US4097345A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Na5 GdSi4 O 12 and related rare earth sodium ion conductors and electrolytic cells therefrom
Assignee: EIDP Inc
•
Filing: 1976-10-15
•
Granted: 1978-06-27
•
Expires: 1996-10-15
Abstract
Abstract Sodium ion conducting compositions are provided having (a) the formula Na 5-x □ x Gd 1-y-x M y M' x Si 4-z Ge z O 12 wherein M is at least one of the rare earths or yttrium, M' is Zr 4+ , Hf 4+ , or Th 4+ , □ is a sodium vacancy to preserve charge neutrality, X is 0 to about 0.5 when Zr 4+ or Hf 4+ is included in M' and 0 to about 0.1 when Th 4+ is included in M', y is 0 to 1, and Z is 0 to 4, with the proviso that y+x is no more than 1, And (b) the rhombohedral Na 5 YSi 4 O 12 crystal structure with space group symmetry R3c. These compositions are useful as solid electrolytes in electrochemical cells such as galvanic cells and electrolytic cells. Certain of the sodium ion conducting compositions are novel compositions of matter.
Inventors
- 👤 Robert Day Shannon
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 08:27
CPC Classifications
H; H01; H01M; H01M10/00; H01M10/36; H01M10/39; H01M10/3909; H01M10/3918; C; C04; C04B; C04B35/00; C04B35/01; C04B35/16; C04B35/622; C04B35/626; C04B35/62605; C04B35/6261; C04B35/6262; C04B35/62645; C04B35/62675; C25; C25C; C25C3/00; C25C3/02; C25C7/00; C25C7/04; G; G01; G01N; G01N27/00; G01N27/26; G01N27/403; G01N27/406; G01N27/407; G01N27/4073; G01N27/4074; H01B; H01B1/00; H01B1/06; H01B1/08; H01M6/00; H01M6/14; H01M6/18; H01M6/185; C04B2235/00; C04B2235/02; C04B2235/30; C04B2235/32; C04B2235/3201; C04B2235/3205; C04B2235/3215; C04B2235/3224; C04B2235/3225; C04B2235/3227; C04B2235/3231; C04B2235/3232; C04B2235/3244; C04B2235/3287; C04B2235/34; C04B2235/3418; C04B2235/3427; C04B2235/44; C04B2235/447; C04B2235/448; C04B2235/65; C04B2235/656; C04B2235/6567; C04B2235/70; C04B2235/74; C04B2235/76; C04B2235/761; C04B2235/767; C04B2235/77; Y; Y02; Y02E; Y02E60/00; Y02E60/10
Claims Analysis
Total Claims: 44
Claim 1
Independent Claim
135 words
The method of conducting sodium ions utilizing a composition having (a) the formula Na 5-x □ x Gd 1-y-x M y M' x Si 4-z Ge z O 12 wherein M is yttrium or at least one of the rare earths other than Gd, M' is Zr 4+ , Hf 4+ , or Th 4+ , □ is a sodium vacancy to preserve charge neutrality, x is 0 to about 0.5 when Zr 4+ or Hf 4+ is included in M' and 0 to about 0.1 when Th 4+ is included in M', y is 0 to 1, and z is 0 to 4, with the proviso that y+x is no more than 1, and (b) the crystal structure of the rhombohedral Na 5 YSi 4 O 12 -type with the space group symmetry R3c.
Claim 2
Independent Claim
135 words
The method of conducting sodium ions utilizing a composition having (a) the formula Na 5-x □ x Gd 1-y-x M y M' x Si 4-z Ge z O 12 wherein M is yttrium or at least one of the rare earths other than Gd, M' is Zr 4+ , Hf 4+ , or Th 4+ , □ is a sodium vacancy to preserve charge neutrality, x is 0 to about 0.5 when Zr 4+ or Hf 4+ is included in M' and 0 to about 0.1 when Th 4+ is included in M', y is 0 to 1, and z is 0 to 4, with the proviso that y+x is no more than 1, and (b) the crystal structure of the rhombohedral Na 5 YSi 4 O 12 -type with the space group symmetry R3c.
Claim 3
Dependent Claim
26 words
The method of claim 1 utilizing a composition having the formula Na 5-x □ x Gd 1-y-x M y M' x Si 4 O 12 .
Claim 4
Dependent Claim
11 words
The method of claim 2 wherein M' is Zr 4+ .
Claim 5
Dependent Claim
88 words
The method of claim 2 wherein M is at least one of Ho 3+ , Sm 3+ , Tb 3+ , Dy 3+ , Nd 3+ , Pr 3+ and La 3+ and y is (1) 0 to 1 when M is Ho 3+ , Sm 3+ , Tb 3+ or Dy 3+ , (2) 0 to about 0.6 when M is Nd 3+ , (3) 0 to about 0.4 when M is Pr 3+ , and (4) 0 to about 0.2 when M is La 3+ .
