JP2017191667A - Active material coating solution - Google Patents
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Abstract
Description
本発明は、活物質被覆用溶液に関する。 The present invention relates to an active material coating solution.
全固体電池の分野において、従来から、固体電解質と電極活物質の界面に着目し、電極活物質の表面に固体電解質を被覆することにより、界面抵抗を低減し、電池の性能の向上を図る試みがある。
例えば、特許文献１には、正極活物質であるコバルト酸リチウムの表面をニオブ酸リチウムによって被覆することにより界面抵抗を低減し、電池の性能の向上を図るための、リチウムと、ニオブ酸のペルオキソ錯体と、クエン酸を含有する活物質被覆用溶液が開示されている。
In the field of all-solid-state batteries, an attempt to reduce the interfacial resistance and improve battery performance by focusing on the interface between the solid electrolyte and electrode active material and coating the surface of the electrode active material with the solid electrolyte There is.
For example, Patent Document 1 discloses that lithium and niobate peroxo are used to reduce the interfacial resistance by covering the surface of lithium cobaltate, which is a positive electrode active material, with lithium niobate and to improve battery performance. An active material coating solution containing a complex and citric acid is disclosed.
しかし、特許文献１に開示されているような活物質被覆用溶液では、ニオブ酸のペルオキソ錯体は不安定で沈殿しやすいため、ニオブ酸のペルオキソ錯体の安定性を確保し、生産効率を向上させるために、安定化剤として多量のクエン酸を添加する必要がある。そのため、活物質の熱処理後に、炭化したクエン酸によるＬｉイオン移動阻害が生じ、ニオブ酸リチウム被覆処理後の活物質のＬｉイオン伝導率が不十分であるという問題がある。
本発明は上記実情を鑑みて成し遂げられたものであり、本発明の目的は、クエン酸を少量添加するよりも保存安定性に優れる活物質被覆用溶液を提供することである。
However, in the active material coating solution as disclosed in Patent Document 1, since the niobic acid peroxo complex is unstable and easily precipitates, the stability of the niobic acid peroxo complex is secured and the production efficiency is improved. Therefore, it is necessary to add a large amount of citric acid as a stabilizer. Therefore, after the heat treatment of the active material, there is a problem that Li ion migration is inhibited by the carbonized citric acid, and the Li ion conductivity of the active material after the lithium niobate coating treatment is insufficient.
The present invention has been accomplished in view of the above circumstances, and an object of the present invention is to provide a solution for coating an active material that is superior in storage stability to the addition of a small amount of citric acid.
本発明の活物質被覆用溶液は、リチウムと、ニオブ酸のペルオキソ錯体と、リン酸系イオンと、を含む、活物質被覆用溶液であって、
前記リン酸系イオンは、（ＰＯ４）３−、（Ｈ２ＰＯ４）−、（ＨＰＯ４）２−、（Ｐ２Ｏ７）４−であり、
前記活物質被覆用溶液に含まれるリン酸系イオン濃度は、ニオブに対するモル比で０．０２以上３．０１以下であることを特徴とする。
The active material coating solution of the present invention is an active material coating solution containing lithium, a peroxo complex of niobic acid, and a phosphate ion,
The phosphate ions are (PO 4 ) 3− , (H 2 PO 4 ) − , (HPO 4 ) 2− , (P 2 O 7 ) 4− ,
The phosphate ion concentration contained in the active material coating solution is 0.02 to 3.01 in terms of a molar ratio to niobium.
本発明によれば、クエン酸を少量添加するよりも保存安定性に優れる活物質被覆用溶液を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the solution for active material coating | cover which is excellent in storage stability rather than adding a small amount of citric acid can be provided.
本発明の活物質被覆用溶液は、リチウムと、ニオブ酸のペルオキソ錯体と、リン酸系イオンと、を含む、活物質被覆用溶液であって、
前記リン酸系イオンは、（ＰＯ４）３−、（Ｈ２ＰＯ４）−、（ＨＰＯ４）２−、（Ｐ２Ｏ７）４−であり、
前記活物質被覆用溶液に含まれるリン酸系イオン濃度は、ニオブに対するモル比で０．０２以上３．０１以下であることを特徴とする。
The active material coating solution of the present invention is an active material coating solution containing lithium, a peroxo complex of niobic acid, and a phosphate ion,
The phosphate ions are (PO 4 ) 3− , (H 2 PO 4 ) − , (HPO 4 ) 2− , (P 2 O 7 ) 4− ,
The phosphate ion concentration contained in the active material coating solution is 0.02 to 3.01 in terms of a molar ratio to niobium.
