JPWO2019187943A1 - A negative electrode active material for a fluoride ion secondary battery, a negative electrode using the active material, a fluoride ion secondary battery, and a method for producing the active material. - Google Patents
A negative electrode active material for a fluoride ion secondary battery, a negative electrode using the active material, a fluoride ion secondary battery, and a method for producing the active material. Download PDFInfo
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 95
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 239000011149 active material Substances 0.000 title abstract description 10
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical class F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 93
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 24
- -1 fluoride ions Chemical class 0.000 claims abstract description 16
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 150000001340 alkali metals Chemical class 0.000 claims description 27
- 229910052783 alkali metal Inorganic materials 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 24
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 229910016569 AlF 3 Inorganic materials 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 14
- 239000007784 solid electrolyte Substances 0.000 claims description 13
- 238000006115 defluorination reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000003795 desorption Methods 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 238000003411 electrode reaction Methods 0.000 abstract description 9
- 230000002441 reversible effect Effects 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 19
- 229910052744 lithium Inorganic materials 0.000 description 19
- 239000013078 crystal Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 235000013365 dairy product Nutrition 0.000 description 2
- FPHIOHCCQGUGKU-UHFFFAOYSA-L difluorolead Chemical compound F[Pb]F FPHIOHCCQGUGKU-UHFFFAOYSA-L 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910016509 CuF 2 Inorganic materials 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910017768 LaF 3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
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- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/50—Fluorides
- C01F7/54—Double compounds containing both aluminium and alkali metals or alkaline-earth metals
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H01M4/139—Processes of manufacture
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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Abstract
フッ化物イオン二次電池における可逆的な負極反応を、高い利用率で発現することのできるフッ化物イオン二次電池用負極活物質、当該活物質を用いた負極、およびフッ化物イオン二次電池、並びに当該活物質の製造方法を提供する。フッ化アルミニウム（ＡｌＦ３）から部分的にフッ化物イオン（Ｆ—）をあらかじめ脱離させ、フッ素原子が存在していた位置に空孔を設けるよう改質した改質フッ化アルミニウム（ＡｌＦ３）を、フッ化物イオン二次電池用負極活物質とする。A negative electrode active material for a fluoride ion secondary battery capable of expressing a reversible negative electrode reaction in a fluoride ion secondary battery with a high utilization rate, a negative electrode using the active material, and a fluoride ion secondary battery. In addition, a method for producing the active material is provided. Modified aluminum fluoride (AlF3), which is modified by partially desorbing fluoride ions (F—) from aluminum fluoride (AlF3) in advance to provide holes at the positions where fluorine atoms were present, is used. Fluoride ion Negative active material for secondary batteries.
Description
本発明は、フッ化物イオン二次電池用負極活物質、当該活物質を用いた負極、およびフッ化物イオン二次電池、並びに当該活物質の製造方法に関する。 The present invention relates to a negative electrode active material for a fluoride ion secondary battery, a negative electrode using the active material, a fluoride ion secondary battery, and a method for producing the active material.
従来、高エネルギー密度を有する二次電池として、リチウムイオン二次電池が幅広く普及している。リチウムイオン二次電池は、正極と負極との間にセパレータを存在させ、液体の電解質（電解液）が充填された構造を有する。 Conventionally, a lithium ion secondary battery has been widely used as a secondary battery having a high energy density. The lithium ion secondary battery has a structure in which a separator is present between the positive electrode and the negative electrode and is filled with a liquid electrolyte (electrolyte solution).
リチウムイオン二次電池の電解液は、通常、可燃性の有機溶媒であるため、特に、熱に対する安全性が問題となる場合があった。そこで、有機系の液体の電解質に代えて、無機系の固体の電解質を用いた固体電池が提案されている（特許文献１参照）。固体電解質による固体電池は、電解液を用いる電池と比較して、熱の問題を解消するとともに、積層により電圧を上昇させることができ、さらに、コンパクト化の要請にも対応することができる。 Since the electrolytic solution of the lithium ion secondary battery is usually a flammable organic solvent, safety against heat may be a problem in particular. Therefore, a solid-state battery using an inorganic solid electrolyte instead of the organic liquid electrolyte has been proposed (see Patent Document 1). Compared with a battery using an electrolytic solution, a solid-state battery using a solid electrolyte can solve the problem of heat, increase the voltage by stacking, and can meet the demand for compactification.
このような固体電解質による電池として、フッ化物イオン二次電池が検討されている。フッ化物イオン二次電池は、フッ化物イオン（Ｆ−）をキャリアとした二次電池であり、高い理論エネルギーを有することが知られている。そして、その電池特性については、リチウムイオン二次電池を上回る期待がある。As a battery using such a solid electrolyte, a fluoride ion secondary battery is being studied. The fluoride ion secondary battery is a secondary battery using fluoride ion (F − ) as a carrier, and is known to have high theoretical energy. The battery characteristics are expected to exceed those of lithium-ion secondary batteries.
ここで、フッ化物イオン二次電池の負極活物質としては、ＭｇＦ２、ＣａＦ２、ＣｅＦ３等が報告されている（非特許文献１および２参照）。しかしながら、現在報告されているこれら負極活物質を用いたフッ化物イオン二次電池は、その充放電効率が１０〜２０％であり、２次電池としてのエネルギー効率が低いという問題があった。また、充放電容量についても、理論容量の１０〜２０％程度しかなく、現行のＬｉイオン２次電池やＮｉ−ＭＨ電池と比べて高容化が図られていない状況であった。 Here, MgF 2 , CaF 2 , CeF 3, and the like have been reported as negative electrode active materials for fluoride ion secondary batteries (see Non-Patent
フッ化物イオン二次電池で使用されている、固体電解質としては、例えば、Ｌａ１−ｘＢａｘＦ３−ｘ、ｘ＝０．０１〜０．２（以下ＬＢＦと呼ぶ）が存在している（非特許文献１〜４参照）。ＬＢＦの還元側電位窓は、図１に示されるように、ギブスエネルギーから算出されるＬａ／ＬａＦ３の電位である−２．４１Ｖ ｖｓ．Ｐｂ／ＰｂＦ２で制約を受ける。Examples of the solid electrolyte used in the fluoride ion secondary battery include La 1-x Ba x F 3-x and x = 0.01 to 0.2 (hereinafter referred to as LBF). (See Non-Patent
これに対して、図１に示されるように、現在報告されているフッ化物イオン二次電池の負極活物質の電位は、ＭｇＦ２が、−２．３５〜−２．８７Ｖ ｖｓ．Ｐｂ／ＰｂＦ２、ＣａＦ２が、−２．８５〜−２．８９Ｖ ｖｓ．Ｐｂ／ＰｂＦ２、ＣｅＦ３が、−２．１８〜−２．３７Ｖ ｖｓ．Ｐｂ／ＰｂＦ２である。したがって、ＬＢＦの還元電位窓である−２．４１Ｖの制約下における上記の負極活物質の脱フッ化／再フッ化反応は、その過電圧を考慮すると、提供できないという課題があった。On the other hand, as shown in FIG. 1, the potential of the negative electrode active material of the fluoride ion secondary battery currently reported is that MgF 2 is -2.35 to -2.87 V vs. Pb / PbF 2 and CaF 2 are -2.85 to -2.89 V vs. Pb / PbF 2 and CeF 3 are -2.18 to -2.37V vs. It is Pb / PbF 2 . Therefore, there is a problem that the defluorination / refluorination reaction of the above-mentioned negative electrode active material under the constraint of -2.41V, which is the reduction potential window of LBF, cannot be provided in consideration of its overvoltage.
