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WO2013045350A1 - Accumulateur lithium-ions rechargeable et utilisation d'un matériau à base de verre - Google Patents

Accumulateur lithium-ions rechargeable et utilisation d'un matériau à base de verre Download PDF

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Publication number
WO2013045350A1
WO2013045350A1 PCT/EP2012/068598 EP2012068598W WO2013045350A1 WO 2013045350 A1 WO2013045350 A1 WO 2013045350A1 EP 2012068598 W EP2012068598 W EP 2012068598W WO 2013045350 A1 WO2013045350 A1 WO 2013045350A1
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WO
WIPO (PCT)
Prior art keywords
glass
use according
based material
oxide
content
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.)
Ceased
Application number
PCT/EP2012/068598
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German (de)
English (en)
Inventor
Olaf Claussen
Ulf Dahlmann
Ulrich Peuchert
Andreas Roters
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Schott AG
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Schott AG
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Filing date
Publication date
Application filed by Schott AG filed Critical Schott AG
Priority to JP2014532327A priority Critical patent/JP2015502627A/ja
Priority to CN201280047862.9A priority patent/CN103858260A/zh
Publication of WO2013045350A1 publication Critical patent/WO2013045350A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • 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 invention relates to a rechargeable lithium-ion secondary battery and the use of a glass-based, non-toxic, temperature-stable material to improve the initial cycling capability of safe lithium-ion secondary batteries.
  • lithium-ion batteries also known as LIB cells
  • weight issues are to be solved with a view to increasing the specific energy and power density.
  • a central factor for assessing the power delivery capacity of LIB cells is the capacity utilization of the LIB cells at high so-called C rates.
  • an IC charge or discharge is a process in which the cell is charged or discharged within one hour to its nominal capacity (in Ah). Accordingly, a 4C charge / discharge corresponds to a charge / discharge in 1/4 of the time, that is 15 minutes. A 10C charge then corresponds to a corresponding operation in just 6 minutes.
  • electrode networks anode or cathode.
  • electrodes for power cells are usually thinner and more open-pored than those of energy cells with the disadvantage of decreasing energy performance.
  • Another parameter for Zykliercreate is - in addition to the highest possible Zyklieriere - the Coulombmetrische efficiency CE.
  • the CE describes the relationship between the charging capacity reached and the discharge capacity in one cycle. In normal operation, this is very close to 100%. In the initial phase of the use of the cell, this is significantly lower for electrochemical reasons. This is due to the fact that some of the lithium ions react irreversibly with the electrolyte solution at the anode and cathode with the formation of cover layers.
  • A1 2 0 3 is mainly used as an additive for a LIB cell or as a coating material for a separator.
  • JP (A) 2005-11614 discloses a use of glass particles described.
  • none of the cited documents deals with the problems of C-rate capability and inital cyclability.
  • the invention is based on the object to provide a LIB cell, which avoids the disadvantages of the prior art as possible.
  • the LIB cell should ensure the highest possible high-rate capability, as far as possible with even high energy density, and should also have as high a safety as possible at high temperatures (HRL).
  • HRL high temperatures
  • the decrease of the nominal capacity compared to a standard IC cycling at high C-rates (about> 4 C) should be kept as low as possible.
  • it should preferably be possible to quickly achieve a high Coulombmetric efficiency CE after a few cycles.
  • This object is achieved by the use of a glass-based material according to claim 1 for a LIB cell and by a LIB cell according to claim 22.
  • the materials used in the invention are characterized, inter alia, by a low density as well as by a good resistance to the chemically aggressive environment of the liquid electrolyte.
  • the density is preferably less than 5 g / cm 3 , preferably less than 3.7 g / cm 3 , more preferably less than 3.5 g / cm 3 , particularly preferably less than or equal to 3 g / cm 3 .
  • Suitable glass-based materials are preferably silicate glasses or glass ceramics produced therefrom.