本発明者は、活物質被覆用溶液に、安定化剤として、リン酸系イオンを添加することによって、クエン酸を少量添加するよりも保存安定性に優れることを見出した。
なお、本発明において「クエン酸を少量添加する」とは、活物質被覆用溶液に含まれるクエン酸濃度がニオブに対するモル比で０．７９以下となるように、後述する錯体溶液にクエン酸を添加することをいう（比較例２〜４参照）。
The present inventor has found that by adding a phosphoric acid ion as a stabilizer to the active material coating solution, the storage stability is superior to adding a small amount of citric acid.
In the present invention, “adding a small amount of citric acid” means that citric acid is added to a complex solution described later so that the concentration of citric acid contained in the active material coating solution is 0.79 or less in terms of a molar ratio to niobium. It means adding (see Comparative Examples 2 to 4).
ニオブ酸のペルオキソ錯体（［Ｎｂ（Ｏ２）４］３−）は、特許文献１に記載されているような従来公知の方法で得ることができ、例えば、過酸化水素水へ、ニオブ酸（Ｎｂ２Ｏ５・ｎＨ２Ｏ）を添加して混合し、得られた懸濁液へ、アンモニア水等のアルカリを添加し、混合することにより透明なニオブ酸のペルオキソ錯体を得ることができる。
ここで、当該混合の際、ニオブ酸１モルに対して、過酸化水素が８モル以上となるようにすることが好ましく、過酸化水素が反応中に分解する可能性があることを考慮すると、ニオブ酸１モルに対して、過酸化水素が１０モル以上となるようにすることが更に好ましい。
また、当該懸濁液へ、アルカリとしてアンモニア水を添加する場合、ニオブ酸１モルに対して、アンモニアが１モル以上となるように添加することが好ましく、アンモニアが反応中に揮発することを考慮すると、ニオブ酸１モルに対して、アンモニアが２モル以上となるように添加することが、さらに好ましい。
さらに、当該アンモニア水に代えて、アルカリ性溶液を添加することもできる。この場合、アルカリ性溶液の添加量は、添加後の溶液のｐＨ値が１０以上、好ましくは、１１以上となる量とする。当該アルカリ性溶液として、水酸化リチウム溶液を添加することもできる。
A peroxo complex of niobic acid ([Nb (O 2 ) 4 ] 3− ) can be obtained by a conventionally known method as described in Patent Document 1, for example, niobic acid ( Nb 2 O 5 .nH 2 O) is added and mixed, and an alkali such as aqueous ammonia is added to and mixed with the obtained suspension, whereby a transparent peroxo complex of niobic acid can be obtained.
Here, at the time of the mixing, it is preferable that hydrogen peroxide is 8 moles or more with respect to 1 mole of niobic acid, and considering that hydrogen peroxide may be decomposed during the reaction, More preferably, the hydrogen peroxide is 10 moles or more per mole of niobic acid.
Moreover, when adding aqueous ammonia as an alkali to the suspension, it is preferable to add ammonia so that the amount of ammonia is 1 mol or more with respect to 1 mol of niobic acid, considering that ammonia volatilizes during the reaction. Then, it is more preferable to add so that ammonia may be 2 mol or more with respect to 1 mol of niobic acid.
Furthermore, instead of the ammonia water, an alkaline solution can be added. In this case, the addition amount of the alkaline solution is such that the pH value of the solution after the addition is 10 or more, preferably 11 or more. A lithium hydroxide solution can also be added as the alkaline solution.
