JP2021098643A5 - - Google Patents
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- JP2021098643A5 JP2021098643A5 JP2020209982A JP2020209982A JP2021098643A5 JP 2021098643 A5 JP2021098643 A5 JP 2021098643A5 JP 2020209982 A JP2020209982 A JP 2020209982A JP 2020209982 A JP2020209982 A JP 2020209982A JP 2021098643 A5 JP2021098643 A5 JP 2021098643A5
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- lithium ion
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- 239000002002 slurry Substances 0.000 description 48
- 239000007864 aqueous solution Substances 0.000 description 44
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 32
- 229910001416 lithium ion Inorganic materials 0.000 description 30
- 239000000843 powder Substances 0.000 description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 22
- 229910052744 lithium Inorganic materials 0.000 description 22
- 229910052782 aluminium Inorganic materials 0.000 description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 18
- 229910052698 phosphorus Inorganic materials 0.000 description 18
- 239000011574 phosphorus Substances 0.000 description 18
- 238000002156 mixing Methods 0.000 description 15
- 229910052732 germanium Inorganic materials 0.000 description 14
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 14
- 230000002378 acidificating effect Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000470 constituent Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000001694 spray drying Methods 0.000 description 7
- 239000002228 NASICON Substances 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 150000002291 germanium compounds Chemical class 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum compound Chemical class 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Description
即ち、上述の課題を解決する為の第１の発明は、
リチウムを、０．５質量％以上６．５質量％以下、
アルミニウムを、０質量％を超え２５．０質量％以下、
ゲルマニウムを、０質量％を超え６５．０質量％以下、
リンを、１０質量％以上３０質量％以下含有し、
ＢＥＴ一点法で計測される比表面積が１５ｍ2／ｇ以上１００ｍ2／ｇ以下である、非晶質リチウムイオン伝導酸化物粉末である。
第２の発明は、
リチウムを、1質量％以上４質量％以下、
アルミニウムを、０質量％を超え６質量％以下、
ゲルマニウムを、１５質量％を超え３５質量％以下含有する、第１の発明に記載の非晶質リチウムイオン伝導酸化物粉末である。
第３の発明は、
さらに、炭素を０．０１質量％以上０．３５質量％以下含有する、第１または第２の発明に記載の非晶質リチウムイオン伝導酸化物粉末である。
第４の発明は、
前記ＢＥＴ一点法で計測される比表面積が２０ｍ2／ｇ以上１００ｍ2／ｇ以下である、第１から第３の発明のいずれか一項に記載の非晶質リチウムイオン伝導酸化物粉末である。
第５の発明は、
さらに、チタン、ジルコニウム、ハフニウムから選択される、少なくとも一種の元素を含有する、第１から第４の発明のいずれか一項に記載の非晶質リチウムイオン伝導酸化物粉末である。
第６の発明は、
さらに、ケイ素を１０質量％以下含有する、第１から第５の発明のいずれか一項に記載の非晶質リチウムイオン伝導酸化物粉末である。
第７の発明は、
前記非晶質リチウムイオン伝導酸化物粉末は、一般式Ｌｉ1+x+w（Ａｌ1-yＭ１y）x（Ｇｅ1-zＭ２z）2-xＰ3-wＳｉwＯ12の式で表され、Ｍ１はガリウム、ランタン、インジウムおよびイットリウムから選ばれる１種以上であり、Ｍ２はチタン、ジルコニウムおよびハフニウムから選ばれる１種以上であり、ｘの範囲は０＜ｘ≦１．０、ｙの範囲は０≦ｙ≦１．０、ｚの範囲は０≦ｚ≦１．０、ｗの範囲は０≦ｗ≦１．０である第１から第６の発明のいずれか一項に記載の非晶質リチウムイオン伝導酸化物粉末である。
第８の発明は、
さらに、ガリウム、ランタン、インジウムおよびイットリウムから選択される、少なくとも一種の元素を含有する、第１から第６の発明のいずれか一項に記載の非晶質リチウムイオン伝導酸化物粉末である。
第９の発明は、
リチウム化合物の水溶液と、アルミ二ウム化合物の水溶液と、ゲルマニウム化合物の水溶液と、リン酸アンモニウム塩の水溶液とを混合し共沈物の懸濁液を得るスラリー形成工程と、
前記スラリーを噴霧乾燥して、スラリー乾燥物を得る工程と、
前記スラリー乾燥物を３００℃以上５００℃以下で焼成する工程とを有する、非晶質リチウムイオン伝導酸化物粉末の製造方法である。
