent to the battery active material Y 2 Ti 2 O 5 S 2 produced by a conventional method not using potassium halide. It was confirmed to have the following performance.
Claims (4)
得られた前記混合物を前記ハロゲン化カリウムの融点以上の温度で焼成する焼成工程と、
を有する、電池用活物質Ｍ２Ｔｉ２Ｏ５Ｓ２の製造方法。
A battery active material M 2 Ti 2 O 5 S 2 containing an M element, a Ti element, an O element, and an S element, which are Group III elements, and containing an M 2 Ti 2 O 5 S 2 crystal phase is manufactured. A mixing step of obtaining a mixture by mixing a raw material for producing and potassium halide;
A firing step of firing the obtained mixture at a temperature equal to or higher than the melting point of the potassium halide ;
The a method for producing a battery active material M 2 Ti 2 O 5 S 2 .
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