DE102016224044A1 - Anode Active Material Particles with Artificial Kronether SEI Layer - Google Patents

Abstract

The present invention relates to a method for producing an anode active material and / or an anode (100) and / or an electrolyte for a lithium cell and / or lithium battery, in particular for a lithium-ion cell and / or lithium-ion battery. Battery, and / or for producing such a lithium cell and / or lithium battery. In order to improve the cycle stability of the lithium cell and / or lithium battery, in the method anode active material particles (1), in particular silicon particles, and / or an electrolyte with at least one crown ether and / or crown ether derivative having at least one polymerizable functional group and / or provided with at least one Kronether and / or Kronether derivative polymer comprising. Moreover, the invention relates to an anode active material, an anode (100), an electrolyte, an electrolyte additive and a lithium cell and / or lithium battery.

Description

The present invention relates to a method for producing an anode active material and / or an anode and / or an electrolyte for a lithium cell and / or lithium battery, in particular for a lithium-ion cell and / or lithium-ion battery, and / or for producing such a lithium cell and / or lithium battery and an anode active material, an anode, an electrolyte and an electrolyte additive and such a lithium cell and / or lithium battery.

State of the art

The anode active material used today for lithium-ion cells and batteries is mainly graphite. However, graphite has only a small storage capacity.

Silicon, as an anode active material for lithium-ion cells and batteries, can offer a significantly higher storage capacity. However, silicon undergoes large volume changes upon cyclization, which may cause an SEI (solid electrolyte interphase) layer to be formed on the silicon surface from electrolyte decomposition products at a volume enlargement of silicon and at a volume reduction of the silicon, so that electrolyte comes in contact again with the silicon surface with each cycle and the SEI formation and electrolyte decomposition continuously progress, which can lead to irreversible loss of lithium (and electrolyte) and thus significantly lower cycle stability and capacity.

The publication US 2014/0248543 A1 relates to nanostructured silicon active materials for lithium-ion batteries.

The publication US 2014/0248543 A1 relates to a lithium-ion battery having an anode with at least one active material and with an electrolyte comprising at least one liquid polymer solvent and at least one polymer additive.

The publication US 2015/0072246 A1 relates to a non-aqueous liquid electrolyte for a battery, which may comprise a polymerizable monomer as an additive.

The publication US 2010/0273066 A1 describes a lithium-air battery with a non-aqueous electrolyte based on an organic solvent comprising a lithium salt and an additive having an alkylene group.

The publication US 2012/0007028 A1 relates to a process for producing polymer-silicon composite particles in which a monomer for forming a polymer matrix and silicon particles are mixed and the mixture is polymerized.

The publication CN 104 362 300 relates to a method for producing a silicon-carbon composite anode material for a lithium-ion battery.

The publication US 2014/0342222 A1 refers to particles having a silicon core and a block co-polymer shell having a block having a relatively high affinity for silicon and a block having a relatively low affinity for silicon.

H. Zhao et al., J. Power Sources, 263, 2014, pp. 288-295 the use of polymerized vinylene carbonate as the anode binder for lithium-ion batteries.

J.-H. Min et al. In Bull. Korean. Chem. Soc., 2013, Vol. 34, no. 4th, p. 1296-1299 the formation of an artificial SEI on silicon particles.

The publication WO 2015/107581 relates to an anode material for non-aqueous electrolyte batteries.

Disclosure of the invention

The present invention relates to a method for producing an anode active material and / or an anode and / or an electrolyte for a lithium cell and / or lithium battery, in particular for a lithium-ion cell and / or lithium-ion battery, and / or for producing a cell and / or lithium battery, in particular a lithium-ion cell and / or lithium-ion battery.

Anode active material particles, for example silicon particles and / or graphite particles and / or tin particles, in particular silicon particles, and / or an electrolyte with at least one crown ether and / or crown ether derivative with at least one polymerisable functional group and / or with at least one crown ether and / or or Kronether derivative comprising polymer, in particular reacted or offset.

By anode active material particles it is possible in particular to be understood as meaning particles which comprise at least one anode active material.

The anode active material particles may include or be, for example, silicon particles and / or graphite particles and / or tin particles.

By silicon particles can be understood in particular particles comprising silicon. By way of example, silicon particles may be understood to mean particles which contain silicon. Silicon particles can therefore be understood as meaning, in particular, silicon-based particles. For example, silicon particles, in particular pure or elemental silicon, for example porous silicon, for example nanoporous silicon, for example having a pore size in the nanometer range, and / or nanosilicon, for example having a particle size in the nanometer range, and / or a silicon alloy matrix or a silicon alloy. Alloy, for example, in which silicon is embedded in an active and / or inactive matrix, and / or comprise a silicon-carbon composite and / or silicon oxide (SiOx) or be formed thereof. For example, the silicon particles may be formed of, in particular pure or elemental, silicon.

Under graphite particles can be understood in particular particles comprising graphite.

Tin particles can be understood as meaning, in particular, particles which comprise tin.

By virtue of the fact that the anode active material particles, in particular silicon particles, and / or the electrolyte are provided with at least one crown ether and / or crown ether derivative having at least one polymerizable functional group and / or polymer comprising at least one crown ether and / or crown ether derivative, can advantageously an artificial SEI protective layer of a polymer can be formed on the particles, which is based on basic units of crown ethers (crown ether polymerization). Kronether and / or Kronether derivatives used as electrolyte additive with at least one polymerizable functional group, for example with at least one double bond, can - for example analogously to other electrolyte additives - react, for example reduced, during the first cycle on the anode surface, and thus advantageously a polymer Form SEI layer on basic building blocks of crown ethers. Polymers based on crown ethers can be advantageously, in particular selectively, ionic-conductive, in particular lithium-ion-conductive, and in particular provide optimal diffusion paths for the alkali metal ions, in particular lithium ions. In addition, polymers based on crown ethers can bond via van der Waals and / or hydrogen bond bonds to the surface of the anode active material particles, in particular silicon particles, and thus improve the adhesion of the polymer layer formed therefrom to the anode active material particles, in particular silicon particles.

An ion-conductive, for example lithium ion-conductive, material, for example monomer or polymer, may in particular be understood as meaning a material, for example monomer or polymer, which itself may be free of the ions to be conducted, for example lithium ions, but is suitable for the ions to be conducted For example, to coordinate and / or solvate lithium ions, and / or counterions of the ions to be conducted, for example, lithium-lead salt anions and, for example, lithium ion conducting with the addition of the conductive ions, for example lithium ions.

In this way, advantageously on the anode active material particles, in particular silicon particles, an artificial SEI layer in the form of a flexible, polymeric protective layer, in particular with a, in particular selective, ion conductivity, for example lithium ion conductivity, and / or with improved adhesion, be formed by this artificial Advantageously, an SEI layer in the form of a flexible, polymeric protective layer can be suppressed for electrolyte decomposition and continuous SEI formation, since the flexible, polymeric protective layer is involved in the volume changes of the anode active material particles, in particular silicon particles, during the cyclization, for example plastically can be stretched and / or compressed, without being destroyed and thus the anode active material particles, in particular silicon particles, passivate and protect against a reaction of the particle surface, in particular silicon surface, with electrolyte. Thus, in turn, advantageously, the cycle stability (English: Coulombic Efficiency) of the equipped with the anode active material lithium cell and / or battery, for example in the form of a lithium-ion cell and / or battery can be increased.

Overall, it is thus advantageously possible to provide an anode active material having increased cycle stability and storage capacity, for example by means of which, among other things, the range of electric vehicles could also be increased.

In particular, the anode active material particles may include or be silicon particles.

The electrolyte may in particular be an anolyte.

An anolyte may, in particular, be understood to mean an electrolyte for an anode.

In particular, the at least one crown ether and / or the at least one crown ether derivative can be polymerized and / or the polymer comprising at least one crown ether and / or crown ether derivative can be formed by polymerization of the at least one crown ether and / or crown ether derivative.

In one embodiment, the anode active material particles and / or the electrolyte (further) with at least one other polymerizable monomer, for example with at least two or three further polymerizable monomers, and / or at least one, by polymerization of the at least one crown ether and / or crown ether Derivatives and at least one other polymerizable monomer, for example, at least two or three other polymerizable monomers, polymer formed, in particular reacted or offset. In this case, the at least one crown ether and / or the at least one crown ether derivative and the at least one further polymerizable monomer can be (co) polymerized in particular and / or the at least one crown ether and / or crown ether derivative comprising (co) polymer by ( Co) polymerization of the at least one crown ether and / or crown ether derivative and the at least one further polymerizable monomer can be formed or be. By such a copolymerization, in particular by a targeted copolymerization, of two, three or more monomers, advantageously the desired properties, in particular the artificial SEI layer, can be set in a targeted manner and, for example, an adaptation or a design of the SEI layer can be achieved at their request. For example, polymer segments for binder reinforcement and / or for adaptation of the mechanical, for example rheological, properties, for example the strength and / or elasticity, can thus be introduced.