第１０の発明は、
前記スラリー形成工程において、さらにガリウム、ランタン、インジウムおよびイットリウムから選択される少なくとも一種の元素を含む化合物の水溶液を混合し共沈物の懸濁液を得る、第９の発明に記載の非晶質リチウムイオン伝導酸化物粉末の製造方法である。
第１１の発明は、
前記スラリー形成工程において、さらにチタン、ジルコニウムおよびハフニウムから選択される少なくとも一種の元素を含む化合物の水溶液を混合し共沈物の懸濁液を得る、第９または第１０の発明に記載の非晶質リチウムイオン伝導酸化物粉末の製造方法である。
第１２の発明は、
前記スラリー形成工程において、さらにケイ素化合物の水溶液を混合し共沈物の懸濁液を得る、第９から第１１の発明のいずれか一項に記載の非晶質リチウムイオン伝導酸化物粉末の製造方法である。
第１３の発明は、
前記スラリー形成工程における前記懸濁液の形成は、ｐＨ８以上に調整した前記ゲルマニウム化合物の水溶液を混合することにより行う、第９から第１２の発明のいずれか一項に記載の非晶質リチウムイオン伝導酸化物粉末の製造方法である。
第１４の発明は、
第１から第８の発明のいずれか一項に記載の非晶質リチウムイオン伝導酸化物粉末を５００℃よりも高い温度で焼成する工程を有する、ＮＡＳＩＣＯＮ型結晶構造を有するリチウムイオン伝導酸化物粉末の製造方法である。
第１５の発明は、
リチウム化合物の水溶液と、アルミ二ウム化合物の水溶液と、ゲルマニウム化合物の水溶液と、リン酸アンモニウム塩の水溶液とを混合し共沈物の懸濁液を得るスラリー形成工程と、
前記スラリーを噴霧乾燥して、スラリー乾燥物を得る工程と、
前記スラリー乾燥物を５００℃よりも高い温度で焼成する工程とを有する、ＮＡＳＩＣＯＮ型結晶構造を有するリチウムイオン伝導酸化物粉末の製造方法である。
That is, the first invention for solving the above-mentioned problems is
Lithium is 0.5% by mass or more and 6.5% by mass or less,
Aluminum, more than 0% by mass and 25.0% by mass or less,
Germanium, more than 0% by mass and 65.0% by mass or less,
Contains 10% by mass or more and 30% by mass or less of phosphorus,
It is an amorphous lithium ion conductive oxide powder having a specific surface area of 15 m 2 / g or more and 100 m 2 / g or less measured by the BET one-point method.
The second invention is
Lithium, 1% by mass or more and 4% by mass or less,
Aluminum, more than 0% by mass and 6% by mass or less,
The amorphous lithium ion conductive oxide powder according to the first invention, which contains germanium in an amount of more than 15% by mass and 35% by mass or less.
The third invention is
Further, it is the amorphous lithium ion conduction oxide powder according to the first or second invention, which contains 0.01% by mass or more and 0.35% by mass or less of carbon.
The fourth invention is
The amorphous lithium ion conductive oxide powder according to any one of the first to third inventions, wherein the specific surface area measured by the BET one-point method is 20 m 2 / g or more and 100 m 2 / g or less. ..
The fifth invention is
Further, the amorphous lithium ion conductive oxide powder according to any one of the first to fourth inventions, which contains at least one element selected from titanium, zirconium, and hafnium.
The sixth invention is
Further, the amorphous lithium ion conductive oxide powder according to any one of the first to fifth inventions, which contains 10% by mass or less of silicon.
The seventh invention is
The amorphous lithium ion conduction oxide powder has a general formula of Li 1 + x + w (Al 1-y M1 y ) x (Ge 1-z M2 z ) 2-x P 3-w Si w O 12 . Represented by, M1 is one or more selected from gallium, lanthanum, indium and yttrium, M2 is one or more selected from titanium, zirconium and hafnium, and the range of x is 0 <x ≤ 1.0, The range of y is 0 ≤ y ≤ 1.0, the range of z is 0 ≤ z ≤ 1.0, and the range of w is 0 ≤ w ≤ 1.0. The above-mentioned amorphous lithium ion conduction oxide powder.
