WO1998002929B1 - A method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells - Google Patents
A method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cellsInfo
- Publication number
- WO1998002929B1 WO1998002929B1 PCT/US1997/011285 US9711285W WO9802929B1 WO 1998002929 B1 WO1998002929 B1 WO 1998002929B1 US 9711285 W US9711285 W US 9711285W WO 9802929 B1 WO9802929 B1 WO 9802929B1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrode material
- metal
- formula
- vanadium metal
- metal oxide
- Prior art date
Links
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title abstract 2
- 229910001935 vanadium oxide Inorganic materials 0.000 title abstract 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title 1
- 229910052744 lithium Inorganic materials 0.000 title 1
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract 12
- 229910052720 vanadium Inorganic materials 0.000 claims abstract 11
- -1 vanadium metal oxides Chemical class 0.000 claims abstract 11
- 229910052751 metal Inorganic materials 0.000 claims abstract 10
- 239000002184 metal Substances 0.000 claims abstract 10
- 239000007773 negative electrode material Substances 0.000 claims abstract 5
- 239000007864 aqueous solution Substances 0.000 claims 5
- 239000002585 base Substances 0.000 claims 4
- 239000007774 positive electrode material Substances 0.000 claims 4
- 229910003002 lithium salt Inorganic materials 0.000 claims 3
- 159000000002 lithium salts Chemical class 0.000 claims 3
- 239000000243 solution Substances 0.000 claims 3
- 150000001447 alkali salts Chemical class 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 2
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical class [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 239000011255 nonaqueous electrolyte Substances 0.000 claims 2
- 229910003006 LixMy Inorganic materials 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052803 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 230000000875 corresponding Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 claims 1
- 239000007772 electrode material Substances 0.000 claims 1
- 230000002349 favourable Effects 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 230000001376 precipitating Effects 0.000 claims 1
- 229910015916 LixMyVzO Inorganic materials 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
Abstract
Methods for preparing amorphous ternary lithiated vanadium metal oxides and amorphous binary non-lithiated metal oxides with the formula LixMyVzO¿(x+5z+ny)/z? and MyVzO¿(5z+ny)/z? respectively. M is a metal, 0 < x < 3, 0 < y < 3, 1 < z < 4, and n=2 or 3. The metal vanadium oxides are formed by aqueous precipitation methods. Rechargeable lithiated intercalation battery cells using the above materials as negative electrode active materials are also disclosed.
Claims
1. A method for preparing an amorphous ternary lithiated vanadium metal oxide of the formula LιxMyV70 (} 52+ny) /2> where M
^ is a metal, 0 < x < 3, 0 < y < 3, 1 < z 4 , and n = 2 or 3 c h a r a c t e r i z e d i n t h a t a) an aqueous solution is prepared of
1 ) at least one metavanadate salt selected from the group consisting of NH4V03 and NaV03, 0 2) a nitrate salt of the formula M(N03)n, where M is said metal, and 3) a large excess of α lithium salt; b) the resulting solution is heated; and c) a sufficient amount of a base is added to the heated 5 solution to obtain a pH suitable for precipitating the amorphous lithiated vanadium metal oxide.
2. A method according to claim 1 c h a r a c t e r i z e d i n t h a t 0 said aqueous solution is prepared by mixing a) a first aqueous solution comprising said metavanadate salt; and b) a second aqueous solution comprising said nitrate and lithium salts. 5
3. A method according to claim 1 wherein said base is selected from the group consisting of ammonia, amines, alkali hydroxides, alkaline earth hydroxides, alkali salts of alcohols, and alkali salts of carboxylic acids. 0
- 27 -
4. A method according to claim 1 wherein said base is added in the form of an aqueous solution of said base.
5. A method according to claim 1 wherein said lithium salt is selected from the group consisting of ιN03, LiOH, LiOH-H.O, and
Lι2C03.
6. A method according to claim 1 wherein said heating comprises heating the solution to a temperature in the range of about 80°C to 95°C.
7. A method according to claim 1 wnerein said metal is at least one metal selected from the qroup consisting of manganese, cobalt, iron, copper, cadmium, nickel, chromium, indium, aluminum, and magnesium.