  • the glass-based material here may contain in particular at least the following constituents (in% by weight based on oxide):
  • Refining agents in usual amounts of up to 2%, wherein R 2 0 is the sum amount of sodium oxide and potassium oxide, wherein RO is the sum amount of oxides of the type MgO, CaO, BaO, SrO, ZnO, and wherein apart from incidental impurities no titanium oxide is contained.
  • the impurities are usually below 1000 ppm, preferably below 500 ppm, more preferably below 200 ppm, or even below 100 ppm.
  • the sum content of sodium oxide and potassium oxide is at most 12 wt .-%, preferably at most 5 wt .-%, or less than 1 wt .-% or even zero, apart from accidental impurities.
  • the content of sodium oxide is at most 5 wt .-%, preferably at most 1 wt .-%, more preferably at most 0.5 wt .-%.
  • the material is free of sodium oxide.
  • the content of aluminum oxide is at least 1 wt .-%, in particular at least 3 wt .-%, in particular at least 9 wt .-%, in particular at least 30 wt .-% or at least 35 wt .-%, preferably at most 41% by weight.
  • the content of B 2 0 3 is at least 3 wt .-%, in particular at least 5, preferably at least 9 wt .-%, preferably at most 15 wt .-%.
  • the content of Zr0 2 is at least 1 wt .-%, in particular at least 4 wt .-%, preferably at most 10% by weight.
  • the content of RO is at least 20, in particular at least 30, in particular at least 40 or at least 50 wt .-%, preferably at most 80 wt .-%.
  • the content of BaO is at least at least 20 wt .-%, in particular at least 50 wt.%, Preferably at most 73 wt .-%.
  • the content of MgO is at least 10, in particular at least 30 wt .-%, preferably at most 45 wt .-%.
  • the content of calcium oxide is at least 25, in particular at least 30 wt .-%, preferably at most 45 wt .-%.
  • the content of Si0 2 is at least 20, in particular at least 35, in particular at least 40, at least 45, at least 50 or at least 60 wt .-%, preferably at most 70 wt .-%.
  • the glass-based material contains at least the following constituents (in% by weight based on oxide):
  • Refining agent in usual amounts of up to 2%.
  • the glass-based material contains at least the following constituents (in% by weight based on oxide): Si0 2 35-45
  • Refining agent in usual amounts of up to 2%.
  • the glass-based material contains at least the following constituents (in% by weight based on oxide):
  • Refining agent in usual amounts of up to 2%.
  • the glass-based material contains at least the following constituents (in% by weight based on oxide):
  • Refining agent in usual amounts of up to 2%.
  • the glass-based material contains at least the following constituents (in% by weight based on oxide):
  • Refining agent in usual amounts of up to 2%.
  • the glass-based material contains at least the following constituents (in% by weight based on oxide): Si0 2 60 - 70
  • Refining agent in usual amounts of up to 2%.
  • the glass-based material contains at least the following constituents (in% by weight based on oxide):
  • Refining agent in usual amounts of up to 2%.
  • the glass-based material contains at least the following constituents (in% by weight based on oxide):
  • Refining agent in usual amounts of up to 2%.
  • the glass-based material contains at least the following constituents (in% by weight based on oxide):
  • Refining agent in usual amounts of up to 2%.
  • refining Sn0 2 , As 2 0 3 , Sb 2 0 3 , sulfur, Ce0 2 , etc. can be used.
  • polyvalent refining agents are unavoidable, their proportion should be kept as low as possible, ideally below 500 ppm, for reasons of electrochemical stability.
  • refining agents can preferably also be completely dispensed with, provided that the glass is produced in application-oriented geometry, ie as a fine powder, and the requirement for freedom from bubbles is not high. Since refining agents, due to their polyvalence in an accumulator, tend to cause uncontrolled redox reactions, they should be avoided as much as possible.
  • the glass-based material contains no refining agents other than accidental impurities.
  • the content of refining agents is ⁇ 500 ppm or even ⁇ 200 ppm, more preferably ⁇ 100 ppm.
  • the glass-based material is used in a lithium-ion secondary battery with liquid electrolyte as filler preferably in powder form.