Claim 6
Dependent Claim
11 words
The method of claim 4 wherein M' is Zr 4+ .
Claim 7
Dependent Claim
18 words
The method of claim 2 wherein said composition has the formula Na 5 GdSi 4 O 12 .
Claim 8
Dependent Claim
18 words
The method of claim 2 wherein said composition has the formula Na 5 SmSi 4 O 12 .
Claim 9
Dependent Claim
18 words
The method of claim 2 wherein said composition has the formula Na 5 HoSi 4 O 12 .
Claim 10
Dependent Claim
18 words
The method of claim 2 wherein said composition has the formula Na 5 TbSi 4 O 12 .
Claim 11
Dependent Claim
21 words
The method of claim 2 wherein said composition has the formula Na 4 .9-4.8 Gd.sub..9-.8 Zr.sub..1-.2 Si 4 O 12 .
Claim 12
Dependent Claim
20 words
The method of claim 2 wherein said composition has the formula Na 5 Gd.sub..8-.4 Nd.sub..2-.6 Si 4 O 12 .
Claim 13
Dependent Claim
20 words
The method of claim 2 wherein said composition has the formula Na 5 Gd.sub..8 La.sub..2 Si 4 O 12 .
Claim 14
Dependent Claim
22 words
The method of claim 2 wherein said composition has the formula Na 4 .9 Gd.sub..7 Nd.sub..2 Zr.sub..1 Si 4 O 12 .
Claim 15
Dependent Claim
20 words
The method of claim 2 wherein said composition has the formula Na 5 Gd.sub..8-.6 Pr.sub..2-.4 Si 4 O 12 .
Claim 16
Dependent Claim
195 words
A composition of matter having (a) the formula Na 5-x □ x Gd 1-y-x M y M' x Si 4-z Ge z O 12 wherein M is at least one of Ho 3+ , Sm 3+ , Tb 3+ , Dy 3+ , Nd 3+ , Pr 3+ and La 3+ , M' is Zr 4+ , Hf 4+ , or Th 4+ , □ is a sodium vacancy to preserve charge neutrality, z is 0 to 4, x is 0 to about 0.5 when Zr 4+ or Hf 4+ is included in M' and 0 to about 0.1 when Th 4+ is included in M', y is (1) 0 to 1 when M is Ho 3+ , Sm 3+ , Tb 3+ , or Dy 3+ , (2) 0 to about 0.6 when M is Nd 3+ , (3) 0 to about 0.4 when M is Pr 3+ , and (4) 0 to about 0.2 when M is La 3+ , with the proviso that y + x can be no more than 1 and (b) the crystal structure of the rhombohedral Na 5 YSi 4 O 12 -type with space group symmetry R3c.
Claim 17
Dependent Claim
195 words
A composition of matter having (a) the formula Na 5-x □ x Gd 1-y-x M y M' x Si 4-z Ge z O 12 wherein M is at least one of Ho 3+ , Sm 3+ , Tb 3+ , Dy 3+ , Nd 3+ , Pr 3+ and La 3+ , M' is Zr 4+ , Hf 4+ , or Th 4+ , □ is a sodium vacancy to preserve charge neutrality, z is 0 to 4, x is 0 to about 0.5 when Zr 4+ or Hf 4+ is included in M' and 0 to about 0.1 when Th 4+ is included in M', y is (1) 0 to 1 when M is Ho 3+ , Sm 3+ , Tb 3+ , or Dy 3+ , (2) 0 to about 0.6 when M is Nd 3+ , (3) 0 to about 0.4 when M is Pr 3+ , and (4) 0 to about 0.2 when M is La 3+ , with the proviso that y + x can be no more than 1 and (b) the crystal structure of the rhombohedral Na 5 YSi 4 O 12 -type with space group symmetry R3c.
Claim 18
Dependent Claim
9 words
The composition of claim 15 wherein z is 0.
Claim 19
Dependent Claim
11 words
The composition of claim 16 wherein M' is Zr 4+ .
Claim 20
Dependent Claim
9 words
The composition of claim 16 wherein x is 0.
Claim 21
Dependent Claim
9 words
The composition of claim 17 wherein y is 0.
Claim 22
Dependent Claim
24 words
The method of claim 1 wherein the said composition is admixed with up to 20 mole percent Na 2 Si 2 O 5 .
Claim 23
Dependent Claim
24 words
The method of claim 2 wherein the said composition is admixed with up to 20 mole percent Na 2 Si 2 O 5 .
