TWI434452B - 具有石榴石結構之離子導體 - Google Patents
具有石榴石結構之離子導體 Download PDFInfo
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- TWI434452B TWI434452B TW097124935A TW97124935A TWI434452B TW I434452 B TWI434452 B TW I434452B TW 097124935 A TW097124935 A TW 097124935A TW 97124935 A TW97124935 A TW 97124935A TW I434452 B TWI434452 B TW I434452B
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- Prior art keywords
- solid
- ionic conductor
- garnet
- conductivity
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- 239000010416 ion conductor Substances 0.000 title claims description 49
- 239000002223 garnet Substances 0.000 title description 12
- 239000007787 solid Substances 0.000 claims description 33
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 150000001768 cations Chemical class 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkaline earth metal cation Chemical class 0.000 claims description 4
- 239000011244 liquid electrolyte Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 238000003746 solid phase reaction Methods 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000000499 gel Substances 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims 3
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000000446 fuel Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 19
- 239000000463 material Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 239000010955 niobium Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000007784 solid electrolyte Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052758 niobium Inorganic materials 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 229910052715 tantalum Inorganic materials 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910010500 Li2.9PO3.3N0.46 Inorganic materials 0.000 description 3
- 229910010640 Li6BaLa2Ta2O12 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001144 powder X-ray diffraction data Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000010671 solid-state reaction Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 102100025905 C-Jun-amino-terminal kinase-interacting protein 4 Human genes 0.000 description 1
- 102100025338 Calcium-binding tyrosine phosphorylation-regulated protein Human genes 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101001076862 Homo sapiens C-Jun-amino-terminal kinase-interacting protein 4 Proteins 0.000 description 1
- 101000935132 Homo sapiens Calcium-binding tyrosine phosphorylation-regulated protein Proteins 0.000 description 1
- 229910013439 LiZr Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000005184 irreversible process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- YUSUJSHEOICGOO-UHFFFAOYSA-N molybdenum rhenium Chemical compound [Mo].[Mo].[Re].[Re].[Re] YUSUJSHEOICGOO-UHFFFAOYSA-N 0.000 description 1
- 238000001683 neutron diffraction Methods 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Description
本發明係關於具有石榴石樣結構之化學性穩定的固態離子導體在電池、超級電容器、蓄電池及電致變色裝置、化學感測器及熱電轉換器中的用途,以及適用於該等用途的新穎化合物。
可再充電(二次)電池係在電氣設備及電子設備需要或至少部分時間需要獨立於電網而操作的情況下使用。在此背景下,針對此使用形式對作為電解質材料的固態離子導體進行研究為當前材料研究之一重要方面。電池僅由固體組成的優點在於確保無滲漏、小型化、電化學穩定性、相對較高的能量密度及相對較長的壽命。
在各種電池技術中,基於鋰離子的電池系統近年來變得日益完善。其尤其以其可達成的高電能密度及功率而著名,此可歸因於鋰離子之高化學反應性及低質量以及其高遷移率。固態鋰離子導體之開發近年來已頗引人注意。實例為Li2.9
PO3.3
N0.46
或Li3
N及Li-β-氧化鋁。然而,Li2.9
PO3.3
N0.46
具有比液態電解質顯著更低的離子電導率。Li3
N及Li-β-氧化鋁對於濕氣很敏感。此外,Li3
N在室溫下、在低至0.445V的電壓下分解,且Li-β-氧化鋁化學性不穩定性。
具有石榴石樣結構的鋰離子導體首次描述於Thangadurai等人之研究中,"Novel Fast Lithium Ion Conduction in Garnet-Type Li5
La3
M2
O12
(M=Nb, Ta)", J. Am. Ceram. Soc.
86, 437-440, 2003。石榴石樣Li5
La3
M2
O12
化合物具有明顯的鋰離子電導率。
就結構而言,石榴石為以立方晶系結晶、具有一般組成X3
Y2
(SiO4
)3
之正矽酸鹽,其中X及Y為八配位及六配位陽離子位點。個別SiO4
四面體彼此間經由填隙式B陽離子藉由離子鍵相連。
與理想的石榴石結構相比,Thangadurai等人之上述研究中所述之式Li5
La3
M2
O12
(M=Nb、Ta)之石榴石樣化合物含有過量的Li離子。La3+
及M5+
離子佔據八配位及六配位位點,而鋰離子佔據具有六配位的位置。
PCT申請案WO 2005/085138報導,其他石榴石樣鋰離子導體在形式上係由式Li5
La3
M2
O12
(其中M=Nb或Ta)之化合物藉由異價取代獲得。La3+
位點之異價取代可增強網路連接性,且使得能夠修改可用之空位數。電荷平衡較佳經由Li+
離子(L)達成。為本發明之目的,"異價取代"意謂,作為形成陽離子空位、陰離子空位、填隙式陽離子及/或填隙式陰離子的結果,離子被具有不同氧化態的離子置換。固態鋰離子導體具有化學穩定性,且具有3.4×10-6
S/cm之離子電導率。由於其離子電導率高,同時電子電導率可忽略不計,因此其可用作固態電解質。
WO 2005/085138中所述的化合物一般具有化學計量組成L5+x
Ay
Gz
M2
O12
,其中:L在各種情況下獨立地為任何較佳單價陽離子;A在各種情況下獨立地為單價、二價、三價或四價陽離
子;G在各種情況下獨立地為單價、二價、三價或四價陽離子;M在各種情況下獨立地為三價、四價或五價陽離子;0<x3,0y3,0z3;且O可部分或完全地經二價及/或三價陰離子(諸如N3-
)置換。
在所述離子導體中,M在各種情況下為金屬Nb與Ta中之一者。未給出金屬離子之其他實例。經由鋰離子(L=Li)發生離子導電。
具有石榴石結構的鋰離子導體之其他實例近年來已經檢證(V. Thangadurai, W. Weppner,Adv. Funct. Mater
. 2005, 15, 107-112; V. Thangadurai, W. Weppner,J. Power Sources,
2005, 142, 339-344)。此處,Li6
BaLa2
Ta2
O12
在22℃下具有4×10-5
Scm-1
之最高Li+
離子電導率,活化能為0.40 eV。雖然Li6