In another embodiment, the anode active material particles are provided with at least one polymer, in particular coated, which is formed from at least one crown ether and / or crown ether derivative having at least one polymerizable functional group, in particular by polymerization of the at least one crown ether and / or crown ether derivative and / or the electrolyte is mixed, in particular mixed, with at least one crown ether and / or crown ether derivative having at least one polymerisable functional group, in particular with the at least one crown ether and / or crown ether derivative. For example, the anode active material particles may be coated with at least one (co) polymer formed by (co) polymerization of the at least one crown ether and / or crown ether derivative and the at least one further polymerizable monomer and / or the electrolyte with the at least one crown ether and or Kronether derivative and mixed with the at least one further polymerizable monomer, in particular mixed.

The at least one crown ether and / or the at least one crown-ether derivative can be polymerized or copolymerized, for example, by free-radical polymerization and / or polymerization by condensation reaction and / or by ionic, for example anionic or cationic, polymerization. For example, the polymerization may therefore be free-radical polymerization and / or condensation reaction polymerization and / or ionic, for example anionic or cationic, polymerization.

For example, the polymerization of a radical polymerization and / or the at least one crown ethers and / or the at least one crown ether derivative and / or the at least one further polymerizable monomer can be polymerized and / or polymerized by a free-radical polymerization.

In particular, the polymerization of a living radical polymerization and / or the at least one crown ethers and / or the at least one crown ether derivative and / or the at least one further polymerizable monomer can be polymerizable and / or polymerized by a living free-radical polymerization.

Living radical polymerization is based on the principle that a dynamic balance is created between a relatively small number of active species, namely growth promoting free radicals, and a large number of deactivated species. This can be achieved in particular by a radical buffer which is capable of capturing and releasing the active species, namely free radicals, in the form of a deactivated species. In particular, therefore, at least one radical buffer can be used in the polymerization. Thus, irreversible chain transfer and chain termination reactions, which in particular can lead to a reduction in the number of active species and to a broadening of the molecular weight distribution, can be strongly suppressed. In particular, living radical polymerization can also be referred to as Living Free Radical Polymerization (LFRP) or Controlled Free Radical Polymerization (CFRP) or Living Controlled Free Radical Polymerization.

Examples of a living radical polymerization are the living atom transfer radical transfer (ATRP), for example, with electron transfer regenerated activators (ARGET-ATRP) (ARGET, English: Activators regenerated by electron transfer), Reversible Addition Fragmentation Chain Transfer Polymerization (RAFT), stable free radical polymerization (SFRP), in particular nitroxide-mediated polymerization (US Pat. NMP, English: Nitroxide-mediated Polymerization) and / or Verdazyl-mediated polymerization (VMP, English: Verdazyl Mediated Polymerization), and the iodine transfer polymerization (ITP).

By a living free-radical polymerization, in particular by a living radical polymerization with atom transfer and / or a stable free radical polymerization, for example a nitroxide-mediated polymerization and / or verdazyl-mediated polymerization, in particular a nitroxide-mediated polymerization, and / or a reversible addition Fragmentation chain transfer polymerization, advantageously a narrow molecular weight distribution or a low polydispersity (breadth of the molecular weight distribution) and / or improved control over the chain length of the polymer and, for example, a homogeneous polymer coating can be achieved. In this case, the molecular weight distribution and / or polymer layer thickness can be adjusted, for example, as a function of the chemical concentrations, for example monomer concentration, and / or reaction time and / or temperature.

In one embodiment, the polymerization is a living radical atom transfer (ATRP) polymerization and / or the at least one crown ether and / or the at least one crown ether derivative and / or the at least one further polymerizable monomer by a living radical polymerization with atom transfer ( ATRP) and / or the at least one crown ether and / or the at least one crown ether derivative and / or the at least one further polymerizable monomer is polymerized by a living free-radical radical polymerization (ATRP).

In a further embodiment, the polymerization is a stable free-radical polymerization (SFRP), for example nitroxide-mediated polymerization (NMP) and / or a Verdazyl-mediated polymerization (VMP), in particular a nitroxide-mediated polymerization (NMP) and / or is the at least one crown ether and / or the at least one crown ether derivative and / or the at least one further polymerizable monomer by a stable free radical polymerization (SFRP), for example by a nitroxide-mediated polymerization (NMP) and / or a Verdazyl-mediated Polymerization (VMP), in particular by a nitroxide-mediated polymerization (NMP), polymerizable and / or the at least one crown ether and / or the at least one crown ether derivative and / or the at least one further polymerizable monomer by a stable free radical polymerization ( SFRP), for example by nitroxide-mediated polymerization (NMP) and / or e in Verdazyl-mediated polymerization (VMP), in particular by a nitroxide-mediated polymerization (NMP), polymerized.

In a further embodiment, the polymerization is a reversible addition-fragmentation chain transfer polymerization (RAFT) and / or is the at least one crown ethers and / or the at least one crown-ether derivative, the at least one further polymerizable monomer by a reversible addition-fragmentation chain transfer polymerization (RAFT) polymerizable and / or the at least one crown ether and / or the at least one crown ether derivative, the at least one further polymerizable monomer by a reversible addition-fragmentation chain transfer polymerization (RAFT).

Within the scope of a further embodiment, the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative comprises or is at least one polymerisable double bond, for example at least one carbon-carbon double bond, in particular at least one vinyl group and / or at least one vinylene group and / or or at least one vinylidene group and / or at least one allyl group, for example an allyloxyalkyl group, for example an allyloxymethyl group, and / or at least one acrylate group and / or at least one methacrylate group and / or at least one phenylethene group (styrene group), and / or at least one hydroxy group. By means of these functional groups, advantageously a polymerization can be achieved. For example, the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative can have at least one vinyl group and / or at least one vinylidene group and / or at least one vinylidene group and / or at least one allyl group, for example allyloxyalkyl group, for example allyloxymethyl group, and / or at least one acrylate group and / or at least one methacrylate group and / or at least one hydroxy group, in particular alkylene hydroxy group, include or be. By means of at least one hydroxy group, the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative can be polymerized or copolymerized by condensation reaction or by anionic polymerization. For example, the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative may have at least one polymerizable double bond, for example at least one carbon-carbon double bond, in particular at least one vinyl group and / or at least one vinylene group and / or at least one vinylidene group and or at least one allyl group, for example allyloxyalkyl group, for example allyloxymethyl group, and / or at least one acrylate group and / or at least one methacrylate group and / or at least one phenylethene group (styrene group) comprise or be. This has proved to be particularly advantageous for the polymerization, in particular by means of a living radical polymerization, such as ATRP, NMP or RAFT.

The at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative can for example be attached directly to the crown ether or crown ether derivative. However, for steric reasons in particular, it may also be advantageous to provide a linker or a bridge segment, such as a benzene ring or cyclohexane ring, between the crown ether or crown ether derivative and the at least one polymerizable functional group, for example additionally. By polymerizing the at least one polymerizable double bond, in particular carbon-carbon double bond, it is possible in particular to form a polymer back, for example a C-C polymer backbone (C-C backbone), for example which has a crown ether-based functionality on every other carbon atom.

Within the scope of a further embodiment, the at least one crown ether and / or the at least one crown ether derivative and / or the polymer comprising at least one crown ether and / or crown ether derivative further comprises, in particular in addition to the at least one polymerizable functional group, at least one silane group , By virtue of the at least one silane group, the at least one crown ether and / or the at least one crown ether derivative and / or the polymer comprising at least one crown ether and / or crown ether derivative can advantageously be attached to the surface of the anode active material particles, in particular silicon particles, for example covalently. Thus, advantageously, a polymer layer can be formed with improved adhesion.

The provision of the anode active material particles, in particular silicon particles, with the polymer comprising at least one crown ether and / or crown ether derivative can be carried out, for example, by polymerization, optionally copolymerization, of the at least one crown ether and / or crown ether derivative in the presence of the anode active material particles, in particular silicon particles, and / or the electrolyte is carried out (in-situ polymerization) and / or - for example by means of at least one silane group and / or by means of, in particular by addition, at least one silane compound with at least one polymerizable and / or polymerization initiating and / or polymerization-controlling functional group - surface-initiated (graft from polymerization). By the at least one silane group and / or copolymerization of the at least one crown ether and / or crown ether derivative with the at least one silane compound having at least one polymerizable and / or polymerization initiating and / or polymerization-controlling functional group can, for example, advantageously a, in particular covalent, bond between the active material particles, in particular silicon particles, and the (at least one crown ethers and / or crown ether derivative or the at least one crown ether and / or Kronether derivative comprehensive (co) polymer, in particular be achieved by means of the silane function.