Claim 24
Dependent Claim
24 words
The method of claim 4 wherein the said composition is admixed with up to 20 mole percent Na 2 Si 2 O 5 .
Claim 25
Dependent Claim
30 words
The method of claim 1 wherein the said composition is admixed with about 5-30 mole percent Na 3 BaGdSi 4 O 12 or Na 3 BaYSi 4 O 12 .
Claim 26
Dependent Claim
30 words
The method of claim 2 wherein the said composition is admixed with about 5-30 mole percent Na 3 BaGdSi 4 O 12 or Na 3 BaYSi 4 O 12 .
Claim 27
Dependent Claim
30 words
The method of claim 4 wherein the said composition is admixed with about 5-30 mole percent Na 3 BaGdSi 4 O 12 or Na 3 BaYSi 4 O 12 .
Claim 28
Dependent Claim
27 words
The method of claim 1 wherein the said composition is admixed with about 1-2 mole percent of Na 2 SO 4 or Na 3 PO 4 .
Claim 29
Dependent Claim
27 words
The method of claim 2 wherein the said composition is admixed with about 1-2 mole percent of Na 2 SO 4 or Na 3 PO 4 .
Claim 30
Dependent Claim
27 words
The method of claim 4 wherein the said composition is admixed with about 1-2 mole percent of Na 2 SO 4 or Na 3 PO 4 .
Claim 31
Dependent Claim
61 words
In an electrochemical device having (a) two electrodes, one of which is a sodium-containing electrode capable of supplying sodium ions, (b) a solid electrolyte separating the two electrodes and (c) an inert connecting electrical connector to complete an electrical circuit between the two electrodes, the improvement wherein the solid electrolyte consists essentially of the sodium ion conducting composition of claim 1.
Claim 32
Dependent Claim
31 words
The electrochemical device of claim 29 wherein the solid electrolyte is the sodium ion conducting composition Na 5-x □ x Gd 1-y-x M y M' x Si 4 O 12 .
Claim 33
Dependent Claim
115 words
The electrochemical device of claim 29 wherein the solid electrolyte is the sodium ion conducting composition Na 5-x □ x Gd 1-y-x M y M' x Si 4 O 12 wherein M is at least one of Ho 3+ , Sm 3+ , Tb 3+ , Dy 3+ , Nd 3+ , Pr 3+ , and La 3+ and y is (1) 0 to 1 when M is Ho 3+ , Sm 3+ , Tb 3+ , or Dy 3+ , (2) 0 to about 0.6 when M is Nd 3+ , (3) 0 to about 0.4 when M is Nd 3+ , and (4) 0 to about 0.2 when M is La 3+ .
Claim 34
Dependent Claim
23 words
The electrochemical device of claim 29 wherein the solid electrolyte is the sodium ion conducting composition Na 5 GdSi 4 O 12 .
Claim 35
Dependent Claim
26 words
The electrochemical device of claim 29 wherein the solid electrolyte is the sodium ion conducting composition Na 4 .9-4.8 Gd.sub..9-.8 Zr.sub..1-.2 Si 4 O 12 .
Claim 36
Dependent Claim
24 words
The electrochemical device of claim 29 wherein the solid electrolyte composition contains up to 20 mole percent Na 2 Si 2 O 5 .
Claim 37
Dependent Claim
29 words
The electrochemical device of claim 29 wherein the solid electrolyte contains about 5-30 mole percent Na 3 BaGdSi 4 O 12 or Na 3 BaYSi 4 O 12 .
Claim 38
Dependent Claim
26 words
The electrochemical device of claim 29 wherein the solid electrolyte contains about 1-2 mole percent of Na 2 SO 4 or Na 3 PO 4 .
Claim 39
Dependent Claim
12 words
The electrochemical device of claim 29 wherein it is an electrolytic cell.
Claim 40
Dependent Claim
12 words
The electrochemical device of claim 29 wherein it is a galvanic cell.
Claim 41
Dependent Claim
16 words
The galvanic cell of claim 38 wherein the anode is sodium and the cathode is sulfur.
Claim 42
Dependent Claim
18 words
The galvanic cell of claim 38 wherein the anode is sodium and the cathode is TiS 2 .
Claim 43
Dependent Claim
14 words
The electrolytic cell of claim 37 which is a NaCl-AlCl 3 -Na electrowinning cell.
Claim 44
Dependent Claim
13 words
The electrolytic cell of claim 37 which is a sodium amalgam-sodium electrowinning cell.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-06-26 | 1981-12-26 | 1982-06-27 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-06-26 | 1985-12-26 | 1986-06-27 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-06-26 | 1989-12-26 | 1990-06-27 | $7700.00 | Window Closed / Lapsed |