BaLa2
Ta2
O12
對與金屬鋰、濕氣、空氣及常用電極材料的反應具有穩定性,但在室溫下,體積電導率及總電導率仍不夠高至使得能夠開發理想的可再充電固態鋰離子電池。
與先前技術之上述離子導體相關聯的另一問題為,所提議之金屬鈮及鉭相對較貴且不易獲得。此外,使用完全由所述石榴石樣化合物組成的固體電解質複雜且成本高。
因此,本發明之一目標為提供其中至少部分克服上述缺陷之經改良之固態離子導體。
根據本發明,現已發現鋯可用作石榴石樣離子導體中之金屬M。與鈮及鉭相比,鋯易獲得且形成很穩定的固態結構。雖然Nb及Ta形式上以氧化態+V存在於石榴石結構中,但Zr較佳呈氧化態+IV。
因此,本發明在一實施例中提供具有石榴石樣晶體結構且具有化學計量組成L7+x
Ax
G3-x
Zr2
O12
的固態離子導體,其中L在各種情況下獨立地為單價陽離子;A在各種情況下獨立地為二價陽離子;G在各種情況下獨立地為三價陽離子;0x3;且O可部分或完全地經二價及/或三價陰離子(諸如N3-
)置換。
L尤其較佳地為鹼金屬離子,例如Li+
、Na+
或K+
。詳言之,L亦可為各種鹼金屬離子之組合。在本發明之一尤其較佳實施例中,L=Na+
。鈉非常低廉且可以任意量獲得。小的Na+
離子在石榴石樣結構中易移動,且可與鋯組合而給出化學性穩定的晶體結構。
A為任何二價陽離子或該等陽離子之任何組合。A較佳可使用二價金屬陽離子。鹼土金屬離子(諸如Ca、Sr、Ba及/或Mg)以及二價過渡金屬陽離子(諸如Zn)尤其較佳。已發現該等離子在本發明之石榴石樣化合物中移動很小(即使有的話),因此離子導電實質上經由L發生。
在上述組成中,0x2亦較佳且0x1尤其較佳。
在本發明之一實施例中,x=0,因此A不存在於石榴石樣化合物中。
G為任何三價陽離子或該等陽離子之任何組合。G較佳可使用三價金屬陽離子。G=La尤其較佳。
在具有上述組成之結構中,O2-
可部分或完全地經其他陰離子置換。舉例而言,用其他二價陰離子將O2-
完全或部分地置換為有利的。此外,O2-
亦可在適當的電荷補償下經三價陰離子異價置換。
在另一態樣中,本發明提供具有化學計量組成L7+x
Ax
La3-x
Zr2
O12
之固態離子導體,其中A為二價金屬且L為Li或Na。Na因其易得性而尤其較佳。在一較佳實施例中,x=0,因此組成為L7
La3
Zr2
O12
。
A較佳選自鹼土金屬,較佳Ca、Sr、Ba及/或Mg。A選自二價過渡金屬亦較佳,例如A=Zn。A=Sr或Ba最佳。
具有組成L7+x
Ax
La3-x
Zr2
O12
之離子導體具有石榴石樣晶體結構。與具有組成L5
La3
Nb2
O12
(L=Li)之已知化合物相比,該兩個Nb(+V)陽離子形式上已經兩個Zr(+IV)陽離子及兩個單價L陽離子置換。此外,La(+III)可經A(+II)及L(+I)置換。以此方式,該結構中之L之總比例已增大。L較佳為Li或Na,具有石榴石結構之化合物經由其發生離子導電。因此,本發明之化合物使提供顯著改良之離子導體成為可能。
與先前技術之化合物相比,具有組成L7+x
Ax
La3-x
Zr2
O12
之材料呈現增大的離子電導率。由於本發明之化合物之石
榴石結構為三維各向同性結構,因此離子導電在三維進行而無優先方向係可能的。
另一方面,本發明之化合物之電子電導率相對較低。本發明之化合物之多晶樣本亦具有低晶界電阻,以使得總電導率實質上完全由體積電導率構成。
該等材料之另一優點為其化學穩定性高。詳言之,該等材料在與熔融鋰接觸加熱時不呈現可辨識的變化。在高達350℃的溫度及高達6 V的直流電壓下,未觀測到化學分解。
具有石榴石結構之本發明之尤其較佳化合物之一實例為Li7
La3
Zr2
O12
。高的鋰離子電導率、良好熱穩定性及化學穩定性(就與可能電極之反應而言)、環境相容性、原料之可取得性、低製造成本及簡單生產及密封性使得Li7
La3
Zr2
O12
成為尤其適用於可再充電鋰離子電池的有前景之固體電解質。
根據另一態樣,本發明提供一種製備具有石榴石樣結構之固態離子導體的方法。該等化合物可藉由所存在元素之適當鹽及/或氧化物之反應(例如經由固態反應)形成。特別有用的原料為在反應過程中轉化為相應氧化物的硝酸鹽、碳酸鹽及氫氧化物。
更特定而言,本發明係關於一種製備具有組成L7+x
Ax
G3-x
Zr2
O12
(例如Na6
ALa2
Zr2
O12
)之固態離子導體的方法。該等材料可藉由A、G及Zr之適當鹽及/或氧化物與L之氫氧化物、硝酸鹽或碳酸鹽以固態反應方式進行反應來獲得。A係如上所
定義。二價金屬A較佳以硝酸鹽之形式使用。此處,較佳為Ca(NO3
)2
、Sr(NO3
)2
及Ba(NO3
)2
。在G之情況下,較佳使用La,La較佳以La2
O3
之形式使用。Zr以氧化物(較佳ZrO2
)之形式使用有利。L較佳以LOH、LNO3
或L2
CO3
之形式使用。舉例而言,較佳可使用LiOH.H2
O或NaOH.H2
O。為在樣本之熱處理期間補償L(例如L=Li、Na)之重量損失,較佳使用過量(例如過量10 wt%)的各別鹽。
在第一步驟中將原料混合,且(例如)可在使用氧化鋯研磨介質的球磨中於2-丙醇中研磨。隨後將以此方式獲得的混合物在空氣中在較佳400-1000℃範圍內之溫度下加熱數小時,較佳2-10小時。600-800℃之溫度(例如約700℃)及4-8小時之熱處理時間(例如約6小時)特別適宜。接著再次進行研磨,較佳亦在使用氧化鋯研磨介質的球磨中於2-丙醇中進行研磨。隨後將反應產物單向或較佳均衡施壓以獲得成形件,例如片粒。接著將該等成形件在較佳700-1200℃、更佳800-1000℃範圍內的溫度下燒結數小時,較佳10-50小時,更佳20-30小時。此處,約900℃之溫度及約24小時之熱處理時間特別適宜。在此燒結過程中,為避免L氧化物之過多損耗,用具有相同組成之粉末覆蓋樣本係有利的。
由於全部組分皆存在可溶性鹽,因此易用於製備化合物的可能方法為前驅物方法(例如,Pecchini方法)、甘胺酸方法或沈澱反應法。
本發明之固態離子導體(例如,鋰或鈉離子導體)作為固
態電解質為一種寶貴的原料。由於該等材料具有非常高的離子電導率,同時電子傳導可忽略不計,因此其可用作具有很高能量密度之電池(例如鋰或鈉電池)之固體電解質。該等材料之高穩定性(就例如與元素鋰及常用電極材料之化學反應而言)促使(例如)本發明之固態離子導體能夠實際使用於電池中。
與常用固體電解質材料相比,本發明之固體電解質與電極之間之相界電阻亦極小。因此,具有相對較高功率(高電流)的電池可使用本發明之材料製造。與使用液態電解質相比,使用本發明之固態電解質亦導致改良之安全性。當機動車輛中使用該等電解質時,此特別有利。
在另一態樣中,除用於電池外,本發明亦提供該等固態離子導體(例如鋰離子導體)在電致變色系統(視窗、VDU、外牆等)中的用途及在超級電容器用於瞬時能量儲存與釋放的用途。使用本發明之離子導體時,可達成100 F/cm3
或100 F/cm3
以上之電容器能量密度。本發明之另一態樣為石榴石樣固態離子導體用作感測器、尤其多種氣體感測器的用途。根據本發明,亦可將該材料用於使熱有效地直接轉換為電能的熱電轉換器中。
具有石榴石樣結構的離子導體亦可與其他電解質(例如習知的非質子性液態電解質)組合用作緩衝層。因此,無需使用完全由石榴石樣結構組成的電解質。相反,可將任何已知的電解質(例如,可以液體、凝膠或固體形式存在的電解質)與新穎的石榴石樣離子導體組合使用。
因此,本發明在另一態樣中提供具有石榴石樣晶體結構之固態離子導體用作電極前之保護層以便改良針對電解質之化學穩定性的用途。為此目的,不僅可使用本發明之含鋯石榴石樣結構,而且可使用(例如)WO 2005/085138中所述的石榴石樣化合物。使用離子導體作為電極前之緩衝結構可防止短路,且使得有可能產生並施加相對較高電壓以便達成顯著更大的能量密度及壽命。
以下實例用於說明本發明之特別較佳實施例。
化學計量量之在各種情況下皆高度純之原料:在200℃下預乾燥6小時、過量10 wt%以補償燒結過程中之Li損失的LiOH(Alfa Aesar, >99%);在900℃預乾燥24小時的La2
O3
(Alfa Aesar,>99.99%);及ZrO2
(Aldrich,>99%)皆以固態反應方式進行反應。
使用氧化鋯容器及磨球將原料於2-丙醇中球磨約12小時。之後,在900℃及1125℃下、在空氣中熱處理12小時。接著將所得產物再次球磨。隨後對反應產物均衡施壓以形成片粒並在1230℃下燒結36小時。在此程序期間將樣本用具有相同組成的粉末覆蓋,以免鋰過多損耗。所有處理中的加熱速率為每分鐘1℃。將經燒結的壓片經由金剛石鋸切成更薄的片粒。使用X射線粉末繞射術(XRD)(SEIFERT 3000, CuKα
, Germany)監測相形成。依據粉末
XRD資料、使用最小二乘法測定晶格常數。
在空氣中,使用不同厚度的兩個片粒(厚片:1.02cm厚且直徑0.92cm;及薄片:0.18cm厚且直徑0.98cm)進行電導率之量測。使用Li離子阻斷性Au電極(在700℃下固化1小時而得的Au膏)在18至350℃的溫度範圍內、經由阻抗與增益相位分析儀(HP 4192 A, Hewlett-Packard Co., Palo Alto, CA)(5 Hz-13 MHz)進行量測。每次量測阻抗之前,使樣本在恆溫下均衡3至6小時。每個片粒以兩個連續加熱與冷卻循環進行阻抗量測。在空氣中、在29-900-20℃之溫度範圍內、在每分鐘2℃之加熱速率及冷卻速率下量測且在900℃下以等溫方式量測熱解重量分析(TGA)及差熱分析(NETZSCH STA 409 C/CD)之資料。
在充氬手套工作箱中、藉由使片粒與大量過剩的熔融鋰在鉬坩堝中反應48小時來檢查Li7
La3
Zr2
O12
對熔融鋰的穩定性。
儘管已對Li5
La3
M2
O12
(M=Nb、Ta)石榴石進行過很多X-射線繞射(XRD)研究,但在鋰陽離子之空間群及位置方面,尚存在關於結構的爭議(a)D. Mazza, Mater. Lett. 1988, 7, 205-207; b)H. Hyooma, K. Hayashi, Mater. Res. Bull. 1988, 23, 1399-1407; c)J. Isasi, M.L. Veiga, R. Saez-Puche, A. Jereze, C. Pico, J. Alloys Compd. 1991, 177, 251-257)。最近,中子繞射研究已指示,Li5
La3
M2
O12
(M=Nb、Ta)以空間群Ia3d結晶且Li位於四面體位置及八面體位置且兩類位置中皆存在空位(a)E.J. Cussen, Chem. Commun.
