EP2550695A1 - Pile bouton protégée contre les courts-circuits - Google Patents

Pile bouton protégée contre les courts-circuits

Info

Publication number
EP2550695A1
EP2550695A1 EP11708486A EP11708486A EP2550695A1 EP 2550695 A1 EP2550695 A1 EP 2550695A1 EP 11708486 A EP11708486 A EP 11708486A EP 11708486 A EP11708486 A EP 11708486A EP 2550695 A1 EP2550695 A1 EP 2550695A1
Authority
EP
European Patent Office
Prior art keywords
cover part
cup
separator
button cell
seal
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP11708486A
Other languages
German (de)
English (en)
Inventor
Rolf Brenner
Eduard Pytlik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
VARTA Microbattery GmbH
Original Assignee
VARTA Microbattery GmbH
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 VARTA Microbattery GmbH filed Critical VARTA Microbattery GmbH
Publication of EP2550695A1 publication Critical patent/EP2550695A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/147—Lids or covers
    • H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
    • H01M50/171—Lids or covers characterised by the methods of assembling casings with lids using adhesives or sealing agents
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/186—Sealing members characterised by the disposition of the sealing members
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H01M50/19—Sealing members characterised by the material
    • H01M50/193—Organic material
    • 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
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making
    • Y10T29/4911—Electric battery cell making including sealing