The eighth invention is
Further, the amorphous lithium ion conductive oxide powder according to any one of the first to sixth inventions, which contains at least one element selected from gallium, lanthanum, indium and yttrium.
The ninth invention is
A slurry forming step of mixing an aqueous solution of a lithium compound, an aqueous solution of an aluminum compound, an aqueous solution of a germanium compound, and an aqueous solution of an ammonium phosphate salt to obtain a suspension of a co-precipitate.
The step of spray-drying the slurry to obtain a dried slurry, and
A method for producing an amorphous lithium ion conductive oxide powder, which comprises a step of calcining the dried slurry at a temperature of 300 ° C. or higher and 500 ° C. or lower.
The tenth invention is
Amorphous according to the ninth invention, wherein in the slurry forming step, an aqueous solution of a compound containing at least one element selected from gallium, lanthanum, indium and yttrium is further mixed to obtain a suspension of a co-precipitate. This is a method for producing a lithium ion conductive oxide powder.
The eleventh invention is
The amorphous according to the ninth or tenth invention, wherein in the slurry forming step, an aqueous solution of a compound containing at least one element selected from titanium, zirconium and hafnium is further mixed to obtain a suspension of a co-precipitate. It is a method for producing a quality lithium ion conductive oxide powder.
The twelfth invention is
The production of the amorphous lithium ion conductive oxide powder according to any one of the ninth to eleventh inventions, wherein in the slurry forming step, an aqueous solution of a silicon compound is further mixed to obtain a suspension of a co-precipitate. The method.
The thirteenth invention is
The amorphous lithium ion according to any one of the ninth to twelfth inventions, wherein the suspension is formed in the slurry forming step by mixing an aqueous solution of the germanium compound adjusted to pH 8 or higher. This is a method for producing a conductive oxide powder.
The fourteenth invention is
A lithium ion conductive oxide powder having a NASICON type crystal structure, which comprises a step of calcining the amorphous lithium ion conductive oxide powder according to any one of the first to eighth inventions at a temperature higher than 500 ° C. It is a manufacturing method of.
The fifteenth invention is
A slurry forming step of mixing an aqueous solution of a lithium compound, an aqueous solution of an aluminum compound, an aqueous solution of a germanium compound, and an aqueous solution of an ammonium phosphate salt to obtain a suspension of a co-precipitate.
The step of spray-drying the slurry to obtain a dried slurry, and
It is a method for producing a lithium ion conductive oxide powder having a NASICON type crystal structure, which comprises a step of calcining the dried slurry product at a temperature higher than 500 ° C.
ここで、主な構成物質の含有割合について説明する。
リチウムは、リチウム元素として０．５質量％以上６．５質量％以下が含有されている。
これは、リチウムの含有量が０．５質量％以上であれば、リチウムイオン伝導度が担保されるからである。一方、リチウムの含有量が６．５質量％以下であれば、結晶化した際、リチウムイオン伝導酸化物粉末がＮＡＳＩＣＯＮ型結晶構造となるからである。リチウムの含有量は好ましくは１．０質量％以上、より好ましくは１．５質量％以上、さらに好ましくは１．８質量％以上であり、一方、好ましくは４．０質量％以下、好ましくは３．５質量％以下、さらに好ましくは３．３質量％以下である。
Here, the content ratios of the main constituent substances will be described.
Lithium contains 0.5% by mass or more and 6.5% by mass or less as a lithium element.
This is because if the lithium content is 0.5% by mass or more, the lithium ion conductivity is guaranteed. On the other hand, when the lithium content is 6.5% by mass or less, the lithium ion conductive oxide powder has a NASICON type crystal structure when crystallized. The lithium content is preferably 1.0% by mass or more, more preferably 1.5% by mass or more, still more preferably 1.8% by mass or more, while preferably 4.0% by mass or less, preferably 3 It is 5.5% by mass or less, more preferably 3.3% by mass or less.