2006, 412-413; b)M.P. O'Callaghan, D.R. Lynham, E.J. Cussen, G.Z. Chen, Chem. Mater. 2006, 18, 4681-4689)。所測Li7
La3
Zr2
O12
之粉末XRD圖案與已知石榴石相Li5
La3
Mb2
O12
之標準圖案非常一致,且證明石榴石結構能夠併有不同氧化態及不同尺寸之陽離子而對稱性無過度變化。測定具有A=12.9682 (6)Å之晶格常數之立方晶胞的繞射圖案。
在18℃下所得之Li7
La3
Zr2
O12
厚片之典型阻抗曲線展示於圖1中。當電極被離子性阻斷時在低頻區域出現的上升指示所檢材料為離子導體(a)V. Thangadurai, R.A. Huggins, W. Weppner, J. Power Sources 2002, 108, 64-69; b)J.T.S. Irvine, D.C. Sinclair, A.R. West, Adv. Mater. 1990, 2, 132-138)。對先前所研究之具有石榴石樣結構的材料已觀測到類似特性。阻抗曲線可分解成體積電阻、晶界電阻及電極電阻。圖1中之連續線呈現(Rb
Qb
)(Rgb
Qgb
)(Qel
)之等效電路之資料(使用EQUIVALENT程式)。在18℃下所量測之Li7
La3
Zr2
O12
薄片之阻抗曲線以圖1中之插圖展示。在不同溫度下所觀測之Li7
La3
Zr2
O12
厚片(1.02cm厚且直徑0.92cm)及薄片(0.18cm厚且直徑0.98cm)之體積電導率及總電導率由高頻半圓及低頻半圓與軸之交點獲得,且總結於表1中。圖1及表1中所示的資料指示Li7
La3
Zr2
O12
厚片與薄片之類似電特性。與厚片相比,薄片呈現稍微更高的體積電導率及總電導率。此外,有趣的是,對於厚片與薄片皆注意到,晶界電阻對總電阻的貢獻小於50%,且隨溫度
增加而減少(表1)。在較高溫度(對於厚片,75℃以上;且對於薄片,50℃以上)下,與體積電阻貢獻相比,難以精確地測定晶界電阻貢獻;因此展示體積電阻與晶界電阻貢獻之總值用於在所檢查之溫度範圍內測定電導率。與所有其他固態鋰離子導體及所有先前所述之鋰石榴石相比,具有石榴石樣結構之新穎快速結晶鋰離子導體Li7
La3
Zr2
O12
在室溫下的總電導率(在25℃下,3×10-4
S/cm)更佳。
此結果(亦即,總電導率與體積電導率具有相同量值級)為與其他陶瓷鋰離子導體相比,此處所檢查之Li7
La3
Zr2
O12
石榴石結構之尤其有利特性。對於固體電解質在電化學裝置(諸如電池、感測器及電致變色顯示器)中的多種應用,總電導率應儘可能高。此外,體積電導率及總電導率可經由Li7
La3
Zr2
O12
之低溫合成及經由使用適當燒結法進一步緻密化來進一步改良。
以兩個加熱與冷卻循環所得之Li7
La3
Zr2
O12
厚片之體積電導率及總電導率之Arrhenius曲線展示於圖2a中。在兩次循環之間,電導率不存在明顯變化。此意謂,所檢查之石榴石樣結構具有熱穩定性,且在所檢查之溫度範圍(亦即室溫至350℃)內未發生相變。對於Li7
La3
Zr2
O12
薄片亦觀測到類似的Arrhenius特性。在圖2b中,對在各種情況下在首次加熱試驗中獲得之Li7
La3
Zr2
O12
厚片與薄片之資料進行比較。所得針對薄片之體積電導率與總電導率之活化能(在18-50℃下為0.32 eV,且在18-300℃下為0.30 eV)稍微低於針對厚片之體積電導率與總電導率之活化能(在18-70℃
下為0.34 eV,且在18-300℃下為0.31 eV)。所得薄片之電導率稍微高於厚片之電導率。
除阻抗分析外,電導率之離子性質亦藉由EMF量測法證明,其中使用Li7
La3
Zr2
O12
作為元素鋰與Al之間(LiAl)的固體電解質。將樣本在上側用鋁層覆蓋且置於鋰上,鋰在充有惰性Ar氣體的手套工作箱中已熔融。鋁藉由化學反應與鋰合金化,且亦藉由電量滴定法使鋰自其反向定位之鋰電極進入鋁中而合金化。所得電壓接近理論值。差異可歸於因不可逆過程所致的非均一溫度分布及相應現象。
圖3展示Li7
La3
Zr2
O12
與正考慮結合電池使用之其他已知鋰離子導體之鋰離子電導率的比較。Li7
La3
Zr2
O12
電導率高於Li-β-氧化鋁、薄層Lipon(Li2.9
PO3.3
N0.46
)、Li9
SiAlO8
、Lil+40mol Al2
O3
、LiZr2
(PO4
)3
、Li3.5
Si0.5
P0.5
O4
、Li5
La3
Ta2
O12
及Li6
BaLa2
Ta2
O12
之電導率。可觀測到的比其他含鋰石榴石高的鋰電導率及低活化能可能係由於立方晶格常數增大、鋰離子濃度增大、鋰離子與形成晶格之其他離子之間的化學相互作用減小且部分地由於經改良之緻密化(理論密度之92%)。在相對較低的溫度下,穩定性較小之多晶Li3
N之電導率(在27℃下,6.6×10-4
S/cm)可與Li7
La3
Zr2
O12
之電導率相當。然而,在更高溫度下,Li7
La3
Zr2
O12
呈現更高的總電導率。
Li7
La3
Zr2
O12
之熱穩定性(其為結晶鋰離子導體之基本優勢)可藉由熱解重量量測法(TGA)及差熱分析法(DTA)證明。在空氣氣氛下所量測之TG-DTA資料指示,在加熱期
間與冷卻期間,在20℃至900℃之溫度範圍內,無顯著的質量變化且無可辨識的相變。經數週觀測期發現,含鋯Li7
La3
Zr2
O12
對熔融鋰具有穩定性,且對濕氣及空氣之作用亦具有化學穩定性。
在18℃下、在空氣中對Li7
La3
Zr2
O12
之厚片(1.02cm厚及直徑0.92cm)所量測之AC阻抗曲線。連續線表示等效電路之模擬資料(使用EQUIVALENT程式(B.A. Boukamp, Equivalent Circuit, 4.55版,1997, Faculty of Chemical Technology, University of Twente, 7500 AE Enschede (The Netherlands),第CT88/265/128/CT89/214/128號報導,1989年5月)),模擬資料包含(Rb
Qb
)(Rgb
Qgb
)(Qel
)(其中R為電阻且Q為恆相元素,且指數g、gb及el指示顆粒體積、晶界及電極)。在18℃下、在空氣中對Li7
La3
Zr2
O12
薄片(0.18cm厚且直徑0.98cm)所量測的阻抗曲線展示於插圖中。
a)以兩個連續加熱與冷卻循環所得之Li7
La3
Zr2
O12
厚片之體積電導率及總電導率(體積與晶界)的Arrhenius曲線。
b)在首次加熱試驗(18-300℃)期間所得之Li7
La3
Zr2
O12
厚片與薄片之Arrhenius曲線之比較。
Li7
La3
Zr2
O12
與討論用於電池應用之其他已知鋰離子導體之總電導率(體積+晶界)之比較。
所測Li7
La3
Zr2
O12
之粉末XRD圖案與根據粉末繞射標準聯合委員會(Joint Committee on Powder Diffraction Standards)之已知石榴石相Li5
La3
Nb2
O12
之標準圖案
(JCPDS: 80-0457)。
在25℃及50℃下、在空氣中對Li7
La3
Zr2
O12
厚片所量測的AC阻抗曲線。
在25℃及50℃下、在空氣中對Li7
La3
Zr2
O12
薄片所量測的AC阻抗曲線。在較高頻率下之另一曲線以插圖形式展示。
以兩個連續加熱與冷卻循環所得之Li7
La3
Zr2
O12
薄片之體積電導率與總電導率(體積+晶界)之Arrhenius曲線。
a)Li7
La3
Zr2
O12
片粒與鉬坩堝暴露於熔融鋰之前之像片;b)熔融鋰中之Li7
La3
Zr2
O12
片粒之像片;及c)剛暴露於熔融鋰48小時後之Li7
La3
Zr2
O12
片粒與鉬坩堝之像片。圖c)所示之像片展示片粒顏色保持不變(象牙色)且未形成反應產物。
(無元件符號說明)
Claims (22)
- 一種具有石榴石樣晶體結構之固態離子導體用作電極塗層或電極前之保護層的用途。
- 一種經塗覆具有石榴石樣晶體結構之固態離子導體的電極。
- 一種包含一或多個如請求項2之電極的電池。
- 一種具有石榴石樣晶體結構且具有化學計量組成L7+x Ax G3-x Zr2 O12 的固態離子導體,其中:L在各種情況下獨立地為單價陽離子;A在各種情況下獨立地為二價陽離子;G在各種情況下獨立地為三價陽離子;0x3;且O可部分或完全地經二價陰離子或諸如N3- 之三價陰離子置換。
- 如請求項4之固態離子導體,其中0x1。
- 如請求項4或5之固態離子導體,其中L係選自Li、Na及/或K。
- 如請求項6之固態離子導體,其中L=Na。
- 如請求項4或5之固態離子導體,其中A為二價鹼土金屬陽離子。
- 如請求項4或5之固態離子導體,其中A係選自Ca、Sr及/或Ba。
- 如請求項4或5之固態離子導體,其中該化學計量組成為Li7 La3 Zr2 O12 。
- 一種製備如請求項4至10中任一項之固態離子導體的方法,其特徵在於使L、A、G及Zr之鹽及/或氧化物彼此反應。
- 如請求項11之方法,其特徵在於該反應係藉由前驅物方法進行,例如藉由Pechini方法進行,藉由甘胺酸方法及藉由該等組分之溶解鹽類之沈澱反應進行。
- 如請求項11之方法,其特徵在於該反應係以固相反應進行。
- 如請求項11或13之方法,其特徵在於L及A係以硝酸鹽、碳酸鹽或氫氧化物之形式使用且與G2 O3 及ZrO2 反應。
- 如請求項11或13之方法,其包含以下步驟:a)將原料混合,且使用氧化鋯容器及磨球較佳於2-丙醇中進行球磨;b)在空氣中將獲自a)之混合物在400℃至1000℃下加熱2至10小時;c)球磨,較佳使用氧化鋯容器及磨球於2-丙醇中球磨;d)將該混合物均衡施壓以產生所要形狀;且e)在700℃至1200℃下,將經具有相同組成之粉末覆蓋之獲自步驟d)之產物燒結10至50小時。
- 如請求項15之方法,其中該混合物係在步驟b)中在700℃下加熱6小時,且在步驟e)中在900℃下燒結24小時。
- 一種如請求項4至10中任一項之固態離子導體在電池、蓄電池、超級電容器、燃料電池、感測器、熱電轉換器及/或諸如視窗、VDU及外牆之電致變色裝置中的用途。
- 如請求項1之用途,其中使用一如請求項4至10中任一項之離子導體。
- 如請求項2之電極,其中使用一如請求項4至10中任一項之離子導體。
- 一種包含一或多個如請求項19之電極的電池。
- 如請求項1之用途,其中該固態離子導體係與呈液體、凝膠或固體形式存在之其他電解質併用。
- 如請求項1之用途,其中該固態離子導體係與其他液體電解質併用。
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Families Citing this family (179)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9793523B2 (en) | 2002-08-09 | 2017-10-17 | Sapurast Research Llc | Electrochemical apparatus with barrier layer protected substrate |
US8394522B2 (en) | 2002-08-09 | 2013-03-12 | Infinite Power Solutions, Inc. | Robust metal film encapsulation |
