WO2002073716A2 - Compositions cathodiques et leurs utilisations, notamment dans les generateurs electrochimiques - Google Patents
Compositions cathodiques et leurs utilisations, notamment dans les generateurs electrochimiques Download PDFInfo
- Publication number
- WO2002073716A2 WO2002073716A2 PCT/CA2002/000341 CA0200341W WO02073716A2 WO 2002073716 A2 WO2002073716 A2 WO 2002073716A2 CA 0200341 W CA0200341 W CA 0200341W WO 02073716 A2 WO02073716 A2 WO 02073716A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- battery according
- composition according
- mixture
- optionally
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to new cathode compositions and their uses, in particular in electrochemical generators.
- the invention also relates to electrochemical cells comprising at least one electrode comprising a composition according to the invention.
- A Mg, Zn, Al, Fe, Cr, Co, Mn, Ni, Zn, Ga, 0 ⁇ x, y, a, f ⁇ 1.
- Another disadvantage is the low mass capacity of these materials, between 90 and 130 mAh / g. These materials are used in electronics, and the potential standard of 4.1 - 4.2 V is required in most portable electronics systems.
- these materials are non-toxic and formed from abundant elements.
- operating in a very narrow potential range is an advantage in terms of simplification of the electronics, especially since the resistance of these materials to overcharging and over-discharging is excellent.
- these materials have an electronic conductivity too low and require the addition either of a large mass fraction of carbon for their use in primary or secondary generators, or of an extremely thin deposit of carbonaceous material distributed over the surface of the grains. In this case, the apparent density, therefore the connectivity of the grains, must be as high as possible so as to obtain a good electronic exchange. This results in the need for large volume fractions of double phosphate in the composite material serving as cathode.
- the invention relates to a positive electrode composition containing at least one mixed oxide of spinel or lamellar structure of general formula.
- A Mg, Zn, Al, Fe, Cr, Co, Mn, Ni, Zn Ga, 0 ⁇ x, y, a, f ⁇ l,
- the mixed oxide is preferably Lii- x Co ⁇ 2 or Li ⁇ _ x Nii-yC ⁇ y ⁇ 2 for which 0.1 ⁇ y ⁇ 0.4, while the mixed phosphate is preferably Li ⁇ _
- the proportion of mixed phosphate relative to the mixed oxide is between 5 and 95% by weight, preferably between
- the mixed phosphate can be covered on the surface with a homogeneous conductive carbon-based deposit or with a pyrolyzed organic material.
- the active cathode mixture can be added with a polymer serving as a binder and optionally as an electrolytic conductor by addition of a salt containing at least partly lithium ions, and optionally with a polar liquid.
- the active cathode mixture can be added with an electronic conductor allowing exchanges between the current collector and the grains of electrode material, in particular carbon black, graphite or their mixture.
- the invention also relates to an electrochemical cell comprising at least one electrode containing at least one material consisting of a composition as defined above.
- this electrochemical cell comprises a positive electrode of composition as defined above, and it functions as a primary or secondary battery, or as a super-capacity.
- the electrolyte is a polymer, solvating or not, optionally plasticized or gelled with a polar solvent and containing in solution one or more metal salts, in particular a lithium salt.
- the electrolyte can also be a polar liquid containing in solution one or more metal salts, in particular a lithium salt, optionally immobilized in a microporous separator, in particular a polyolefin, a polyester, nanoparticles of silica, alumina or lithium aluminate LiA10 2 or a mixture thereof as a composite.
- a metal salts in particular a lithium salt
- a microporous separator in particular a polyolefin, a polyester, nanoparticles of silica, alumina or lithium aluminate LiA10 2 or a mixture thereof as a composite.
- the polymer containing a salt and optionally a polar liquid is preferably formed from oxyethylene, oxypropylene, acrylonitrile, vinylidene fluoride units, esters of acrylic or methacrylic acid, esters of itaconic acid with alkyl groups or oxa-alkyls, in particular containing the oxyethylene units.
- the polymer contains in particular powders of nanoparticles such as silica, titanium oxide, alumina, LiA10 3 .
- the polar liquid is preferably chosen from cyclic or linear carbonates, carboxylic esters, alpha-omega ethers of oligoethylene glycols, N-methylpyrrolididone, gamma-butyrolactone, tetraalkyl sulfonamides and their mixtures, a fraction of the atoms of hydrogen which may be substituted by fluorine atoms.
- the negative electrode of the battery according to the invention can contain metallic lithium or one of its alloys, in particular with aluminum, a compound for inserting lithium into carbon, in particular graphite. or the pyrolytic carbons, LiFe0 2 , Li 2 Mn 2 0 or Li 4 Ti 5 0 ⁇ 2 or the solid solutions formed between these oxides.