一方、本発明に係る非晶質リチウムイオン伝導酸化物粉末は、リチウム元素、アルミニウム元素、ゲルマニウム元素、所望により添加された上述の置換金属元素、リン元素、炭素、酸素以外に、１０質量％程度、好ましくは３．０質量％程度の不純物を含む場合がある。当該不純物は、当該非晶質リチウムイオン伝導酸化物粉末を製造する際に用いられたビーズのジルコニア等であると考えられるが、この程度の含有量であれば、ＮＡＳＩＣＯＮ型結晶構造のリチウムイオン伝導体となった際のリチウムイオン伝導特性に、特に悪影響を与えることはない。 On the other hand, the amorphous lithium ion conductive oxide powder according to the present invention is about 10% by mass in addition to the lithium element, the aluminum element, the germanium element, the above-mentioned substituted metal element added as desired, the phosphorus element, carbon and oxygen. It may contain impurities of about 3.0% by mass, preferably. The impurities are considered to be zirconia of beads used in producing the amorphous lithium ion conductive oxide powder, but if the content is at this level, lithium ions having a NASICON type crystal structure are considered to be present. It does not particularly adversely affect the lithium ion conduction characteristics when it becomes a conductor.
以下、本発明に係る非晶質リチウムイオン伝導酸化物粉末、並びに、ＮＡＳＩＣＯＮ型結晶構造を有するリチウムイオン伝導酸化物粉末の製造方法について、当該非晶質リチウムイオン伝導酸化物粉末の製造工程を示すフロー図である図１を参照しながら、（１）原料水溶液調製、（２）混合、（３）噴霧乾燥、（４）焼成、（５）粉砕、（６）乾燥、（７）焼成、（８）ＮＡＳＩＣＯＮ型結晶構造を有するリチウムイオン伝導酸化物粉末の製造、の順に説明する。 Hereinafter, the manufacturing process of the amorphous lithium ion conductive oxide powder according to the present invention and the method for manufacturing the lithium ion conductive oxide powder having a NASICON type crystal structure will be shown. With reference to FIG. 1, which is a flow diagram, (1) raw material aqueous solution preparation, (2) mixing, (3) spray drying , (4) firing, (5) pulverization, (6) drying, (7) firing, ( 8) Production of a lithium ion conductive oxide powder having a NASICON type crystal structure will be described in this order.
（２）混合（スラリー化）
前記（１）にて調製した原料水溶液を、ねらいのリチウムイオン伝導酸化物粉末の組成に合わせて混合し、共沈法によりリチウムイオン伝導体の構成元素を含むスラリーを得る工程である。例えば、アンモニアで溶解させたアルカリ性のゲルマニウム水溶液に、硝酸リチウム、硝酸アルミニウム９水和物、りん酸二水素アンモニウムを溶解させた酸性の水溶液を添加すると直後に濁り、共沈法によってリチウム、アルミニウム、ゲルマニウム、リン等を含有したスラリーを得ることが出来る。この混合工程では液温は特に検討する必要はなく、加温しても、しなくても良い。当該スラリー中には、水酸化物として析出した構成元素と、イオンとして存在している構成元素とが存在していると考えられる。尚、スラリー中における炭酸由来の炭素量を低減する為に、当該スラリーを窒素パージすることも好ましい構成である。
(2) Mixing (slurry)
This is a step of mixing the raw material aqueous solution prepared in (1) according to the composition of the target lithium ion conductive oxide powder and obtaining a slurry containing the constituent elements of the lithium ion conductor by the coprecipitation method. For example, when an acidic aqueous solution in which lithium nitrate, aluminum nitrate nine hydrate, and ammonium dihydrogen phosphate are dissolved is added to an alkaline germanium aqueous solution dissolved in ammonia, it becomes turbid immediately and becomes turbid immediately, and lithium, aluminum, by the co-precipitation method. A slurry containing germanium, phosphorus and the like can be obtained. In this mixing step, the liquid temperature does not need to be particularly examined and may or may not be heated. It is considered that the constituent elements precipitated as hydroxides and the constituent elements existing as ions are present in the slurry. In order to reduce the amount of carbonic acid-derived carbon in the slurry, it is also preferable to purge the slurry with nitrogen.