そして、得られたニオブ酸のペルオキソ錯体を含有する水溶液に、リチウム化合物を添加することにより、リチウムとニオブ酸のペルオキソ錯体とを含有する溶液を得ることができる。添加するリチウム化合物のリチウムのモル数は、前記水溶液中に含まれるニオブ酸のペルオキソ錯体のニオブのモル数に対して、任意に設定することが出来る。添加するリチウム化合物のリチウムのモル数は、前記水溶液中に含まれるニオブ錯体のニオブのモル数に対して、任意に設定することができ、ニオブ１モルに対してリチウムが１以上、１．３モル以下であることが好ましい。
リチウム化合物としては、水酸化リチウム（ＬｉＯＨ）、硝酸リチウム（ＬｉＮＯ３）、硫酸リチウム（Ｌｉ２ＳＯ４）等が挙げられる。
A solution containing lithium and a niobic acid peroxo complex can be obtained by adding a lithium compound to the aqueous solution containing the niobic acid peroxo complex. The number of moles of lithium in the lithium compound to be added can be arbitrarily set with respect to the number of moles of niobium in the peroxo complex of niobic acid contained in the aqueous solution. The number of moles of lithium in the lithium compound to be added can be arbitrarily set with respect to the number of moles of niobium in the niobium complex contained in the aqueous solution. It is preferably less than or equal to a mole.
Examples of the lithium compound include lithium hydroxide (LiOH), lithium nitrate (LiNO 3 ), and lithium sulfate (Li 2 SO 4 ).
活物質被覆用溶液に、含まれるリン酸系イオンは、（ＰＯ４）３−、（Ｈ２ＰＯ４）−、（ＨＰＯ４）２−、（Ｐ２Ｏ７）４−である。
上記リチウムとニオブ酸のペルオキソ錯体とを含有する溶液に安定化剤として添加するリン酸系化合物としては、例えば、リン酸、リン酸二水素アンモニウム、リン酸水素二アンモニウム、ピロリン酸四ナトリウム等が挙げられる。
活物質被覆用溶液に含まれるリン酸系イオン濃度は、下限値は、ニオブに対するモル比で０．０２以上であり、上限値は、ニオブに対するモル比で３．０１以下であり、１．００以下が好ましく、０．７１以下がより好ましい。
Phosphate ions contained in the active material coating solution are (PO 4 ) 3− , (H 2 PO 4 ) − , (HPO 4 ) 2− , (P 2 O 7 ) 4− .
Examples of the phosphate compound added as a stabilizer to the solution containing the lithium and niobic acid peroxo complex include phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and tetrasodium pyrophosphate. Can be mentioned.
As for the phosphate ion concentration contained in the active material coating solution, the lower limit is 0.02 or more in terms of the molar ratio to niobium, and the upper limit is 3.01 or less in terms of the molar ratio to niobium. The following is preferable, and 0.71 or less is more preferable.
（実施例１）
［ペルオキソ錯体溶液の調製］
濃度３０質量％の過酸化水素水４３．５ｇへ、イオン交換水４９．５ｇ、ニオブ酸（Ｎｂ２Ｏ５・ｎＨ２Ｏ（Ｎｂ２Ｏ５含有率７７％））２．０８ｇを添加した。
次に、濃度２８質量％のアンモニア水４．４ｇを添加し、十分に攪拌して透明溶液を得た。
得られた透明溶液に水酸化リチウム・１水和物（ＬｉＯＨ・Ｈ２Ｏ）０．５ｇを加えて、リチウムとニオブ錯体とを含有する水溶液を得た。
得られた錯体溶液のＬｉ、Ｎｂのモル濃度は各０．１２ｍｏｌ／ｋｇであった。
Example 1
[Preparation of peroxo complex solution]
49.5 g of ion-exchanged water and 2.08 g of niobic acid (Nb 2 O 5 .nH 2 O (Nb 2 O 5 content 77%)) were added to 43.5 g of hydrogen peroxide water having a concentration of 30% by mass.
Next, 4.4 g of ammonia water having a concentration of 28% by mass was added and sufficiently stirred to obtain a transparent solution.
To the obtained transparent solution, 0.5 g of lithium hydroxide monohydrate (LiOH.H 2 O) was added to obtain an aqueous solution containing lithium and a niobium complex.
The molar concentration of Li and Nb in the obtained complex solution was 0.12 mol / kg.