一方で、正極反応についてみると、たとえばＣｕ／ＣｕＦ２、Ｂｉ／ＢｉＦ３等の正極活物質は、高い利用率や可逆反応を示す充放電試験の結果が報告されている（非特許文献１〜３、および特許文献２参照）。On the other hand, regarding the positive electrode reaction, for example , positive electrode active materials such as Cu / CuF 2 and Bi / BiF 3 have been reported to have high utilization rates and reversible reaction results (Non-Patent
したがって、フッ化物イオン二次電池において、正／負極反応を組み合わせた実用的な全電池反応を成立させるためには、可逆的な負極反応を高い利用率で発現する負極活物質材料が必要とされていた。 Therefore, in a fluoride ion secondary battery, a negative electrode active material that exhibits a reversible negative electrode reaction with a high utilization rate is required in order to establish a practical all-battery reaction that combines a positive / negative electrode reaction. Was there.
本発明は上記の背景技術に鑑みてなされたものであり、その目的は、フッ化物イオン二次電池において、可逆的な負極反応を高い利用率で発現することのできるフッ化物イオン二次電池用負極活物質、当該活物質を用いた負極、およびフッ化物イオン二次電池、並びに当該活物質の製造方法を提供することにある。 The present invention has been made in view of the above background technique, and an object thereof is for a fluoride ion secondary battery capable of exhibiting a reversible negative electrode reaction with a high utilization rate in the fluoride ion secondary battery. It is an object of the present invention to provide a negative electrode active material, a negative electrode using the active material, a fluoride ion secondary battery, and a method for producing the active material.
本発明者は、フッ化物イオン固体電解質であるＬＢＦの電位窓−２．４１Ｖの制約内に充放電反応（脱フッ化／再フッ化反応）が存在するフッ化アルミニウム（ＡｌＦ３：−１．７８Ｖ ｖｓ．Ｐｂ／ＰｂＦ２）に着目した。フッ化アルミニウム（ＡｌＦ３）は、負極反応の過電圧を０．５Ｖ程度と想定しても、ＬＢＦの還元側電位窓内（−２．４１Ｖ ｖｓ．Ｐｂ／ＰｂＦ２）に十分な酸化還元電位を有する。 The present inventor has made aluminum fluoride (AlF 3 : -1.) In which a charge / discharge reaction (defluorination / refluorination reaction) exists within the constraint of the potential window -2.41V of LBF, which is a fluoride ion solid electrolyte. We focused on 78V vs. Pb / PbF2). Aluminum fluoride (AlF 3 ) has a sufficient oxidation-reduction potential in the reduction side potential window (-2.41V vs. Pb / PbF2) of LBF even if the overvoltage of the negative electrode reaction is assumed to be about 0.5V. ..
しかし、フッ化アルミニウム（ＡｌＦ３）は、図２に示すように、イオン的、電子的にほぼ伝導率がゼロの絶縁体であることが知られている（文献５参照）。このため、フッ化アルミニウム（ＡｌＦ３）からのフッ化物イオン（Ｆ−）の脱離および再挿入（本明細書においては、これを脱フッ化／再フッ化反応と称する）を原理とする、負極反応は発現しない。
文献５：Ｐｈｙｓ．Ｒｅｖ．Ｂ．６９，０５４１０９（２００４）However, as shown in FIG. 2, aluminum fluoride (AlF 3 ) is known to be an insulator having almost zero conductivity ionically and electronically (see Reference 5). Therefore, the principle is the elimination and reinsertion of fluoride ion (F − ) from aluminum fluoride (AlF 3 ) (in the present specification, this is referred to as a defluorination / refluorination reaction). Negative reaction does not occur.
Reference 5: Phys. Rev. B. 69,054109 (2004)
そこで、本発明者は、フッ化アルミニウム（ＡｌＦ３）の結晶構造に着目した。図３に示すように、フッ化アルミニウム（ＡｌＦ３）は、６配位八面体の完全結晶の構造を有する。本発明者は、この結晶構造が、脱フッ化／再フッ化反応を妨げていると考えた。Therefore, the present inventor paid attention to the crystal structure of aluminum fluoride (AlF 3). As shown in FIG. 3, aluminum fluoride (AlF 3 ) has a hexacoordinated octahedral perfect crystal structure. The present inventor considered that this crystal structure hindered the defluorination / refluorination reaction.
そして、フッ化アルミニウム（ＡｌＦ３）から部分的にフッ化物イオン（Ｆ―）をあらかじめ脱離させ、フッ素原子が存在していた位置に空孔を設けるようフッ化アルミニウム（ＡｌＦ３）を改質すれば、当該空孔が脱フッ化／再フッ化反応の起点となり、所望の負極反応を、高い利用率および可逆性で発現させることができることを見出し、本発明を完成させるに至った。Then, aluminum fluoride (AlF 3) partially fluoride ions from - reforming were previously desorbed, aluminum fluoride so as to provide pores in the position where the fluorine atom was present (AlF 3) (F) Then, it was found that the pores became the starting point of the defluorination / refluorination reaction, and the desired negative electrode reaction could be expressed with high utilization rate and reversibility, and the present invention was completed.
すなわち本発明は、フッ化物イオンの脱離による空孔を有する改質フッ化アルミニウムである、フッ化物イオン二次電池用負極活物質である。 That is, the present invention is a negative electrode active material for a fluoride ion secondary battery, which is a modified aluminum fluoride having pores due to desorption of fluoride ions.
前記空孔は、脱フッ化反応および再フッ化反応の起点となっていてもよい。 The pores may serve as a starting point for the defluorination reaction and the refluorination reaction.
前記空孔は、改質前のフッ化アルミニウムにおいて、フッ素原子が存在していた領域であってもよい。 The pores may be regions where fluorine atoms were present in the aluminum fluoride before modification.
前記フッ化物イオンの脱離は、フッ化アルミニウムに、アルカリ金属またはアルカリ土類金属を接触させたものであってもよい。 The desorption of fluoride ions may be carried out by contacting aluminum fluoride with an alkali metal or an alkaline earth metal.
また別の本発明は、上記のフッ化物イオン二次電池用負極活物質を含む、フッ化物イオン二次電池用負極である。 Another invention is a negative electrode for a fluoride ion secondary battery containing the above-mentioned negative electrode active material for a fluoride ion secondary battery.
また別の本発明は、上記の記載のフッ化物イオン二次電池用負極と、固体電解質と、正極と、を備えるフッ化物イオン二次電池である。 Another invention is a fluoride ion secondary battery including the above-described negative electrode for a fluoride ion secondary battery, a solid electrolyte, and a positive electrode.