これに対し、構成元素を完全に溶解させた原料水溶液から脱水することとした場合は、溶解度の変化による析出であって、上述した共沈法のようにｐＨ変化による急激な過飽和状態を経過しない。この結果、生成する沈殿物の核数の数は減少し、析出する沈殿物の粒子径は大きくなる。さらに構成元素により溶解度が異なるため、脱水の過程において溶解度の低い構成元素は先に析出し、溶解度の高い構成元素は後に析出することになる為、生成した粒子の不均一性が生じる可能性もある。 On the other hand, when dehydration is performed from the raw material aqueous solution in which the constituent elements are completely dissolved, the precipitation is due to a change in solubility, and a rapid supersaturation state due to a pH change is elapsed as in the coprecipitation method described above. do not do. As a result, the number of nuclei of the precipitate produced decreases, and the particle size of the precipitate increases. Furthermore, since the solubility differs depending on the constituent elements, the constituent elements with low solubility are precipitated first and the constituent elements with high solubility are precipitated later in the process of dehydration, which may cause non-uniformity of the generated particles. be.
（３）噴霧乾燥
前記（２）にて得られたスラリーを、スプレードライヤー等を用いて噴霧乾燥して前記スラリー中の水分を蒸発させ、粉体を得る工程である。
ここで、乾燥工程を設けるのは、前記（２）にて得られたスラリー中には構成元素であるリチウム、アルミニウム、ゲルマニウム、リン、および、所望により添加された上述の置換金属元素の大部分が共沈しているが、イオンで存在しているものもある為である。例えば、当該スラリーから濾過工程によって回収された粉体を用いると、目論見の組成を有するリチウムイオン伝導体を得ることが出来ないと考えられる。
(3) Spray drying
This is a step of spray-drying the slurry obtained in (2) above using a spray dryer or the like to evaporate the water content in the slurry to obtain a powder.
Here, the drying step is provided in the slurry obtained in (2) above, which are the constituent elements lithium, aluminum, germanium, phosphorus, and most of the above-mentioned substituted metal elements added as desired. Is coprecipitating, but some are present as ions. For example, if the powder recovered from the slurry by the filtration step is used, it is considered that a lithium ion conductor having the intended composition cannot be obtained.
（２）混合（スラリー化）
前記アルカリ性であるゲルマニウム水溶液７２０ｇを分取し攪拌しながら４０℃に加温し、そこへ前記酸性であるリチウム、アルミニウム、リン含有水溶液の全量（２８３．７ｇ）を添加したところ、水溶液は当該添加直後に白濁し、白色スラリーを得た。得られた白色スラリーのｐＨ値は４．３であった。
(2) Mixing (slurry)
720 g of the alkaline germanium aqueous solution was separated and heated to 40 ° C. with stirring, and the entire amount (283.7 g) of the acidic lithium, aluminum and phosphorus-containing aqueous solution was added thereto. Immediately after the addition, it became cloudy and a white slurry was obtained. The pH value of the obtained white slurry was 4.3.
（３）噴霧乾燥
前記白色スラリーを、噴霧乾燥機（東京理化器械株式会社製 ＳＤ－１０００）を用いて噴霧乾燥して、前記白色スラリー中の水分を蒸発させて一気に固相析出させ、白色の粉末を得た。尚、噴霧乾燥の条件としては、入口温度１８０℃、出口温度９０℃、前記白色スラリーの添加速度１０ｇ／ｍｉｎとした。
(3) Spray drying
The white slurry was spray-dried using a spray dryer (SD-1000 manufactured by Tokyo Rika Kikai Co., Ltd.) to evaporate the water content in the white slurry and precipitate it in a solid phase at once to obtain a white powder. The conditions for spray drying were an inlet temperature of 180 ° C., an outlet temperature of 90 ° C., and an addition rate of the white slurry of 10 g / min.
（２）混合（スラリー化）
前記アルカリ性であるゲルマニウム水溶液８１６ｇを分取し攪拌しながら４０℃に加温し、そこへ前記酸性であるリチウム、アルミニウム、リン含有水溶液の全量を添加したところ、水溶液は当該添加直後に白濁し、白色スラリーを得た。得られた白色スラリーのｐＨ値は６．７であった。
(2) Mixing (slurry)
When 816 g of the alkaline germanium aqueous solution was separated and heated to 40 ° C. while stirring, and the entire amount of the acidic lithium, aluminum, and phosphorus-containing aqueous solution was added thereto, the aqueous solution became cloudy immediately after the addition. , A white slurry was obtained. The pH value of the obtained white slurry was 6.7.
