WO2002082571A1 - Piles electrochimiques et leur procede de fabrication - Google Patents

Piles electrochimiques et leur procede de fabrication Download PDF

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Publication number
WO2002082571A1
WO2002082571A1 PCT/EP2001/004291 EP0104291W WO02082571A1 WO 2002082571 A1 WO2002082571 A1 WO 2002082571A1 EP 0104291 W EP0104291 W EP 0104291W WO 02082571 A1 WO02082571 A1 WO 02082571A1
Authority
WO
WIPO (PCT)
Prior art keywords
vdf
cross
linking
binder
film
Prior art date
Application number
PCT/EP2001/004291
Other languages
English (en)
Inventor
Michel Coulon
Pierre-Yves Silvert
Josiane Irissin-Mangata
Bruno Ameduri
Original Assignee
Le Carbone Lorraine
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Le Carbone Lorraine filed Critical Le Carbone Lorraine
Priority to PCT/EP2001/004291 priority Critical patent/WO2002082571A1/fr
Priority to AU2002325211A priority patent/AU2002325211A1/en
Priority to PCT/EP2002/005209 priority patent/WO2002101865A2/fr
Publication of WO2002082571A1 publication Critical patent/WO2002082571A1/fr

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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to electrochemical cells with alkaline ion chemistry, such as lithium ion chemistry, and polymer type technology.
  • the invention relates more particularly to secondary batteries comprising polymer binders.
  • Electrochemical cells with alkaline ion chemistry comprise several layers including a positive collector (C+), a positive electrode (E+), a separator (S), a negative electrode (E-) and a.negative collector (C-).
  • a positive collector C+
  • E+ positive electrode
  • S separator
  • E- negative electrode
  • C- negative collector
  • C- negative collector
  • Different basic combinations of layers, known as cells, are possible, such as the basic unit cells (C+/E+/S/E-/C-) and bicells (C+/E+/S/E-/C-/E-/S/E+/C+). These cells may be connected in series, in parallel, or a combination of the two, and mounted in a pack to form batteries having the designed voltage and charge capacity.
  • Liquid electrolyte a unit cell is obtained by stacking the various layers upon each other, winding the stack so obtained, inserting the wound stack in a can and filling the can with an electrolyte.
  • the confinement provided by the winding and packing steps keeps the layers together and exerts sufficient pressure to ensure adequate contact and proper working of the cell.
  • the layers of the stack are welded to each other by a sequence of lamination steps. That technology is termed “Plastic” when the polymer has plastic properties.
  • the separator is a polymer impregnated with an electrolyte. That technology has a number of benefits because the stacks can be packaged in light and soft plastic envelopes as there is no longer any need to exert pressure on the stacks. Hence it is possible to produce light and thin batteries suitable for the electric supply of portable devices, such as mobile phones, notebook computers, camcorders, etc.
  • the stacking of the layers is obtained by laminating continuous films at high speed.
  • the quality and consistency of the sequence of lamination steps are very critical since one single defect in the adhesion between two layers is likely to cause the final waste of the entire battery, which may contain up to 100 layers.
  • handling the films automatically at high speed subjects them to high stresses which these must withstand without being damaged.
  • the binder generally used for Li-ion batteries is polyvinylidene fluoride (PVDF). Whereas homopolymers are used in the liquid electrolyte technology, these are not fit to the plastic technology since they make films too brittle to withstand the stresses generated by the process. In the latter case vinylidene fluoride/hexafluoropropylene (VDF/HFP) copolymers are usually preferred because they can be better plasticized. The higher the HFP contents of the VDF/HFP copolymers the more efficient the plasticizing. The higher the FHP contents the easier the lamination of the films. In particular, U.S. Patent No. 5,418,091 recommends using a VDF:FHP ratio equal to 88:12. However, the batteries using such copolymers display an irreversible decrease of their capacity (known as "fading") together with an increase of their electrical impedance that are more rapid the higher the temperature. Summary of the invention
  • the present invention is directed to a polymer alkaline ion electrochemical cell with improved thermal and chemical stability and to a method of fabricating the same.
  • the present invention is also directed to a film suitable for making electrochemical cells and to a method for making the same.
  • the present invention is further directed to a secondary battery including at least one such electrochemical cell or one such film and to a method for making the same.
  • the invention provides an alkaline ion polymer electrochemical cell comprising a positive collector, a negative collector, a positive electrode, a negative electrode, a separator and an electrolyte, said separator comprising a binder and a filler, each of said electrodes comprising a binder, wherein at least one of said binders is a VDF/HFP copolymer which has been made insoluble in said electrolyte.
  • the invention provides a film which comprises a binder and which is suitable for making an alkaline ion polymer electrochemical cell comprising an electrolyte, wherein said binder is a VDF/HFP copolymer which can be made insoluble in said electrolyte by a subsequent heat treatment.