However, it is also possible to polymerize or prepare the polymer comprising at least one crown ether and / or crown ether derivative in the absence of the anode active material particles, in particular silicon particles, and / or of the electrolyte (ex situ polymerization). In this case, the anode active material particles, in particular silicon particles, for example, be provided in such a way with the at least one crown ether and / or Kronether derivative polymer that the at least one crown ethers and / or Kronether derivative comprehensive polymer produced in at least one solvent and / or dissolved in that the anode active material particles, in particular silicon particles, are added to the solution and the at least one solvent, for example by evaporation, is removed again. Thus, an active material-crown ether-polymer composite can be obtained in which the active material particles are bonded to the Kronether polymer at least via van der Waals and / or hydrogen bond bonds. By virtue of the at least one silane group and / or by copolymerization of the at least one crown ether and / or crown ether derivative with at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group, for example, one, in particular covalent, Binding between the active material particles, in particular silicon particles, and the at least one crown ether and / or crown ether derivative comprising co-polymer, in particular by means of the silane function, achieved (graft-to-polymerization).

In one embodiment, the anode active material particles, in particular silicon particles, are mixed with the at least one crown ether and / or crown ether derivative with at least one polymerizable functional group and polymerized (in-situ polymerization). In this case, the polymerization of the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative can be started by means of, for example, by adding at least one polymerization initiator. Advantageously, by means of the at least one polymerization initiator, the polymerization can be started in a targeted manner and the anode active material particles, in particular silicon particles, advantageously specifically provided with the polymer formed by the polymerization, in particular coated. By means of this in-situ polymerization, an artificial SEI layer in the form of a flexible, polymeric protective layer of the polymer formed by the polymerization can advantageously be formed on the anode active material particles.

In the context of a further embodiment, the at least one silane group of the at least one crown ether and / or crown ether derivative is immobilized on the surface of the anode active material particles, in particular silicon particles, and the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative is polymerized (graft -from polymerization). The at least one further polymerizable monomer can be added, in particular, together with the at least one crown ether and / or crown ether derivative or after the immobilization of the at least one silane group of the at least one crown ether and / or crown ether derivative, and in particular (co) polymerized , By virtue of the fact that the at least one silane group of the at least one crown ether and / or crown ether derivative is immobilized on the surface of the anode active material particles, in particular silicon particles, advantageously a stable, for example covalent, binding of the polymer obtained by the polymerization of the at least one polymerizable functional group of the at least obtained a Kronethers and / or Kronether derivative formed polymer to the anode active material particles, in particular silicon particles, and thus a polymer layer having an improved adhesion to the anode active material particles, in particular silicon particles, are formed.

Within the scope of a further embodiment, at least one silane compound having at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group is immobilized on the surface of the anode active material particles, in particular silicon particles, and the at least one crown ether and / or the at least one crown ether derivative are added and, in particular polymerized (graft-from-polymerization). The at least one further polymerizable monomer can be added, in particular, together with the at least one crown ether and / or crown ether derivative, and in particular (co) polymerized. By immobilizing the at least one silane compound having at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group on the surface of the anode active material particles, in particular silicon particles, it is advantageously possible to permit polymerization from the surface the anode active material particles, in particular silicon particles to start from. Thus, advantageously, a graft-from polymerization, for example, a surface-initiated living radical polymerization, such as a surface-initiated, living radical atom transfer (ATRP heterogeneous ATRP) polymerization (ATRP, Atom Transfer Radical Polymerization or Atomic Transfer Radical Polymerization) or a surface-initiated, stable free-radical polymerization (surface-initiated SFRP, heterogeneous SFRP) (SFRP, English: Stable Free Radical Polymerization), such as surface-initiated, nitroxide-mediated polymerization (surface-initiated NMP; heterogeneous NMP polymerization) (NMP, English : Nitroxide-mediated Polymerization), or a surface-initiated, reversible addition-fragmentation chain transfer polymerization (surface-initiated RAFT, heterogeneous RAFT polymerization) (RAFT, Reversible Addition Fr agementation chain transfer polymerization) or a surface-initiated iodine transfer polymerization (ITP) (Iodine Transfer Polymerization). By a polymerization proceeding from the surface of the anode active material particles, in particular silicon particles, advantageously a stable, for example covalent and / or physical / mechanical, connection and / or adhesion between the anode active material particles, in particular silicon particles, and the polymer formed by the polymerization can be achieved Polymer layer with improved adhesion to the anode active material particles, in particular silicon particles, are formed.

Within the scope of a further embodiment (ex situ polymerization), the at least one crown ether and / or the at least one crown ether derivative, if appropriate in at least one solvent, are polymerized and, in particular then, anode active material particles, in particular silicon particles, for example to the solution, added and / or the polymer comprising at least one crown ether and / or Kronether derivative is dissolved in at least one solvent and are added to the solution anode active material particles, in particular silicon particles. The at least one solvent can, in particular then be removed again, for example by evaporation. Within the scope of one embodiment thereof, the at least one crown ether and / or the at least one crown ether derivative and / or the polymer comprising at least one crown ether and / or crown ether derivative has at least one silane group and / or is reacted with at least one silane compound having at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group, for example polymerized (graft-to-polymerization). Thus, advantageously, a polymer or co-polymer can be formed or used with a silane function which, in addition to the addition of anode active material particles, in particular silicon particles, can additionally enter via the silane function an especially covalent bond with the anode active material particles, in particular silicon particles (graft-to polymerization). In this way, the adhesion of the polymer layer formed on the anode active material particles, in particular silicon particles, can be further improved-in particular in addition to van der Waals and / or hydrogen bond bonds-by an especially covalent bond via the silane function.

und/oder einen 15-5-Kroneether:

und/oder einen Aza-Kronether, beispielsweise einen (Di-)Aza-Kronether, beispielsweise einen Aza-12-4-Kronether, zum Beispiel einen 1-Aza-12-4-Kronether, zum Beispiel:

und/oder einen Aza-15-5-Kroneether, beispielsweise einen Di-Aza-Kronenether, zum Beispiel einen Di-Aza-12-4-Kronether und/oder einen Di-Aza-15-5-Kroneether, zum Beispiel:

und/oder einen, insbesondere N-substituierten, (Di-)Aza-Kronether, beispielsweise einen N-Alkyl-(Di-)Aza-12-4-Kronether und/oder N-Alkyl-(Di-)Aza-15-5-Kronether, und/oder
einen Benzo-Kronether, insbesondere einen Benzo-12-4-Kronether und/oder Benzo-15-5-Kroneether, zum Beispiel:

beispielsweise einen Di-Benzo-Kronether, zum Beispiel einen Di-Benzo-12-4-Kronether, zum Beispiel:

und/oder einen Di-Benzo-15-5-Kroneether, und/oder einen Cyclohexano-Kronether, insbesondere einen Cyclohexano-12-4-Kronether und/oder Cyclohexano-15-5-Kroneether, beispielsweise einen Di-Cyclohexano-Kronenether, zum Beispiel einen Di-Cyclohexano-12-4-Kronether, zum Beispiel:

und/oder einen Di-Cyclohexano-15-5-Kroneether, umfassen oder darauf basieren.In particular, the at least one crown ether and / or the at least one crown ether derivative
a crown ether, especially one
12-4-crown ether:

and / or a 15-5 crown ether:

and / or an aza-crown ether, for example a (di-) aza-crown ether, for example an aza-12-4-crown ether, for example a 1-aza-12-4-crown ether, for example:

and / or an aza-15-5-crown ether, for example a di-aza-crown ether, for example a di-aza-12-4-crown ether and / or a di-aza-15-5-crown ether, for example:

and / or one, in particular N-substituted, (di) aza-crown ethers, for example an N-alkyl (di) aza-12-4-crown ether and / or N-alkyl- (di-) aza-15- 5-crown ethers, and / or
a benzo-crown ether, in particular a benzo-12-4-crown ether and / or benzo-15-5-crown ether, for example:

for example a di-benzo-crown ether, for example a di-benzo-12-4-crown ether, for example:

and / or a di-benzo-15-5-crown ether, and / or a cyclohexano-crown ether, in particular a cyclohexano-12-4-crown ether and / or cyclohexano-15-5-crown ether, for example a di-cyclohexano-crown ether, for example a di-cyclohexano-12-4-crown ether, for example:

and / or a di-cyclohexano-15-5 crown ether, or based thereon.

In a further embodiment, the at least one crown ether and / or the at least one crown ether derivative comprises a crown ether or a crown ether derivative of the general chemical formula:

In particular, Q1, Q2, Q3 and Qk may each independently of one another denote oxygen (O) or nitrogen (N) or an amine, for example a secondary amine (NH) and / or a tertiary amine, for example an alkyl- or arylamine, ( NR), stand.

G may in particular be at least one polymerisable functional group, for example with which one of the carbon atoms and / or Q1 and / or Q2 and / or Q3 and / or Qk is substituted.

g may be in particular for the number of polymerisable functional groups G and in particular 1 ≦ g, for example 1 ≦ g ≦ 5, for example 1 ≦ g ≦ 2.

In particular, k can stand for the number of units in parentheses, and in particular 1 ≦ k, for example 1 ≦ k ≦ 3, for example 1 ≦ k ≦ 2.

In particular, G may have at least one polymerisable double bond, for example at least one carbon-carbon double bond, for example at least one vinyl group and / or at least one vinylidene group and / or at least one vinylene group and / or at least one allyl group, for example allyloxyalkyl group, for example allyloxymethyl group, and / or at least one hydroxy group, for example alkylene hydroxy group, for example methylene hydroxy group.