Definitions

  • the present invention relates to a button cell with a housing of a cup-shaped cup part and a cup-shaped cover part, which are spatially and electrically separated from each other by a film seal.
  • a positive and a negative electrode are arranged and between the electrodes, a separator which separates them.
  • Button cells usually have a housing of two Gehot endeavour puzzle, a cup part and a lid part, on. These can be made, for example, from nickel-plated deep-drawn sheet metal as punched drawing parts. Usually the cup part is positive and the lid part is negatively poled.
  • the housing can contain a wide variety of electrochemical systems, for example zinc / manganese dioxide, primary and secondary lithium systems or secondary systems such as nickel / cadmium or nickel / metal hydride.
  • cup part and lid part plastic ring serves as a rule at the same time as a seal and as an insulator, which separates the cup part spatially and electrically from the cover part.
  • button cells are known for example from DE 31 13309.
  • the sealing elements required for button cells are conventionally produced by injection molding, for example from polyamides.
  • the necessary injection tools are very expensive and expensive.
  • DE 19647593 describes the use of a sealing element which is produced by deep drawing from a film. From a heated film is pulled by means of a drawing die and a forming die under vacuum, a cup-shaped molding. As preferred film material polyamides are given. The deformation takes place, depending on the desired diameter / height ratio, in one or more stepped operations. In the bottom region of the cup-shaped molded part produced by deep-drawing then a punched out by means of a cutting punch and a cutting bush. The sealing element thus produced is mounted on a lid part, which can then be inserted into a cup part. Since such produced film seals have only very small thicknesses, the resulting button cells are capacity optimized. The use of foil seals offers clear advantages compared to the classic use of seals made of injection-molded parts.
  • the present invention is based on the development described in DE 19647593. Its task was to provide button cells, which are characterized by optimized capacity, a simple structure and an efficient separation of positive and negative electrode within the button cell housing.
  • buttons cell with the features of claim 1 and by the method having the features of claim 8.
  • Preferred embodiments of the button cell according to the invention are given in the dependent claims 2 to 7.
  • Preferred embodiments of the method according to the invention can be found in the dependent claims 9 or 10. The wording of all Claims are hereby incorporated by reference into the content of this specification.
  • a coin cell according to the invention comprises a cup-shaped cup part and a cup-shaped lid part.
  • the cup part comprises a first planar bottom region, which is followed by a jacket region extending up to a first cutting edge.
  • the cover part comprises a second planar bottom region, adjoined by a second jacket region extending up to a second cutting edge.
  • the cover part is inserted with the cutting edge first in the cup part and forms with this a closed housing.
  • the bottom portions of cup portion and lid portion are arranged parallel to each other in a ready-mounted button cell and form in use the top and bottom of the button cell, where usually the power is removed by a consumer.
  • the jacket areas form the side walls of the button cell.
  • Cup part and lid part are spatially and electrically separated by a seal. In addition to its insulating function, this seal usually also ensures that the housing is sealed liquid-tight lid part and cup part.
  • a positive and a negative electrode Inside the case are a positive and a negative electrode.
  • the positive electrode is in electrical contact with the flat bottom area of the cup part, the negative electrode with the flat bottom area of the lid part.
  • the positive and negative electrodes such as the cup part and the lid part must not touch each other directly.
  • a separator is positioned between the positive and the negative electrode, which separates them spatially.
  • the separator preferably forms a flat layer, which is aligned substantially parallel to the planar bottom regions of the cup and lid part, or comprises at least one such layer. The separator divides the interior of the housing into two compartments, in which the positive and the negative electrode are arranged separately from one another.
  • the separator used is preferably ion-permeable materials such as porous membranes made of plastic or nonwovens.
  • ion-permeable materials such as porous membranes made of plastic or nonwovens.
  • the person skilled in the corresponding button cell suitable separators materials are known.
  • the seal used in a button cell according to the invention is a film seal, as already mentioned at the outset.
  • a film seal should in particular be understood to mean a seal which is formed from a molded part produced by deep drawing from a plastic film, in particular such a seal as described in DE 19647593.
  • this foil seal surrounds the outside of the cover part in the jacket region in the manner of a sleeve, but at the same time has a circumferential section which is turned inwards around the cutting edge of the cover part.
  • the film seal preferably has a thickness of less than 0.15 mm, more preferably less than 0.1 mm.