また別の本発明は、フッ化物イオン二次電池用負極活物質となる改質フッ化アルミニウムを製造する方法であって、フッ化アルミニウムと、アルカリ金属またはアルカリ土類金属とを接触させて、前記フッ化アルミニウムからフッ化物イオンを脱離させることにより、前記フッ化物イオンとして脱離したフッ素原子の存在位置を空孔として改質フッ化アルミニウムとする、フッ化物イオン二次電池用負極活物質の製造方法である。 Another invention is a method for producing modified aluminum fluoride, which is a negative electrode active material for a fluoride ion secondary battery, in which aluminum fluoride is brought into contact with an alkali metal or an alkaline earth metal. By desorbing fluoride ions from the aluminum fluoride, the position of the fluorine atom desorbed as the fluoride ion is used as a pore to obtain modified aluminum fluoride, which is a negative electrode active material for a fluoride ion secondary battery. It is a manufacturing method of.
上記の製造方法においては、前記アルカリ金属またはアルカリ土類金属はフッ化物となり、前記フッ化アルミニウムは一部のフッ素原子が引き抜かれ、アルミニウム金属にはならないものであってもよい。 In the above production method, the alkali metal or alkaline earth metal may be a fluoride, and the aluminum fluoride may be one in which some fluorine atoms are extracted and the metal does not become an aluminum metal.
前記アルカリ金属または前記アルカリ土類金属の比率は、前記フッ化アルミニウムとの合計に対して５〜２０ｍｏｌ％であってもよい。 The ratio of the alkali metal or the alkaline earth metal may be 5 to 20 mol% with respect to the total with the aluminum fluoride.
前記フッ化アルミニウムは、α−ＡｌＦ３であってもよい。The aluminum fluoride may be α-AlF 3.
前記アルカリ金属は、Ｌｉ金属であってもよい。 The alkali metal may be a Li metal.
本発明のフッ化物イオン二次電池用負極活物質によれば、フッ化物イオン二次電池における可逆的な負極反応を、高い利用率および高い可逆性で発現することができる。また、本発明のフッ化物イオン二次電池用負極活物質によれば、フッ化物イオン二次電池の充放電容量を、大幅に増加することができる。 According to the negative electrode active material for a fluoride ion secondary battery of the present invention, a reversible negative electrode reaction in a fluoride ion secondary battery can be exhibited with high utilization rate and high reversibility. Further, according to the negative electrode active material for a fluoride ion secondary battery of the present invention, the charge / discharge capacity of the fluoride ion secondary battery can be significantly increased.
以下、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
＜フッ化物イオン二次電池用負極活物質＞
フッ化物イオン二次電池の負極は、放電時にフッ化物イオン（Ｆ−）を収容し、充電時にフッ化物イオン（Ｆ−）を放出可能なものである必要がある。<Negative electrode active material for fluoride ion secondary batteries>
The negative electrode of the fluoride ion secondary battery, fluoride ions during discharge (F -) accommodates, fluoride ions during charging - should those capable of releasing (F).
本発明のフッ化物イオン二次電池用負極活物質は、フッ化物イオンの脱離による空孔を有する改質フッ化アルミニウムである。 The negative electrode active material for a fluoride ion secondary battery of the present invention is modified aluminum fluoride having pores due to desorption of fluoride ions.
上記した通り、フッ化アルミニウム（ＡｌＦ３）は、図２に示すように、イオン的、電子的にほぼ伝導率がゼロの絶縁体であるため、フッ化アルミニウム（ＡｌＦ３）からのフッ化物イオン（Ｆ−）の脱離および再挿入（脱フッ化／再フッ化反応）による負極反応は進行しない。このため、従来、フッ化アルミニウム（ＡｌＦ３）の単体を活物質として用いた先行例は、リチウムイオン電池用正極活物質としては報告されているが（文献６参照）、フッ化物イオン（Ｆ−）をキャリアとしたフッ化物イオン二次電池では報告されていない。
文献６：Ｊ．Ａｐｐｌ Ｅｌｅｃｔｒｏｃｈｅｍ（２０１７）４７ ４１７−４３１As described above, as shown in FIG. 2, aluminum fluoride (AlF 3 ) is an insulator having almost zero conductivity ionically and electronically, and therefore, fluoride ions from aluminum fluoride (AlF 3). The negative electrode reaction due to the desorption and reinsertion (defluorination / refluorination reaction) of (F −) does not proceed. For this reason, a prior example in which aluminum fluoride (AlF 3 ) alone is used as an active material has been reported as a positive electrode active material for a lithium ion battery (see Reference 6), but fluoride ion (F-). ) Has not been reported for fluoride ion secondary batteries.
Reference 6: J. Appl Electrochem (2017) 47 417-431
［空孔］
本発明のフッ化物イオン二次電池用負極活物質となる改質フッ化アルミニウムは、フッ化物イオン（Ｆ−）の脱離により、フッ化アルミニウム（ＡｌＦ３）に空孔を有する。[Vacancy]
The modified aluminum fluoride, which is the negative electrode active material for the fluoride ion secondary battery of the present invention, has pores in the aluminum fluoride (AlF 3 ) due to the desorption of fluoride ions (F−).
改質フッ化アルミニウムが有する空孔は、脱フッ化反応および再フッ化反応の起点となる。すなわち、空孔が存在することにより、イオン的、電子的にほぼ伝導率がゼロの絶縁体であったフッ化アルミニウム（ＡｌＦ３）が改質され、高い利用率、および高い可逆性で、負極反応が進行するようになる。The pores of the modified aluminum fluoride serve as the starting point for the defluorination reaction and the refluorination reaction. That is, the presence of pores modifies aluminum fluoride (AlF 3 ), which was an insulator with almost zero conductivity ionic and electronically, resulting in high utilization and high reversibility, and a negative electrode. The reaction will proceed.
図３は、フッ化アルミニウム（ＡｌＦ３）の結晶構造のひとつであるα−ＡｌＦ３の構造を示す図である。図３に示されるように、結晶構造の構成単位となるフッ化アルミニウム（ＡｌＦ３）の構造は、Ａｌ原子１が中心に配置され、頂点が６つのフッ素原子２で構成される６配位八面体である。FIG. 3 is a diagram showing a structure of α-AlF 3 , which is one of the crystal structures of aluminum fluoride (AlF 3). As shown in FIG. 3, the structure of aluminum fluoride (AlF 3 ), which is a constituent unit of the crystal structure, has a 6-coordination 8 in which the
空孔は、原料となる改質前のフッ化アルミニウム（ＡｌＦ３）において、フッ素原子が存在していた領域に形成される。すなわち、図３に示される、Ａｌ原子１が中心に配置され、頂点に存在する６つのフッ素原子２のうち、一部のフッ素原子２が引き抜かれ、引き抜かれて脱離したフッ素原子２が存在していた位置が、空孔となる。The pores are formed in the region where the fluorine atom was present in the raw material aluminum fluoride (AlF 3) before modification. That is, among the six
なお、本発明の改質フッ化アルミニウムは、フッ化アルミニウム（ＡｌＦ３）において、６つのフッ素原子の全てが脱離するのではなく、すなわち、フッ化アルミニウム（ＡｌＦ３）はアルミニウム金属にはならず、一部のフッ素原子のみが引き抜かれたものである。Incidentally, it modified aluminum fluoride of the present invention, in the aluminum fluoride (AlF 3), instead of all six fluorine atoms are eliminated, i.e., aluminum fluoride (AlF 3) is not in the aluminum metal However, only some of the fluorine atoms were extracted.