  • the invention provides a method for making a film comprising a binder, said film being suitable for making alkaline ion polymer electrochemical cells comprising an electrolyte, wherein said binder is a VDF/HFP copolymer which can be made insoluble in said electrolyte by a subsequent heat treatment.
  • the invention provides a method of making an alkaline ion electrochemical cell comprising a positive collector, a negative collector, a positive electrode, a negative electrode, a separator and an electrolyte, said separator comprising a binder and a filler, each of said electrodes comprising a binder, at least one of said binders being a VDF/HFP copolymer, said method including cross- linking said VDF/HFP copolymer by a heat treatment so as to make it insoluble in said electrolyte.
  • the VDF/HFP copolymers indeed are partially soluble in the electrolytes most commonly used in Li-ion polymer cells, which contain e.g.
  • organic carbonates such as dimethyl carbonate (DMC) or gamma butyrolactone.
  • DMC dimethyl carbonate
  • gamma butyrolactone gamma butyrolactone
  • the binders may be made insoluble by any known means.
  • the binders are made insoluble in the electrolyte by thermally cross-linking the binders.
  • said cross-linking is effected by a cross-linking agent capable of making the binders insoluble in said solvents after a heat treatment.
  • cross-linking agent had to be compatible with the method of making the cells and with the harsh working conditions of the latter.
  • cross-linking agents that do not contain chemical compounds capable of perturbing the electrochemical functioning of the cells whose constituents are subjected to highly reducing or oxidizing conditions.
  • Said cross-linking agent advantageously are an aliphatic or a cycloaliphatic diamine or branched diamine, or a mixture thereof.
  • the applicant obtained excellent results by using one of 2-butyl-2-ethyl-l,5-pentanediamine and C,C,C-trimethyl hexane diamine. Mixtures of the latter diamines may also be used.
  • Figure 1 exhibits the results of cycling tests performed on lithium ion electrochemical cells of prior art and of the invention. Detailed description of the invention
  • An alkaline ion polymer electrochemical cell comprises at least one positive collector, one negative collector, one positive electrode, one negative electrode, one separator and an electrolyte, said separator comprising a binder and a filler, each of said electrodes comprising a binder, wherein at least one of said binders is a VDF/HFP copolymer which has been made insoluble in said electrolyte.
  • All said separator and electrodes may comprise VDF/HFP copolymer which has been made insoluble in said electrolyte.
  • the separator is impregnated with a fluid electrolyte containing an organic solvent and an alkaline salt (such as LiClO , LiPF 6 or LiBF ).
  • Said electrolyte typically contains an organic carbonate, such as dimethyl carbonate or gamma butyrolactone.
  • the filler (or "filler material”) typically used for the separator is any compound that can increase the mechanical strength of the separator, such as silica, alumina or calcium silicate.
  • the electrodes also comprise a filler, which is usually different from that used for the separators and which includes at least one active material powder and at least one electrically conducting material, such as carbon black.
  • the collectors are typically in the form of grids.
  • Said electrodes and said separator may comprise a film comprising a binder which is a VDF/HFP copolymer and which has been made insoluble in said electrolyte.
  • Said electrochemical cell is typically a lithium ion electrochemical cell.
  • An alkaline ion electrochemical cell according to the invention may be fabricated by a method including cross-linking so as to make the binders insoluble in said electrolyte.
  • the cross-linking agent is an aliphatic or a cycloaliphatic diamine or branched diamine such as 2-butyl-2-ethyl-l,5-pentanediamine or C,C,C-trimethyl hexane diamine, for these compounds were found to greatly improve the retaining of the capacity of the cells upon cycling.
  • These compounds are also advantageous as they do not require using any accelerator nor extracting the plasticizer prior to being contacted with the polymer, hence avoiding adding several steps to the process of making the cells.
  • Said cross-linking is preferably effected by using an amount of one said diarnines, or of a mixture thereof, between 0.5 and 20 parts by weight per 100 parts of said
  • VDF/HFP copolymer and more preferably between 1 and 10 parts by weight per 100 parts of said VDF/HFP copolymer. These amounts are typically added to the slurries used for making the films - typically by solvent casting - which are used for making the electrodes and separators.
  • the weight ratio of VDF to HFP in said VDF/HFP copolymer is preferably between
  • the binders may be plastic or may be made plastic by any known means, preferably by plasticizing said binders with a plasticizer.
  • Said plasticizer is preferably propylene carbonate or a mixture of propylene carbonate and dibutyl phtalate.
  • Cross-linking may be effected by a process comprising heat treating a stack of films or a cell, at a temperature between 120° and 220°C, and preferably between 120° and 160°C.
  • a film according to the invention may be made by a method including : - preparing a slurry by mixing at least a binder, a cross-linking agent, a filler and a solvent together, the solvent typically being acetone ; - forming a film by shaping the slurry, typically by solvent casting in the form of a strip ;