  • the glass-based material is applied as a coating on the surface of a separator, in particular applied to the surface of a polymer-based separator, or used for infiltration of a polymer-based separator.
  • the glass-based material is compounded with polymers to form a self-supporting separator.
  • the glass-based material is used to coat an electrode.
  • the glass-based material is contained in an electrode as an additive, preferably as a homogeneously distributed additive with a proportion of up to 50 wt .-% in an electrode, which preferably consists of graphite.
  • the glass-based material is present as homogeneously distributed additive in a proportion of 5 to 35 wt .-% in an electrode made of graphite.
  • the expensive electrode material can be replaced without the properties being adversely affected. In part, even improved properties can be achieved.
  • the materials used according to the invention have a sufficiently high chemical resistance.
  • FIG. 1 shows a LIB cell in a schematic representation.
  • a LIB cell is shown schematically and designated 10 in total.
  • the LIB cell 10 has a housing 18 with two electrode feedthroughs 12.
  • the electrode passages are connected to a first electrode 14, which consists of Cu and coated with anode material, or to a second electrode 16, which may be coated with a cathode material AI -Ableiterfolie.
  • a separator 22 which may be a polymer film coated with glass particles.
  • the interior of the housing 18 is filled with electrolyte liquid 20.
  • anodes were prepared with A1 2 0 3 as a reference and those with glass powder.
  • the anodes were cycled in an electrochemical half cell to test initial cyclability (coulometric efficiency), cycle stability, and C rate dependence.
  • a copper foil was coated with the slurry by means of a doctor blade, the wet thickness being 200 ⁇ m. Subsequently, the copper strip is dried at 80 ° C for 12 hours. Subsequently, a sample of suitable size was punched out of the coated Cu strip (thickness about 45 mm) and then pressed (1 t / cm 2 , 30 s), after which the thickness was only about 23 ⁇ m. Finally, this sample (the actual electrode) was dried at 110 ° C for 24 h. The average coating density was around 2 mg / cm 2 .
  • the electrode was assembled in the dry room into a half cell in the button cell design.
  • a 0.05 mm thick lithium foil (from the company Chemetall, battery grade) served as a counter electrode.
  • the separator used was a polypropylene material from Celgard (type 2400).
  • the electrolyte used was a solution of the salt LiPF 6 (1 molar) in a mixture consisting of three parts of EC (ethylene carbonate) and 7 parts of EMC (ethyl methacrylate) plus small amounts of additives. These additives were used to form the necessary SEI layer (Solid Electrolyte Interface: this is a necessary to protect the electrodes cover layer).
  • the nominal capacity was around 350 mAh.
  • the cyclic measuring program was as follows:
  • test separators were prepared with particle coatings of A1 2 0 3 (for reference) or glass.
  • the coated separators were cycled in a full electrochemical cell to test initial cyclability (coulometric efficiency), cycle stability, and C rate dependence.
  • Porous polymer separators based on polypropylene were coated by hand doctor blade with an organic particle suspension.
  • the suspension was based on the solvent NMP (N-methyl-2-pyrrolidone) and contained appropriate amounts of PVDF-based binder (PVDF: polyvinylidene fluoride).
  • NMP N-methyl-2-pyrrolidone
  • PVDF polyvinylidene fluoride
  • the coated separators After drying (4 hours at 60 ° C.), the coated separators had layer thicknesses of 33-41 ⁇ m. The thickness of the polypropylene separator was 25 ⁇ m.
  • the coated separators were characterized by impedance spectroscopy.
  • Impedance spectroscopy is an AC voltage measurement to determine resistances.
  • the cathode material used was LiCoO 2 (LCO).
  • LCO LiCoO 2
  • an aluminum sample was coated with a mixture of LCO, carbon black (acetylene black) and binder (PVDF) in a ratio of 94: 3: 3.
  • the cathode had a diameter of 13 mm.
  • the anode material used was graphite.
  • a copper sample was coated with a mixture of graphite, carbon black (acetylene black) and binder (PVDF) in a ratio of 90: 5: 5.