8. A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and an non-aqueous electrolyte c h a r a c t e r i z e d i n t h a t said active positive electrode material is an amorphous vanadium metal oxide selected from the group consisting of: a) ternary lithiated vanadium metal oxides of the formula LιxMyVzO(x+5Z+ny)/2, where M is a metal, 0 < x < 3, 0 < y < 3, 1 < z < 4, and n = 2 or 3; and b) binary non-lithiated vanadium metal oxides of the formula MyVzO(5z+ny) 2, where M is a metal, 0 < y < 3, 1 < z < 4, and n = 2 or 3.
9. A cell according to claim 8 wherein said active positive electrode material is a ternary lithiated vanadium metal oxide prepared by a process according to claim 1.
10. A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and an non-aqueous electrolyte c h a r a c t e r i z e d i n t h a t said active negative electrode material is an amorphous vanadium metal oxide selected from the group consisting of: a) ternary lithiated vanadium metal oxides of the formula LixMyVΞ0(x+5z+ny) 2, where M is a metal, 0 < x < 3, 0 < y < 3, 1 < z < 4, and n = 2 or 3; and b) binary non-lithiated vanadium metal oxides of the formula MyVzO(5z+ny) /2, where M is a metal, 0 < y < 3, 1 < z < 4 , and n = 2 or 3.
11. A cell according to claim 10 wherein said active negative electrode material is a ternary lithiated vanadium metal oxide prepared by a process according to claim 1.
- 29 - STATEMENT UNDER ARTICLE 19
The present application has been amended to more particularly recite in claims 8 and 10 the characterizing aspects of the battery cell electrode materials which distinguish the cited art. Claims 8 through 12 have been cancelled m order to obviate any possible conflict with the cited references.
The foregoing amendments are identical to those made in the U.S. priority application in order to render allowable claims corresponding to those in the present application.
In view of the foregoing, Applicant submits that the instant application meets the standards of formality and clarity, as well as the criteria set out in PCT Article 33(1) . The Examiner's consideration and favorable Report to that effect are earnestly solicited.
30 -
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002259590A CA2259590C (en) | 1996-07-11 | 1997-06-27 | A method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells |
| JP10506049A JP2000503622A (en) | 1996-07-11 | 1997-06-27 | Method for producing mixed amorphous vanadium oxide and its use as electrode in rechargeable lithium batteries |
| EP97933196A EP0913007A1 (en) | 1996-07-11 | 1997-06-27 | A method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells |
| AU36443/97A AU715258B2 (en) | 1996-07-11 | 1997-06-27 | A method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells |
| IL12770797A IL127707A (en) | 1996-07-11 | 1997-06-27 | Method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/678,210 US5700598A (en) | 1996-07-11 | 1996-07-11 | Method for preparing mixed amorphous vanadium oxides and their use as electrodes in reachargeable lithium cells |
| US08/678,210 | 1996-07-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO1998002929A1 WO1998002929A1 (en) | 1998-01-22 |
| WO1998002929B1 true WO1998002929B1 (en) | 1998-02-19 |
Family
ID=24721854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1997/011285 WO1998002929A1 (en) | 1996-07-11 | 1997-06-27 | A method for preparing mixed amorphous vanadium oxides and their use as electrodes in rechargeable lithium cells |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5700598A (en) |
| EP (1) | EP0913007A1 (en) |
| JP (2) | JP2000503622A (en) |
| AU (1) | AU715258B2 (en) |
| CA (1) | CA2259590C (en) |
| ID (1) | ID17594A (en) |
| IL (1) | IL127707A (en) |
| MY (1) | MY133690A (en) |
| TW (1) | TW362296B (en) |
| WO (1) | WO1998002929A1 (en) |