（２）混合（スラリー化）
前記アルカリ性であるゲルマニウム水溶液８１６ｇを分取し攪拌しながら４０℃に加温し、そこへ前記酸性であるリチウム、アルミニウム、リン含有水溶液の全量を添加したところ、水溶液は当該添加直後に白濁し、白色スラリーを得た。得られた白色スラリーのｐＨ値は４．１であった。
(2) Mixing (slurry)
When 816 g of the alkaline germanium aqueous solution was separated and heated to 40 ° C. while stirring, and the entire amount of the acidic lithium, aluminum, and phosphorus-containing aqueous solution was added thereto, the aqueous solution became cloudy immediately after the addition. , A white slurry was obtained. The pH value of the obtained white slurry was 4.1.
（２）混合（スラリー化）
前記アルカリ性であるゲルマニウム水溶液６００ｇを分取し攪拌しながら４０℃に加温し、そこへ前記酸性であるリチウム、アルミニウム、リン含有水溶液の全量を添加したところ、水溶液は当該添加直後に白濁し、白色スラリーを得た。得られた白色スラリーのｐＨ値は３．９であった。
(2) Mixing (slurry)
When 600 g of the alkaline germanium aqueous solution was separated and heated to 40 ° C. while stirring, and the entire amount of the acidic lithium, aluminum, and phosphorus-containing aqueous solution was added thereto, the aqueous solution became cloudy immediately after the addition. , A white slurry was obtained. The pH value of the obtained white slurry was 3.9.
（２）混合（スラリー化）
前記アルカリ性であるゲルマニウム水溶液６８４ｇを分取し攪拌しながら４０℃に加温し、そこへ前記酸性であるリチウム、アルミニウム、リン、チタン含有水溶液の全量を添加したところ、水溶液は当該添加直後に白濁し、白色スラリーを得た。得られた白色スラリーのｐＨ値は６．７であった。
(2) Mixing (slurry)
684 g of the alkaline germanium aqueous solution was separated and heated to 40 ° C. with stirring, and the entire amount of the acidic lithium, aluminum, phosphorus, and titanium-containing aqueous solution was added thereto. The aqueous solution was immediately after the addition. It became cloudy and a white slurry was obtained. The pH value of the obtained white slurry was 6.7.
（ＩＩ）リチウム、アルミニウム、リン含有水溶液
純水１５０ｇへ、硝酸リチウム２１．７ｇと硝酸アルミニウム９水和物３９．４ｇとリン酸二水素アンモニウム７２．５ｇとを加え、リチウム、アルミニウム、リン含有水溶液を調製した。調製したリチウム、アルミニウム、リン含有水溶液におけるｐＨ値は０．９であり、酸性であった。
（２）混合（スラリー化）
前記アルカリ性であるゲルマニウム水溶液６８４ｇを分取し攪拌しながら４０℃に加温し、オキシ硝酸ジルコニウム４．１ｇを加え完全に溶解させた。そこへ前記酸性であるリチウム、アルミニウム、リン含有水溶液の全量を添加したところ、水溶液は当該添加直後に白濁し、白色スラリーを得た。得られた白色スラリーのｐＨ値は３．９であった。
(II) Lithium, aluminum, phosphorus-containing aqueous solution To 150 g of pure water, 21.7 g of lithium nitrate, 39.4 g of aluminum nitrate nine hydrate, and 72.5 g of ammonium dihydrogen phosphate are added, and an aqueous solution containing lithium, aluminum, and phosphorus is added. Was prepared. The pH value of the prepared lithium, aluminum, and phosphorus-containing aqueous solution was 0.9, which was acidic.
(2) Mixing (slurry)
684 g of the alkaline aqueous germanium solution was separated and heated to 40 ° C. with stirring, and 4.1 g of zirconium oxynitrite was added to completely dissolve the solution. When the entire amount of the acidic lithium, aluminum, and phosphorus-containing aqueous solution was added thereto, the aqueous solution became cloudy immediately after the addition, and a white slurry was obtained. The pH value of the obtained white slurry was 3.9.