  • the electrolyte used was a solution of the salt LiPF 6 (1 molar) in a mixture consisting of one part of EC (ethylene carbonate) and one part of EMC (ethylmethyl carbonate).
  • the measurement protocol was as follows:
  • Impedance spectroscopy 1 cycle with 0.1C, impedance spectroscopy, 2 cycles with 0.1C, 3 cycles with IC, 3 cycles with 4C, impedance spectroscopy.
  • limit voltage 3-4.2V
  • charge with constant current at 0.1 C and constant voltage at 0.01C discharge with constant current at 0, IC to 4C.
  • the production took place by: - Melting in a Pt / Irl crucible at temperatures> 1550 ° C
  • the other example glasses were prepared essentially analogously to ABl. Deviations concern, in particular, smelting in a tray lined with refractory bricks in the case of ABl, but the other glasses can also be melted in a tray lined with refractory materials if required.
  • the glasses have a high temperature resistance of> 400 ° C and are therefore generally suitable as a filler or coating material for separators and electrodes in the sense of providing an effective HRL. If the cell is e.g. heated by a short circuit so much that the polymer separator melts, the particles also ensure a distance between the two electrodes.
  • the glasses have a density ⁇ 5.0 g / ccm3, in particular ⁇ 4.0 g / ccm3, preferably ⁇ 3.7 g / cm3, more preferably ⁇ 3.2 g / ccm3, in some cases even ⁇ 2.8 g / ccm3 (see Tab.l).
  • the powders are fine-grained, exemplary grits are according to CILAS laser scattering methods measured d50 [pm] ⁇ 0.1 - 10 pm
  • the powder data were determined by laser scattering measurements on the previously dispersed powders or suspensions (CILAS 1064 wet), the SSA (Specific Surface Area) determined by BET measurement.
  • the process steps in powder production can be selected so that targeted bimodal powder characteristics arise.
  • the mixture of the glass with ceramic particles such as A1 2 0 3 , Si0 2 (quartz), BaTi0 3 , MgO, Ti0 2 , Zr0 2 or other simple oxides is possible.
  • Shapes can be fibrous, rod-shaped, round, oval, angular, angular (primary), dumbbell-shaped, pyramidal, as platelets or flakes.
  • the grains may occur as primary or agglomerated.
  • the particles can be superficially edged or flattened or rounded.
  • Preferred is a grain shape or geometry with an aspect ratio of about 0.1 (ratio short / long side) and sharp-edged grains. This results in a stable toothing of the grains in a still quite open structure of the particle packing.
  • anodes in addition to graphite as active material silicate glasses (particle size about 1.5 pm, exemplary composition (in% by mass) SiO z 55, B 2 0 3 10, A1 2 0 3 10th , BaO 25), a significantly lower decrease in IOC cyclability than comparable anodes containing either graphite or graphite alone and A1 2 0 3 as the active material, based on the scenarios with A1 2 0 3 .
  • Analogous results, now at 4C discharge rate were also found in cycling cells with glass particles coated polymeric separators (Test II) compared to Al 2 0 3 -coated polymeric separators.
  • the Coulombmetric Efficiency (CE) after the third cycle is when introducing glass (eg binary Ba-silicate glasses or silicate glasses (in Ma%) with the composition Si0 2 55, B 2 0 3 10, A1 2 0 3 10, BaO 25) in a cell (eg as an anode material or as a material on a separator) compared to the introduction of A1 2 0 3 increases.
  • glass eg binary Ba-silicate glasses or silicate glasses (in Ma%) with the composition Si0 2 55, B 2 0 3 10, A1 2 0 3 10, BaO 25
  • a cell eg as an anode material or as a material on a separator
  • a positive and a negative electrode must be integrated into a housing, a separator for separating the two electrodes from each other are integrated and cavity are soaked in the electrolyte.
  • the individual steps are briefly explained below. 6. Production of glass powders and slurries
  • the glass is melted, cooled, hot-formed into suitable easily separable geometry (ribbons, fibers, balls) and rapidly cooled.