Furthermore, G may, for example, one or more other groups, for example, which serve as a linker - ie a bridging unit or as a bridge segment - include. For example, G may further include at least one benzo group and / or cyclohexano group.

umfassen.In particular, Q1, Q2, Q3 and Qk may be oxygen. For example, the at least one crown ether and / or the at least one crown ether derivative may be a crown ether or a crown ether derivative of the general chemical formula:

include.

und/oder

und/oder

und/oder

und/oder

umfassen, insbesondere wobei 0 ≤ k', beispielsweise 0 ≤ k' ≤ 2, zum Beispiel 0 ≤ k' ≤ 1, ist.For example, the at least one crown ether and / or the at least one crown ether derivative may be a crown ether or a crown ether derivative of the general chemical formula:

and or

and or

and or

and or

in particular, where 0 ≦ k ', for example 0 ≦ k' ≦ 2, for example 0 ≦ k '≦ 1.

By polymerization, for example living radical polymerization, of the double bonds, polymers with a carbon-carbon-polymer backbone (CC backbone) and crown ether or crown ether derivative side groups can be formed, for example:

Alternatively or additionally, it is also possible, for example, to form polymers with crown ether or crown ether derivative groups, in particular directly, in the polymer backbone or in the polymer chain. This can be achieved, for example, by polymerization, for example by condensation reaction, for example etherification, of (di) benzoic and / (di) cyclohexano-crown ethers and / or crown ether derivatives, for example having at least two, optionally four, hydroxyl groups, for example to the Benzo and / or cyclohexano rings, possible.

In a further embodiment, the at least one crown ether and / or the at least one crown ether derivative comprises a crown ether or a crown ether derivative of the general chemical formula:

G 'may in particular stand for at least one polymerisable functional group. In particular, G 'may have at least one polymerizable double bond, for example at least one carbon-carbon double bond, for example at least one vinyl group and / or at least one vinylidene group and / or at least one vinylene group and / or at least one allyl group, for example allyloxyalkyl, for example allyloxymethyl, and or at least one hydroxy group, for example alkylene hydroxy group, for example methylene hydroxy group.

Furthermore, G 'may comprise, for example, one or more further groups, for example which serve as linkers - ie a bridging unit or bridge segment. For example, G 'may further comprise at least one benzo group and / or cyclohexano group.

g 'may in particular be the number of polymerisable functional groups G' and in particular 1 ≦ g ', for example 1 ≦ g' ≦ 4, for example 1 ≦ g '≦ 2.

und/oder

umfassen.For example, the at least one crown ether and / or the at least one crown ether derivative may be a crown ether or a crown ether derivative of the general chemical formula:

and or

include.

beziehungsweise

By polymerization, for example by condensation reaction, in particular etherification, of the hydroxy groups, it is possible to form polymers, in particular based on etherified benzo crown ethers, with crown ethers or crown ether derivative groups in the polymer back, for example:

respectively

Such crown ethers and / or crown ether derivatives can advantageously be combined by reaction with at least one silane compound having at least one polymerisable functional group, for example by condensation reaction, for example covalently, with the anode active material particles, in particular silicon particles.

wobei R1, R2, R3 insbesondere jeweils unabhängig voneinander für ein Halogenatom, insbesondere Chlor (-CI), oder eine Alkoxygruppe, insbesondere eine Methoxygruppe (-OCH₃) oder eine Ethoxygruppe (-OC₂H₅), oder eine Alkylgruppe, beispielsweise eine lineare Alkylgruppe (-(CH₂)_x-CH₃) mit x ≥ 0, insbesondere eine Methylgruppe (-CH₃), oder eine Aminogruppe (-NH₂, -NH-) oder eine Silazangruppe (-NH-Si-) oder eine Hydroxygruppe (-OH) oder Wasserstoff (-H) stehen, mittels Kondensationsreaktion, insbesondere durch Reaktion der Hydroxygruppe des Kronethers mit dem Chloratom der Silanverbindung, miteinander und, insbesondere durch Reaktion von R1, R2 und/oder R3 der Silanverbindung mit Hydroxygruppen, insbesondere Siliciumhydroxidgruppen beziehungsweise Silanolgruppen (Si-OH), auf der Oberfläche der Anodenaktivmaterialpartikel, insbesondere Siliciumpartikel, mit den Anodenaktivmaterialpartikeln, insbesondere Siliciumpartikeln, beispielsweise kovalent, verbunden werden.For example, a crown ether and a silane compound of the general chemical formulas:

in which, in each case, R 1, R _2, R ₃ independently of one another represent a halogen atom, in particular chlorine (-CI), or an alkoxy group, in particular a methoxy group (-OCH ₃ ) or an ethoxy group (-OC ₂ H ₅ ), or an alkyl group, for example one linear alkyl group (- (CH ₂ ) _x -CH ₃ ) where x ≥ 0, in particular a methyl group (-CH ₃ ), or an amino group (-NH ₂ , -NH-) or a silazane group (-NH-Si) or a hydroxy group (-OH) or hydrogen (-H), by condensation reaction, in particular by reaction of the hydroxy group of the crown ether with the chlorine atom of the silane compound with each other and, in particular by reaction of R1, R2 and / or R3 of the silane compound with hydroxyl groups, in particular Silicon hydroxide groups or silanol groups (Si-OH), on the surface of the anode active material particles, in particular silicon particles, with the anode active material particles, in particular silicon particles, for example covalently, are connected.

Within the scope of a further embodiment, the at least one crown ether and / or the at least one crown ether derivative comprises a crown ether or a crown ether derivative of the general chemical formula:

In particular, Q1, Q2, Q3 and Qk may each independently of one another denote oxygen (O) or nitrogen (N) or an amine, for example a secondary amine (NH) and / or a tertiary amine, for example an alkyl- or arylamine, ( NR), stand.

G may in particular be at least one polymerisable functional group, for example with which one of the carbon atoms and / or Q1 and / or Q2 and / or Q3 and / or Qk is substituted. In particular, G may have at least one polymerisable double bond, for example at least one carbon-carbon double bond, for example at least one vinyl group and / or vinylidene group and / or vinylene group and / or allyl group, for example allyloxyalkyl group, for example allyloxymethyl group, and / or at least one hydroxy group, for example Alkylene hydroxy group, for example methylene hydroxy group.

Furthermore, G may, for example, one or more other groups, for example, which serve as a linker - ie a bridging unit or as a bridge segment - include. For example, G may further include at least one benzo group and / or cyclohexano group.

g may be in particular for the number of polymerisable functional groups G and in particular 1 ≦ g, for example 1 ≦ g ≦ 5, for example 1 ≦ g ≦ 2.

In particular, k can stand for the number of units in parentheses, and in particular 1 ≦ k, for example 1 ≦ k ≦ 3, for example 1 ≦ k ≦ 2.

Y 'can in particular stand for a linker, ie a bridging unit. For example, Y 'can be at least one alkylene group (-C _n H _2n -) with n ≥ 0, in particular n ≥ 1, and / or at least one alkylene oxide group (-C _n H _2n -O-) with n ≥ 1 and / or at least one Carboxylic ester group (-C = OO-) and / or at least one phenylene group (-C ₆ H ₄ -) include. For example, Y 'may here stand for an alkylene group -C _n H _2n - where 0 ≦ _n ≦ 5, for example n = 1 or 2 or 3.

s may be in particular for the number of silane groups (-SiR1R2R3), in particular via linker Y ', and in particular 1≤s, for example 1≤S≤5, for example 1≤S≤2.

R 1, R _2, R ₃ may each, in each case independently of one another, denote a halogen atom, in particular chlorine (-CI), or an alkoxy group, in particular a methoxy group (-OCH ₃ ) or an ethoxy group (-OC ₂ H ₅ ), or an alkyl group, for example a linear alkyl group (- (CH ₂ ) _x -CH ₃ ) where x ≥ 0, in particular a methyl group (-CH ₃ ), or an amino group (-NH ₂ , -NH-) or a silazane group (-NH-Si) or a hydroxy group (-OH) or hydrogen (-H). For example, R1, R2 and R3 may be chlorine.

umfassen.In particular, Q1, Q2, Q3 and Qk may be oxygen. By way of example, the at least one crown ether and / or the at least one crown-ether derivative may be a crown ether or a crown-ether derivative of the general chemical formula:

include.

und/oder

Examples of crown ethers or a Kronether derivative are:

and or

Such crown ethers or a crown-ether derivative can advantageously bind via the silane group to the anode active material particles, in particular silicon particles, and additionally serve as silane-based adhesion promoters.