（Ｉ）酸素量計算
非晶質リチウムイオン伝導酸化物粉末に含まれるジルコニウムに係る酸素量を以下の通り算出した。
４価であるジルコニウムの酸化物はＺｒＯ2であることから、ジルコニウム酸化物に係る酸素量は以下の式で標記される。
ジルコニウム酸化物に係る酸素量＝（Ｚｒ濃度×（ＺｒＯ2の式量／ＺｒＯ2のＺｒ原子の個数）÷Ｚｒの式量）－Ｚｒ濃度・・・（式）
一方、ジルコニウム濃度のＩＣＰの分析結果は１．５質量％であるから、
ジルコニウム酸化物に係る酸素量＝（１．５×（１２３．２２／１）÷９１．２２）－１．５＝０．５３質量％
となる。
(I) Oxygen amount calculation The oxygen amount related to zirconium contained in the amorphous lithium ion conductive oxide powder was calculated as follows.
Since the tetravalent zirconium oxide is ZrO 2 , the amount of oxygen related to the zirconium oxide is described by the following formula.
Amount of oxygen related to zirconium oxide = (Zr concentration × (formula of ZrO 2 / number of Zr atoms of ZrO 2 ) ÷ formula of Zr) -Zr concentration ... (formula)
On the other hand, the analysis result of ICP of zirconium concentration is 1.5% by mass.
Amount of oxygen related to zirconium oxide = (1.5 × (123.22 / 1) ÷ 91.22) -1.5 = 0.53% by mass
Will be.
（２）混合（スラリー化）
前記アルカリ性であるゲルマニウム水溶液７２０ｇを分取し、Ｌｉ2Ｏ11Ｓｉ5溶液（シグマアルドリッチ製）を１０．２ｇ添加した。その液を攪拌しながら４０℃に加温し、そこへ前記酸性であるリチウム、アルミニウム、リン含有水溶液の全量を添加したところ、水溶液は当該添加直後に白濁し、白色スラリーを得た。
(2) Mixing (slurry)
720 g of the alkaline aqueous germanium solution was dispensed, and 10.2 g of a Li 2 O 11 Si 5 solution (manufactured by Sigma-Aldrich) was added. The solution was heated to 40 ° C. with stirring, and the entire amount of the acidic lithium, aluminum, and phosphorus-containing aqueous solution was added thereto. The aqueous solution became cloudy immediately after the addition, and a white slurry was obtained.
（ＩＩ）リチウム、アルミニウム、リン含有水溶液
純水１５０ｇへ、硝酸リチウム２２．９ｇと硝酸アルミニウム９水和物３９．４ｇとリン酸二水素アンモニウム７２．５ｇとを加え、リチウム、アルミニウム、リン含有水溶液を調製した。調製したリチウム、アルミニウム、リン含有水溶液におけるｐＨ値は１．８であり、酸性であった。
(II) Lithium, aluminum, phosphorus-containing aqueous solution To 150 g of pure water, 22.9 g of lithium nitrate , 39.4 g of aluminum nitrate nine hydrate, and 72.5 g of ammonium dihydrogen phosphate are added, and lithium, aluminum, and phosphorus are contained. An aqueous solution was prepared. The pH value of the prepared lithium, aluminum, and phosphorus-containing aqueous solution was 1.8, which was acidic.
（２）混合（スラリー化）
前記アルカリ性であるゲルマニウム水溶液７２０ｇを分取し攪拌しながら４０℃に加温し、そこへ前記酸性であるリチウム、アルミニウム、リン含有水溶液の全量を添加したところ、水溶液は当該添加直後に白濁し、白色スラリーを得た。得られた白色スラリーのｐＨ値は４．５であった。
(2) Mixing (slurry)
When 720 g of the alkaline germanium aqueous solution was separated and heated to 40 ° C. while stirring, and the entire amount of the acidic lithium, aluminum, and phosphorus-containing aqueous solution was added thereto, the aqueous solution became cloudy immediately after the addition. , A white slurry was obtained. The pH value of the obtained white slurry was 4.5.
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