  • the glass is transferred via grinding and optionally subsequent drying (freeze-drying, spray drying) in powder.
  • drying freeze-drying, spray drying
  • the suspension resulting from the wet grinding process can be used directly later.
  • fine amorphous glass powders may also be prepared via a sol-gel process.
  • a sol is prepared from the alkoxides or similar compounds which, like the alkoxides, are readily capable of carrying out crosslinking reactions by hydrolysis and condensation reactions of the corresponding elements.
  • the resulting colloidal solution is treated by suitable means such as adjustment of pH or addition of water to effect gelation of the sol.
  • the sol may be subjected to spray-drying.
  • the solid formed in this way which consists of particles, can be further subjected to a calcination reaction in order to eliminate any organic impurities.
  • small glass particles can be prepared by melting finely ground raw materials in flight, for example by using a plasma.
  • the particles in intimate contact with organic polymers, if necessary, using Banl upon. Solvents, binders and, where appropriate, piastiziern as pasty mass rolled out in a self-supporting form or poured onto a support foil or geräkelt.
  • polymers can be used: crosslinkable liquid or pasty resin systems z.
  • B Resins of crosslinkable addition polymers or condensation resins., Crosslinkable polyolefins or polyesters, curable epoxy resins, crosslinkable polycarbonates, polystyrene, polyurethane or polyvinylidene fluoride (PVDF), polysaccharides. Thermoplastics or thermo-elastomers.
  • the use can be carried out as a finished polymer, polymer precursors or prepolymers, if appropriate also using a swelling agent adapted to the abovementioned polymers.
  • Flexibility can be a plastisizer (plasticizer used). This can be dissolved out chemically after processing the membrane.
  • one or more of the glasses mentioned is stirred into PVDF-HFP, dibutyl phthalate and acetone. The pasty mass is then applied, for example, to an auxiliary substrate. cured, cured by UV, T treatment or by incorporation into chemical reagents. b) coating or infiltration of polymeric separator carriers
  • the glass particles are applied to membranes or nonwovens by suitable particle separation processes.
  • Porous carriers can be: dry-drawn membranes (for example from Celgard) or wet-extracted membranes (for example from Tonen). These are usually made of PE, PP or PE / PP mixtures or multilayer membranes produced therefrom. Alternatively, fiber waffle, so-called nonwovens made of polyolefins or PET can be used. In the latter case, the glass or glass-ceramic particles not only function as add-on functionality for increasing the temperature resistance, but are also essential for the adjustment of the basic functionality, i.e., the provision of a suitable porosity.
  • the coating is preferably applied as a suspension to the substrate. This can be done for example by printing, pressing, pressing, rolling, doctoring, brushing, dipping, spraying or pouring.
  • a suspension from the milling process can already be used in the case of wet coating.
  • an already existing glass powder can also be redispersed.
  • the use of the grinding suspension is preferred, for storage and transport reasons, the use of powders is preferred.
  • binders or adhesion promoters are added as additives to the coating suspension. These can be both organic and inorganic.
  • particles may be applied to the cathode and / or the anode.
  • the above methods can be used.
  • the specific media or slurries or processes used for the production of anodes or cathodes can or must be used.
  • the integration process can be such that one or more electrodes are brought into contact with the pore membrane solution - the latter consisting of glass particle clusters and possibly binders. This includes e.g. immersion, spraying or knife coating. It is also conceivable to completely dispense with the separation of the particles on the electrodes on a Separatorteil as such. In this case, the function of the separator is taken over by the coatings on the electrodes. d) Partial replacement of active electrode material
  • Active electrode material may be partially replaced by glass-based material.
  • active anode material graphite with conductive carbon black
  • a conductive carrier for example a copper foil (see Test 1).
  • e) introduction of particles into the liquid electrolyte Another possibility is the introduction of the particles into the liquid electrolyte. In this case, the particles are not spatially fixed or bound, but act as a loosely spaced bulk. The application can only be made in powder form, unless the milling was carried out in a nonaqueous medium.8. Examples of integrationGlas AB2 was melted in a Pt crucible aggregate and made into ribbons by means of a rolling machine (2 water-cooled rolls).