Insofar as the at least one crown ether and / or the at least one crown ether derivative comprises a (di) aza-crown ether derivative, for example with vinyl functionality, NH group (s) can be substituted before the polymerization or provided with a protective group, for example alkylated, preferably methylated. Thus, it can be prevented that the NH group (s) interfere with the polymerization, for example, a radical (co) polymerization and / or an anionic (co) polymerization. In addition, substituted or tertiary amine groups or N-R bonds can be more resistant to alkali metals.

zum Beispiel

, beispielsweise wobei 0 ≤ i ≤ 4 ist, verwendet werden.Alternatively or additionally, however, it is also possible, for example, to use a reaction of the NH group (s) of (di) aza-crown ether derivatives in a targeted manner in the polymerization, for example, nitrogen-substituted (di) aza-crown ethers -Derivat polymers and / or block co-polymers, for example by reaction of at least one, in particular terminal, polymerizable double bond, for example vinyl and / or allyl group, the at least one (di) aza-Kronether derivative having at least one polymerizable double bond at least one further polymerizable monomer or polymer formed therefrom, for example with styrene, form. For example, for this purpose, the NH group (s) of (di) aza-crown ether derivatives can be coupled via (CH ₂ ) _n bridges, in particular by reaction with at least one alpha-omega-alkylene compound and / or alpha-omega-diamines, for Example hexamethylenediamine, for the synthesis of a (di) aza-Kronether derivative polymer, for example a poly-n-alkylene-di-aza-crown ether, for example the general chemical formula:

for example

, for example, where 0≤i≤4, may be used.

The at least one crown ether and / or the at least one crown ether derivative and / or the at least one further polymerizable monomer may be in particular ion-conductive or ion-conducting, in particular lithium-ion-conductive or lithium-ion-conducting, and / or fluorinated and / or designed to form a gel polymer or at least one ion-conducting or ion-conducting, in particular lithium-ion-conducting or lithium ion-conducting, polymerizable monomer and / or at least one fluorinated, polymerizable monomer, for example having at least one fluorinated alkyl group and / or at least one fluorinated alkoxy group and / or at least one fluorinated alkylene oxide group and / or at least one fluorinated Phenyl group, and / or comprise at least one polymerizable monomer to form a gel polymer or be.

By polymerizing ion-conductive or ion-conducting and / or fluorinated and / or gel-polymer-forming monomers, an artificial polymer-SEI protective layer can advantageously be formed on the anode active material particles, in particular silicon particles, which are ion-conductive or ion-conducting and / or fluorinated and / or for formation a gel polymer is designed. By ion-conducting or ion-conducting polymer and / or gel polymers, advantageously, a high efficiency of the cell or battery equipped with the anode active material can be achieved and, for example, an electrolyte coating or a gel electrolyte coating can be formed directly on the anode active material particles, in particular silicon particles. Fluorine-based polymers can have a high thermodynamic and in particular also electrochemical stability and advantageously be particularly stable in a potential window used in lithium-ion cells and / or batteries.

In one embodiment, the at least one further polymerizable monomer or comprise at least two, for example three, further polymerizable monomers (each) at least one polymerizable double bond, for example at least one carbon-carbon double bond, in particular at least one vinyl group and / or at least one vinyl group and / or at least one vinylidene group and / or at least one allyl group, for example an allyloxyalkyl group, for example an allyloxymethyl group, and / or at least one acrylate group and / or at least one methacrylate group and / or at least one phenylethene group (styrene group), and / or at least one hydroxy group , By means of these functional groups, advantageously a polymerization can be achieved. In particular, the at least one further polymerizable monomer or the at least two, for example three, further polymerizable monomers (each) at least one polymerizable double bond, for example at least one carbon-carbon double bond, in particular at least one vinyl group and / or at least one vinylene group and / or at least one vinylidene group and / or at least one allyl group, for example allyloxyalkyl group, for example allyloxymethyl group, and / or at least one acrylate group and / or at least one methacrylate group and / or at least one phenylethene group (styrene group). This has proved to be particularly advantageous for the polymerization, in particular by means of a living radical polymerization, such as ATRP, NMP or RAFT. By at least one hydroxyl group, the at least one further polymerizable monomer or the at least two other polymerizable monomers can be polymerized or copolymerized by condensation reaction or by anionic polymerization.

Within the scope of a further embodiment, the at least one crown ether and / or the at least one Kronether derivative and / or the at least one further polymerizable monomer (further) at least one, in particular unfluorinated, alkylene oxide group, for example ethylene oxide group, for example polyalkylene oxide group, for example polyethylene oxide group or polyethylene glycol group , and / or at least one fluorinated alkylene oxide group and / or at least one fluorinated alkoxy group and / or at least one fluorinated alkyl group and / or at least one fluorinated phenyl group.

Polymers which comprise alkylene oxide groups or are formed from alkylene oxide monomers or are based on a polyalkylene oxide, such as polyethylene oxide (PEO) or polyethylene glycol (PEG), may advantageously be ion-conductive, for example lithium ion conductive. Thus, advantageously, an ionic conductive, for example, lithium ion conductive, artificial SEI protective layer, for example, from a polyethylene oxide (PEO) or polyethylene glycol (PEG) based polymer, are formed on the particles. In the presence of at least one conducting salt, for example lithium conducting salt, polymers having alkylene oxide groups or based on a polyalkylene oxide, such as polyethylene oxide (PEO) or polyethylene glycol (PEG), can be ion-conducting, for example lithium ion-conducting. With such polymers provided, in particular coated, anode active material particles, in particular silicon particles, in a Zellbeziehungsweise battery assembly with at least one conductive salt, such as lithium conductive salt, come into contact and in this way ion-conducting, for example, lithium ion-conducting. In order to achieve a high efficiency of the cell or battery equipped with the anode active material and in particular a high ionic conductivity, coated, in particular coated, anode active material particles, in particular silicon particles, but in particular, for example, before the cell and / or battery assembly, with at least one conductive salt For example, lithium-conducting salt, for example, lithium hexafluorophosphate (LiPF ₆ ), bis (trifluoromethane) sulfonimide (LiTFSI) and / or lithium perchlorate (LiClO ₄ ), are treated. In addition, such polymers in the presence of at least one electrolyte solvent or at least one liquid electrolyte, for example based on a solution of at least one conductive salt in at least one electrolyte solvent, for example before or during cell and / or battery assembly, form a gel and be used, for example, as a gel electrolyte , For example, therefore, provided, in particular coated, particles, for example, before the cell and / or battery assembly, with at least one electrolyte solvent and / or at least one liquid electrolyte, in particular from at least one conductive salt, for example lithium conductive salt, for example lithium hexafluorophosphate (LiPF ₆ ), bis (trifluoromethane) sulfonimide (LiTFSI) and / or lithium perchlorate (LiClO ₄ ), and at least one electrolyte solvent. Thus, advantageously in addition to an artificial SEI protective layer for passivating the anode active material particles, in particular silicon particles, an electrolyte coating or a gel electrolyte coating can be formed directly on the anode active material particles, in particular silicon particles. In particular, however, insofar as only the anode active material particles, in particular silicon particles, are coated with an electrolyte coating or gel electrolyte coating, the anode can furthermore comprise at least one electrolyte, for example liquid electrolytes, for example based on carbonate.

• - mindestens eine polymerisierbare Carbonsäure, beispielsweise Acrylsäure und/oder Methacrylsäure, und/oder
• - mindestens ein polymerisierbares Carbonsäure-Derivat, insbesondere
  • - mindestens polymerisierbares organische Carbonat, beispielsweise Vinylencarbonat und/oder Vinylethylencarbonat, und/oder Anhydrid, insbesondere mindestens ein Carbonsäureanhydrid, beispielsweise Maleinsäureanhydrid, und/oder
  • - mindestens einen Carbonsäureester, beispielsweise mindestens ein Acrylat, zum Beispiel mindestens ein Etheracrylat, beispielsweise Poly(ethylenglykol)methyletheracrylat, und/oder mindestens ein Methacrylat, beispielsweise Methylmethacrylat, und/oder mindestens ein Acetat, zum Beispiel Vinylacetat, und/oder
  • - mindestens ein Carbonsäurenitril, beispielsweise Acrylnitril, und/oder
• - mindestens einen, beispielsweise unfluorierten oder fluorierten, Ether, insbesondere mindestens einen weiteren Kronether und/oder mindestens ein weiteres Kronether-Derivat und/oder mindestens einen Vinylether, zum Beispiel Trifluorvinylether, und/oder
• - mindestens ein, beispielsweise unfluoriertes oder fluoriertes, Alkylenoxid, beispielsweise Ethylenoxid, und/oder
• - mindestens einen, beispielsweise aliphatischen oder aromatischen, zum Beispiel unfluorierten oder fluorierten, ungesättigten Kohlenwasserstoff, beispielsweise mindestens ein Alken, zum Beispiel Ethen, wie 1,1-Difluorethen (1,1-Difluoroethylen, Vinylidenfluorid) und/oder Tetrafluorethylen (TFE), und/oder Propen, wie Hexafluorpropen, und/oder Hexen, wie 3,3,4,4,5,5,6,6,6-Nonafluorhexen, und/oder Phenylethen, wie 2,3,4,5,6-Pentafluorphenylethen (2,3,4,5,6-Pentafluorstyrol) und/oder 4-(Trifluormethyl)phenylethen (4-(Trifluoromethyl)styrol) und/oder Styrol, umfassen oder sein.

