JP7220370B2 - 固体電解質およびそれを備えた蓄電デバイス - Google Patents
固体電解質およびそれを備えた蓄電デバイス Download PDFInfo
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- JP7220370B2 JP7220370B2 JP2019124528A JP2019124528A JP7220370B2 JP 7220370 B2 JP7220370 B2 JP 7220370B2 JP 2019124528 A JP2019124528 A JP 2019124528A JP 2019124528 A JP2019124528 A JP 2019124528A JP 7220370 B2 JP7220370 B2 JP 7220370B2
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910021561 transition metal fluoride Inorganic materials 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Description
化学組成Li7(1+x)α3β2+aO12+3.5x+bを有する結晶相
ここで、
αは、Prを含み、
βは、Zrを含み、
-0.05≦x≦0.35
-0.5≦a≦0.5、および
-0.5≦b≦0.5、
を含有する。
実施の形態1における固体電解質は、化学組成Li7(1+x)α3β2+aO12+3.5x+bを有する結晶相を含有する。αは、Prを含む。βは、Zrを含む。以下3つの数式(I)~(III)が充足される。
-0.05≦x≦0.35 (I)
-0.5≦a≦0.5 (II)
-0.5≦b≦0.5 (III)
実施の形態2における蓄電デバイスには、実施の形態1で説明された固体電解質が使用されている。実施の形態2において、実施の形態1で説明された事項は適宜省略される。
(i) LiTi2(PO4)3またはその元素置換体のようなNASICON型固体電解質、
(ii) (LaLi)TiO3系のペロブスカイト型固体電解質、
(iii) Li14ZnGe4O16、Li4SiO4、LiGeO4またはそれらの元素置換体のようなLISICON型固体電解質、
(iv) Li7La3Zr2O12またはその元素置換体のようなガーネット型固体電解質、
(v) Li3NまたはそのH置換体、または
(vi) Li3PO4またはそのN置換体
である。
(i) テトラアルキルアンモニウムのような脂肪族鎖状第4級アンモニウム塩のカチオン、
(ii) テトラアルキルホスホニウムのような脂肪族鎖状第4級ホスホニウム塩のカチオン、
(iii) ピロリジニウム、モルホリニウム、イミダゾリニウム、テトラヒドロピリミジニウム、ピペラジニウム、またはピペリジニウムのような脂肪族環状アンモニウム、または
(iv)ピリジニウムまたはイミダゾリウムのような窒素含有ヘテロ環芳香族カチオン
である。
(i) 天然黒鉛または人造黒鉛のようなグラファイト
(ii) アセチレンブラックまたはケッチェンブラックのようなカーボンブラック、
(iii) 炭素繊維または金属繊維のような導電性繊維、
(iv) フッ化カーボン、
(v) アルミニウム粉末のような金属粉末、
(vi) 酸化亜鉛ウィスカーまたはチタン酸カリウムウィスカーのような導電性ウィスカー、
(vii) 酸化チタンのような導電性金属酸化物、または
(viii) ポリアニリン、ポリピロール、またはポリチオフェンのような導電性高分子化合物
である。
(i) LiNbO3のようなLi-Nb-O化合物、
(ii) LiBO2またはLi3BO3のようなLi-B-O化合物、
(iii) LiAlO2のようなLi-Al-O化合物、
(iv) Li4SiO4のようなLi-Si-O化合物、
(v) Li2SO4、
(vi) Li4Ti5O12のようなLi-Ti-O化合物、
(vi) Li2ZrO3のようなLi-Zr-O化合物、
(viii) Li2MoO3のようなLi-Mo-O化合物、
(ix) LiV2O5のようなLi-V-O化合物、または