  • the ribbons were converted into fine powders in a two-stage dry & wet grinding process.
  • a dry grinding process was used (drum mill, A1 2 0 3 , 24h), the final grain fraction was achieved by a subsequent wet grinding process (agitator ball mill, Zr0 2 , 5-10 hours depending on the desired fines).
  • the wet grinding was carried out in an aqueous medium without the addition of additives.
  • the resulting slurry was converted by spray drying into a fine powder having approximately comparable properties:
  • the glass powder grains were predominantly edged and had a platy to squat prismatic habit.
  • the powders were redispersed in water.
  • the resulting suspension was stable for several days and could be easily homogenized again at deposition without formation of a solid sediment.
  • the addition of an actuating agent was therefore omitted.
  • the appropriate material eg glass
  • a suitable polymer binder such as poly (lithium 4-styrene sulfonate)
  • a suitable solvent such as N, N-dimethylacetamide + Water
  • the separator is integrated into an exemplary cell construction.
  • the separator 22 is placed approximately as shown in FIG. 1 between two with active media (anode: graphite, cathode LiCo0 2 ) particle-coated current conductors 14, 16 made of aluminum and Cu sheet.
  • active media anode: graphite, cathode LiCo0 2
  • endless belts of anode (graphite), cathode (LiCo0 2 ) and separator are rolled up and thus formed into cylinders.
  • the rolls or stacks are optionally inserted into a housing 18 made of aluminum or steel or placed between laminating foils made of plastic-coated aluminum.
  • the liquid electrolyte 20 Prior to capping (hard case) or final laminating (in the case of a pad cell), the liquid electrolyte 20 is introduced or sucked into the unit by applying a vacuum.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Cell Separators (AREA)
  • Glass Compositions (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un matériau à base de verre utilisé comme additif pour un accumulateur lithium-ions rechargeable, de préférence à électrolyte liquide, afin d'améliorer sa cyclabilité. Le matériau à base de verre comprend au minimum les constituants suivants (en % en poids d'oxyde) : somme de SiO2 + F + P2O5 20 à 95% ; Al2O3 0 à 30%. Sa densité est de préférence inférieure à 5 g/cm3 (Fig. 1).
PCT/EP2012/068598 2011-09-29 2012-09-21 Accumulateur lithium-ions rechargeable et utilisation d'un matériau à base de verre Ceased WO2013045350A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2014532327A JP2015502627A (ja) 2011-09-29 2012-09-21 再充電可能なリチウムイオン電池及び再充電可能なリチウムイオン電池へのガラス系材料の使用
CN201280047862.9A CN103858260A (zh) 2011-09-29 2012-09-21 可充电锂离子电池和玻璃基材料用于其的用途

Applications Claiming Priority (2)

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DE102011114876.4 2011-09-29
DE102011114876A DE102011114876A1 (de) 2011-09-29 2011-09-29 Wiederaufladbarer Lithium-Ionen-Akkumulator und Verwendung eines glasbasierten Materials hierfür

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WO2013045350A1 true WO2013045350A1 (fr) 2013-04-04

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Cited By (3)

* Cited by examiner, † Cited by third party
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DE102013112015A1 (de) 2013-10-31 2015-04-30 Schott Ag Wiederaufladbarer Lithium-Ionen Akkumulator