  • the circumferential portion is turned so far inward that it forms a closed cavity together with the separator and the cover part, in which the negative electrode is arranged (in classical button cells, this cavity is formed only by the cover part and the separator).
  • buttons cells as they are known from the prior art, for example, from DE 102007003519, are usually just so far turned around the cutting edge of a cell cover around that the cut edge completely from the film is covered. This serves to avoid gas developments inside the housing.
  • the housing parts of button cells often consist of trimetal with the layer sequence nickel, steel and copper, with copper usually forms the inside of the button cell housing.
  • the comparatively base steel layer between the nickel and copper layers is freely accessible. This is where gassing phenomena are particularly frequent, as a result of which button cells can leak out and be irreparably damaged.
  • the film seal of a button cell according to the invention is generally dimensioned so that it can cover at least larger sections of the inside of the shell area of the cover part to a depth in which the separator is positioned or in preferred embodiments on the inner walls of the cover part is applied.
  • the film seal together with the separator thus ensures a complete and efficient separation of cathode and anode space. Short circuit problems within the button cell according to the invention are thereby largely excluded.
  • a button cell according to the invention is particularly preferably characterized in that the film seal surrounds the separator in an annular manner and exerts a radial pressure on it (variant A). Ideally, the film seal is in an elastically deformed, in particular an elastically stretched, state.
  • Such a condition can be achieved by suitably tuning the diameter and radius of the inwardly turned portion of the film seal to the diameter and radius of the separator annularly enclosed by it.
  • the section of the film seal that has been turned inwards can be thermally treated, for example, so that its throughput diameter / radius reduced by shrinkage compared to the diameter / radius of the outside of the cover part in the shell area enclosing part of the film seal.
  • diameter and radius of the folded-over section fall off after such a treatment, starting from the cut edge of the cover part in the direction of the bottom region of the cover part.
  • the diameter / radius of the separator is chosen to be sufficiently large, it can only be positioned with radial expansion and expansion of the folded section in the button cell. The radially expanded portion then exerts the mentioned radial pressure on the separator.
  • the separator is designed and positioned in the housing in such a way that it presses the film seal folded inwards radially against the inside of the cover part (variant B).
  • This variant can represent an extreme case of the mentioned radial widening of the folded portion (ie be an embodiment of variant A), but also be implemented completely independently thereof.
  • the separator of a button cell according to the invention is in a preferred embodiment disk-like, in particular as a circular disc formed.
  • the edges of the disc can radially expand the foil seal and / or press it against the inside of the lid part.
  • the radius of the disc preferably corresponds substantially to the inner radius of the cover part in the jacket region or even exceeds this, preferably by between 1% and 25%.
  • the radius of the disc is preferably at least 90% of the inner radius of the lid part and is at most 25% higher.
  • the section of the film seal folded inwards has at least one partial area in which its radius is smaller than the maximum radius of the separator.
  • the separator may be formed cup-shaped with a flat, designed as a disc base and an adjoining, preferably aligned perpendicular to the base peripheral edge region.
  • the opening edge of the cup, in a button cell according to the invention preferably points in the direction of the bottom region of the cup part, while the base surface is preferably aligned parallel to the flat bottom and top region of the cup and lid part.
  • Such a separator preferably has its maximum radius in the region of the peripheral edge region.
  • the radius of the base preferably corresponds substantially to the inner radius of the cover part in the jacket area.
  • the peripheral edge region is preferably flat on the inside of the lid and overlaps there with the folded portion of the film seal.
  • Such a cup-shaped separator is formed, for example, by using a separator disk whose radius clearly exceeds the inner radius of the cover part and whose edge region correspondingly folds counter to the insertion direction when the separator is pushed into the cover part.
  • the radius of the base surface preferably undershoots the inner radius of the cover part in the jacket region.
  • the cut edge of the lid part preferably sits in a button cell according to the invention in the flat bottom area or on the bottom of the cup part.
  • a support ring is conceivable, for example, to prevent damage to the film seal at the cutting edge of the cover part.
  • the film seal is preferably a seal made of a thermoplastic film, in particular of a material such as polyamide or polyetheretherketone (PEEK). With regard to other preferred features of the film seal, reference is made to the already mentioned DE 102007003519 and DE 19647593.
  • the method according to the invention for the production of button cells is used in particular for the production of button cells, as described above.
  • the negative electrode material is a hydrogen storage alloy, such as an AB 5 alloy