＜フッ化物イオン二次電池用負極＞
本発明のフッ化物イオン二次電池用負極は、本発明のフッ化物イオン二次電池用負極活物質を含むことを特徴とする。本発明のフッ化物イオン二次電池用負極活物質を含んでいれば、その他の構成は特に限定されるものではない。<Negative electrode for fluoride ion secondary battery>
The negative electrode for a fluoride ion secondary battery of the present invention is characterized by containing the negative electrode active material for a fluoride ion secondary battery of the present invention. Other configurations are not particularly limited as long as the negative electrode active material for the fluoride ion secondary battery of the present invention is contained.
フッ化物イオン二次電池の電気化学反応効率を高めるためには、負極を構成する材料の表面積を拡大することが有効である。そこで、本発明のフッ化物イオン二次電池用負極は、多孔質構造等、その表面積が高い構造として、固体電解質との接触面積を増加させる構造を有することが好ましい。 In order to increase the electrochemical reaction efficiency of the fluoride ion secondary battery, it is effective to increase the surface area of the material constituting the negative electrode. Therefore, it is preferable that the negative electrode for a fluoride ion secondary battery of the present invention has a structure such as a porous structure having a high surface area to increase the contact area with the solid electrolyte.
また、本発明のフッ化物イオン二次電池用負極は、本発明のフッ化物イオン二次電池用負極活物質以外に、他の成分を含んでいてもよい。他の成分としては、例えば、導電助剤やバインダー等が挙げられる。 Further, the negative electrode for a fluoride ion secondary battery of the present invention may contain other components in addition to the negative electrode active material for a fluoride ion secondary battery of the present invention. Examples of other components include conductive aids and binders.
本発明のフッ化物イオン二次電池用負極は、例えば、本発明のフッ化物イオン二次電池用負極活物質と、導電助剤と、バインダーとを含む混合物を、集電体上に塗布して乾燥することにより得ることができる。 In the negative electrode for a fluoride ion secondary battery of the present invention, for example, a mixture containing the negative electrode active material for a fluoride ion secondary battery of the present invention, a conductive auxiliary agent, and a binder is applied onto a current collector. It can be obtained by drying.
＜フッ化物イオン二次電池＞
本発明のフッ化物イオン二次電池は、本発明のフッ化物イオン二次電池用負極活物質を含むフッ化物イオン二次電池用負極と、固体電解質と、正極と、を備える。本発明のフッ化物イオン二次電池は、本発明のフッ化物イオン二次電池用負極活物質を含む負極を用いていれば、その他の構成は特に限定されるものではない。<Fluoride ion secondary battery>
The fluoride ion secondary battery of the present invention includes a negative electrode for a fluoride ion secondary battery containing the negative electrode active material for the fluoride ion secondary battery of the present invention, a solid electrolyte, and a positive electrode. The fluoride ion secondary battery of the present invention is not particularly limited in other configurations as long as it uses a negative electrode containing the negative electrode active material for the fluoride ion secondary battery of the present invention.
本発明においては、本発明のフッ化物イオン二次電池用負極活物質を含むフッ化物イオン二次電池用負極の標準電極電位に対して、十分に高い標準電極電位を提供する正極材料を選択することにより、フッ化物イオン二次電池としての特性が高く、また、所望の電池電圧を実現することが可能となる。 In the present invention, a positive electrode material that provides a sufficiently high standard electrode potential with respect to the standard electrode potential of the negative electrode for a fluoride ion secondary battery containing the negative electrode active material for the fluoride ion secondary battery of the present invention is selected. As a result, the characteristics as a fluoride ion secondary battery are high, and a desired battery voltage can be realized.
＜フッ化物イオン二次電池用負極活物質の製造方法＞
本発明のフッ化物イオン二次電池用負極活物質となる改質フッ化アルミニウムの製造方法は、フッ化アルミニウムと、アルカリ金属またはアルカリ土類金属とを接触させて、前記フッ化アルミニウムからフッ化物イオンを脱離させることにより、前記フッ化物イオンとして脱離したフッ素原子の存在位置を空孔として、フッ化アルミニウムを改質する。<Manufacturing method of negative electrode active material for fluoride ion secondary battery>
In the method for producing modified aluminum fluoride, which is the negative electrode active material for a fluoride ion secondary battery of the present invention, aluminum fluoride is brought into contact with an alkali metal or an alkaline earth metal to form a fluoride from the aluminum fluoride. By desorbing the ions, the aluminum fluoride is modified by using the positions of the fluorine atoms desorbed as fluoride ions as vacancies.
［改質前のフッ化アルミニウム（ＡｌＦ３）］
フッ化アルミニウム（ＡｌＦ３）には、様々な結晶構造が存在する。結晶構造としては、例えば、α−ＡｌＦ３、β−ＡｌＦ３、θ−ＡｌＦ３、等が挙げられる。しかしながら、いずれの結晶構造においても、その構成単位は同一の構造である。[Aluminum fluoride before modification (AlF 3 )]
Aluminum fluoride (AlF 3 ) has various crystal structures. Examples of the crystal structure include α-AlF 3 , β-AlF 3 , θ-AlF 3 , and the like. However, in each crystal structure, the structural unit is the same structure.
具体的には、フッ化アルミニウム（ＡｌＦ３）の結晶構造のひとつであるα−ＡｌＦ３の構造を示す図３に示されるように、結晶構造の構成単位となるフッ化アルミニウム（ＡｌＦ３）の構造は、Ａｌ原子が中心に配置され、頂点が６つのフッ素原子で構成される６配位八面体である。Specifically, as shown in FIG. 3 showing the structure of a is alpha-AlF 3 single crystal structure of aluminum fluoride (AlF 3), aluminum fluoride as the constituent unit of the crystal structure (AlF 3) The structure is a hexacoordinate octahedron in which the Al atom is arranged in the center and the apex is composed of 6 fluorine atoms.
本発明においては、原料として用いるフッ化アルミニウム（ＡｌＦ３）の構造は、特に限定されるものではなく、いずれの結晶構造のフッ化アルミニウム（ＡｌＦ３）も用いることができる。フッ化アルミニウム（ＡｌＦ３）の中では、入手が容易で最も安価な観点から、α−ＡｌＦ３を用いることが好ましい。α−ＡｌＦ３の市販品としては、例えば、シグマアルドリッチ社製ＡｌＦ３（純度９９．９％）や、Ａｌｆａ Ａｅｓａｒ社製ＡｌＦ３（純度９９．９％）等を挙げることができる。In the present invention, the structure of the aluminum fluoride used as a starting material (AlF 3) is not limited particularly, aluminum fluoride of any crystal structure (AlF 3) may also be used. Among aluminum fluoride (AlF 3 ), it is preferable to use α-AlF 3 from the viewpoint of being easily available and the cheapest. Examples of commercially available products of α-AlF 3 include AlF 3 manufactured by Sigma-Aldrich (purity 99.9%) and AlF 3 manufactured by Alfa Aesar (purity 99.9%).
