WO2015124406A1 - Additif inhibant la formation d'une interface électrolyte solide pour matériau d'anode - Google Patents

Additif inhibant la formation d'une interface électrolyte solide pour matériau d'anode Download PDF

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Publication number
WO2015124406A1
WO2015124406A1 PCT/EP2015/051902 EP2015051902W WO2015124406A1 WO 2015124406 A1 WO2015124406 A1 WO 2015124406A1 EP 2015051902 W EP2015051902 W EP 2015051902W WO 2015124406 A1 WO2015124406 A1 WO 2015124406A1
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WO
WIPO (PCT)
Prior art keywords
radiation
additive
anode
process step
lithium
Prior art date
Application number
PCT/EP2015/051902
Other languages
German (de)
English (en)
Inventor
Pallavi Verma
Vikram Anil GODBOLE
Original Assignee
Robert Bosch 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 Robert Bosch Gmbh filed Critical Robert Bosch Gmbh
Publication of WO2015124406A1 publication Critical patent/WO2015124406A1/fr

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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
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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 a manufacturing method for an anode of a lithium cell, a corresponding anode material and a so
  • Lithium-ion batteries are used in a variety of products ranging from mobile phones to electric vehicles.
  • a lithium ion battery usually has an anode material
  • SEI Solid Electrolyte Interphase
  • the present invention is a production method for an anode of a lithium cell, comprising the method steps:
  • An anode active material may, in particular, be understood as meaning a substance which can reversibly store and displace lithium ions.
  • the at least one anode active material may be a lithium Intercalation material, in particular graphite, and / or a lithium alloy material, in particular silicon or a silicon alloy.
  • polymer precursor By a polymer starting material, in particular a so-called polymer precursor can be understood.
  • step a) Characterized in that in the course of mixing in process step a) a activatable by heat and / or radiation, polymerizable additive is added, which is activated in step c) for polymerization, advantageously both the stability of the anode material increasing bonds on the surface of the anode material , as well as forming a stable polymer layer around the surface of the anode material.
  • the electrode layer is covered by a stable layer which reduces or prevents SEI formation.
  • a SEI-education-related capacity loss can be reduced or even completely prevented.
  • Process step d) to dry Process step d) can be carried out, for example, insofar as in process step c) only one treatment is carried out by radiation.
  • At least one binder is further admixed in process step a). So can advantageously the mechanical stability of the anode layer can be increased.
  • the at least one binder may in particular be water-soluble.
  • the at least one solvent may be or comprise water.
  • At least one electrical conducting agent is further admixed in method step a).
  • the at least one electrical conducting agent may be carbon-based.
  • the at least one electrical conductive agent may be carbon black, for example
  • Carbon black include or be.
  • method step a) comprises method steps a1) and a2):
  • the at least one binder in process step a), can be dissolved in the at least one solvent.
  • the distribution of the at least one binder and thus the mechanical stability of the anode material can be improved.
  • the anode layer is heated to a temperature which is above the
  • Polymerization temperature of the at least one polymer starting material of the at least one additive is Polymerization temperature of the at least one polymer starting material of the at least one additive.
  • the polymerization temperature may be understood to mean, in particular, the temperature at which the at least one polymer starting material of the at least one additive polymerizes.
  • the at least one polymer starting material of the at least one additive in a further embodiment, in a
  • the anode layer in process step c) to a Temperature are> 150 ° C, for example, about 150 ° C, is located. This has proved to be particularly advantageous for the production, since in method step c) both the at least one polymer starting material of the at least one additive can be polymerized and the anode layer can be dried.
  • a polymerizable by radiation polymer starting material a polymerization can be advantageously induced in a gentle manner and, for example, a degradation of components, such as the binder can be avoided.
  • the at least one additive may, for example, comprise at least one polymer starting polymerizable by heat and / or radiation, for example electromagnetic radiation and / or electron radiation.
  • the anode layer can be treated, for example, with heat and / or radiation, for example electromagnetic radiation and / or electron radiation, in particular wherein the at least one polymer starting material of the at least one additive polymerizes.