- the current collector of the electrode containing the electrode material according to the invention is made of aluminum, optionally in the form of expanded or expanded metal.
- the power capable of being delivered by these systems is greater than that obtained with the oxides used alone in the cathode mixture, in particular when very high powers are required.
- Figure 1 shows charge and discharge profiles at different speeds obtained at room temperature for LiCo0 2 and LiFeP0 4 batteries.
- Figure 2 represents charge and discharge profiles at different regimes obtained at room temperature for batteries containing a mixture composed of 72% LiCo0 2 and 28% LiFeP0 4 .
- Figure 3 represents the evolution of the capacity supplied as a function of the intensity of the charge and discharge current for batteries containing
- LiCo0 2 between 4.1 and 3 V
- LiFeP0 4 between 4.1 and 2.5 V
- a mixture composed of 72% LiCo0 2 and 28% of LiFeP0 4 between 4.1 and 2.5 V and between 4.1 and
- Figure 4 shows the charge and discharge profiles of batteries containing LiMn 2 0 4 on the one hand and a mixture of LiMn 2 0 4 and LiFeP0 4 on the other hand.
- the electrodes containing one or mixtures of the two families of the aforementioned electrode materials, double oxides or double phosphates can function advantageously, whether in terms of capacity and available power. This behavior is unexpected with regard to the dilution and the decrease in the contacts between grains of phosphate that these mixtures imply.
- the grains of phosphate-based materials are very poorly conductive and cannot ensure a continuum of high electronic conductivity in the mixture, a condition necessary for rapid electrochemical kinetics.
- the conductive coating possibly deposited on the surface of the phosphate grains which is the subject of US Pat. No.
- Cathode composed of a mixture of LiFeP0 4 and LiCo0 2
- the cathodes consist of a mixture of active material, carbon black, and a binding agent (PVDF in solution in N-methyl pyrolidone) in the proportions 85: 5: 10.
- PVDF in solution in N-methyl pyrolidone
- the composite is spread on a collector aluminum current. After drying, 1.3 cm electrodes with a capacity of about 1.6 mAh are cut out with a cookie cutter.
- the batteries are assembled in a glove box, under an inert atmosphere.
- the measurements were carried out in an electrolyte containing LiC10 1M in a mixture EC: DMC 1: 1.
- the anode consists of lithium.
- the tests are carried out at room temperature.
- the batteries containing LiCo0 2 alone as well as the mixture were charged in galvanostatic mode up to 4.1 V with maintenance of the potential until the current is less than 25 micro-amperes.
- the battery containing LiFeP0 4 was generally charged up to 4.1 V except for the 5C regime where the maintenance in potential was imposed.
- the cathodes consist of a mixture of active material, carbon black, and a binding agent (PVDF in solution in N-methyl pyrolidone) in the proportions 90: 3: 7.
- the composite is spread on a collector aluminum current. After drying, electrodes of 1.3 cm and about 11 mg of active material are cut out with a cookie cutter.
- the batteries are assembled in a glove box, under an inert atmosphere.
- the measurements were carried out in an electrolyte containing LiC10 4 1M in a mixture EC: DMC 1: 1.
- the anode consists of lithium. The tests are carried out at room temperature.
- the batteries were charged up to 4.2 V and discharged up to 2.5 V at a current of 400 ⁇ A.
- FIG. 4 shows the charge and discharge profiles of LiMn 2 0 4 alone and of the LiMn 2 0 4 LiFeP0 4 mixture.