(x) Li2WO4のようなLi-W-O化合物
である。
以下、本開示を以下の実施例を参照しながらより詳細に説明する。
本実施例においては、表1Aおよび表1Bに示される化学組成を有する固体電解質が以下の方法により作製された。
以下のように、固体電解質のイオン導電率を測定した。さらに、固体電解質の密度を算出した。固体電解質の結晶相が特定された。
固体電解質のイオン導電率を、固体電解質のインピーダンス特性、厚み、および電極面積(すなわち、およそ28.26平方ミリメートル)から算出した。固体電解質のインピーダンス特性は、インピーダンス測定システム(ソーラートロン社製、商品名:12608W)を用いて、摂氏25度±摂氏1度に維持された恒温槽中で、10Hzから10MHzまでの測定周波数の範囲で測定された。
固体電解質の密度は、固体電解質の重量を固体電解質の外形に基づいて得られた体積によって除することにより算出された。
固体電解質の結晶相は、固体電解質の内部の結晶相の解析結果および固体電解質の全表面の結晶相の解析結果の両者に基づいて特定された。
大気安定性を評価するため、摂氏25度±摂氏10度の温度範囲(すなわち、摂氏15度以上摂氏35度以下の温度範囲)かつ50%以上80%以下の湿度範囲の室温環境下で、試料番号2、13、19、および23の固体電解質の変化を500時間、観察した。
本発明者らは、500時間が経過した時に測定された固体電解質のイオン導電率の、0時間が経過した時に測定されたイオン導電率(すなわち、固体電解質が得られた時に測定されたイオン導電率)に対する変化率を、イオン導電率の変化率として測定した。イオン導電率の変化率は、表2に示される。
101 正極
102 電解質層
103 負極
104 正極活物質粒子
105 負極活物質粒子
2000 電池
201 第一内部電極
202 第一活物質層
203 第二内部電極
204 第二活物質層
205 電解質層
206 外部電極
Claims (27)
- 固体電解質であって、
化学組成Li7(1+x)α3β2+aO12+3.5x+bを有する結晶相
ここで、
αは、Prを含み、
βは、Zrを含み、
0<x≦0.35
-0.5≦a≦0.5、および
-0.5≦b≦0.5、
を含有する、
固体電解質。 - 請求項1に記載の固体電解質であって、
以下の数式、
0.02≦x≦0.35
が充足される、
固体電解質。 - 請求項2に記載の固体電解質であって、
以下の数式、
0.05≦x≦0.35
が充足される、
固体電解質。 - 請求項3に記載の固体電解質であって、
以下の数式、
0.1≦x≦0.35
が充足される、
固体電解質。 - 請求項4に記載の固体電解質であって、
以下の数式、
0.15≦x≦0.35
が充足される、
固体電解質。 - 請求項5に記載の固体電解質であって、
以下の数式、
0.2≦x≦0.35
が充足される、
固体電解質。 - 請求項1に記載の固体電解質であって、
以下の数式
0<x≦0.3
が充足される、
固体電解質。 - 請求項1から7に記載の固体電解質であって、
Prのα全体に対するモル比は0.8以上であり、かつ
Zrのβ全体に対するモル比は0.8以上である、
固体電解質。 - 請求項8に記載の固体電解質であって、
αは、Prであり、かつ
βは、Zrである、
固体電解質。 - 請求項1から9のいずれか一項に記載の固体電解質であって、
以下の2つの数式
a=0、および、
b=0
が充足される、
固体電解質。 - 請求項1から10のいずれか一項に記載の固体電解質であって、
前記結晶相は、立方晶系ガーネット型の結晶構造を有する、
固体電解質。 - 請求項1から11のいずれか一項に記載の固体電解質であって、
前記固体電解質は、4.0g/cm3以上の密度を有する、
固体電解質。 - 蓄電デバイスであって、
第一電極、
第二電極、および
請求項1から12のいずれか一項に記載の固体電解質、
を備える、
蓄電デバイス。 - 請求項13に記載の蓄電デバイスであって、
前記第一電極および第二電極は、摂氏1100度以下の融点を有する金属を含む、
蓄電デバイス。 - 請求項14に記載の蓄電デバイスであって、
前記金属は、Ag-Pd系合金である、
蓄電デバイス。 - 請求項13に記載の蓄電デバイスであって、