  • said binder is a VDF/HFP copolymer which can be made insoluble in the electrolyte used in the cell.
  • plasticizer may be added to said slurry during its preparation and the method further includes a step for eliminating said plasticizer.
  • the method for eliminating the plasticizer depends on its vapor pressure.
  • the vapor pressure of the plasticizer is low, the latter is usually eliminated by extraction in a solvent.
  • the vapor pressure of the plasticizer is high, the latter is usually eliminated by heating the film under vacuum.
  • the elimination step may advantageously be merged with the heat treatment step provided that the former thus comprises heating the film at a temperature between 120° and 220°C, and preferably between 120° and 160°C, for at least about 10 to 20 minutes.
  • the heat treatment may also advantageously include the drying operation.
  • an alkaline ion electrochemical cell according to the invention may be made by a method including :
  • each one of these components being made by a process including preparing a slurry by mixing at least a binder, a cross-linking agent, a filler, if necessary a plasticizer, and a solvent (such as acetone) together, forming a film by shaping the slurry, typically by solvent casting in the form of a strip, and drying said film, said binder being a VDF/HFP copolymer which can be made insoluble in the electrolyte used in the cell ;
  • the elimination step may advantageously be merged with the heat treatment step if the vapor pressure of the plasticizer is high and if the former thus comprises heating the laminate at a temperature between 125 and 220°C, and preferably between 120° and 160°C, for at least about 10 to 20 minutes.
  • the heat treatments also favor the removal of moisture from the films or laminate and stabilize them.
  • Example 1 corresponds to the separators most widely used to date in the secondary battery technology.
  • the filler (which is typically silica, alumina or calcium silicate) has been omitted in order to make the results of the different treatments on the polymer more visible.
  • Kynarflex 2801 ® as binder and propylene carbonate (PC) as plasticizer.
  • the separators were made by using the following steps : - a slurry was made by mixing a binder (which was a Kynarflex 2801 ® in all cases), a plasticizer (which was PC in all cases), a cross-linking agent (except in Example 1) and acetone ⁇
  • the film was laminated at 130°C so as to simulate the forming of a laminate ;
  • Table I gives the composition of separators, the duration and temperature of the heat treatment performed on the separators after the solvent casting step and the results obtained for the solubility and "reswelling by PC” tests for each of these examples.
  • Letter A, B and C designate bisphenol AF, C,C,C-trimethyl hexane and 2-butyl-2- ethyl-1 ,5-pentanediamine, respectively.
  • cross-linking agent A does not make the film insoluble in acetone in the range of conditions that were used (as indicated in Table I), whereas C,C,C-trimethyl hexane (cross-linking agent B) and 2-butyl-2- ethyl-l,5-pentanediamine (cross-linking agent C) do make the films insoluble in acetone.
  • compositions provide an important reswelling of the separators by PC, which is an indication of a suitable ionic conductivity.
  • a cell was formed by making a laminate composed of : - Two separator films, each 20 ⁇ m thick, cast from a slurry containing 8 parts by weight of fumed silica (as filler material), 13 parts by weight of PC, 10 parts by weight of Kynarflex 2801 ® and 70 parts by weight of acetone ;
  • One anodic (i.e. negative) film was cast from a slurry containing 12 parts by weight of PC, 6 parts by weight of Kynarflex 2801 ®, 43 parts by weight of artificial graphite powder and 1.5 part by weight of carbon black (to improve electrical conductivity). After casting and drying the film was laminated on one side with a copper grid current collector and on the other side with a separator film, thus producing an "anodic" laminate ;
  • Two cathodic (i.e. positive) films were cast from a slurry containing 44 parts by weight of LiCoO 2 powder, 8 parts by weight of PC, 3 parts by weight of carbon black and 5 parts of Kynarflex 2801 ®. After casting and drying, the two films were laminated on both sides of an aluminium current collector grid and, in a subsequent step, with a separator on one side of the laminate, thus producing a "cathodic" laminate.
  • a final laminate was obtained by laminating anodic and cathodic laminates, the separator side of each laminate being in contact.
  • the final laminate was heated under vacuum at 125°C, impregnated by a solution of LiPF 6 1M in a mixture of 1 ethylene carbonate / 1 dimethyl carbonate, and then sealed in a bag.
  • the steps of impregnating and packaging were executed in a glove box under a dry and inert atmosphere.
  • the cell so obtained was cycled 50 times under a C/5 regime in an oven at 70°C.
  • the discharge capacities are shown in Figure 1 as a function of the cycle number and rated as a percentage of the initial discharge capacity.
  • Example 11 A second cell was made as in Example 10 except that 0.2 parts by weight of C,C,C- trimethyl hexane was added in the slurry of the separator and that 0.1 part by weight of diamine was added to the slurry of the anode and to the slurry of the cathode.
  • the results of the cycling of this cell which are exhibited in Figure 1, show that the use of a cross-linking agent capable of making the binder of the separator and electrodes insoluble in the electrolyte significantly reduces the fading of the capacity of the cell.