US8404376B2 (en) | 2002-08-09 | 2013-03-26 | Infinite Power Solutions, Inc. | Metal film encapsulation |
US8021778B2 (en) | 2002-08-09 | 2011-09-20 | Infinite Power Solutions, Inc. | Electrochemical apparatus with barrier layer protected substrate |
US8431264B2 (en) | 2002-08-09 | 2013-04-30 | Infinite Power Solutions, Inc. | Hybrid thin-film battery |
US20070264564A1 (en) | 2006-03-16 | 2007-11-15 | Infinite Power Solutions, Inc. | Thin film battery on an integrated circuit or circuit board and method thereof |
US8236443B2 (en) | 2002-08-09 | 2012-08-07 | Infinite Power Solutions, Inc. | Metal film encapsulation |
US8445130B2 (en) | 2002-08-09 | 2013-05-21 | Infinite Power Solutions, Inc. | Hybrid thin-film battery |
US7645543B2 (en) | 2002-10-15 | 2010-01-12 | Polyplus Battery Company | Active metal/aqueous electrochemical cells and systems |
US20080057386A1 (en) | 2002-10-15 | 2008-03-06 | Polyplus Battery Company | Ionically conductive membranes for protection of active metal anodes and battery cells |
US9368775B2 (en) | 2004-02-06 | 2016-06-14 | Polyplus Battery Company | Protected lithium electrodes having porous ceramic separators, including an integrated structure of porous and dense Li ion conducting garnet solid electrolyte layers |
US7282295B2 (en) | 2004-02-06 | 2007-10-16 | Polyplus Battery Company | Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture |
DE602005017512D1 (de) | 2004-12-08 | 2009-12-17 | Symmorphix Inc | Abscheidung von licoo2 |
US7959769B2 (en) | 2004-12-08 | 2011-06-14 | Infinite Power Solutions, Inc. | Deposition of LiCoO2 |
JP2010505044A (ja) | 2006-09-29 | 2010-02-18 | インフィニット パワー ソリューションズ, インコーポレイテッド | フレキシブル基板のマスキングおよびフレキシブル基板上にバッテリ層を堆積させるための材料拘束 |
US8197781B2 (en) | 2006-11-07 | 2012-06-12 | Infinite Power Solutions, Inc. | Sputtering target of Li3PO4 and method for producing same |
US20120196189A1 (en) | 2007-06-29 | 2012-08-02 | Johnson Ip Holding, Llc | Amorphous ionically conductive metal oxides and sol gel method of preparation |
US8211496B2 (en) | 2007-06-29 | 2012-07-03 | Johnson Ip Holding, Llc | Amorphous lithium lanthanum titanate thin films manufacturing method |
US9034525B2 (en) | 2008-06-27 | 2015-05-19 | Johnson Ip Holding, Llc | Ionically-conductive amorphous lithium lanthanum zirconium oxide |
DE102007030604A1 (de) * | 2007-07-02 | 2009-01-08 | Weppner, Werner, Prof. Dr. | Ionenleiter mit Granatstruktur |
US20090092903A1 (en) * | 2007-08-29 | 2009-04-09 | Johnson Lonnie G | Low Cost Solid State Rechargeable Battery and Method of Manufacturing Same |
US8268488B2 (en) | 2007-12-21 | 2012-09-18 | Infinite Power Solutions, Inc. | Thin film electrolyte for thin film batteries |
KR20150128817A (ko) | 2007-12-21 | 2015-11-18 | 사푸라스트 리써치 엘엘씨 | 전해질 막을 위한 표적을 스퍼터링하는 방법 |
WO2009089417A1 (en) | 2008-01-11 | 2009-07-16 | Infinite Power Solutions, Inc. | Thin film encapsulation for thin film batteries and other devices |
JP5595377B2 (ja) | 2008-04-02 | 2014-09-24 | インフィニット パワー ソリューションズ, インコーポレイテッド | エネルギー取入れに関連したエネルギー貯蔵デバイスに対する受動的過不足電圧の制御および保護 |
WO2010005686A2 (en) | 2008-06-16 | 2010-01-14 | Polyplus Battery Company | Aqueous lithium/air battery cells |
JP2010045019A (ja) * | 2008-07-16 | 2010-02-25 | Tokyo Metropolitan Univ | 全固体リチウム二次電池及びその製造方法 |
JP2012500610A (ja) | 2008-08-11 | 2012-01-05 | インフィニット パワー ソリューションズ, インコーポレイテッド | 電磁エネルギー獲得ための統合コレクタ表面を有するエネルギーデバイスおよびその方法 |
JP5132639B2 (ja) | 2008-08-21 | 2013-01-30 | 日本碍子株式会社 | セラミックス材料及びその製造方法 |
JP5650646B2 (ja) | 2008-09-12 | 2015-01-07 | インフィニット パワー ソリューションズ, インコーポレイテッド | 電磁エネルギーを介したデータ通信のための一体型伝導性表面を有するエネルギーデバイスおよび電磁エネルギーを介したデータ通信のための方法 |
US8508193B2 (en) | 2008-10-08 | 2013-08-13 | Infinite Power Solutions, Inc. | Environmentally-powered wireless sensor module |
JP5262572B2 (ja) * | 2008-10-23 | 2013-08-14 | 株式会社豊田中央研究所 | リチウム含有ガーネット型酸化物、リチウム二次電池及び固体電解質の製造方法 |
JP5083336B2 (ja) * | 2009-02-04 | 2012-11-28 | 株式会社豊田中央研究所 | ガーネット型リチウムイオン伝導性酸化物 |
US8986895B2 (en) | 2009-02-04 | 2015-03-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Garnet-type lithium ion-conducting oxide and all-solid-state lithium ion secondary battery containing the same |
JP5287499B2 (ja) * | 2009-05-21 | 2013-09-11 | 株式会社豊田中央研究所 | 全固体型リチウムイオン二次電池 |
JP5492998B2 (ja) | 2009-09-01 | 2014-05-14 | インフィニット パワー ソリューションズ, インコーポレイテッド | 薄膜バッテリを組み込んだプリント回路基板 |
JP5525388B2 (ja) * | 2009-09-03 | 2014-06-18 | 日本碍子株式会社 | セラミックス材料及びその製造方法 |
JP5376252B2 (ja) * | 2009-09-03 | 2013-12-25 | 日本碍子株式会社 | セラミックス材料及びその利用 |
JP5283188B2 (ja) * | 2009-09-03 | 2013-09-04 | 日本碍子株式会社 | 全固体二次電池およびその製造方法 |
JP5273732B2 (ja) * | 2009-09-03 | 2013-08-28 | 日本碍子株式会社 | セラミックス材料の製造方法 |
JP5413090B2 (ja) * | 2009-09-25 | 2014-02-12 | 株式会社豊田中央研究所 | 全固体型リチウム二次電池 |
JP5381640B2 (ja) * | 2009-11-24 | 2014-01-08 | 株式会社豊田中央研究所 | リチウム二次電池 |
DE102010001632A1 (de) | 2009-12-23 | 2011-06-30 | Robert Bosch GmbH, 70469 | Lithiumzelle mit verbesserter Kathodenstruktur und Herstellungsverfahren hierfür |