- the activity of LiFeP0 4 is located between the two pairs of manganese spinel and is clearly differentiated from the two plateaus of the latter.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02708069A EP1384276A2 (fr) | 2001-03-13 | 2002-03-13 | Compositions cathodiques et leurs utilisations, notamment dans les generateurs electrochimiques |
US10/275,284 US20040029011A1 (en) | 2001-03-13 | 2002-03-13 | Cathode compositions and use thereof, particularly in electrochemical generators |
AU2002242525A AU2002242525A1 (en) | 2001-03-13 | 2002-03-13 | Cathode compositions and use thereof, particularly in electrochemical generators |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2,340,798 | 2001-03-13 | ||
CA002340798A CA2340798A1 (fr) | 2001-03-13 | 2001-03-13 | Compositions cathodiques et leurs utilisations, notamment dans les generateurs electrochimiques |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002073716A2 true WO2002073716A2 (fr) | 2002-09-19 |
WO2002073716A3 WO2002073716A3 (fr) | 2003-09-25 |
Family
ID=4168594
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CA2002/000341 WO2002073716A2 (fr) | 2001-03-13 | 2002-03-13 | Compositions cathodiques et leurs utilisations, notamment dans les generateurs electrochimiques |
Country Status (5)
Country | Link |
---|---|
US (1) | US20040029011A1 (fr) |
EP (1) | EP1384276A2 (fr) |
AU (1) | AU2002242525A1 (fr) |
CA (1) | CA2340798A1 (fr) |
WO (1) | WO2002073716A2 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2864349A1 (fr) * | 2003-12-23 | 2005-06-24 | Cit Alcatel | Matiere electrochimiquement active pour electrode positive de generateur electrochimique rechargeable au lithium |
EP1625596A2 (fr) * | 2003-04-03 | 2006-02-15 | Valence Technology, Inc. | Electrodes comportant des particules actives melangees |
US7632317B2 (en) | 2002-11-04 | 2009-12-15 | Quallion Llc | Method for making a battery |
US8524397B1 (en) | 2004-11-08 | 2013-09-03 | Quallion Llc | Battery having high rate and high capacity capabilities |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070141468A1 (en) * | 2003-04-03 | 2007-06-21 | Jeremy Barker | Electrodes Comprising Mixed Active Particles |
FR2872633B1 (fr) * | 2004-07-02 | 2006-09-15 | Commissariat Energie Atomique | Procede de charge d'un accumulateur lithium-ion a electrode negative |
US20070057228A1 (en) * | 2005-09-15 | 2007-03-15 | T/J Technologies, Inc. | High performance composite electrode materials |
US20070111099A1 (en) * | 2005-11-15 | 2007-05-17 | Nanjundaswamy Kirakodu S | Primary lithium ion electrochemical cells |
JP5250948B2 (ja) * | 2006-07-28 | 2013-07-31 | 株式会社Gsユアサ | 非水電解質二次電池 |
KR101175375B1 (ko) * | 2006-09-14 | 2012-08-20 | 주식회사 엘지화학 | 리튬 이차 전지 및 그 제조방법 |
US8197719B2 (en) * | 2006-11-17 | 2012-06-12 | American Lithium Energy Corp. | Electroactive agglomerated particles |
US20080240480A1 (en) * | 2007-03-26 | 2008-10-02 | Pinnell Leslie J | Secondary Batteries for Hearing Aids |
US20080241645A1 (en) * | 2007-03-26 | 2008-10-02 | Pinnell Leslie J | Lithium ion secondary batteries |
US20080248375A1 (en) * | 2007-03-26 | 2008-10-09 | Cintra George M | Lithium secondary batteries |
US8052897B2 (en) * | 2008-02-29 | 2011-11-08 | Byd Company Limited | Composite compound with mixed crystalline structure |
US8062559B2 (en) * | 2008-02-29 | 2011-11-22 | Byd Company Limited | Composite compound with mixed crystalline structure |
US8057711B2 (en) * | 2008-02-29 | 2011-11-15 | Byd Company Limited | Composite compound with mixed crystalline structure |
US8062560B2 (en) * | 2008-02-29 | 2011-11-22 | Byd Company Limited | Composite compound with mixed crystalline structure |
US20090220858A1 (en) * | 2008-02-29 | 2009-09-03 | Byd Company Limited | Composite Compound With Mixed Crystalline Structure |
JP5244966B2 (ja) * | 2008-03-26 | 2013-07-24 | ビーワイディー カンパニー リミテッド | リチウム電池用正極材料 |
US20090297950A1 (en) * | 2008-05-30 | 2009-12-03 | Dongguan Amperex Technology Co., Ltd. | Lithium battery |
JP5376894B2 (ja) | 2008-10-20 | 2013-12-25 | 古河電池株式会社 | オリビン構造を有する多元系リン酸型リチウム化合物粒子、その製造方法及びこれを正極材料に用いたリチウム二次電池 |
US9231252B2 (en) | 2009-08-09 | 2016-01-05 | American Lithium Energy Corp. | Electroactive particles, and electrodes and batteries comprising the same |
JP2013004421A (ja) * | 2011-06-20 | 2013-01-07 | Namics Corp | リチウムイオン二次電池 |