DE102017205653A1 (de) 2017-04-03 2018-10-04 Vitrulan Textile Glass Gmbh Glasbasierter Batterieseparator
DE102017007858A1 (de) 2017-04-03 2018-10-04 Thorsten Gerdes Verfahren zum direkten Aufbringen von glasbasierten Separatoren auf Batterieelektroden

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012215824A1 (de) 2012-07-26 2014-11-13 Schott Ag Zusatzstoff für elektrochemische Energiespeicher und elektrochemischer Energiespeicher
KR102184372B1 (ko) * 2014-02-10 2020-11-30 삼성에스디아이 주식회사 복합양극활물질, 그 제조방법 및 이를 채용한 양극 및 리튬전지
JP6883230B2 (ja) * 2017-03-29 2021-06-09 昭和電工マテリアルズ株式会社 リチウムイオン二次電池用材料、正極合材、リチウムイオン二次電池用正極及びリチウムイオン二次電池
US20230047398A1 (en) * 2019-12-27 2023-02-16 Microvast Power Systems Co.,Ltd. Electrolyte containing solid particles and lithium ion secondary battery
CN116323772A (zh) * 2020-10-14 2023-06-23 株式会社日本制钢所 涂敷液、多孔质膜和锂离子电池

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1050913A1 (fr) * 1999-05-05 2000-11-08 Wilson Greatbatch Limited Cellules électrochimiques au oxyhalogénure de lithium fonctionnant à haute température
DE10208277A1 (de) 2002-02-26 2003-09-04 Creavis Tech & Innovation Gmbh Elektrischer Separator, Verfahren zu dessen Herstellung und Verwendung
DE10238944A1 (de) 2002-08-24 2004-03-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Separator zur Verwendung in Hochenergiebatterien sowie Verfahren zu dessen Herstellung
US20050003726A1 (en) * 2002-07-29 2005-01-06 Kvg Technologies, Inc. Glass compositions
JP2005011614A (ja) 2003-06-18 2005-01-13 Teijin Ltd 非水系二次電池用セパレータ及び非水系二次電池
EP1760819A2 (fr) * 2005-08-31 2007-03-07 Ohara Inc. Batterie secondaire à ions de lithium et l' électrolyte solide pour cette batterie
US20090087728A1 (en) 2007-09-28 2009-04-02 A123 Systems, Inc. Batteries having inorganic/organic porous films
WO2009103537A1 (fr) 2008-02-20 2009-08-27 Carl Freudenberg Kg Non-tissé comportant un matériau de réticulation
EP2153990A1 (fr) 2007-06-06 2010-02-17 Asahi Kasei E-materials Corporation Film poreux multicouches
US20100104948A1 (en) * 1999-11-23 2010-04-29 Sion Power Corporation Protection of anodes for electrochemical cells
WO2010095736A1 (fr) * 2009-02-23 2010-08-26 日本電気硝子株式会社 Film de verre pour batterie lithium-ion
WO2011124347A1 (fr) * 2010-03-29 2011-10-13 Schott Ag Composants pour éléments de batteries comportant des constituants inorganiques à faible conductivité thermique
DE102010048919A1 (de) * 2010-10-07 2012-04-12 Schott Ag Elektrochemischer Energiespeicher und Verwendung eines glasbasierten Materials zur Herstellung eines Separators für einen solchen
WO2012045662A2 (fr) * 2010-10-07 2012-04-12 Schott Ag Accumulateur d'énergie électrochimique et utilisation d'un matériau à base de verre pour produire un séparateur pour un tel accumulateur
DE102011012552A1 (de) * 2011-02-24 2012-08-30 Schott Ag Lithium-Ionen-Akkumulator

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000311692A (ja) * 1999-04-27 2000-11-07 Kyocera Corp 電気化学素子の製造方法
JP3643289B2 (ja) * 1999-04-30 2005-04-27 株式会社オハラ ガラスセラミックス複合電解質、及びリチウム二次電池
JP2003346765A (ja) * 2002-05-30 2003-12-05 Japan Storage Battery Co Ltd 複合シート及びそれを用いた非水電解質二次電池
JP4714856B2 (ja) * 2004-07-12 2011-06-29 国立大学法人信州大学 結晶化ガラスおよびその製造方法
JP2010251078A (ja) * 2009-04-15 2010-11-04 Nippon Sheet Glass Co Ltd 有機無機複合多孔質フィルムおよびそれを用いた非水電解質二次電池セパレータ