EP2518795A1 (en) * | 2010-01-22 | 2012-10-31 | Toyota Jidosha Kabushiki Kaisha | Negative electrode structure for aqueous electrolyte battery, and aqueous electrolyte battery comprising the negative electrode structure |
JP5471527B2 (ja) * | 2010-02-02 | 2014-04-16 | 株式会社豊田中央研究所 | リチウム二次電池及びリチウム二次電池用電極 |
JP5649033B2 (ja) * | 2010-03-19 | 2015-01-07 | 独立行政法人産業技術総合研究所 | リチウムイオン伝導性酸化物及びその製造方法、並びにそれを部材として使用した電気化学デバイス |
JP2011195372A (ja) * | 2010-03-19 | 2011-10-06 | National Institute Of Advanced Industrial Science & Technology | リチウムイオン伝導性酸化物の単結晶及びその製造方法、並びにそれを部材として使用した電気化学デバイス |
JP2013528912A (ja) | 2010-06-07 | 2013-07-11 | インフィニット パワー ソリューションズ, インコーポレイテッド | 再充電可能高密度電気化学素子 |
JP5358522B2 (ja) * | 2010-07-07 | 2013-12-04 | 国立大学法人静岡大学 | 固体電解質材料およびリチウム電池 |
JP5742144B2 (ja) * | 2010-09-08 | 2015-07-01 | 株式会社豊田中央研究所 | 複合体の製造方法、複合体及びそれを備えたアルカリ金属二次電池 |
JP5290337B2 (ja) * | 2011-02-24 | 2013-09-18 | 国立大学法人信州大学 | ガーネット型固体電解質、当該ガーネット型固体電解質を含む二次電池、及び当該ガーネット型固体電解質の製造方法 |
DE102011013018B3 (de) | 2011-03-04 | 2012-03-22 | Schott Ag | Lithiumionen leitende Glaskeramik und Verwendung der Glaskeramik |
KR101312275B1 (ko) | 2011-03-30 | 2013-09-25 | 삼성에스디아이 주식회사 | 복합체, 이를 포함한 리튬 이차 전지용 전극 활물질, 그 제조방법, 이를 이용한 리튬 이차 전지용 전극 및 이를 채용한 리튬 이차 전지 |
JP5760638B2 (ja) * | 2011-04-21 | 2015-08-12 | 株式会社豊田中央研究所 | ガーネット型リチウムイオン伝導性酸化物の製造方法 |
US9093717B2 (en) | 2011-05-20 | 2015-07-28 | Board Of Trustees Of Michigan State University | Methods of making and using oxide ceramic solids and products and devices related thereto |
WO2012176808A1 (ja) | 2011-06-20 | 2012-12-27 | 株式会社豊田中央研究所 | 全固体型リチウム二次電池及びその製造方法 |
JP6144007B2 (ja) * | 2011-06-29 | 2017-06-07 | 株式会社豊田中央研究所 | ガーネット型イオン伝導性酸化物及びその製造方法 |
EP2731911A4 (en) | 2011-07-12 | 2016-03-02 | Univ Michigan State | POROUS SOL-GELE AND METHOD AND STRUCTURES THEREFOR |
DE102011079401A1 (de) | 2011-07-19 | 2013-01-24 | Robert Bosch Gmbh | Lithiumionen leitende, granatartige Verbindungen |
WO2013028574A2 (en) | 2011-08-19 | 2013-02-28 | Polyplus Battery Company | Aqueous lithium air batteries |
US20130108920A1 (en) * | 2011-11-01 | 2013-05-02 | Isalah O. Oladeji | Composite electrodes for lithium ion battery and method of making |
US9660265B2 (en) | 2011-11-15 | 2017-05-23 | Polyplus Battery Company | Lithium sulfur batteries and electrolytes and sulfur cathodes thereof |
DE102011088910A1 (de) * | 2011-12-16 | 2013-06-20 | Robert Bosch Gmbh | Lithium-Schwefel-Zellen-Separator mit Polysulfidsperrschicht |
JP6173357B2 (ja) | 2012-03-01 | 2017-08-02 | ジョンソン・アイピー・ホールディング・エルエルシー | 高容量固体複合体カソード、固体複合体セパレータ、固体リチウム二次電池及びそれらの製造方法 |
CN102617140B (zh) * | 2012-03-05 | 2014-08-06 | 内蒙古工业大学 | 一种锑掺杂的类石榴石结构的锂离子晶态固体电解质材料及其合成方法 |
KR102086665B1 (ko) * | 2012-07-06 | 2020-03-09 | 삼성전자주식회사 | 고체이온전도체, 이를 포함하는 고체전해질, 이를 포함하는 리튬전지, 및 이의 제조방법 |
EP2683005B1 (en) * | 2012-07-06 | 2016-06-01 | Samsung Electronics Co., Ltd | Solid ionic conductor, solid electrolyte including the same, lithium battery including said solid electrolyte, and method of manufacturing said lithium battery |
CN103682356B (zh) * | 2012-09-18 | 2016-11-23 | 华为技术有限公司 | 一种锂离子电池正极材料及其制备方法 |
US9793525B2 (en) | 2012-10-09 | 2017-10-17 | Johnson Battery Technologies, Inc. | Solid-state battery electrodes |
US9362546B1 (en) | 2013-01-07 | 2016-06-07 | Quantumscape Corporation | Thin film lithium conducting powder material deposition from flux |
US10388975B2 (en) | 2013-01-31 | 2019-08-20 | Board Of Trustees Of Michigan State University | Template-based methods of making and using ceramic solids |
DE102013101145B4 (de) | 2013-02-05 | 2024-02-22 | Schott Ag | Verfahren zur Herstellung eines lithiumhaltigen Sols |
KR102038621B1 (ko) * | 2013-02-14 | 2019-10-30 | 삼성전자주식회사 | 고체이온전도체, 이를 포함하는 고체전해질, 이를 포함하는 리튬전지, 및 이의 제조방법 |
EP2978004B1 (en) * | 2013-03-18 | 2017-10-18 | Kyocera Corporation | All-solid-state capacitor |
JP6166584B2 (ja) * | 2013-05-10 | 2017-07-19 | 日本碍子株式会社 | リチウムイオン伝導性固体電解質並びにそれを用いた複合体及び電池 |
JP6554267B2 (ja) * | 2013-05-20 | 2019-07-31 | Tdk株式会社 | 固体イオンキャパシタ |
KR102013222B1 (ko) * | 2013-07-05 | 2019-08-23 | 한국전자통신연구원 | 산화물계 고체 전해질 제조방법 |
US9461331B2 (en) | 2013-07-05 | 2016-10-04 | Electronics And Telecommunications Research Institute | Method of preparing an oxide-based solid electrolyte by a hydrothermal reaction |
JP6596194B2 (ja) * | 2013-08-02 | 2019-10-23 | Tdk株式会社 | 固体イオンキャパシタ |
JP6165546B2 (ja) * | 2013-08-09 | 2017-07-19 | 株式会社日立製作所 | 固体電解質および全固体リチウムイオン二次電池 |
JP6028694B2 (ja) | 2013-08-23 | 2016-11-16 | 株式会社豊田中央研究所 | ガーネット型イオン伝導性酸化物の製造方法及び複合体の製造方法 |
CN105636921A (zh) | 2013-10-07 | 2016-06-01 | 昆腾斯科普公司 | 用于锂二次电池的石榴石材料和制造和使用石榴石材料的方法 |
KR101627848B1 (ko) * | 2013-10-21 | 2016-06-08 | 재단법인 포항산업과학연구원 | 리튬 이차 전지용 고체 전해질, 이의 제조 방법, 및 이를 포함하는 리튬 이차 전지 |
JP6393974B2 (ja) * | 2013-11-01 | 2018-09-26 | セントラル硝子株式会社 | 固体電解質前駆体、その製造方法、固体電解質の製造方法、及び固体電解質−電極活物質複合体の製造方法 |
DE102013222784A1 (de) | 2013-11-08 | 2015-05-13 | Robert Bosch Gmbh | Elektrochemische Zelle und Verfahren zu deren Herstellung |