EP2629353A1 (fr) * | 2012-02-17 | 2013-08-21 | Belenos Clean Power Holding AG | Batterie secondaire non aqueuse dotée d'un matériau actif à cathode mélangée |
KR101560862B1 (ko) * | 2012-08-02 | 2015-10-15 | 주식회사 엘지화학 | 출력 특성이 향상된 혼합 양극활물질 및 이를 포함하는 리튬이차전지 |
CN103904329B (zh) * | 2012-12-27 | 2016-12-28 | 清华大学 | 锂离子电池 |
Citations (6)
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EP0680106A1 (fr) * | 1993-11-02 | 1995-11-02 | Mitsubishi Cable Industries, Ltd. | Materiau d'electrode positive pour pile au lithium et procede de production |
EP1150368A2 (fr) * | 2000-04-25 | 2001-10-31 | Sony Corporation | Matière active positive pour électrode et pile à électrolyte non aqueux |
EP1150367A2 (fr) * | 2000-04-25 | 2001-10-31 | Sony Corporation | Matière active positive et cellule à électrolyte non aqueux |
WO2001086741A1 (fr) * | 2000-05-11 | 2001-11-15 | Telcordia Technologies, Inc. | Batterie rechargeable comprenant une anode inorganique |
WO2002027823A1 (fr) * | 2000-09-26 | 2002-04-04 | HYDRO-QUéBEC | Procede de synthese de materiaux redox enrobes de carbone a taille controlee |
JP2002279989A (ja) * | 2001-03-16 | 2002-09-27 | Sony Corp | 電 池 |
Family Cites Families (2)
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DE69404602T2 (de) * | 1993-10-07 | 1998-01-29 | Matsushita Electric Ind Co Ltd | Herstellungsverfahren eines Separators für eine Lithium-Sekundärbatterie und eine Lithium-Sekundärbatterie mit organischem Elektrolyt, die einen solchen Separator verwendet |
US5910382A (en) * | 1996-04-23 | 1999-06-08 | Board Of Regents, University Of Texas Systems | Cathode materials for secondary (rechargeable) lithium batteries |
-
2001
- 2001-03-13 CA CA002340798A patent/CA2340798A1/fr not_active Abandoned
-
2002
- 2002-03-13 US US10/275,284 patent/US20040029011A1/en not_active Abandoned
- 2002-03-13 EP EP02708069A patent/EP1384276A2/fr not_active Withdrawn
- 2002-03-13 WO PCT/CA2002/000341 patent/WO2002073716A2/fr not_active Application Discontinuation
- 2002-03-13 AU AU2002242525A patent/AU2002242525A1/en not_active Abandoned
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0680106A1 (fr) * | 1993-11-02 | 1995-11-02 | Mitsubishi Cable Industries, Ltd. | Materiau d'electrode positive pour pile au lithium et procede de production |
EP1150368A2 (fr) * | 2000-04-25 | 2001-10-31 | Sony Corporation | Matière active positive pour électrode et pile à électrolyte non aqueux |
EP1150367A2 (fr) * | 2000-04-25 | 2001-10-31 | Sony Corporation | Matière active positive et cellule à électrolyte non aqueux |
WO2001086741A1 (fr) * | 2000-05-11 | 2001-11-15 | Telcordia Technologies, Inc. | Batterie rechargeable comprenant une anode inorganique |
WO2002027823A1 (fr) * | 2000-09-26 | 2002-04-04 | HYDRO-QUéBEC | Procede de synthese de materiaux redox enrobes de carbone a taille controlee |
JP2002279989A (ja) * | 2001-03-16 | 2002-09-27 | Sony Corp | 電 池 |
Non-Patent Citations (1)
Title |
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PATENT ABSTRACTS OF JAPAN vol. 2003, no. 01, 14 janvier 2003 (2003-01-14) -& JP 2002 279989 A (SONY CORP), 27 septembre 2002 (2002-09-27) * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7632317B2 (en) | 2002-11-04 | 2009-12-15 | Quallion Llc | Method for making a battery |
EP1625596A2 (fr) * | 2003-04-03 | 2006-02-15 | Valence Technology, Inc. | Electrodes comportant des particules actives melangees |
EP1625596A4 (fr) * | 2003-04-03 | 2010-01-06 | Valence Technology Inc | Electrodes comportant des particules actives melangees |
FR2864349A1 (fr) * | 2003-12-23 | 2005-06-24 | Cit Alcatel | Matiere electrochimiquement active pour electrode positive de generateur electrochimique rechargeable au lithium |
EP1548861A1 (fr) * | 2003-12-23 | 2005-06-29 | Saft | Matière électrochimiquement active pour électrode positive de générateur électrochimique rechargeable au lithium |
US8524397B1 (en) | 2004-11-08 | 2013-09-03 | Quallion Llc | Battery having high rate and high capacity capabilities |
Also Published As
Publication number | Publication date |
---|---|
EP1384276A2 (fr) | 2004-01-28 |
WO2002073716A3 (fr) | 2003-09-25 |
AU2002242525A1 (en) | 2002-09-24 |
CA2340798A1 (fr) | 2002-09-13 |
US20040029011A1 (en) | 2004-02-12 |
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