DE102009056756B4 (de) * 2009-12-04 2020-10-15 Schott Ag Material für Batterie-Elektroden, dieses enthaltende Batterie-Elektroden sowie Batterien mit diesen Elektroden und Verfahren zu deren Herstellung
DE102010048922A1 (de) * 2010-10-07 2012-04-12 Schott Ag Elektrochemischer Energiespeicher und Verwendung eines glasbasierten Materials zur Herstellung eines Separators für einen solchen

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1050913A1 (fr) * 1999-05-05 2000-11-08 Wilson Greatbatch Limited Cellules électrochimiques au oxyhalogénure de lithium fonctionnant à haute température
US20100104948A1 (en) * 1999-11-23 2010-04-29 Sion Power Corporation Protection of anodes for electrochemical cells
DE10208277A1 (de) 2002-02-26 2003-09-04 Creavis Tech & Innovation Gmbh Elektrischer Separator, Verfahren zu dessen Herstellung und Verwendung
US20050003726A1 (en) * 2002-07-29 2005-01-06 Kvg Technologies, Inc. Glass compositions
DE10238944A1 (de) 2002-08-24 2004-03-04 Creavis Gesellschaft Für Technologie Und Innovation Mbh Separator zur Verwendung in Hochenergiebatterien sowie Verfahren zu dessen Herstellung
JP2005011614A (ja) 2003-06-18 2005-01-13 Teijin Ltd 非水系二次電池用セパレータ及び非水系二次電池
EP1760819A2 (fr) * 2005-08-31 2007-03-07 Ohara Inc. Batterie secondaire à ions de lithium et l' électrolyte solide pour cette batterie
EP2153990A1 (fr) 2007-06-06 2010-02-17 Asahi Kasei E-materials Corporation Film poreux multicouches
US20090087728A1 (en) 2007-09-28 2009-04-02 A123 Systems, Inc. Batteries having inorganic/organic porous films
WO2009103537A1 (fr) 2008-02-20 2009-08-27 Carl Freudenberg Kg Non-tissé comportant un matériau de réticulation
WO2010095736A1 (fr) * 2009-02-23 2010-08-26 日本電気硝子株式会社 Film de verre pour batterie lithium-ion
WO2011124347A1 (fr) * 2010-03-29 2011-10-13 Schott Ag Composants pour éléments de batteries comportant des constituants inorganiques à faible conductivité thermique
DE102010048919A1 (de) * 2010-10-07 2012-04-12 Schott Ag Elektrochemischer Energiespeicher und Verwendung eines glasbasierten Materials zur Herstellung eines Separators für einen solchen
WO2012045662A2 (fr) * 2010-10-07 2012-04-12 Schott Ag Accumulateur d'énergie électrochimique et utilisation d'un matériau à base de verre pour produire un séparateur pour un tel accumulateur
DE102011012552A1 (de) * 2011-02-24 2012-08-30 Schott Ag Lithium-Ionen-Akkumulator

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013112015A1 (de) 2013-10-31 2015-04-30 Schott Ag Wiederaufladbarer Lithium-Ionen Akkumulator
WO2015063096A1 (fr) 2013-10-31 2015-05-07 Schott Ag Accumulateur rechargeable aux ions de lithium
KR20160081951A (ko) * 2013-10-31 2016-07-08 쇼오트 아게 재충전 가능한 리튬 이온 축전지
KR102086197B1 (ko) 2013-10-31 2020-04-24 쇼오트 아게 재충전 가능한 리튬 이온 축전지
DE102017205653A1 (de) 2017-04-03 2018-10-04 Vitrulan Textile Glass Gmbh Glasbasierter Batterieseparator
DE102017007858A1 (de) 2017-04-03 2018-10-04 Thorsten Gerdes Verfahren zum direkten Aufbringen von glasbasierten Separatoren auf Batterieelektroden
WO2018185075A2 (fr) 2017-04-03 2018-10-11 Vitrulan Textile Glass Gmbh Séparateur à base de verre
WO2018185075A3 (fr) * 2017-04-03 2018-11-29 Vitrulan Textile Glass Gmbh Séparateur à base de verre
US11152666B2 (en) 2017-04-03 2021-10-19 Vitrulan Textile Glass Gmbh Glass-based battery separator

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