［安定化剤の添加］
上記錯体溶液に安定化剤としてリン酸を添加し混合し、活物質被覆用溶液を得た。
リン酸の添加量はニオブに対するモル比で０．０２とした。
[Addition of stabilizer]
Phosphoric acid as a stabilizer was added to the complex solution and mixed to obtain an active material coating solution.
The amount of phosphoric acid added was 0.02 in terms of a molar ratio to niobium.
［吸光度、ｐＨの測定］
得られた活物質被覆用溶液を室温にて静置した。
そして、吸光度、及び、ｐＨの変化を記録した。結果を表１に示す。
吸光度、及び、ｐＨは以下の装置を用いて測定した。
吸光度：分光光度計（ＵＶ−３６００、島津製作所社製）。４２０〜７８０ｎｍにおける最大吸光度を吸光度とした。
ｐＨ：ｐＨメーター（Ｄ−７２、堀場製作所社製）。
[Measurement of absorbance and pH]
The obtained active material coating solution was allowed to stand at room temperature.
Then, changes in absorbance and pH were recorded. The results are shown in Table 1.
Absorbance and pH were measured using the following apparatus.
Absorbance: spectrophotometer (UV-3600, manufactured by Shimadzu Corporation). The maximum absorbance at 420 to 780 nm was defined as absorbance.
pH: pH meter (D-72, manufactured by Horiba, Ltd.).
［Ｌｉイオン伝導率測定］
上記活物質被覆用溶液をホットプレート上で乾燥後（１２０℃）、熱処理（大気雰囲気、２００℃、５ｈ）を加えることでＬｉＮｂＯ３粉体を得た。
内径断面積１ｃｍ２の筒状セラミックスに、得られたＬｉＮｂＯ３粉体１００ｍｇを入れ、平滑にし、４．３ｔｏｎで１分プレスし、ペレット化した後、ステンレス棒を両極に入れ、１ｔｏｎで拘束して、Ｌｉイオン伝導率測定セルとした。
ナイキストプロットにより得られた円弧をイオン移動抵抗とし、ペレット厚みよりＬｉＮｂＯ３のＬｉイオン伝導率を計算した。結果を表１に示す。
[Li ion conductivity measurement]
The above active material coating solution was dried on a hot plate (120 ° C.) and then heat-treated (atmospheric atmosphere, 200 ° C., 5 h) to obtain LiNbO 3 powder.
Put 100 mg of the obtained LiNbO 3 powder into cylindrical ceramics with an inner diameter cross-sectional area of 1 cm 2 , smooth, press at 4.3 ton for 1 minute, pelletize, put stainless steel rod into both poles and restrain at 1 ton. Thus, a Li ion conductivity measuring cell was obtained.
The arc obtained by the Nyquist plot was used as the ion migration resistance, and the Li ion conductivity of LiNbO 3 was calculated from the pellet thickness. The results are shown in Table 1.
（実施例２〜９、参考例１０、実施例１１〜２５）
上記錯体溶液に、安定化剤として、リン酸（実施例２〜９、参考例１０）、リン酸二水素アンモニウム（実施例１１〜１６）、リン酸水素二アンモニウム（実施例１７〜２１）、ピロリン酸四ナトリウム（実施例２２〜２６）を、表１〜４に示すニオブに対するモル比になる量を添加し、混合したこと以外は、実施例１と同様に活物質被覆用溶液を得た。
そして、実施例１と同様に吸光度、ｐＨ、Ｌｉイオン伝導率を測定した。結果を表１（実施例２〜９、参考例１０）、表２（実施例１１〜１６）、表３（実施例１７〜２１）、表４（実施例２２〜２６）に示す。
(Examples 2-9, Reference Example 10, Examples 11-25)
In the complex solution, phosphoric acid (Examples 2 to 9, Reference Example 10), ammonium dihydrogen phosphate (Examples 11 to 16), diammonium hydrogen phosphate (Examples 17 to 21) as stabilizers, An active material coating solution was obtained in the same manner as in Example 1 except that tetrasodium pyrophosphate (Examples 22 to 26) was added and mixed in an amount to give a molar ratio to niobium shown in Tables 1 to 4. .