なお、フッ化アルミニウム（ＡｌＦ３）は、大気中の水分を吸湿し、より安定な０．５水和物もしくは３水和物を形成する。このため、脱水処理をおこなったフッ化アルミニウム（ＡｌＦ３）を用いることが、さらに好ましい。脱水処理の方法としては、例えば、２５０〜３００℃程度の温度で、真空焼成する方法等が挙げられる。Aluminum fluoride (AlF 3 ) absorbs moisture in the atmosphere to form a more stable 0.5 hydrate or trihydrate. Therefore, it is more preferable to use dehydrated aluminum fluoride (AlF 3). Examples of the dehydration treatment method include a method of vacuum firing at a temperature of about 250 to 300 ° C.
［アルカリ金属またはアルカリ土類金属］
本発明のフッ化物イオン二次電池用負極活物質を製造するために用いるアルカリ金属またはアルカリ土類金属は、特に限定されるものではない。アルカリ金属としては、例えば、リチウム（Ｌｉ）、ナトリウム（Ｎａ）、カリウム（Ｋ）、ルビジウム（Ｒｂ）、セシウム（Ｃｓ）、等を挙げることができ、アルカリ土類金属としては、例えば、マグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）、等を挙げることができる。[Alkali metal or alkaline earth metal]
The alkali metal or alkaline earth metal used for producing the negative electrode active material for a fluoride ion secondary battery of the present invention is not particularly limited. Examples of the alkali metal include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and the like, and examples of the alkaline earth metal include magnesium ( Mg), calcium (Ca), strontium (Sr), barium (Ba), and the like can be mentioned.
本発明のフッ化物イオン二次電池用負極活物質の製造方法においては、アルカリ金属またはアルカリ土類金属の中でも、リチウム（Ｌｉ）金属を用いることが好ましい。リチウム（Ｌｉ）金属は、全ての金属元素の中で最も軽いため、フッ化アルミニウムと混合した後の活物質重量あたりの容量（ｍＡｈ／ｇ）を高く維持することができる。 In the method for producing a negative electrode active material for a fluoride ion secondary battery of the present invention, it is preferable to use a lithium (Li) metal among alkali metals or alkaline earth metals. Since lithium (Li) metal is the lightest of all metal elements, it is possible to maintain a high capacity (mAh / g) per weight of active material after mixing with aluminum fluoride.
市販のリチウム（Ｌｉ）金属としては、例えば、本城金属社製Ｌｉ箔（純度９９．８％）等が挙げられる。リチウム（Ｌｉ）金属の形状は、特に制限されるものではないが、フッ化アルミニウム（ＡｌＦ３）との混合が容易となる観点から、チップ状、またはビーズ状であることが好ましい。Examples of commercially available lithium (Li) metal include Li foil (purity 99.8%) manufactured by Honjo Metal Co., Ltd. The shape of the lithium (Li) metal is not particularly limited, but is preferably chip-shaped or bead-shaped from the viewpoint of facilitating mixing with aluminum fluoride (AlF 3).
［フッ化アルミニウム（ＡｌＦ３）と、アルカリ金属またはアルカリ土類金属との接触］
本発明のフッ化物イオン二次電池用負極活物質の製造方法は、上記のフッ化アルミニウム（ＡｌＦ３）と、上記のアルカリ金属またはアルカリ土類金属とを接触させて、改質フッ化アルミニウムを得るものである。[Contact between aluminum fluoride (AlF 3 ) and alkali metal or alkaline earth metal]
In the method for producing a negative electrode active material for a fluoride ion secondary battery of the present invention, the above-mentioned aluminum fluoride (AlF 3 ) is brought into contact with the above-mentioned alkali metal or alkaline earth metal to obtain modified aluminum fluoride. What you get.
フッ化アルミニウム（ＡｌＦ３）と、アルカリ金属またはアルカリ土類金属とを接触させることにより、フッ化アルミニウムからフッ化物イオンを脱離させ、フッ化物イオンとして脱離したフッ素原子の存在位置を空孔として、改質フッ化アルミニウムを得る。By contacting aluminum fluoride (AlF 3 ) with an alkali metal or alkaline earth metal, fluoride ions are desorbed from aluminum fluoride, and the positions of fluorine atoms desorbed as fluoride ions are vacated. To obtain modified aluminum fluoride.
（反応機構）
フッ化アルミニウム（ＡｌＦ３）の脱フッ化／再フッ化反応電位に対して、より卑な電位を示すアルカリ金属またはアルカリ土類金属を接触させることにより、アルカリ金属またはアルカリ土類金属はフッ化物を形成し、フッ化アルミニウム（ＡｌＦ３）からは一部のフッ素原子が引き抜かれる反応が起こる。このような卑金属との接触によるフッ化物からの部分的なフッ素原子の引き抜きは、先行例として確認されていない。(Reaction mechanism)
By contacting an alkali metal or alkaline earth metal showing a lower potential with respect to the defluorination / refluorination reaction potential of aluminum fluoride (AlF 3), the alkali metal or alkaline earth metal becomes fluoride. A reaction occurs in which some fluorine atoms are extracted from aluminum fluoride (AlF 3). Partial extraction of fluorine atoms from fluoride by contact with such base metals has not been confirmed as a precedent.
なお、本発明のフッ化物イオン二次電池用負極活物質の製造方法は、フッ化アルミニウム（ＡｌＦ３）における、６つのフッ素原子の全てを脱離させるものではない。すなわち、一部のフッ素原子のみを引き抜き、フッ化アルミニウム（ＡｌＦ３）がアルミニウム金属となるまで反応はさせない。The method for producing a negative electrode active material for a fluoride ion secondary battery of the present invention does not desorb all six fluorine atoms in aluminum fluoride (AlF 3). That is, only a part of fluorine atoms are extracted, and the reaction is not carried out until aluminum fluoride (AlF 3) becomes an aluminum metal.
フッ化アルミニウム（ＡｌＦ３）と、アルカリ金属またはアルカリ土類金属とを接触させたときの反応の例を、以下に示す。以下は、アルカリ金属であるリチウム（Ｌｉ）金属とフッ化アルミニウム（ＡｌＦ３）との反応である。An example of the reaction when aluminum fluoride (AlF 3 ) is brought into contact with an alkali metal or an alkaline earth metal is shown below. The following is the reaction between lithium (Li) metal, which is an alkali metal, and aluminum fluoride (AlF 3).
ｘＬｉ ＋ （１−ｘ）ＡｌＦ３
（１） → ｘＬｉＦ ＋ （１−ｘ）ＡｌＦ３−４Ｘ／（１−Ｘ）
（２） → ｘＬｉＦ ＋ （１−４ｘ/３）ＡｌＦ３ ＋ （ｘ/３）Ａｌ
（３） → （ｘ/３）Ｌｉ３ＡｌＦ６ ＋ （１−５ｘ/３）ＡｌＦ３ ＋ （ｘ/３）ＡｌxLi + (1-x) AlF 3
(1) → xLiF + (1-x) AlF 3-4X / (1-X)
(2) → xLiF + (1-4x / 3) AlF 3 + (x / 3) Al
(3) → (x / 3) Li 3 AlF 6 + (1-5x / 3) AlF 3 + (x / 3) Al
本発明においては、フッ化アルミニウム（ＡｌＦ３）がアルミニウム金属となる式（２）および式（３）の段階までは反応を進めず、一部のフッ素原子のみが引き抜かれた式（１）の段階で、反応をとどめる。In the present invention, the reaction does not proceed until the steps of the formulas (2) and (3 ) in which aluminum fluoride (AlF 3) becomes an aluminum metal, and only a part of the fluorine atoms is extracted from the formula (1). Stop the reaction at the stage.