In the context of an alternative or additional embodiment, this comprises or is at least one further polymerizable monomer or are the at least two, in particular three, further polymerizable monomers selected from the group comprising:

• at least one polymerisable carboxylic acid, for example acrylic acid and / or methacrylic acid, and / or
• - At least one polymerizable carboxylic acid derivative, in particular
  • at least polymerizable organic carbonate, for example vinylene carbonate and / or vinyl ethylene carbonate, and / or anhydride, in particular at least one carboxylic anhydride, for example maleic anhydride, and / or
  • at least one carboxylic acid ester, for example at least one acrylate, for example at least one ether acrylate, for example poly (ethylene glycol) methyl ether acrylate, and / or at least one methacrylate, for example methyl methacrylate, and / or at least one acetate, for example vinyl acetate, and / or
  • at least one carbonitrile, for example acrylonitrile, and / or
• at least one, for example, unfluorinated or fluorinated, ether, in particular at least one further crown ether and / or at least one further crown ether derivative and / or at least one vinyl ether, for example trifluorovinyl ether, and / or
• at least one, for example unfluorinated or fluorinated, alkylene oxide, for example ethylene oxide, and / or
• at least one, for example aliphatic or aromatic, for example unfluorinated or fluorinated, unsaturated hydrocarbon, for example at least one alkene, for example ethene, such as 1,1-difluoroethene (1,1-difluoroethylene, vinylidene fluoride) and / or tetrafluoroethylene (TFE), and / or propene, such as hexafluoropropene, and / or hexene, such as 3,3,4,4,5,5,6, 6,6-Nonafluorhexen, and / or phenylethene, such as 2,3,4,5,6-pentafluorophenylethene (2,3,4,5,6-pentafluorostyrene) and / or 4- (trifluoromethyl) phenylethene (4- (trifluoromethyl ) styrene) and / or styrene, include or be.

In one embodiment, the at least one further polymerizable monomer or comprise the at least two, in particular three, further polymerizable monomers at least one polymerizable carboxylic acid.

und/oder ein Derivat davon.In the context of one embodiment of this embodiment, this comprises or is at least one further polymerizable monomer or comprise at least two, in particular three, further polymerizable monomers of acrylic acid:

and / or a derivative thereof.

In another, alternative or additional embodiment of this embodiment, the at least one further polymerizable monomer or comprises at least two, in particular three, further polymerizable monomers methacrylic acid and / or a derivative thereof.

By polymerization of acrylic acid or methacrylic acid, an artificial SEI protective layer can be formed from a polymer based on polyacrylic acid or polymethacrylic acid on the particles. In this case, the polyacrylic acid or polymethacrylic acid-based polymer via carboxylic acid groups (-COOH) to hydroxy groups, in particular silicon hydroxide groups or silanol groups (Si-OH), at the surface of the anode active material particles, in particular silicon particles, for example covalently via a condensation reaction and / or via hydrogen bonds connect. In addition to a passivation of the particles by a protective layer of the polyacrylic acid or polymethacrylic acid-based polymer, the polyacrylic acid or polymethacrylic acid-based polymer can advantageously serve as a binder reinforcement and / or binder and in this way the binding property of the anode active material can be improved. By virtue of the fact that the polymer based on polyacrylic acid or polymethacrylic acid is prepared in the presence of the anode active material particles, in particular silicon particles, a more homogeneous mixture can advantageously be formed than is possible by admixing ex situ-produced polyacrylic acid or polymethacrylic acid to anode active material particles, in particular silicon particles.

In a further embodiment, the polymer formed from the at least one further polymerizable monomer, in particular its carboxylic acid groups, at least partially with at least one alkali metal hydroxide, for example lithium hydroxide (LiOH) and / or sodium hydroxide (NaOH) and / or potassium hydroxide (KOH), in particular Formation of an alkali metal carboxylate, for example, lithium carboxylate or sodium carboxylate or potassium carboxylate, neutralized. Thus, the rheological properties can be improved and / or an irreversible loss of capacity, in particular in the first cycle of a cell or battery equipped with the anode active material, can be minimized.

In the context of an alternative or additional, further embodiment, the at least one further polymerizable monomer or comprise the at least two, in particular three, further polymerizable monomers at least one polymerizable carboxylic acid derivative.

Within the scope of a further embodiment, the at least one further polymerizable monomer or comprising at least two, in particular three, further polymerisable monomers comprises or is at least one polymerisable, organic carbonate and / or anhydride, in particular at least one carboxylic acid anhydride. In particular, the at least one further polymerizable monomer may comprise or be at least one polymerisable, organic carbonate. Organic carbonates have proven to be particularly advantageous for forming an artificial SEI layer. In addition, organic carbonates can advantageously be ion-conductive, in particular lithium-ion-conductive.

Within the scope of a further embodiment, the at least one further polymerizable monomer comprises or is vinylene carbonate and / or vinyl ethylene carbonate and / or maleic anhydride and / or a derivative thereof. This has proved to be advantageous for forming an artificial SEI layer, in particular ion-conductive, for example lithium ion-conductive, artificial SEI layer.

Within the scope of a specific embodiment of this embodiment, the at least one further polymerizable monomer comprises or is vinylene carbonate. By polymerizing vinylene carbonate, in particular polyvinylene carbonate can be formed, which has proved to be particularly advantageous as a polymer for an artificial SEI layer.

In the context of an alternative or additional, further embodiment, the at least one further polymerizable monomer or comprises the at least two, in particular three, further polymerizable monomers at least one carboxylic acid ester.

und/oder mindestens ein Methacrylat, beispielsweise Methylmethacrylat, und/oder mindestens ein Acetat, zum Beispiel Vinylacetat, und/oder ein Derivat davon umfassen oder sein.For example, the at least one further polymerizable monomer or the at least two, in particular three, further polymerizable monomers can be at least one acrylate, for example at least one ether acrylate, such as poly (ethylene glycol) methyl ether acrylate, for example:

and / or at least one methacrylate, for example methyl methacrylate, and / or at least one acetate, for example vinyl acetate, and / or a derivative thereof include or be.

By polymerizing acrylates, for example, ether acrylates, such as poly (ethylene glycol) methyl ether acrylate, and / or methacrylates, such as methyl methacrylate (MMA), an artificial SEI protective layer of polyacrylate or polymethyl methacrylate (PMMA) based polymer can be formed on the particles. Polymers based on polyacrylate, for example ether acrylate-based polymers or polymethyl methacrylates, can advantageously be prepared in the presence of at least one electrolyte solvent, for example at least one liquid, organic carbonate, such as ethylene carbonate (EC) and / or ethyl methyl carbonate (EMC) and / or dimethyl carbonate (DMC). and / or diethyl carbonate (DEC), or at least one liquid electrolyte, for example based on one, for example 1 M, solution of at least one conducting salt, for example lithium hexafluorophosphate (LiPF ₆ ) and / or bis (trifluoromethane) sulfonimide (LiTFSI) and / or lithium perchlorate (LiClO ₄ ), in at least one electrolyte solvent, for example, at least one liquid organic carbonate, such as ethylene carbonate (EC) and / or ethyl methyl carbonate (EMC) and / or dimethyl carbonate (DMC) and / or diethyl carbonate (DEC), for example cell and / or battery assembly, form a gel and b For example, be used as a gel electrolyte. Thus, advantageously, in addition to an artificial SEI protective layer for passivating the anode active material particles, in particular silicon particles, a gel electrolyte coating can be formed directly on the anode active material particles, in particular silicon particles. In a first cycle of a cell or battery equipped therewith, the electrolyte in the polymer gel matrix of the gel electrolyte coating may decompose and mechanically stabilize the, especially artificial or naturally occurring, SEI protective layer. This advantageously makes it possible to dispense with the addition of SEI-stabilizing additives, such as vinylene carbonate (VC) or fluoroethylene carbonate (FEC), in particular to the liquid electrolyte, in cell and / or battery assembly. Polymers based on ether acrylates, such as poly (ethylene glycol) methyl ether acrylate, may additionally be ion-conductive, for example lithium ion conductive, and in the presence of at least one conducting salt, for example lithium conducting salt, for example by bringing it into contact with at least one conducting salt, for example lithium conducting salt Cell or battery assembly, ion-conducting, for example, lithium ion-conducting, are. In order to achieve a high efficiency of the cell or battery equipped with the anode active material and, in particular, a high ionic conductivity, coated, in particular coated, anode active material particles, in particular silicon particles, but in particular, for example prior to cell and / or battery assembly, may contain at least one conductive salt For example, lithium-conducting salt, for example, lithium hexafluorophosphate (LiPF6), bis (trifluoromethane) sulfonimide (LiTFSI) and / or lithium perchlorate (LiClO ₄ ) are treated.