  • the at least one polymer starting material of the at least one additive polymerizes.
  • the at least one polymer may, for example, comprise at least one polymer starting polymerizable by heat and / or radiation, for example electromagnetic radiation and / or electron radiation.
  • Starting material of the at least one additive by ultraviolet radiation and / or gamma radiation and / or electron radiation polymerizable.
  • the anode layer can be irradiated with ultraviolet radiation and / or gamma radiation and / or electron radiation.
  • the at least one polymer starting material of the at least one additive itself can be initiated by polymerization for heat and / or radiation.
  • the method can advantageously be carried out particularly easily and inexpensively.
  • the at least one polymer starting material of the at least one additive can be initiated by a heat-activatable and / or radiation-activatable initiator for the polymerization.
  • the Initiator be mixed.
  • the at least one polymer starting material can be selected from a wide range of materials.
  • polymer precursors can be used for the at least one additive to provide a stable
  • the at least one polymer starting material of the at least one additive can be selected from the group of (itself) monomers which can be initiated thermally for polymerization, which (themselves)
  • the initiators for polymerization by monomers which can be initiated by thermally activatable initiators the monomers which can be initiated by polymerization for photoinitiators and combinations or mixtures thereof.
  • Polymer starting materials of these groups can be advantageously used to form the polymer layer according to the invention.
  • thermally polymerizable monomers can be understood in particular monomers in which a treatment with heat, in particular without the use of an initiator, is sufficient to effect a polymerization of the monomers.
  • examples of (self) thermally polymerizable monomers are Methylmethacyrlat and / or
  • Methyl methacrylate can be thermally initiated at a temperature of about 131 ° C, especially without the use of an initiator. Vinyl acetate can - especially without the use of an initiator - be thermally initiated at a temperature of about 100 ° C.
  • Treatment with radiation is sufficient to effect a polymerization of the monomers.
  • a treatment with electron radiation and / or electromagnetic radiation can be carried out.
  • Examples of (self) radiation-initiatable monomers include methacrylate and / or acrylate-poly (ethylene glycol) (PEG) and / or 2-ethylhexyl acrylate become.
  • the initiation can be effected by a pulsed or unpulsed electron beam, for example with> 12.6 Gy / pulse to ⁇ 71, 2 Gy / pulse.
  • Polymerization can be initiated, in particular monomers can be understood, the polymerization can be initiated by an initiator, wherein the initiator decomposes under heating or thermally and thereby activates a polymerization of the monomers.
  • an initiator wherein the initiator decomposes under heating or thermally and thereby activates a polymerization of the monomers.
  • Such monomers may be, for example, free-radical or cationic, in particular free-radical,
  • olefins examples of monomers which can be initiated by thermally activatable initiators for, in particular free-radical, polymerization
  • acetyl peroxides for example with a
  • Azobisisobutyronitrile for example, with an activation temperature in a range of> 50 ° C to ⁇ 70 ° C, and / or benzoyl peroxides, for example with an activation temperature in a range of> 80 ° C to ⁇ 95 ° C, as initiators be used.
  • thermally activated for example, with an activation temperature in a range of> 50 ° C to ⁇ 70 ° C, and / or benzoyl peroxides, for example with an activation temperature in a range of> 80 ° C to ⁇ 95 ° C, as initiators be used.
  • Initiators for, in particular cationic, polymerization-initiatable monomers are vinyl ethers.
  • photoinitiators for the polymerization of monomers can be understood in particular monomers whose polymerization can be initiated by an initiator, wherein the initiator and thereby polymerization of the monomers by electromagnetic radiation or photons, such as photoinitiation, is activated.
  • monomers which can be initiated by polymerization for photoinitiators are aromatic ketones and / or methyl methacrylate (MMA).
  • Aromatic ketones can be used particularly advantageously for thin films because of their low penetration.
  • a dye such as thionine, and / or a co-initiator such as triethanolamine, and / or an iron (III) salt, for example, a hydroxide (OH “ ) and / or chloride (CI " ), may be used to polymerize methyl methacrylate. , used as an initiator.
  • iron (III) can be reduced to iron (II) at a radiation of 3650 ⁇ .
  • the at least one additive can be used in particular in a small amount.
  • the at least one additive can be used in an amount which is selected such that the weight of the polymer formed from the at least one polymer starting material is at most 10% by weight, based on the weight of the at least one