（接触方法）
フッ化アルミニウム（ＡｌＦ３）と、アルカリ金属またはアルカリ土類金属との接触方法は、フッ化アルミニウム（ＡｌＦ３）がアルミニウム金属となるまで反応を進めさせない方法であれば、特に限定されるものではない。(Contact method)
The method of contacting aluminum fluoride (AlF 3 ) with an alkali metal or an alkaline earth metal is not particularly limited as long as the reaction is not allowed to proceed until the aluminum fluoride (AlF 3) becomes an aluminum metal. Absent.
例えば、必要量のフッ化アルミニウム（ＡｌＦ３）と、アルカリ金属またはアルカリ土類金属とをそれぞれ秤量し、必要に応じて予備混合を実施し、ボールミル等によって混合処理する方法が挙げられる。For example, a method in which a required amount of aluminum fluoride (AlF 3 ) and an alkali metal or an alkaline earth metal are weighed, premixed as necessary, and mixed by a ball mill or the like can be mentioned.
なお、フッ化アルミニウム（ＡｌＦ３）と、アルカリ金属またはアルカリ土類金属は、いずれも水分との反応が極めて高いため、グローブボックス等、大気中の水分との接触を回避できる環境にて、接触を実施することが好ましい。Since aluminum fluoride (AlF 3 ) and alkali metal or alkaline earth metal both have extremely high reactions with moisture, they come into contact with each other in an environment such as a glove box where contact with moisture in the atmosphere can be avoided. It is preferable to carry out.
（反応組成）
また、本発明のフッ化物イオン二次電池用負極活物質の製造方法においては、用いるアルカリ金属またはアルカリ土類金属の比率は、フッ化アルミニウムとの合計に対して５〜２０ｍｏｌ％とすることが好ましい。５〜２０ｍｏｌ％とすることにより、大きな充放電容量が得られ、同時に、反応過電圧が減少し、充放電効率が増加したフッ化物イオン二次電池を形成することができる。アルカリ金属またはアルカリ土類金属の比率は、フッ化アルミニウムとの合計に対して５〜１５ｍｏｌ％とすることがさらに好ましく、１０〜１５ｍｏｌ％とすることが最も好ましい。(Reaction composition)
Further, in the method for producing a negative electrode active material for a fluoride ion secondary battery of the present invention, the ratio of the alkali metal or alkaline earth metal used may be 5 to 20 mol% with respect to the total with aluminum fluoride. preferable. By setting the content to 5 to 20 mol%, a large charge / discharge capacity can be obtained, and at the same time, a fluoride ion secondary battery in which the reaction overvoltage is reduced and the charge / discharge efficiency is increased can be formed. The ratio of the alkali metal or alkaline earth metal is more preferably 5 to 15 mol%, and most preferably 10 to 15 mol% with respect to the total with aluminum fluoride.
次に、本発明の実施例について説明するが、本発明はこれら実施例に限定されるものではない。 Next, examples of the present invention will be described, but the present invention is not limited to these examples.
＜実施例１〜６＞
実施例１〜６においては、リチウム（Ｌｉ）金属を用いて、フッ化アルミニウム（ＡｌＦ３）を改質フッ化アルミニウムとした。<Examples 1 to 6>
In Examples 1 to 6, lithium (Li) metal was used and aluminum fluoride (AlF 3 ) was used as modified aluminum fluoride.
［改質フッ化アルミニウムの製造］
（原料の秤量・予備混合）
フッ化アルミニウム（ＡｌＦ３）、およびリチウム（Ｌｉ）金属を、表１に示すモル比率で、全量が６．０グラムになるよう秤量し、メノウ製の乳鉢と乳棒を用いて、約１時間、予備混合して、原料混合粉末を得た。[Manufacturing of modified aluminum fluoride]
(Weighing and premixing of raw materials)
Aluminum fluoride (AlF 3 ) and lithium (Li) metal were weighed in the molar ratio shown in Table 1 to a total weight of 6.0 grams, and using an agate mortar and pestle for about 1 hour. Premixing was performed to obtain a raw material mixed powder.
なお、フッ化アルミニウム（ＡｌＦ３）、およびリチウム（Ｌｉ）金属はいずれも、水分との反応性が極めて高いため、原料の秤量および予備混合は、グローブボックス（（株）美和製作所製、型式ＤＢＯ−１．５ＢＮＫ−ＳＱ１）内にて実施した。Since both aluminum fluoride (AlF 3 ) and lithium (Li) metal have extremely high reactivity with water, the raw materials are weighed and premixed by the glove box (Miwa Seisakusho Co., Ltd., model DBO). It was carried out within -1.5BNK-SQ1).
（接触処理）
得られた原料混合粉末を、窒化ケイ素製ボールミル容器（独フリッチュ社製、内容積：８０ｃｃ、ＰＬ−７専用容器）に投入し、直径２ｍｍの窒化ケイ素製ボールを４０グラム投入し、密封した。(Contact processing)
The obtained raw material mixed powder was put into a silicon nitride ball mill container (manufactured by Fritsch, Germany, internal volume: 80 cc, PL-7 dedicated container), and 40 g of silicon nitride balls having a diameter of 2 mm were put into the container and sealed.
引き続き、密封した容器を、回転数６００ｒｐｍで１５時間回転させ、ボールミル処理を実施した。ボールミル処理の後、処理された粉末を回収した。 Subsequently, the sealed container was rotated at a rotation speed of 600 rpm for 15 hours to carry out ball milling. After ball milling, the treated powder was recovered.
＜比較例１＞
リチウム（Ｌｉ）金属を用いず、フッ化アルミニウム（ＡｌＦ３）のみを用いて、実施例と同様の操作を実施し、ボールミル処理された粉末を得た。<Comparative example 1>
The same operation as in Example was carried out using only aluminum fluoride (AlF 3 ) without using a lithium (Li) metal to obtain a ball milled powder.
＜改質フッ化アルミニウムの評価＞
［Ｘ線回折パターン］
ＸＲＤ（リガク社製、ＳｍａｒｔＬａＢ、Ｃｕ−Ｋα線源、λ＝１．５４１８Å）を用いて、実施例および比較例で得られた改質フッ化アルミニウムの結晶構造を解析した。ＸＲＤチャートを、図４に示す。<Evaluation of modified aluminum fluoride>
[X-ray diffraction pattern]
The crystal structures of the modified aluminum fluoride obtained in Examples and Comparative Examples were analyzed using XRD (SmartLaB, Cu-Kα source, λ = 1.5418 Å, manufactured by Rigaku). The XRD chart is shown in FIG.