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| US6277521B1 (en) | 1997-05-15 | 2001-08-21 | Fmc Corporation | Lithium metal oxide containing multiple dopants and method of preparing same |
| ZA983867B (en) * | 1997-05-16 | 1998-11-13 | Henkel Corp | Lithium and vanadium containing sealing composition and process therewith |
| DE69827700T2 (en) * | 1997-05-22 | 2005-10-06 | Matsushita Electric Industrial Co., Ltd., Kadoma | Secondary battery with non-aqueous electrolyte |
| US6017654A (en) * | 1997-08-04 | 2000-01-25 | Carnegie Mellon University | Cathode materials for lithium-ion secondary cells |
| US6517974B1 (en) * | 1998-01-30 | 2003-02-11 | Canon Kabushiki Kaisha | Lithium secondary battery and method of manufacturing the lithium secondary battery |
| US5980855A (en) * | 1998-05-26 | 1999-11-09 | Rentech, Inc. | Method for preparing lithiated metal oxides |
| US5939043A (en) * | 1998-06-26 | 1999-08-17 | Ga-Tek Inc. | Process for preparing Lix Mn2 O4 intercalation compounds |
| US6267943B1 (en) | 1998-10-15 | 2001-07-31 | Fmc Corporation | Lithium manganese oxide spinel compound and method of preparing same |
| KR100473413B1 (en) | 1998-11-13 | 2005-03-08 | 에프엠씨 코포레이션 | Layered lithium metal oxides free of localized cubic spinel-like structural phases and methods of making same |
| CN1170773C (en) | 1998-11-20 | 2004-10-13 | Fmc公司 | Multiple doped lithium manganese oxide compounds and methods of preparing same |
| US6322928B1 (en) * | 1999-09-23 | 2001-11-27 | 3M Innovative Properties Company | Modified lithium vanadium oxide electrode materials and products |
| JP4960561B2 (en) | 1999-12-10 | 2012-06-27 | エフエムシー・コーポレイション | Lithium cobalt oxide and method for producing the same |
| CN1209834C (en) * | 2000-04-19 | 2005-07-06 | 日本电池株式会社 | Positive electrode active material for secondary cell, method for producing same and nonaqueous electrolyte secondary cell comprising same |
| US6716555B2 (en) * | 2000-06-13 | 2004-04-06 | Japan Storage Battery Co., Ltd. | Positive active material for secondary battery, process for preparation thereof and non-aqueous secondary battery comprising same |
| AU2002249557A1 (en) * | 2002-03-28 | 2003-10-13 | Council Of Scientific And Industrial Research | COMBUSTION PROCESS FOR THE PREPARATION OF LiCoVO4 |
| US20030235761A1 (en) * | 2002-04-26 | 2003-12-25 | Prabaharan S.R. Sahaya | Rechargeable lithium-containing battery employing brannerite type LiVMoO5.5 cathode and method of preparing same |
| US20040048157A1 (en) * | 2002-09-11 | 2004-03-11 | Neudecker Bernd J. | Lithium vanadium oxide thin-film battery |
| US8026003B2 (en) * | 2003-08-21 | 2011-09-27 | Samsung Sdi Co., Ltd. | Negative active material for a non-aqueous electrolyte battery, and a non-aqueous electrolyte battery comprising the same |
| US7682746B2 (en) * | 2005-03-31 | 2010-03-23 | Panasonic Corporation | Negative electrode for non-aqueous secondary battery |
| US7399457B2 (en) * | 2005-04-12 | 2008-07-15 | Conocophillips Company | Process for the removal of heavy metals from gases, and compositions therefor and therewith |
| KR100759410B1 (en) * | 2006-11-20 | 2007-09-19 | 삼성에스디아이 주식회사 | Negative active material for lithium secondary battery, method of preparing same, and lithium secondary battery comprising same |
| KR100814880B1 (en) * | 2006-11-22 | 2008-03-18 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery, method of preparing thereof, and rechargeable lithium battery comprising the same |
| KR100778450B1 (en) * | 2006-11-22 | 2007-11-28 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery, method of preparing same, and rechargeable lithium battery comprising same |
| JP5270089B2 (en) * | 2006-12-18 | 2013-08-21 | 三星エスディアイ株式会社 | Method for producing negative electrode material for non-aqueous secondary battery and method for producing non-aqueous secondary battery using the same |