  • the mass from process step a) may in particular be a sludge (English: slurry).
  • an electrically conductive substrate is coated with the composition of method step a).
  • the substrate may be formed of copper, for example a copper foil.
  • Another object is an anode material for a lithium cell, which is available or produced by a method according to the invention.
  • the anode material may be an anode material for a lithium-ion cell.
  • Anode materials in particular have a polymeric surface layer on the anode material.
  • the invention relates to a lithium cell, which comprises an anode material according to the invention.
  • the cell may be a lithium-ion cell.
  • the invention relates to a lithium battery, which comprises at least two cells according to the invention.
  • the battery may be a lithium
  • the battery may be a cylindrical or prismatic battery with a hardshell case or a pouch.
  • the battery may be a medium energy battery or a high energy battery, especially a high energy battery.
  • Under a high-energy battery can be understood in particular a battery with a capacity of> 40 Ah, for example, with about 60 Ah.
  • Fig. 2 shows schematic cross sections through a, by an inventive
  • FIG. 1 shows an embodiment of a method according to the invention in which method step a) is subdivided into two method steps a1) and a2).
  • FIG. 1 illustrates that in process step a1) at least one binder 14 is dissolved and mixed in at least one solvent 12, for example water. Then in the process step a2) the others
  • Components namely at least one anode active material 1 1, for example a lithium intercalation material, for example graphite, at least one electrical conductive agent 15, for example Leitruß, and at least one additive 13 in the binder solution from process step a1) dispersed.
  • the at least one additive 13 comprises at least one, by heat and / or
  • FIG. 1 further shows that an anode layer 10 is then formed in a process step b) from the mass 11 -15 from process step a), in particular a1), which may be, for example, a slurry (English: slurry).
  • a process step b) an electrically conductive substrate 1, for example a copper foil, having the mass 1 1 -15 from method step a) can be coated.
  • FIG. 1 further illustrates that, in a method step c), the anode layer 10 is treated with heat and / or radiation, the at least one polymer starting material of the at least one additive 13 polymerizing 13a.
  • the anode layer 10 may be heated to a temperature which is about 150 ° C.
  • a temperature which is about 150 ° C is about 150 ° C.
  • thermally polymerizable polymer starting material of the at least one additive 13 can be polymerized, but also water evaporates and thereby the
  • Anode layer 10 are dried. So can advantageously a
  • Process step can be saved.
  • the at least one polymer starting material of the at least one additive 13 can also be produced, for example, by radiation, for example ultraviolet radiation and / or gamma radiation and / or electron radiation,
  • Process step c) is carried out only a treatment by radiation, the anode layer 10 can be dried, for example in a process step d) (not shown).
  • FIG. 2 shows schematic cross sections through, through
  • FIG. 2 shows that the anode comprises a layer of anode material 10 applied to a copper foil 1.
  • FIG. 2 shows that in this case the anode layer 10 has already been charged before the first charging or cyclization
  • Surface layer 13a is provided, which by heat and / or
  • the additive was added to a mass from which the anode material layer 10 was formed.
  • Figure 2 illustrates that by the fact that by heat and / or
  • FIG. 2 illustrates that no SEI layer has formed after charging or cyclization and a loss of capacity due to SEI formation has been prevented by the surface layer 13a.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne un procédé de production d'une anode d'une cellule au lithium. L'invention vise à éviter une perte de capacité de la cellule, liée à la formation d'une interface électrolyte solide. A cet effet, au cours d'une étape de procédé, a) au moins un matériau actif d'anode (11), au moins un solvant (12) et au moins un additif (13), lequel comprend au moins une matière de départ polymère pouvant être polymérisée par de la chaleur et/ou un rayonnement, sont mélangés. Au cours d'une étape de procédé b), une couche d'anode (10) est formée à partir de la masse (11-15) de l'étape de procédé a), et la couche d'anode (10) est traitée au cours d'une étape de procédé c) avec de la chaleur et/ou un rayonnement, la ou les matières de départ polymères de l'additif ou des additifs (13) étant polymérisées (13a). L'invention concerne en outre un matériau d'anode de ce type ainsi qu'une cellule au lithium et une batterie au lithium comprenant ce dernier.
PCT/EP2015/051902 2014-02-24 2015-01-30 Additif inhibant la formation d'une interface électrolyte solide pour matériau d'anode WO2015124406A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014203218.0A DE102014203218A1 (de) 2014-02-24 2014-02-24 SEI-bildungshemmendes Anodenmaterialadditiv
DE102014203218.0 2014-02-24