By polymerizing vinyl acetate, an artificial SEI protective layer of a polyvinyl acetate (PVAC) based polymer can be formed on the particles. The polyvinyl acetate-based polymer can then be saponified, for example, to polyvinyl alcohol (PVAL). To avoid side reactions with other electrode components, in this case, for example, the polymerization of the at least one further polymerizable monomer and, in particular, the saponification of the polymer formed thereby can be carried out separately from further electrode components. The polyvinyl alcohol-based polymer can advantageously via hydroxy groups (-OH), in particular silicon hydroxide groups or silanol groups (Si-OH), at the surface of the anode active material particles, in particular silicon particles, for example covalently via a condensation reaction and / or via hydrogen bonds connect. In addition to passivating the particles through a protective layer of the polyvinyl alcohol-based polymer, the polyvinyl alcohol-based polymer may advantageously serve as a binder reinforcement and thus improve the binding property of the anode active material. In addition, because the polyvinyl alcohol-based polymer is produced in the presence of the anode active material particles, in particular silicon particles, a more homogeneous mixture can advantageously be formed than is possible by admixing ex situ-produced polyvinyl alcohol to anode active material particles, in particular silicon particles.

In the context of an alternative or additional, further embodiment, the at least one further polymerizable monomer or the at least two, in particular three, polymerizable monomers comprises or is at least one carbonitrile. For example, the at least one further polymerizable monomer or the at least two, in particular three, polymerizable monomers may comprise or be acrylonitrile and / or a derivative thereof. By polymerizing acrylonitrile, an artificial SEI protective layer of polyacrylonitrile (PAN) based polymer can be formed on the particles. Polymers based on polyacrylonitrile (PAN) can advantageously be prepared in the presence of at least one electrolyte solvent, for example at least one liquid, organic carbonate, such as ethylene carbonate (EC) and / or ethylmethyl carbonate (EMC) and / or dimethyl carbonate (DMC) and / or diethyl carbonate (DEC ), or at least one liquid electrolyte, for example based on one, for example 1 M, solution of at least one conducting salt, for example of lithium hexafluorophosphate (LiPF ₆ ) and / or bis (trifluoromethane) sulfonimide (LiTFSI) and / or lithium perchlorate (LiClO ₄ ) , in at least one electrolyte solvent, for example at least one liquid, organic carbonate, such as ethylene carbonate (EC) and / or ethyl methyl carbonate (EMC) and / or dimethyl carbonate (DMC) and / or diethyl carbonate (DEC), for example in the cell and / or Battery assembly, form a gel and be used for example as a gel electrolyte. Thus, advantageously, in addition to an artificial SEI protective layer for passivating the anode active material particles, in particular silicon particles, a gel electrolyte coating can be formed directly on the anode active material particles, in particular silicon particles. In a first cycle of a cell or battery equipped therewith, the electrolyte in the polymer gel matrix of the gel electrolyte coating may decompose and mechanically stabilize the SEI protective layer. This advantageously makes it possible to dispense with the addition of SEI-stabilizing additives, such as vinylene carbonate (VC) or fluoroethylene carbonate (FEC), in particular to the liquid electrolyte, in cell and / or battery assembly.

In the context of an alternative or additional, further embodiment, the at least one further polymerizable monomer or comprise the at least two, in particular three, further polymerizable monomers at least one, for example, unfluorinated or fluorinated, ethers. In particular, the at least one further polymerizable monomer or the at least two, in particular three, further polymerizable monomers at least one, for example, unfluorinated or fluorinated, ethers having at least one polymerizable functional group, in particular having at least one polymerizable double bond, for example having at least one carbon-carbon Double bond, for example with at least one vinyl group and / or allyl group and / or allyloxyalkyl group, for example allyloxymethyl group, and / or with at least one hydroxy group, for example alkylene hydroxy group, for example methylene hydroxy group, include or be

For example, the at least one further polymerizable monomer or the at least two, in particular three, further polymerizable monomers may comprise or be at least one further crown ether and / or at least one further crown ether derivative and / or at least one vinyl ether, for example trifluorovinyl ether.

For example, the at least one further polymerizable monomer or the at least two, in particular three, further polymerizable monomers may contain at least one further crown ether and / or at least one further crown ether derivative having at least one polymerizable monomer functional group, in particular having at least one polymerizable double bond, for example having at least one vinyl group and / or at least one vinylidene group and / or at least one vinylene group and / or at least one allyl group. For example, allyloxyalkyl, and / or at least one acrylate group and / or at least one methacrylate group, for example having at least one carbon-carbon double bond, for example with at least one vinyl group and / or at least one vinylidene group and / or at least one vinylene group and / or at least one allyl group For example, allyloxyalkyl group, for example, allyloxymethyl group, and / or having at least one hydroxy group, for example, alkylene hydroxy group, for example, methylene hydroxy group include or be. For example, the at least one further crown ether and / or the at least one further Kronether derivative by free-radical polymerization, for example living radical polymerization, such as ATRP and / or SFRP, for example NMP, and / or RAFT, and / or polymerization by condensation reaction and / or by ionic, for example anionic or cationic, polymerization, be polymerized or (co) polymerized. The at least one further crown ether and / or the at least one further crown-ether derivative can be configured, for example, as described in connection with the at least one crown ether and / or crown ether derivative, for example, but different thereto.

In the context of an alternative or additional, further embodiment, the at least one further polymerizable monomer or comprise the at least two, in particular three, further polymerizable monomers at least one, for example, unfluorinated or fluorinated, alkylene oxide, for example ethylene oxide.

In the context of an alternative or additional further embodiment, the at least one further polymerizable monomer or comprise the at least two, in particular three, further polymerizable monomers at least one, for example aliphatic or aromatic, for example, unfluorinated or fluorinated, unsaturated hydrocarbon.

For example, the at least one further polymerizable monomer or the at least two, in particular three, polymerizable monomers can be at least one alkene, for example ethene, such as 1,1-difluoroethene (1,1-difluoroethylene, vinylidene fluoride) and / or tetrafluoroethylene (TFE), and / or propene, such as hexafluoropropene, and / or hexene, such as 3,3,4,4,5,5,6,6,6-nonafluorohexene, and / or phenylethene, such as 2,3,4,5,6- Pentafluorophenylethen (2,3,4,5,6-pentafluorostyrene) and / or 4- (trifluoromethyl) phenylethene (4- (trifluoromethyl) styrene) and / or styrene, include or be.

und/oder mindestens ein fluoriertes Hexen, wie 3,3,4,4,5,5,6,6,6-Nonafluorhexen:

beispielsweise erhältlich unter dem Handelsnamen Zonyl PFBE Fluorotelomer Intermediate, und/oder mindestens ein fluoriertes Phenylethen, wie
2,3,4,5,6-Pentafluorstyrol:

und/oder 4-(Trifluormethyl)styrol:

und/oder mindestens einen fluorierten Vinylether, wie 2-(Perfluorpropoxy)perfluorpropyltrifluorvinylether:

umfassen oder sein.For example, the at least one further polymerizable monomer or the at least two, in particular three, further polymerizable monomers can be at least one fluorinated alkene, for example at least one fluorinated ethene, such as 1,1-difluoroethene (1,1-difluoroethylene, vinylidene fluoride) and / or Tetrafluoroethylene (TFE), and / or at least one fluorinated propene, such as
hexafluoropropene:

and / or at least one fluorinated hexane, such as 3,3,4,4,5,5,6,6,6-nonafluorohexene:

for example, available under the trade name Zonyl PFBE Fluorotelomer Intermediate, and / or at least one fluorinated phenylethene, such as
2,3,4,5,6-pentafluoro styrene:

and / or 4- (trifluoromethyl) styrene:

and / or at least one fluorinated vinyl ether, such as 2- (perfluoropropoxy) perfluoropropyltrifluorovinyl ether:

include or be.

By polymerizing fluorinated alkenes such as 1,1-difluoroethylene, an artificial SEI protective layer of a fluorinated, for example polyvinylidene fluoride (PVdF) based, polymer can advantageously be formed on the particles. Such polymers can advantageously be prepared in the presence of at least one electrolyte solvent, for example at least one liquid, organic carbonate, such as ethylene carbonate (EC) and / or ethylmethylcarbonate (EMC) and / or dimethylcarbonate (DMC) and / or diethylcarbonate (DEC), or at least one liquid electrolyte, for example, based on, for example 1 M, solution of at least one conductive salt, for example of lithium hexafluorophosphate (LiPF ₆ ) and / or bis (trifluoromethane) sulfonimide (LiTFSI) and / or lithium perchlorate (LiClO ₄ ), in at least one electrolyte solvent, for example at least one liquid, organic carbonate, such as ethylene carbonate (EC) and / or ethyl methyl carbonate (EMC) and / or dimethyl carbonate (DMC) and / or diethyl carbonate (DEC), for example in the cell and / or battery assembly, form a gel and, for example be used as a gel electrolyte. Thus, advantageously, in addition to an artificial SEI protective layer for passivating the anode active material particles, in particular silicon particles, a gel electrolyte coating can be formed directly on the anode active material particles, in particular silicon particles. In a first cycle of a cell or battery equipped therewith, the electrolyte in the polymer gel matrix of the gel electrolyte coating may decompose and mechanically stabilize the SEI protective layer. This advantageously makes it possible to dispense with the addition of SEI-stabilizing additives, such as vinylene carbonate (VC) or fluoroethylene carbonate (FEC), in particular to the liquid electrolyte, in cell and / or battery assembly.