Then, the absorbance, pH, and Li ion conductivity were measured in the same manner as in Example 1. The results are shown in Table 1 (Examples 2 to 9, Reference Example 10), Table 2 (Examples 11 to 16), Table 3 (Examples 17 to 21), and Table 4 (Examples 22 to 26).
（比較例１）
上記錯体溶液に、安定化剤として、リン酸を添加しなかったこと以外は、実施例１と同様に活物質被覆用溶液を得た。
そして、実施例１と同様に吸光度、ｐＨ、Ｌｉイオン伝導率を測定した。結果を表５に示す。
(Comparative Example 1)
An active material coating solution was obtained in the same manner as in Example 1 except that phosphoric acid was not added as a stabilizer to the complex solution.
Then, the absorbance, pH, and Li ion conductivity were measured in the same manner as in Example 1. The results are shown in Table 5.
（比較例２〜４７）
上記錯体溶液に、安定化剤として、クエン酸（比較例２〜６）、アセトアニリド（比較例７〜１１）、尿酸（比較例１２〜１６）、塩酸（比較例１７〜２２）、ホウ酸（比較例２３〜２７）、硫酸（比較例２８〜３２）、硝酸（比較例３３〜３７）、ホスホン酸（比較例３８〜４２）、ホスフィン酸（比較例４３〜４７）を、表６〜１４に示すニオブに対するモル比になる量を添加し、混合したこと以外は、実施例１と同様に活物質被覆用溶液を得た。
そして、実施例１と同様に吸光度、ｐＨ、Ｌｉイオン伝導率を測定した。結果を表６（比較例２〜６）、表７（比較例７〜１１）、表８（比較例１２〜１６）、表９（比較例１７〜２２）、表１０（比較例２３〜２７）、表１１（比較例２８〜３２）、表１２（比較例３３〜３７）、表１３（比較例３８〜４２）、表１４（比較例４３〜４７）に示す。
(Comparative Examples 2-47)
In the complex solution, citric acid (Comparative Examples 2 to 6), acetanilide (Comparative Examples 7 to 11), uric acid (Comparative Examples 12 to 16), hydrochloric acid (Comparative Examples 17 to 22), boric acid (as a stabilizer) Comparative Examples 23-27), sulfuric acid (Comparative Examples 28-32), nitric acid (Comparative Examples 33-37), phosphonic acid (Comparative Examples 38-42), and phosphinic acid (Comparative Examples 43-47) are shown in Tables 6-14. An active material coating solution was obtained in the same manner as in Example 1 except that an amount corresponding to the molar ratio with respect to niobium was added and mixed.
Then, the absorbance, pH, and Li ion conductivity were measured in the same manner as in Example 1. The results are shown in Table 6 (Comparative Examples 2 to 6), Table 7 (Comparative Examples 7 to 11), Table 8 (Comparative Examples 12 to 16), Table 9 (Comparative Examples 17 to 22), and Table 10 (Comparative Examples 23 to 27). ), Table 11 (Comparative Examples 28 to 32), Table 12 (Comparative Examples 33 to 37), Table 13 (Comparative Examples 38 to 42), and Table 14 (Comparative Examples 43 to 47).