Abstract

Cette invention concerne une pile électrochimique d'ions de base polymère dotée d'une stabilité thermique et chimique, ainsi que son procédé de fabrication. La pile de ladite invention comprend un collecteur positif, un collecteur négatif, une électrode positive, une électrode négative, un séparateur et un électrolyte, ledit séparateur comportant un liant et une charge et chacune desdites électrodes renfermant un liant. La pile électrochimique est caractérisée en ce qu'au moins un desdits liants est un copolymère de fluorure de vinylidène et d'hexafluoropropylène (VDF/HFP), qu'on a rendu insoluble dans ledit électrolyte en utilisant un traitement thermique. Dans un mode de réalisation préféré, ce copolymère est rendu insoluble par réticulation.
PCT/EP2001/004291 2001-04-03 2001-04-03 Piles electrochimiques et leur procede de fabrication WO2002082571A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/EP2001/004291 WO2002082571A1 (fr) 2001-04-03 2001-04-03 Piles electrochimiques et leur procede de fabrication
AU2002325211A AU2002325211A1 (en) 2001-04-03 2002-03-28 Electrochemical cells and method of making the same
PCT/EP2002/005209 WO2002101865A2 (fr) 2001-04-03 2002-03-28 Electrochemical cells and method of making the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2001/004291 WO2002082571A1 (fr) 2001-04-03 2001-04-03 Piles electrochimiques et leur procede de fabrication