KR101526703B1 (ko) | 2013-11-12 | 2015-06-05 | 현대자동차주식회사 | Al 치환된 가넷의 합성 방법 |
DE102013224045B4 (de) | 2013-11-25 | 2022-12-08 | Schott Ag | Verfahren zur Herstellung eines lithiumionenleitfähigen Materials mit granatartiger Kristallstruktur, Verwendung des Materials und Verfahren zur Herstellung eines Zwischenproduktes |
US9548512B2 (en) | 2013-12-12 | 2017-01-17 | Ut-Battelle, Llc | High conducting oxide—sulfide composite lithium superionic conductor |
DE102014100684B4 (de) | 2014-01-22 | 2017-05-11 | Schott Ag | lonenleitende Glaskeramik mit granatartiger Kristallstruktur, Verfahren zur Herstellung und Verwendung einer solchen Glaskeramik |
US10629959B2 (en) | 2014-02-07 | 2020-04-21 | Basf Se | Electrode unit for an electrochemical device |
US20150267316A1 (en) * | 2014-03-19 | 2015-09-24 | Sandia Corporation | Electrochemical Ion Separation in Molten Salts |
DE102014205945A1 (de) | 2014-03-31 | 2015-10-01 | Bayerische Motoren Werke Aktiengesellschaft | Aktives Kathodenmaterial für sekundäre Lithium-Zellen und Batterien |
US9660270B2 (en) | 2014-04-24 | 2017-05-23 | Daiichi Kigenso Kagaku Kogyo Co., Ltd. | Method for producing garnet-type compound, garnet-type compound, and all-solid lithium secondary cell containing said garnet-type compound |
EP2944611A1 (de) | 2014-05-16 | 2015-11-18 | Evonik Degussa GmbH | Verfahren zur Herstellung eines kubisch kristallinen, Aluminium, Lithium, Lanthan und Zirkon enthaltenden Mischoxides mit Granatstruktur |
KR101940240B1 (ko) * | 2014-05-28 | 2019-01-21 | 한국전자통신연구원 | 산화물계 고체 전해질 및 그 제조방법 |
DE102014108254A1 (de) | 2014-06-12 | 2015-12-17 | Karlsruher Institut für Technologie Innovationsmanagement | Elektrolyt, Zelle und Batterie umfassend den Elektrolyt und dessen Verwendung |
FR3023417B1 (fr) | 2014-07-01 | 2016-07-15 | I-Ten | Batterie entierement solide comprenant un electrolyte solide et une couche de materiau polymere solide |
FR3023418B1 (fr) | 2014-07-01 | 2016-07-15 | I Ten | Batterie entierement solide comprenant un electrolyte en materiau polymere solide reticule |
JP6632240B2 (ja) * | 2014-08-12 | 2020-01-22 | 日本特殊陶業株式会社 | リチウムイオン伝導性セラミックス材料及びリチウム電池 |
KR101592752B1 (ko) | 2014-08-18 | 2016-02-12 | 현대자동차주식회사 | 가넷 분말, 이의 제조방법, 핫프레스를 이용한 고체전해질 시트 및 이의 제조방법 |
JP5858410B2 (ja) * | 2014-09-25 | 2016-02-10 | 国立研究開発法人産業技術総合研究所 | リチウムイオン伝導性酸化物の単結晶及びその製造方法、並びにそれを部材として使用した電気化学デバイス |
US10026990B2 (en) | 2014-10-16 | 2018-07-17 | Corning Incorporated | Lithium-ion conductive garnet and method of making membranes thereof |
US10211481B2 (en) | 2014-11-26 | 2019-02-19 | Corning Incorporated | Stabilized solid garnet electrolyte and methods thereof |
US10164289B2 (en) | 2014-12-02 | 2018-12-25 | Polyplus Battery Company | Vitreous solid electrolyte sheets of Li ion conducting sulfur-based glass and associated structures, cells and methods |
US11749834B2 (en) | 2014-12-02 | 2023-09-05 | Polyplus Battery Company | Methods of making lithium ion conducting sulfide glass |
US10147968B2 (en) | 2014-12-02 | 2018-12-04 | Polyplus Battery Company | Standalone sulfide based lithium ion-conducting glass solid electrolyte and associated structures, cells and methods |
US11984553B2 (en) | 2014-12-02 | 2024-05-14 | Polyplus Battery Company | Lithium ion conducting sulfide glass fabrication |
EP3283450A4 (en) | 2015-04-16 | 2018-10-17 | QuantumScape Corporation | Setter plates for solid electrolyte fabrication and methods of using the same to prepare dense solid electrolytes |
WO2016178321A1 (ja) * | 2015-05-07 | 2016-11-10 | 株式会社豊田自動織機 | ガーネット型イオン伝導体を含む構造体 |
DE102015209981A1 (de) * | 2015-05-29 | 2016-12-01 | Robert Bosch Gmbh | Festelektrolytseparator für Lithium-Konversionszelle |
DE102015210752A1 (de) | 2015-06-12 | 2016-12-15 | Robert Bosch Gmbh | Lithium-Sauerstoff-Zellen-Kathodenadditive für Quasi-Konstantspannungschritt |
CN107750406B (zh) * | 2015-06-18 | 2021-02-12 | 德克萨斯大学系统董事会 | 水溶剂化玻璃/非晶态固体离子导体 |
JP6956641B2 (ja) | 2015-06-24 | 2021-11-02 | クアンタムスケイプ バテリー, インク. | 複合電解質 |
DE102015213973A1 (de) | 2015-07-23 | 2017-01-26 | Bayerische Motoren Werke Aktiengesellschaft | Anorganischer Separator |
JP2017033926A (ja) | 2015-07-29 | 2017-02-09 | セントラル硝子株式会社 | ガーネット型酸化物焼結体及びその製造方法 |
CN105489927A (zh) * | 2015-11-24 | 2016-04-13 | 青岛能迅新能源科技有限公司 | 一种提高全固态锂离子电解质材料Li7La3Zr2O12常温离子电导的方法 |
US10987735B2 (en) | 2015-12-16 | 2021-04-27 | 6K Inc. | Spheroidal titanium metallic powders with custom microstructures |
EP4324577A1 (en) | 2015-12-16 | 2024-02-21 | 6K Inc. | Method of producing spheroidal dehydrogenated titanium alloy particles |
CN108604665B (zh) | 2015-12-21 | 2022-04-22 | 约翰逊Ip控股有限公司 | 固态电池、隔板、电极和制造方法 |
US10218044B2 (en) | 2016-01-22 | 2019-02-26 | Johnson Ip Holding, Llc | Johnson lithium oxygen electrochemical engine |
US9966630B2 (en) | 2016-01-27 | 2018-05-08 | Quantumscape Corporation | Annealed garnet electrolyte separators |
US10707536B2 (en) | 2016-05-10 | 2020-07-07 | Polyplus Battery Company | Solid-state laminate electrode assemblies and methods of making |