表１〜４の実施例で示すようにリン酸系イオンを添加することで、表６に示すクエン酸を少量添加した比較例２〜４に対して沈殿までの時間が大幅に延長されることがわかった。すなわち、少量のクエン酸（比較例２〜４）では、１４時間以上の保存安定性効果は得られないが、実施例１〜９、１１〜２６では、１４時間以上の保存安定性効果が得られ、さらに、実施例１〜９、１１〜２０、２２〜２６では、７７時間以上の保存安定性効果が得られることがわかる。
一方、表１〜４で示すようにリン酸系イオンの添加量の増加に伴いＬｉイオン伝導率は低下することがわかる。しかし、実施例１〜７、１１〜１３、１５、１７〜２１では、比較例２よりもＬｉイオン伝導率が高いことがわかる。
表７〜８で示すようにアセトアニリド（比較例７〜１１）、尿酸（１２〜１６）の結果より、アセトアニリドでは７７時間以上の保存安定性効果は得られず、尿酸では保存安定性効果は得られないことがわかる。したがって、過酸化水素安定剤の全てに優れた保存安定性効果があるわけではないことがわかる。
表９〜１２で示すように塩酸（比較例１７〜２２）、ホウ酸（比較例２３〜２７）、硫酸（比較例２８〜３２）、硝酸（比較例３３〜３７）の結果より、塩酸では７５時間以上の保存安定性効果は得られず、ホウ酸、硫酸、及び、硝酸では６９時間以上の保存安定性効果は得られないことがわかる。したがって、無機酸の全てに優れた保存安定性効果があるわけではないことがわかる。
表１３〜１４で示すようにホスホン酸（比較例３８〜４２）、ホスフィン酸（比較例４３〜４７）の結果より、ホスホン酸、及び、ホスフィン酸では６９時間以上の保存安定性効果は得られないことがわかる。したがって、リン化合物の全てに優れた保存安定性効果があるわけではないことがわかる。
以上の結果から、詳細メカニズムは不明だが、リン酸（イオン）が部分配位等、ニオブ酸のペルオキソ錯体に対して何らかの安定化効果をもつため、少量添加で溶液の保存安定性が向上したと推定される。
As shown in the examples of Tables 1 to 4, by adding phosphoric acid ions, the time until precipitation is greatly extended compared to Comparative Examples 2 to 4 in which a small amount of citric acid shown in Table 6 is added. I understood. That is, with a small amount of citric acid (Comparative Examples 2 to 4), a storage stability effect of 14 hours or more cannot be obtained, but in Examples 1 to 9, 11 to 26, a storage stability effect of 14 hours or more was obtained. Furthermore, in Examples 1-9, 11-20, 22-26, it turns out that the storage stability effect of 77 hours or more is acquired.
On the other hand, as shown in Tables 1 to 4, it can be seen that the Li ion conductivity decreases as the amount of phosphate ions added increases. However, in Examples 1-7, 11-13, 15, 17-17, it turns out that Li ion conductivity is higher than Comparative Example 2.
As shown in Tables 7 to 8, from the results of acetanilide (Comparative Examples 7 to 11) and uric acid (12 to 16), acetanilide does not provide a storage stability effect of 77 hours or more, and uric acid provides a storage stability effect. I can't understand. Thus, it can be seen that not all hydrogen peroxide stabilizers have an excellent storage stability effect.
As shown in Tables 9 to 12, from the results of hydrochloric acid (Comparative Examples 17 to 22), boric acid (Comparative Examples 23 to 27), sulfuric acid (Comparative Examples 28 to 32), and nitric acid (Comparative Examples 33 to 37), It can be seen that the storage stability effect of 75 hours or more cannot be obtained, and the storage stability effect of 69 hours or more cannot be obtained with boric acid, sulfuric acid and nitric acid. Therefore, it can be seen that not all inorganic acids have an excellent storage stability effect.
As shown in Tables 13 to 14, from the results of phosphonic acid (Comparative Examples 38 to 42) and phosphinic acid (Comparative Examples 43 to 47), phosphonic acid and phosphinic acid have a storage stability effect of 69 hours or more. I understand that there is no. Therefore, it can be seen that not all phosphorus compounds have an excellent storage stability effect.
Although the detailed mechanism is unknown from the above results, phosphoric acid (ion) has some stabilizing effect on the peroxo complex of niobic acid, such as partial distribution position, so that the storage stability of the solution was improved by adding a small amount Presumed.
Claims (1)
前記リン酸系イオンは、（ＰＯ４）３−、（Ｈ２ＰＯ４）−、（ＨＰＯ４）２−、（Ｐ２Ｏ７）４−であり、
前記活物質被覆用溶液に含まれるリン酸系イオン濃度は、ニオブに対するモル比で０．０２以上３．０１以下であることを特徴とする活物質被覆用溶液。 An active material coating solution containing lithium, a peroxo complex of niobic acid, and a phosphate ion,
The phosphate ions are (PO 4 ) 3− , (H 2 PO 4 ) − , (HPO 4 ) 2− , (P 2 O 7 ) 4− ,
The active material coating solution is characterized in that the phosphate ion concentration contained in the active material coating solution is 0.02 or more and 3.01 or less in molar ratio to niobium.
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