Publications (1)

Publication Number Publication Date
WO2015124406A1 true WO2015124406A1 (fr) 2015-08-27

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WO (1) WO2015124406A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102015224373A1 (de) * 2015-12-04 2017-06-08 Robert Bosch Gmbh Siliciumpartikel mit künstlicher SEI
DE102016224021A1 (de) * 2016-12-02 2018-06-07 Robert Bosch Gmbh Anodenaktivmaterialpartikel mit künstlicher SEI-Schicht mittels lebender radikalischer Polymerisation

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999063609A1 (fr) * 1998-06-02 1999-12-09 Ultralife Batteries, Inc. Composants polymeres reticules d'accumulateurs rechargeables au lithium a l'etat solide et procedes de production
EP0999223A1 (fr) * 1997-07-24 2000-05-10 Kureha Kagaku Kogyo Kabushiki Kaisha Copolymere de fluorure de vinylidene permettant de former un electrolyte solide gelifie, electrolyte solide et pile
US6096101A (en) * 1997-03-05 2000-08-01 Valence Technology, Inc. Method of preparing electrochemical cells
US20060257740A1 (en) * 2005-04-12 2006-11-16 Young-Min Kim Lithium secondary battery containing silicon-based or tin-based anode active material
US20070087267A1 (en) * 2005-09-29 2007-04-19 Kim Soo J Electrode with enhanced performance and electrochemical device comprising the same
US20110081575A1 (en) * 2009-10-07 2011-04-07 Miltec Corporation Actinic and electron beam radiation curable electrode binders and electrodes incorporating same
US20120153219A1 (en) * 2010-12-21 2012-06-21 Zhengcheng Zhang Polysiloxane binder for lithium ion battery electrodes

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6096101A (en) * 1997-03-05 2000-08-01 Valence Technology, Inc. Method of preparing electrochemical cells
EP0999223A1 (fr) * 1997-07-24 2000-05-10 Kureha Kagaku Kogyo Kabushiki Kaisha Copolymere de fluorure de vinylidene permettant de former un electrolyte solide gelifie, electrolyte solide et pile
WO1999063609A1 (fr) * 1998-06-02 1999-12-09 Ultralife Batteries, Inc. Composants polymeres reticules d'accumulateurs rechargeables au lithium a l'etat solide et procedes de production
US20060257740A1 (en) * 2005-04-12 2006-11-16 Young-Min Kim Lithium secondary battery containing silicon-based or tin-based anode active material
US20070087267A1 (en) * 2005-09-29 2007-04-19 Kim Soo J Electrode with enhanced performance and electrochemical device comprising the same
US20110081575A1 (en) * 2009-10-07 2011-04-07 Miltec Corporation Actinic and electron beam radiation curable electrode binders and electrodes incorporating same
US20120153219A1 (en) * 2010-12-21 2012-06-21 Zhengcheng Zhang Polysiloxane binder for lithium ion battery electrodes

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