［Ｘ線光電子分光スペクトル］
Ｘ線光電子分光：ＸＰＳ（アルバックファイ社製、ＰＨＩ５０００ Ｖｅｒｓａ ＰｒｏｂｅII、Ａｌ−Ｋα線源）を用いて、実施例および比較例で得られた改質フッ化アルミニウムの結晶構造を解析した。図５（ａ）に、Ｌｉ １ｓスペクトルを、図５（ｂ）に、Ａｌ ２ｐスペクトルを示す。[X-ray photoelectron spectroscopy spectrum]
X-ray photoelectron spectroscopy: XPS (PHI5000 Versa ProbeII, Al-Kα source, manufactured by ULVAC-PHI) was used to analyze the crystal structure of the modified aluminum fluoride obtained in Examples and Comparative Examples. FIG. 5 (a) shows the Li 1s spectrum, and FIG. 5 (b) shows the Al 2p spectrum.
［評価］
図４のＸＲＤチャートより、リチウム（Ｌｉ）金属が５．０ｍｏｌ％〜２０ｍｏｌ％である実施例１〜４の回折ピーク位置は、リチウム（Ｌｉ）金属を用いなかった比較例１（ＡｌＦ３のみ）の回折ピーク位置と同一であり、結晶構造の変化は認められなかった。[Evaluation]
From the XRD chart of FIG. 4, the diffraction peak positions of Examples 1 to 4 in which the lithium (Li) metal is 5.0 mol% to 20 mol% are Comparative Example 1 (AlF 3 only) in which the lithium (Li) metal was not used. It was the same as the diffraction peak position of, and no change in crystal structure was observed.
一方で、リチウム（Ｌｉ）金属が３０ｍｏｌ％以上の実施例５および６では、アルミニウム（Ａｌ）金属、ＬｉＦ、Ｌｉ３ＡｌＦ６に帰属するピークが確認された。すなわち、リチウム（Ｌｉ）金属を３０ｍｏｌ％以上とした範囲では、Ｌｉ３ＡｌＦ６が存在していることから、上記した式（３）まで、反応が進んでいることとなる。On the other hand, in Examples 5 and 6 in which the lithium (Li) metal content was 30 mol% or more, peaks attributed to the aluminum (Al) metal, LiF, and Li 3 AlF 6 were confirmed. That is, since Li 3 AlF 6 is present in the range where the lithium (Li) metal is 30 mol% or more, the reaction proceeds to the above formula (3).
また、図５（ａ）に示されるＬｉ １ｓスペクトルより、全ての実施例において、ＬｉＦの生成が確認され、図５（ｂ）に示されるＡｌ ２ｐスペクトルより、リチウム（Ｌｉ）金属が３０ｍｏｌ％以上の実施例５および６では、Ａｌ金属の生成が認められた。すなわち、上記した式（２）まで、反応が進んでいることとなる。 Further, from the Li 1s spectrum shown in FIG. 5 (a), the formation of LiF was confirmed in all the examples, and from the Al 2p spectrum shown in FIG. 5 (b), the lithium (Li) metal content was 30 mol% or more. In Examples 5 and 6 of the above, the formation of Al metal was observed. That is, the reaction has proceeded to the above formula (2).
Ｘ線回折パターンおよびＸ線光電子分光スペクトルより、上記した式（１）までで反応をとどめるためには、リチウム（Ｌｉ）金属の配合量は、２０ｍｏｌ％以下とすることが好ましい。 From the X-ray diffraction pattern and the X-ray photoelectron spectroscopic spectrum, in order to keep the reaction up to the above formula (1), the blending amount of the lithium (Li) metal is preferably 20 mol% or less.
＜フッ化物イオン二次電池の作製＞
以下の材料を用いて、以下の方法で、フッ化物イオン二次電池を作製した。<Manufacturing of fluoride ion secondary battery>
A fluoride ion secondary battery was prepared by the following method using the following materials.
（固体電解質）
タイソナイト系の固体電解質であるＬａ０．９５Ｂａ０．０５Ｆ２．９５（ＬＢＦ）を用いた。ＬＢＦは公知の化合物（文献７〜９参照）であり、文献７に記載された方法にて作製した。
文献７：ＡＣＳ Ａｐｐｌ．Ｍａｔｅｒ．Ｉｎｔｅｒｆａｃｅｓ ２０１４，６，２１０３−２１１０
文献８：Ｊ．Ｐｈｙｓ．Ｃｈｅｍ．Ｃ ２０１３，１１７，４９４３−４９５０
文献９：Ｊ．Ｐｈｙｓ．Ｃｈｅｍ．Ｃ ２０１４，１１８，７１１７−７１２９(Solid electrolyte)
La 0.95 Ba 0.05 F 2.95 (LBF), which is a tysonite-based solid electrolyte, was used. LBF is a known compound (see Documents 7 to 9) and was prepared by the method described in Document 7.
Reference 7: ACS Appl. Mater. Interfaces 2014, 6, 2103-1110
Reference 8: J. Phys. Chem. C 2013, 117,4943-4950
Reference 9: J. Phys. Chem. C 2014, 118, 7117-7129
（負極合剤粉末）
実施例で作製した改質または比較例１のフッ化アルミニウム（ＡｌＦ３）、イオン伝導経路を付与するための固体電解質（ＬＢＦ）、および電子伝導経路を付与するためのアセチレンブラック（電気化学工業製）を、１０：８０：１０の質量比で秤量し、メノウ製の乳鉢と乳棒を用いて十分に混合し、負極合剤粉末とした。(Negative electrode mixture powder)
Aluminum fluoride (AlF 3 ) of the modified or comparative example 1 prepared in Examples, a solid electrolyte (LBF) for imparting an ionic conduction path, and acetylene black (manufactured by Electrochemical Industry) for imparting an electron conduction path. ) Was weighed at a mass ratio of 10:80:10 and sufficiently mixed using a Menou dairy pot and a dairy rod to prepare a negative electrode mixture powder.
（正極）
鉛箔（（株）ニラコ製、純度：９９．９９％、厚さ：２００ｕｍ）を、直径１０ｍｍに加工し、正極として用いた。(Positive electrode)
A lead foil (manufactured by Nirako Co., Ltd., purity: 99.99%, thickness: 200 um) was processed to a diameter of 10 mm and used as a positive electrode.
（フッ化物イオン二次電池）
上記のように準備した負極合剤粉末（２０ｍｇ）、固体電解質（４００ｍｇ）、正極を、直径１０ｍｍΦの金型中で４ｔｏｎ／ｃｍ２の圧力で一体成形し、フッ化物イオン二次電池となる成型体を得た。得られた成型体の正／負極面に、カーボンペーストにより、充放電測定に使用する端子として用いるための金線を接着した。(Fluoride ion secondary battery)
The negative electrode mixture powder (20 mg), solid electrolyte (400 mg), and positive electrode prepared as described above are integrally molded in a mold having a diameter of 10 mmΦ at a pressure of 4 ton / cm 2 , to form a fluoride ion secondary battery. I got a body. A gold wire for use as a terminal used for charge / discharge measurement was adhered to the positive / negative electrode surfaces of the obtained molded body with carbon paste.