US20170331092A1 (en) | 2016-05-13 | 2017-11-16 | Quantumscape Corporation | Solid electrolyte separator bonding agent |
EP3252024B1 (en) | 2016-05-27 | 2019-12-18 | Toyota Jidosha Kabushiki Kaisha | Oxide electrolyte sintered body and method for producing the same |
JP6620770B2 (ja) * | 2016-05-27 | 2019-12-18 | トヨタ自動車株式会社 | 酸化物電解質焼結体、及び、当該酸化物電解質焼結体の製造方法 |
US10818965B2 (en) | 2016-07-11 | 2020-10-27 | The Regents Of The University Of Michigan | Ceramic garnet based ionically conducting material |
US11158880B2 (en) | 2016-08-05 | 2021-10-26 | Quantumscape Battery, Inc. | Translucent and transparent separators |
KR20190055842A (ko) | 2016-10-07 | 2019-05-23 | 더 리젠츠 오브 더 유니버시티 오브 미시건 | 고체 상태 배터리용 안정화 코팅 |
US11916200B2 (en) | 2016-10-21 | 2024-02-27 | Quantumscape Battery, Inc. | Lithium-stuffed garnet electrolytes with a reduced surface defect density and methods of making and using the same |
WO2018075972A1 (en) | 2016-10-21 | 2018-04-26 | Quantumscape Corporation | Electrolyte separators including lithium borohydride and composite electrolyte separators of lithium-stuffed garnet and lithium borohydride |
US10903484B2 (en) | 2016-10-26 | 2021-01-26 | The Regents Of The University Of Michigan | Metal infiltrated electrodes for solid state batteries |
US11011776B2 (en) | 2017-03-15 | 2021-05-18 | Ngk Spark Plug Co., Ltd. | Lithium-ion-conductive ceramic material, lithium-ion-conductive ceramic sintered body, and lithium battery |
CN108727025A (zh) | 2017-04-17 | 2018-11-02 | 中国科学院上海硅酸盐研究所 | 锂石榴石复合陶瓷、其制备方法及其用途 |
US11489193B2 (en) | 2017-06-23 | 2022-11-01 | Quantumscape Battery, Inc. | Lithium-stuffed garnet electrolytes with secondary phase inclusions |
US10347937B2 (en) | 2017-06-23 | 2019-07-09 | Quantumscape Corporation | Lithium-stuffed garnet electrolytes with secondary phase inclusions |
US10868293B2 (en) | 2017-07-07 | 2020-12-15 | Polyplus Battery Company | Treating sulfide glass surfaces and making solid state laminate electrode assemblies |
US10629950B2 (en) | 2017-07-07 | 2020-04-21 | Polyplus Battery Company | Encapsulated sulfide glass solid electrolytes and solid-state laminate electrode assemblies |
JP2019046721A (ja) | 2017-09-05 | 2019-03-22 | トヨタ自動車株式会社 | スラリー、固体電解質層の製造方法、及び、全固体電池の製造方法 |
JP6962094B2 (ja) | 2017-09-21 | 2021-11-05 | トヨタ自動車株式会社 | ガーネット型イオン伝導性酸化物、及び、酸化物電解質焼結体の製造方法 |
WO2019078897A1 (en) | 2017-10-20 | 2019-04-25 | Quantumscape Corporation | INTERFACIAL LAYER BOROHYDRIDE-SULFIDE IN A TOTALLY SOLID BATTERY |
US11600850B2 (en) | 2017-11-06 | 2023-03-07 | Quantumscape Battery, Inc. | Lithium-stuffed garnet thin films and pellets having an oxyfluorinated and/or fluorinated surface and methods of making and using the thin films and pellets |
DE102017128719A1 (de) | 2017-12-04 | 2019-06-06 | Schott Ag | Lithiumionenleitendes Verbundmaterial, umfassend wenigstens ein Polymer und lithiumionenleitende Partikel, und Verfahren zur Herstellung eines Lithiumionenleiters aus dem Verbundmaterial |
JP7017079B2 (ja) | 2017-12-28 | 2022-02-08 | トヨタ自動車株式会社 | 電極の製造方法、電極、及び、電極-電解質層接合体 |
DE102018104291A1 (de) * | 2018-02-26 | 2019-08-29 | Volkswagen Aktiengesellschaft | Beschichtung für ein Werkzeug zur Handhabung von Lithiummetall, Werkzeug und Verfahren zum Herstellen eines solchen Werkzeugs |
EP3810358A1 (en) | 2018-06-19 | 2021-04-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
WO2020022342A1 (ja) * | 2018-07-24 | 2020-01-30 | 公立大学法人大阪 | 全固体ナトリウム電池用の固体電解質とその製造方法及び全固体ナトリウム電池 |
US11251460B2 (en) | 2018-08-01 | 2022-02-15 | Samsung Electronics Co., Ltd. | Solution-processed solid-state electrolyte and method of manufacture thereof |
US11223066B2 (en) | 2018-08-01 | 2022-01-11 | Samsung Electronics Co., Ltd. | Solid-state electrolyte and method of manufacture thereof |
WO2020026971A1 (ja) * | 2018-08-03 | 2020-02-06 | 株式会社カネカ | ガーネット型複合金属酸化物及びその製造方法 |
US11959166B2 (en) | 2018-08-14 | 2024-04-16 | Massachusetts Institute Of Technology | Methods of fabricating thin films comprising lithium-containing materials |
KR102101271B1 (ko) | 2018-08-16 | 2020-04-16 | 아주대학교산학협력단 | 이온 전도성 고체 전해질 화합물, 이의 제조방법 및 이를 포함하는 전기화학 장치 |
KR20200028165A (ko) | 2018-09-06 | 2020-03-16 | 삼성전자주식회사 | 고체 전해질, 그 제조방법 및 이를 포함하는 이차전지 |
DE102018215803A1 (de) | 2018-09-18 | 2020-03-19 | Bayerische Motoren Werke Aktiengesellschaft | Schutzschicht für Elektrode |
MX2021004694A (es) | 2018-11-06 | 2021-08-24 | Quantumscape Battery Inc | Celdas electroquimicas con aditivos catolitos y separadores de granate relleno de litio. |
KR102650658B1 (ko) | 2018-11-15 | 2024-03-25 | 삼성전자주식회사 | 헤테로고리 방향족 구조의 음이온을 포함하는 금속염 및 그 제조방법, 그리고 상기 금속염을 포함하는 전해질 및 전기화학소자 |
US11411246B2 (en) | 2018-12-06 | 2022-08-09 | Samsung Electronics Co., Ltd. | All-solid secondary battery and method of manufacturing all-solid secondary battery |
CN109742442A (zh) * | 2018-12-24 | 2019-05-10 | 北京化工大学 | 石榴石型固态电解质的制备及应用该固态电解质的二次电池 |