  • the positive electrode material is nickel hydroxide.
  • the turning over of the cut edge of the lid part projecting portion of the film seal around the cut edge of the lid part around inside the lid part can basically be done as described in DE 102007003519, so for example by means of a heated punch.
  • the portion to be folded is preferably heated so high that a shrinkage occurs and its radius relative to the radius of the outside of the cover part in the shell area enclosing part of the film seal decreases.
  • the size of the separator can be chosen such that it presses the folded portion of the film seal radially to the inside of the lid part after its positioning in the housing and / or the portion of the film seal is expanded so that it is a radial pressure on the Separator exercises.
  • the method according to the invention may also comprise further steps, for example the metering in of electrolyte, which, however, has nothing to do with the essence of the present invention.
  • the methods according to the invention and the compact batteries according to the invention will be explained in more detail with reference to the drawings, in which the objects according to the invention are shown schematically and which are described below. It should be emphasized at this point that all facultative aspects of the compact batteries according to the invention or the methods according to the invention described in the present application can each be implemented alone or in combination with one or more of the further facultative aspects described in one embodiment of the invention.
  • the following description of preferred embodiments is merely for the purpose of illustrating and understanding the invention and is in no way limiting.
  • Fig. 1 shows in cross section a preferred embodiment of a button cell 100 according to the invention (schematic representation).
  • a bowl-shaped lid part 101 is inserted into a cup-shaped cup part 102.
  • the cover part 101 has a flat bottom portion 103 and a up to a cutting edge 104 extending shell area 105.
  • the housing cup 102 has the flat bottom portion 106 and the shell portion 107. Whose upper part with the cutting edge 108 is flanged inwards, this ensures the cohesion of cup portion 102 and lid portion 101.
  • the film seal 109 is arranged between the cup portion 102 and the lid portion 101. This is folded around the cutting edge 104 of the cover part 101 into the interior of the cover part and is located on the inside in the jacket portion 105 at.
  • the separator 110 which is also cup-shaped.
  • the separator 110 has a base formed as a circular disc and an adjoining, substantially perpendicular to the base aligned peripheral edge region. This edge region presses the foil seal 109, which has been wrapped around the cutting edge 104 of the lid part 101 in its interior, against the inside of the lid part.
  • the described button cell 100 is thus an embodiment according to the above variant B.
  • the separator 110 separates the electrodes 111 and 112 from each other.
  • the electrode 112 is the positive electrode
  • the electrode 111 is the negative electrode.
  • a contact spring 113 is arranged in order to be able to compensate for any changes in volume of the electrodes that may occur.
  • the separator 110, the foil seal 109, and the bottom portion 106 of the cell cup define a sealed cavity in which the positive electrode 112 is disposed. This is cleanly separated from the anode compartment, so a short circuit is almost impossible.
  • Fig. 2 shows in cross-section a preferred embodiment of a button cell 200 according to the invention (schematic representation).
  • a cup-shaped lid part 201 is inserted into a cup-shaped cup part 202.
  • the cover part 201 has a flat bottom portion 203 and a up to a cutting edge 204 extending shell area 205.
  • the housing cup 202 has the planar bottom region 206 and the jacket region 207. Whose upper part with the cutting edge 208 is flanged inwardly, this ensures the cohesion of cup portion 202 and lid portion 201.
  • the film seal 209 is arranged between the cup portion 202 and the lid portion 201. This is turned around the cutting edge 204 of the cover part 201 around inside the lid part.
  • the separator 210 has one as a circular Washer formed base and an adjoining, substantially perpendicular to the base aligned peripheral edge region. This edge region partially overlaps with the film seal 209 wrapped around the cutting edge 204 of the cover part 201 in its interior, which exerts a radial pressure on it. Due to its diameter, the separator 210 could only be positioned in the cover 201 with a radial widening of the section of the film seal 209 which constricted in the direction of the bottom 203.
  • the inwardly folded portion is correspondingly at least in the area in which it overlaps with the edge region of the separator, under tension.
  • the described button cell 200 is thus an embodiment according to the above variant A.
  • the separator 210 separates the electrodes 211 and 212 from each other.
  • the electrode 212 is the positive electrode
  • the electrode 211 is the negative electrode.
  • a contact spring 213 is arranged in order to compensate for any changes in volume of the electrodes may occur.
  • the separator 210, the foil seal 209, and the bottom portion 206 of the cell cup define a sealed cavity in which the positive electrode 212 is disposed. This is cleanly separated from the anode compartment, so short-circuiting is almost impossible.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