| US20080182171A1 (en) * | 2006-12-18 | 2008-07-31 | Hideaki Maeda | Composition for negative electrode of non-aqueous rechargeable battery and non-aqueous rechargeable battery prepared by using same |
| KR100805123B1 (en) * | 2007-02-15 | 2008-02-21 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| KR100953615B1 (en) * | 2007-04-13 | 2010-04-20 | 삼성에스디아이 주식회사 | Negative active material for rechargeable lithium battery, method of preparing same, and rechargeable lithium battery |
| JP5511128B2 (en) * | 2007-06-07 | 2014-06-04 | 三星エスディアイ株式会社 | Anode material for non-aqueous secondary battery and non-aqueous secondary battery |
| KR100918048B1 (en) * | 2007-09-07 | 2009-09-22 | 삼성에스디아이 주식회사 | Rechargeable lithium battery |
| KR100898291B1 (en) * | 2007-09-12 | 2009-05-18 | 삼성에스디아이 주식회사 | Rechargeable lithium battery |
| TW201002623A (en) * | 2008-05-30 | 2010-01-16 | Basf Se | Process for preparing lithium vanadium oxides and their use as cathode material |
| KR101208910B1 (en) | 2010-09-29 | 2012-12-06 | 전자부품연구원 | Manufacturing method of negative composition for Lithium secondary battery using lithium vanadium oxide substituted other metal |
| RU2453014C1 (en) * | 2010-11-23 | 2012-06-10 | Государственное образовательное учреждение высшего профессионального образования Самарский государственный технический университет | Electrolyte for chemical current source |
| KR101418060B1 (en) | 2012-02-20 | 2014-07-10 | 경북대학교 산학협력단 | Preparation method of a positive active for a lithium secondary battery |
| US10297855B2 (en) | 2012-05-29 | 2019-05-21 | Nutech Ventures | Rechargeable multi-cell battery |
| CN103268964B (en) * | 2013-05-09 | 2015-08-05 | 西安交通大学 | A kind of method of sodium vanadate assembling aqueous solution lithium ion battery |
| JP7335053B2 (en) * | 2020-02-26 | 2023-08-29 | エルジー エナジー ソリューション リミテッド | Irreversible additive, positive electrode containing said irreversible additive, lithium secondary battery containing said positive electrode |
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| US4675260A (en) * | 1984-11-12 | 1987-06-23 | Nippon Telegraph And Telephone Corporation | Lithium battery including vanadium pentoxide base amorphous cathode active material |
| IT1231750B (en) * | 1989-05-12 | 1991-12-21 | Consiglio Nazionale Ricerche | HIGH ENERGY AND POWER LITHIUM ACCUMULATORS AND RELATED PRODUCTION METHOD |
| US5284721A (en) * | 1990-08-01 | 1994-02-08 | Alliant Techsystems Inc. | High energy electrochemical cell employing solid-state anode |
| FR2685129B1 (en) * | 1991-12-13 | 1994-03-25 | Centre Nal Etudes Spatiales | USE OF VANADIUM OXIDE BRONZES WITH IRON AND / OR ALUMINUM AS CATHODE MATERIAL IN ELECTROCHEMICAL GENERATORS. |
| US5334334A (en) * | 1993-03-30 | 1994-08-02 | Valence Technology, Inc. | Method of preparing lithium battery electrode compositions |
| JPH07122275A (en) * | 1993-05-25 | 1995-05-12 | Wilson Greatbatch Ltd | Cathode for electrochemical battery, its manufacture and electrochemical battery |
-
1996
- 1996-07-11 US US08/678,210 patent/US5700598A/en not_active Expired - Lifetime
-
1997
- 1997-06-27 CA CA002259590A patent/CA2259590C/en not_active Expired - Fee Related
- 1997-06-27 IL IL12770797A patent/IL127707A/en not_active IP Right Cessation
- 1997-06-27 JP JP10506049A patent/JP2000503622A/en active Pending
- 1997-06-27 WO PCT/US1997/011285 patent/WO1998002929A1/en not_active Application Discontinuation
- 1997-06-27 AU AU36443/97A patent/AU715258B2/en not_active Ceased
- 1997-06-27 EP EP97933196A patent/EP0913007A1/en not_active Withdrawn
- 1997-07-08 MY MYPI97003089A patent/MY133690A/en unknown
- 1997-07-10 ID IDP972381A patent/ID17594A/en unknown
- 1997-07-11 TW TW086109800A patent/TW362296B/en active
-
2002
- 2002-08-22 JP JP2002242077A patent/JP2003142096A/en active Pending
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