Publications (1)

Publication Number Publication Date
WO2002082571A1 true WO2002082571A1 (fr) 2002-10-17

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PCT/EP2001/004291 WO2002082571A1 (fr) 2001-04-03 2001-04-03 Piles electrochimiques et leur procede de fabrication
PCT/EP2002/005209 WO2002101865A2 (fr) 2001-04-03 2002-03-28 Electrochemical cells and method of making the same

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PCT/EP2002/005209 WO2002101865A2 (fr) 2001-04-03 2002-03-28 Electrochemical cells and method of making the same

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WO (2) WO2002082571A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7490160B2 (en) 2003-07-28 2009-02-10 Samsung Electronics Co., Ltd. Method of efficiently transmitting/receiving data using transport layer in a mobile ad hoc network, and network device using the method
US9579320B2 (en) 2008-04-16 2017-02-28 Portola Pharmaceuticals, Inc. Inhibitors of syk and JAK protein kinases
CN114315603A (zh) * 2020-09-30 2022-04-12 上海凯赛生物技术股份有限公司 一种1,5-戊二胺的提取方法及其所得的1,5-戊二胺产品

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090111012A1 (en) * 2007-10-31 2009-04-30 Sony Corporation Secondary battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0633618A1 (fr) * 1992-12-25 1995-01-11 TDK Corporation Element secondaire au lithium
EP0721230A1 (fr) * 1993-09-22 1996-07-10 Kanebo, Ltd. Element electrolytique organique
EP0851521A2 (fr) * 1996-12-26 1998-07-01 Mitsubishi Denki Kabushiki Kaisha Batterie secondaire à ions lithium
WO1999009604A1 (fr) * 1997-08-14 1999-02-25 Valence Technology, Inc. Cellules a ions de lithium a stabilite thermique accrue

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07296815A (ja) * 1994-04-28 1995-11-10 Sony Corp 非水電解液二次電池
JPH10112321A (ja) * 1996-10-07 1998-04-28 Sony Corp 非水電解液二次電池およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0633618A1 (fr) * 1992-12-25 1995-01-11 TDK Corporation Element secondaire au lithium
EP0721230A1 (fr) * 1993-09-22 1996-07-10 Kanebo, Ltd. Element electrolytique organique
EP0851521A2 (fr) * 1996-12-26 1998-07-01 Mitsubishi Denki Kabushiki Kaisha Batterie secondaire à ions lithium
WO1999009604A1 (fr) * 1997-08-14 1999-02-25 Valence Technology, Inc. Cellules a ions de lithium a stabilite thermique accrue

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7490160B2 (en) 2003-07-28 2009-02-10 Samsung Electronics Co., Ltd. Method of efficiently transmitting/receiving data using transport layer in a mobile ad hoc network, and network device using the method
US9579320B2 (en) 2008-04-16 2017-02-28 Portola Pharmaceuticals, Inc. Inhibitors of syk and JAK protein kinases
CN114315603A (zh) * 2020-09-30 2022-04-12 上海凯赛生物技术股份有限公司 一种1,5-戊二胺的提取方法及其所得的1,5-戊二胺产品
CN114315603B (zh) * 2020-09-30 2024-04-05 上海凯赛生物技术股份有限公司 一种1,5-戊二胺的提取方法及其所得的1,5-戊二胺产品

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WO2002101865A3 (fr) 2004-04-08
AU2002325211A1 (en) 2002-12-23
WO2002101865A2 (fr) 2002-12-19

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