L'invention concerne une pile bouton dotée d'un boîtier composé d'une partie godet et d'une partie couvercle qui présentent respectivement une zone de fond et une zone extérieure s'y raccordant et s'étendant jusqu'à une première arête de coupe. Une électrode positive et une électrode négative, séparées par un séparateur, sont disposées dans le boîtier. La partie godet et la partie couvercle sont spatialement et électriquement séparées l'une de l'autre par une garniture d'étanchéité pelliculaire, la garniture d'étanchéité pelliculaire entourant le côté extérieur de la partie couvercle dans la zone extérieure à la manière d'une manchette. La garniture d'étanchéité pelliculaire forme conjointement avec le séparateur et la partie couvercle une cavité fermée dans laquelle est disposée l'électrode négative. L'invention concerne également un procédé permettant de fabriquer de telles piles boutons.
EP11708486A 2010-03-22 2011-03-17 Pile bouton protégée contre les courts-circuits Withdrawn EP2550695A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010012977A DE102010012977A1 (de) 2010-03-22 2010-03-22 Gegen Kurzschluss gesicherte Knopfzelle
PCT/EP2011/054028 WO2011117132A1 (fr) 2010-03-22 2011-03-17 Pile bouton protégée contre les courts-circuits

Publications (1)

Publication Number Publication Date
EP2550695A1 true EP2550695A1 (fr) 2013-01-30

Family

ID=44068306

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11708486A Withdrawn EP2550695A1 (fr) 2010-03-22 2011-03-17 Pile bouton protégée contre les courts-circuits

Country Status (5)

Country Link
US (1) US20130196222A1 (fr)
EP (1) EP2550695A1 (fr)
CN (1) CN103038913A (fr)
DE (1) DE102010012977A1 (fr)
WO (1) WO2011117132A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2966709B1 (fr) * 2014-07-09 2018-01-10 VARTA Microbattery GmbH Élement électrochimique secondaire
CN106471649B (zh) * 2014-07-09 2020-01-14 瓦尔达微电池有限责任公司 二次电化学电池和充电方法
CN106025366A (zh) * 2016-07-13 2016-10-12 深圳市秸川材料科技有限公司 一种锂离子纽扣电池
CN107425145B (zh) * 2017-06-20 2023-06-20 惠州亿纬锂能股份有限公司 一种钮扣式锂电芯密封结构及密封方法
US20210288364A1 (en) * 2017-10-13 2021-09-16 Wayne State University Fabrication of micro/millimeter-scale power sources and the process flow therefor
CN109786647B (zh) * 2017-11-10 2021-11-09 松栢投资有限公司 切割机构、可充电电池及制造可充电电池的外壳的方法
CN108550718B (zh) * 2018-06-15 2024-01-19 宜昌力佳科技有限公司 一种具有底座的扣式电池
KR20210073888A (ko) * 2019-12-11 2021-06-21 삼성에스디아이 주식회사 배터리

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DE3034600A1 (de) * 1980-09-13 1982-09-30 Varta Batterie Ag, 3000 Hannover Galvanische rund- oder knopfzelle
DE3113309A1 (de) 1981-04-02 1982-10-21 Varta Batterie Ag, 3000 Hannover Galvanisches element
JPS61216235A (ja) * 1985-03-20 1986-09-25 Matsushita Electric Ind Co Ltd 密閉電池
JPS6381759A (ja) * 1986-09-26 1988-04-12 Matsushita Electric Ind Co Ltd 密閉電池
US5725967A (en) * 1995-08-15 1998-03-10 Micron Communications, Inc. Battery container and method of manufacture
DE19647593B4 (de) 1996-11-18 2012-06-21 Varta Microbattery Gmbh Verfahren zur Herstellung einer Knopfzelle
US6033799A (en) * 1997-11-14 2000-03-07 Eveready Battery Company, Inc. Miniature galvanic cell having optimum internal volume for the active components
WO2001095412A1 (fr) * 2000-06-09 2001-12-13 Matsushita Electric Industrial Co., Ltd. Dispositif electrochimique
JP2005340046A (ja) * 2004-05-28 2005-12-08 Hitachi Maxell Ltd リード端子付きコイン形電池
DE102007003519A1 (de) 2007-01-18 2008-07-24 Varta Microbattery Gmbh Galvanisches Element mit Foliendichtung
DE102007009295A1 (de) * 2007-02-16 2008-08-21 Varta Microbattery Gmbh Galvanisches Element mit hoher Kapazität

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Title
See references of WO2011117132A1 *

Also Published As

Publication number Publication date
US20130196222A1 (en) 2013-08-01
DE102010012977A1 (de) 2011-09-22
CN103038913A (zh) 2013-04-10
WO2011117132A1 (fr) 2011-09-29

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