CN109713363A (zh) * | 2018-12-29 | 2019-05-03 | 蜂巢能源科技有限公司 | 锂石榴石氧化物固态电解质及其制备方法和应用 |
EP3703170A1 (en) | 2019-02-27 | 2020-09-02 | Technische Universität Graz | Solid ion conductor having a fluoride garnet-like structure |
WO2020223374A1 (en) | 2019-04-30 | 2020-11-05 | 6K Inc. | Lithium lanthanum zirconium oxide (llzo) powder |
US11311938B2 (en) | 2019-04-30 | 2022-04-26 | 6K Inc. | Mechanically alloyed powder feedstock |
US11757127B2 (en) | 2019-06-18 | 2023-09-12 | Samsung Electronics Co., Ltd. | Lithium solid electrolyte and method of manufacture thereof |
EP4061787B1 (en) | 2019-11-18 | 2024-05-01 | 6K Inc. | Unique feedstocks for spherical powders and methods of manufacturing |
US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
US11631889B2 (en) | 2020-01-15 | 2023-04-18 | Polyplus Battery Company | Methods and materials for protection of sulfide glass solid electrolytes |
CN113224374A (zh) * | 2020-01-21 | 2021-08-06 | 天津国安盟固利新材料科技股份有限公司 | 一种复合型电解质膜及其制备方法 |
JP7478414B2 (ja) * | 2020-03-02 | 2024-05-07 | 国立研究開発法人産業技術総合研究所 | 非晶質複合金属酸化物、ガーネット型リチウム複合金属酸化物、焼結体、固体電解質層、電気化学デバイス用電極、電気化学デバイス |
GB202006749D0 (en) | 2020-05-07 | 2020-06-24 | Johnson Matthey Plc | Lithium-ion conductive ceramic material and process |
US11637317B2 (en) | 2020-06-08 | 2023-04-25 | Cmc Materials, Inc. | Solid polymer electrolyte compositions and methods of preparing same |
US11855258B2 (en) | 2020-06-08 | 2023-12-26 | Cmc Materials, Inc. | Secondary battery cell with solid polymer electrolyte |
EP4173060A1 (en) | 2020-06-25 | 2023-05-03 | 6K Inc. | Microcomposite alloy structure |
US12021238B2 (en) | 2020-08-04 | 2024-06-25 | Polyplus Battery Company | Glassy embedded solid-state electrode assemblies, solid-state batteries and methods of making electrode assemblies and solid-state batteries |
US12021187B2 (en) | 2020-08-04 | 2024-06-25 | Polyplus Battery Company | Surface treatment of a sulfide glass solid electrolyte layer |
CA3186082A1 (en) | 2020-09-24 | 2022-03-31 | 6K Inc. | Systems, devices, and methods for starting plasma |
KR20230095080A (ko) | 2020-10-30 | 2023-06-28 | 6케이 인크. | 구상화 금속 분말을 합성하는 시스템 및 방법 |
GB202103712D0 (en) | 2021-03-17 | 2021-04-28 | Thermal Ceramics Uk Ltd | The production of melt formed inorganic ionically conductive electrolytes |
EP4385088A1 (en) | 2021-08-11 | 2024-06-19 | Gelion Technologies Pty Ltd | Lithium ion conductive ceramic material |
DE102022112792A1 (de) | 2022-05-20 | 2023-11-23 | Bayerische Motoren Werke Aktiengesellschaft | Lithiumbatterie umfassend eine Lithiummetallanode mit einem porösen Stromableiter |
CN115950941B (zh) * | 2023-03-13 | 2023-06-20 | 华北理工大学 | 锂离子导体固体电解质型低温传感器及其制备方法与应用 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0389469A (ja) * | 1989-09-01 | 1991-04-15 | Hitachi Ltd | ナトリウム―硫黄電池 |
JP3244291B2 (ja) | 1991-01-23 | 2002-01-07 | 三洋電機株式会社 | 電 池 |
JP3719312B2 (ja) * | 1997-07-07 | 2005-11-24 | 宇部興産株式会社 | 正極シートとこれを用いた非水電解質二次電池 |
JP4081833B2 (ja) * | 1997-08-01 | 2008-04-30 | 宇部興産株式会社 | 密閉型非水電解液二次電池 |
JP4417676B2 (ja) | 2003-09-18 | 2010-02-17 | パナソニック株式会社 | 非水電解質二次電池 |
US20050083986A1 (en) | 2003-10-17 | 2005-04-21 | Eastman Kodak Company | Light-emitting diode pumped laser and method of excitation |
DE102004010892B3 (de) | 2004-03-06 | 2005-11-24 | Christian-Albrechts-Universität Zu Kiel | Chemisch stabiler fester Lithiumionenleiter |
EP1723080B1 (de) | 2004-03-06 | 2014-06-18 | Basf Se | Chemisch stabiler fester lithiumionenleiter |
US20060083986A1 (en) * | 2004-03-16 | 2006-04-20 | Wen Li | Battery with tin-based negative electrode materials |
DE102005001414A1 (de) * | 2005-01-12 | 2006-07-20 | Degussa Ag | Pyrogen hergestelltes Siliciumdioxidpulver |
CN100364153C (zh) * | 2005-05-24 | 2008-01-23 | 中国科学院成都有机化学有限公司 | 一种尖晶石LiMn2O4表面包覆Li4Ti5O12电极材料及其制备方法 |
US7993782B2 (en) | 2005-07-01 | 2011-08-09 | National Institute For Materials Science | All-solid lithium battery |
WO2008063532A1 (en) * | 2006-11-17 | 2008-05-29 | Panasonic Corporation | Electrode active material for non-aqueous secondary batteries |
DE102007030604A1 (de) * | 2007-07-02 | 2009-01-08 | Weppner, Werner, Prof. Dr. | Ionenleiter mit Granatstruktur |
US20090191458A1 (en) * | 2007-07-23 | 2009-07-30 | Matsushita Electric Industrial Co., Ltd. | Porous network negative electrodes for non-aqueous electrolyte secondary battery |
JP5151692B2 (ja) * | 2007-09-11 | 2013-02-27 | 住友電気工業株式会社 | リチウム電池 |
WO2010005686A2 (en) * | 2008-06-16 | 2010-01-14 | Polyplus Battery Company | Aqueous lithium/air battery cells |
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CN101952223A (zh) | 2011-01-19 |
KR101539123B1 (ko) | 2015-07-23 |
US8658317B2 (en) | 2014-02-25 |
US20140205910A1 (en) | 2014-07-24 |
CA2694259C (en) | 2015-06-23 |
US9450271B2 (en) | 2016-09-20 |
DE102007030604A1 (de) | 2009-01-08 |
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JP2010534383A (ja) | 2010-11-04 |
EP2176190A2 (de) | 2010-04-21 |
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