＜フッ化物イオン二次電池の評価＞
（定電流充放電試験）
ポテンショガルバノスタット装置（ソーラトロン社、ＳＩ１２８７／１２５５Ｂ）を用いて、充電０．０２ｍＡ、放電０．０１ｍＡの電流にて、下限電圧−２．３５Ｖ、上限電圧−０．１Ｖ、にて、定電流充放電試験を実施した。充放電曲線を、図６に示す。<Evaluation of fluoride ion secondary battery>
(Constant current charge / discharge test)
Using a potentiogalvanostat device (Solartron, SI1287 / 1255B), constant current charging at a lower limit voltage of -2.35V and an upper limit voltage of -0.1V with a current of 0.02mA for charging and 0.01mA for discharging. A discharge test was carried out. The charge / discharge curve is shown in FIG.
図６より、改質処理を行っていない比較例１の負極活物質を用いたフッ化物イオン二次電池は、充放電容量が数十ｍＡｈ／ｇしか得られなかったのに対して、改質フッ化アルミニウムを用いた実施例の負極活物質を用いたフッ化物イオン二次電池は、充放電容量が大幅に増加していることが確認できる。また、比較例１の負極活物質を用いたフッ化物イオン二次電池と比べて、実施例の負極活物質を用いたフッ化物イオン二次電池は、充放電容量が増加していること、反応過電圧が減少していること、充放電効率が増加していること、の全てについて確認できる。 From FIG. 6, the fluoride ion secondary battery using the negative electrode active material of Comparative Example 1 which was not reformed had a charge / discharge capacity of only several tens of mAh / g, whereas it was reformed. It can be confirmed that the charge / discharge capacity of the fluoride ion secondary battery using the negative electrode active material of the example using aluminum fluoride is significantly increased. Further, as compared with the fluoride ion secondary battery using the negative electrode active material of Comparative Example 1, the fluoride ion secondary battery using the negative electrode active material of Example has an increased charge / discharge capacity and a reaction. It can be confirmed that the overvoltage is decreasing and the charge / discharge efficiency is increasing.
（充放電容量とリチウム（Ｌｉ）金属配合量との関係）
実施例１〜６、および比較例１について、充放電容量とＡｌＦ３改質処理におけるリチウム（Ｌｉ）金属配合量との関係を、図７に示す。図７より、本発明のフッ化アルミニウム（ＡｌＦ３）の改質処理において、特に良好なチウム（Ｌｉ）金属の配合量は、５〜２０ｍｏｌ％であることが確認できる。(Relationship between charge / discharge capacity and lithium (Li) metal compounding amount)
For Examples 1 to 6 and Comparative Example 1, the relationship between the charge / discharge capacity and the amount of lithium (Li) metal compounded in the AlF 3 modification treatment is shown in FIG. From FIG. 7, it can be confirmed that in the modification treatment of aluminum fluoride (AlF 3 ) of the present invention, a particularly good compounding amount of thium (Li) metal is 5 to 20 mol%.
１ Ａｌ原子
２ フッ素原子1
Claims (11)
フッ化アルミニウムと、アルカリ金属またはアルカリ土類金属とを接触させて、前記フッ化アルミニウムからフッ化物イオンを脱離させることにより、前記フッ化物イオンとして脱離したフッ素原子の存在位置を空孔として改質フッ化アルミニウムとする、フッ化物イオン二次電池用負極活物質の製造方法。A method for producing modified aluminum fluoride, which is a negative electrode active material for fluoride ion secondary batteries.
By contacting aluminum fluoride with an alkali metal or alkaline earth metal to desorb fluoride ions from the aluminum fluoride, the position of the fluorine atom desorbed as the fluoride ion is set as a vacancy. A method for producing a negative electrode active material for a fluoride ion secondary battery, which is a modified aluminum fluoride.
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| PCT/JP2019/007699 WO2019187943A1 (en) | 2018-03-27 | 2019-02-27 | Negative electrode active material for fluoride ion secondary batteries, negative electrode using said active material, fluoride ion secondary battery, and method for producing said active material |
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| CN114556650B (en) * | 2019-10-09 | 2024-07-16 | 本田技研工业株式会社 | Fluoride ion secondary battery |
| WO2021070299A1 (en) * | 2019-10-09 | 2021-04-15 | 本田技研工業株式会社 | Fluoride ion secondary battery negative electrode mixture composite, fluoride ion secondary battery negative electrode and secondary battery using fluoride ion secondary battery negative electrode mixture composite, and production method for fluoride ion secondary battery negative electrode mixture composite |
| WO2021070298A1 (en) * | 2019-10-09 | 2021-04-15 | 本田技研工業株式会社 | Negative electrode mixture composite body for fluoride ion secondary batteries, negative electrode for fluoride ion secondary batteries and secondary battery each using said composite body, and method for producing said composite body |
| CN114556649B (en) * | 2019-10-09 | 2024-07-26 | 本田技研工业株式会社 | Negative electrode composite material composite for fluoride ion secondary battery, negative electrode for fluoride ion secondary battery and secondary battery using the composite, and method for producing the composite |
| US20230317944A1 (en) * | 2020-11-19 | 2023-10-05 | Carnegie Mellon University | Fluorinated electrodes and batteries containing the same |
| CN116670845A (en) | 2020-12-24 | 2023-08-29 | 松下控股株式会社 | Fluoride ion secondary battery and method for producing same |
| JP2022114305A (en) * | 2021-01-26 | 2022-08-05 | 本田技研工業株式会社 | Negative electrode for fluoride ion secondary battery and fluoride ion secondary battery having the same |
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| JPS5845372A (en) * | 1981-09-10 | 1983-03-16 | Oyo Kagaku Kenkyusho | Direct formation of film of graphite fluoride on surface of aluminum using carbonaceous material and fluorine |
| JP2016103407A (en) * | 2014-11-28 | 2016-06-02 | 積水化学工業株式会社 | Secondary battery, and method for manufacturing secondary battery |
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| IT1291758B1 (en) * | 1997-05-22 | 1999-01-21 | Ausimont Spa | PROCESS FOR THE PREPARATION OF ALUMINUM FLUORIDE |
| ITMI20030006A1 (en) * | 2003-01-03 | 2004-07-04 | Solvay Solexis Spa | ALUMINUM FLUORIDE CATALYST. |
| JP5271275B2 (en) * | 2007-12-14 | 2013-08-21 | パナソニック株式会社 | Method for producing non-aqueous electrolyte secondary battery |
| CN102754257B (en) * | 2009-11-09 | 2016-06-01 | 拉特格斯,新泽西州立大学 | Metal fluoride composition for self-forming battery |
| US9843041B2 (en) * | 2009-11-11 | 2017-12-12 | Zenlabs Energy, Inc. | Coated positive electrode materials for lithium ion batteries |
| US9048497B2 (en) * | 2012-10-05 | 2015-06-02 | Rutgers, The State University Of New Jersey | Metal fluoride compositions for self formed batteries |
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| JPS5845372A (en) * | 1981-09-10 | 1983-03-16 | Oyo Kagaku Kenkyusho | Direct formation of film of graphite fluoride on surface of aluminum using carbonaceous material and fluorine |
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