前記第一電極および第二電極は、Ag-Pd系合金から構成され、かつ
前記Ag-Pd系合金におけるAgのPdに対するモル比は、6/4よりも大きい、
蓄電デバイス。 - 請求項16に記載の蓄電デバイスであって、
前記モル比は、7/3以下である、
蓄電デバイス。 - 請求項13から17のいずれか一項に記載の蓄電デバイスであって、
前記蓄電デバイスは、電池または積層コンデンサである、
蓄電デバイス。 - 請求項18に記載の蓄電デバイスであって、
前記蓄電デバイスは、電池であり、
前記電池は、前記第一電極および前記第二電極の間に設けられた電解質層を備え、かつ
前記第一電極、前記第二電極、および前記電解質層からなる群より選択される少なくとも1つが、前記固体電解質を含む、
蓄電デバイス。 - 請求項19に記載の蓄電デバイスであって、
前記電解質層が、前記固体電解質を含む、
蓄電デバイス。 - 固体電解質であって、
化学組成Li 7(1+x) α 3 β 2+a O 12+3.5x+b を有する結晶相
ここで、
αは、Prを含み、
βは、Zrを含み、
-0.05≦x≦0.35
-0.5≦a≦0.5、および
-0.5≦b≦0.5、
を含有し、
Prのα全体に対するモル比は0.8以上であり、かつ
Zrのβ全体に対するモル比は0.8以上である、
固体電解質。 - 固体電解質であって、
化学組成Li 7(1+x) α 3 β 2+a O 12+3.5x+b を有する結晶相
ここで、
αは、Prであり、
βは、Zrであり、
-0.05≦x≦0.35
-0.5≦a≦0.5、および
-0.5≦b≦0.5、
を含有する、
固体電解質。 - 固体電解質であって、
化学組成Li 7(1+x) α 3 β 2+a O 12+3.5x+b を有する結晶相
ここで、
αは、Prを含み、
βは、Zrを含み、
-0.05≦x≦0.35
-0.5≦a≦0.5、および
-0.5≦b≦0.5、
を含有し、
前記結晶相は、立方晶系ガーネット型の結晶構造を有する、
固体電解質。 - 固体電解質であって、
化学組成Li 7(1+x) α 3 β 2+a O 12+3.5x+b を有する結晶相
ここで、
αは、Prを含み、
βは、Zrを含み、
-0.05≦x≦0.35
-0.5≦a≦0.5、および
-0.5≦b≦0.5、
を含有し、
前記固体電解質は、4.0g/cm 3 以上の密度を有する、
固体電解質。 - 蓄電デバイスであって、
第一電極、
第二電極、および
固体電解質、
を備え、
前記固体電解質は、化学組成Li 7(1+x) α 3 β 2+a O 12+3.5x+b を有する結晶相
ここで、
αは、Prを含み、
βは、Zrを含み、
-0.05≦x≦0.35
-0.5≦a≦0.5、および
-0.5≦b≦0.5、
を含有し、
前記第一電極および第二電極は、摂氏1100度以下の融点を有する金属を含み、
前記金属は、Ag-Pd系合金である、
蓄電デバイス。 - 蓄電デバイスであって、
第一電極、
第二電極、および
固体電解質、
を備え、
前記固体電解質は、化学組成Li 7(1+x) α 3 β 2+a O 12+3.5x+b を有する結晶相
ここで、
αは、Prを含み、
βは、Zrを含み、
-0.05≦x≦0.35
-0.5≦a≦0.5、および
-0.5≦b≦0.5、
を含有し、
前記第一電極および第二電極は、Ag-Pd系合金から構成され、かつ
前記Ag-Pd系合金におけるAgのPdに対するモル比は、6/4よりも大きい、
蓄電デバイス。 - 蓄電デバイスであって、
第一電極、
第二電極、および
固体電解質、
を備え、
前記固体電解質は、化学組成Li 7(1+x) α 3 β 2+a O 12+3.5x+b を有する結晶相
ここで、
αは、Prを含み、
βは、Zrを含み、
-0.05≦x≦0.35
-0.5≦a≦0.5、および
-0.5≦b≦0.5、
を含有し、
前記第一電極および第二電極は、Ag-Pd系合金から構成され、かつ
前記Ag-Pd系合金におけるAgのPdに対するモル比は、6/4よりも大きく、7/3以下である、
蓄電デバイス。
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