Alternatively or additionally, the at least one further polymerizable monomer or the at least two, in particular three, further polymerizable monomers, for example, in addition, comprise or be at least one unfluorinated alkene, for example at least one unfluorinated Phenylethen such as styrene.

By the use of at least one, for example, unfluorinated or fluorinated, phenyl ethene, for example of styrene, in particular by a copolymerization herewith, can advantageously, in particular, hard segment blocks, for example based on polystyrene, introduced, for example, to increase the resistance to alkali and / or solvents and / or to improve the mechanical properties, such as strength. In this case, the copolymer as a random copolymer or as a block co-polymer, for example, from polystyrene hard segments and differently based soft segments, such as polycrown ether soft segments, are constructed. Polyether-polystyrene block co-polymers may advantageously be thermoplastic elastomers and have high stretchability.

The polymerization of the at least one crown ether and / or crown ether derivative and / or the at least one further monomer can be started, for example, by means of, for example, addition of at least one polymerization initiator and / or by means of, for example, addition of at least one polymerization-initiating functional group of at least one silane compound , Thus, advantageously, the polymerization can be started in a targeted manner and the anode active material particles, in particular silicon particles, advantageously provided with the polymer formed by the polymerization, in particular coated.

The at least one polymerization initiator may be used, for example, to initiate a free-radical polymerization, in particular to initiate a living radical polymerization, for example to initiate a living free-radical radical polymerization (ATRP initiator) and / or to initiate a stable free radical polymerization (SFRP initiator). For example, for starting a nitroxide-mediated polymerization (NMP initiator) and / or for starting a Verdazyl-mediated polymerization (VMP initiator), in particular for starting a nitroxide-mediated polymerization (NMP initiator), and / or for starting a reversible addition-fragmentation chain transfer polymerization (RAFT initiator).

The polymerization of the at least one crown ether and / or crown ether derivative and / or of the at least one further monomer can be carried out, for example, by adding at least one polymerization-controlling agent and / or by adding, for example, the at least one polymerization-controlling functional group of the at least one Silane compound to be controlled.

The at least one polymerization-controlling agent can be used, in particular, for controlling a living radical polymerization, for example for controlling a stable free-radical polymerization (SFRP mediator), for example for controlling a nitroxide-mediated polymerization (NMP mediator) and / or for controlling a verdazyl compound. mediated polymerization (VMP mediator), and / or for controlling a reversible addition-fragmentation chain transfer polymerization (RAFT agent).

For initiating a living radical polymerization with atom transfer (ATRP initiator), the at least one polymerization initiator may in particular comprise or be formed from an alkyl halide. For example, the at least one polymerization initiator may comprise or be methyl bromoisobutyrate and / or benzyl bromide and / or ethyl α-bromophenyl acetate. The at least one polymerization initiator can be used in particular in combination with at least one catalyst. The at least one catalyst may be in particular a transition metal halide, in particular a copper halide, for example copper chloride and / or copper bromide, for example copper (I) bromide, and optionally at least one ligand, for example at least one, in particular multidentate, nitrogen ligands (N-type ligand, English : N-type ligand), for example at least one amine, such as tris [2- (dimethylamino) ethyl] amine (Me6TREN) and / or tris (2-pyridylmethyl) amine (TPMA) and / or 2,2'-bipyridine and or N, N, N ', N ", N" -pentamethyldiethylenetriamine (PMDETA) and / or 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA). For example, the at least one catalyst may be a transition metal complex, especially a transition metal-nitrogen complex. The radical buffer or the deactivated species can be formed in particular from the alkyl halide, the catalyst or complex and the monomer.

To initiate stable free radical polymerization, for example, to initiate nitroxide-mediated polymerization and / or to initiate a digestion-mediated polymerization, particularly to initiate nitroxide-mediated polymerization, and / or to initiate reversible addition-fragmentation chain transfer polymerization The at least one polymerization initiator may in particular comprise or be a radical initiator, for example an azoisobutyronitrile, for example azobis (isobutyronitrile) (AIBN), and / or a benzoyl peroxide, for example dibenzoyl peroxide (BPO). In this case, the at least one polymerization initiator, in particular in combination with at least one polymerization-controlling agent, in particular for a stable free-radical polymerization (SFRP mediator), for example for a nitroxide-mediated polymerization (NMP mediator), for example at least one nitroxide-based mediator, and / or for a Verdazyl-mediated polymerization (VMP mediator) , For example, at least one verdazylbasierten mediator, and / or for a reversible addition fragmentation chain transfer polymerization (RAFT agent), for example with at least one thio compound are used.

beziehungsweise eines Opferinitiators hiervon, wie:

und/oder auf 2,2,5-Trimethyl-4-phenyl-3-azahexan-3-oxyl (TIPNO):

beziehungsweise eines Opferinitiators hiervon, wie:

und/oder auf N-tertButyl-N-[1-diethylphosphono-(2-2-dimethylpropyl)nitroxid] (SG1*):

beziehungsweise eines Opferinitiators hiervon basieren.For a nitroxide-mediated polymerization, the at least one polymerization-controlling agent, the NMP mediator or the at least one nitroxide-based mediator may comprise or be, for example, a nitroxide, in particular a linear or cyclic nitroxide. The at least one nitroxide-based mediator or the nitroxide can be converted, for example, to 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO):

or a victim initiator thereof, such as:

and / or 2,2,5-trimethyl-4-phenyl-3-azahexan-3-oxyl (TIPNO):

or a victim initiator thereof, such as:

and / or on N-tert-butyl-N- [1-diethylphosphono (2-2-dimethylpropyl) nitroxide] (SG1 *):

or a victim initiator thereof.

For a reversible addition-fragmentation chain transfer polymerization, the at least one polymerization controlling agent, the RAFT agent or the at least one thio compound may be, for example, a trithiocarbonate or a dithioester or a dithiocarbamate or a xanthate.

The radical buffer or the deactivated species can be formed in particular by reaction of the active species, namely free radicals, with stable radicals based on the nitroxide-based mediator or the thio compound.

Within the scope of a further embodiment, in particular in addition to the at least one crown ether and / or crown ether derivative, at least one silane compound having at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group is used. As already explained, the at least one silane compound having at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group can be reacted, for example, first with the anode active material particles, in particular silicon particles, or together with the at least one crown ether and / or crown ether derivative and / or or the at least one further polymerizable monomer or the at least two further polymerizable monomers to the anode active material particles, in particular silicon particles, mixed or even after the reaction with the at least one crown ether and / or crown ether derivative and / or the at least one further polymerizable monomer or the at least two further polymerizable monomers are added to the anode active material particles, in particular silicon particles.

In this case, the silane function of the at least one silane compound can advantageously be attached to the surface of the anode active material particles, in particular silicon particles, for example covalently.

The at least one polymerisable functional group of the at least one silane compound can-in particular copolymerize with the at least one crown ether and / or crown ether derivative and / or the at least one further polymerizable monomer or the at least two further polymerizable monomers. By copolymerization of the at least one silane compound having at least one polymerizable functional group and the at least one crown ether and / or Kronether derivative can advantageously, for example by means of the silane function of the silane at least one silane compound, a bond between the active material particles, in particular silicon particles, and the Co formed therefrom Polymer, be achieved. A silane compound having at least one polymerizable functional group can therefore advantageously serve as adhesion promoter, in particular for the polymer layer formed by the polymerization on the particles.

The at least one polymerizable functional group of the at least one silane compound may be, for example, by free-radical polymerization, in particular by living radical polymerization, for example by living radical atom transfer or by stable free radical polymerization, for example by nitroxide-mediated polymerization or by a Verdazyl-mediated polymerization, in particular by a nitroxide-mediated polymerization, or by a reversible addition-fragmentation chain transfer polymerization, be polymerizable.

The at least one polymerisable functional group of the at least one silane compound may be, for example, at least one polymerisable double bond, for example at least one carbon atom. Carbon double bond, in particular at least one vinyl group and / or at least one vinylene group and / or at least one vinylidene group and / or at least one allyl group, for example an allyloxyalkyl group, for example an allyloxymethyl group, and / or at least one acrylate group and / or at least one methacrylate group and / or at least one phenylethene group (styrene group) and / or at least one hydroxy group. In particular, the at least one polymerisable functional group of the at least one silane compound may have at least one polymerizable double bond, for example at least one carbon-carbon double bond, in particular at least one vinyl group and / or at least one vinylene group and / or at least one vinylidene group and / or at least one allyl group, for example an allyloxyalkyl group, for example an allyloxymethyl group, and / or at least one acrylate group and / or at least one methacrylate group and / or at least one phenylethene group (styrene group), or include. This has proved to be particularly advantageous for the polymerization, in particular by means of a living radical polymerization, such as ATRP, NMP or RAFT. By means of at least one hydroxyl group, the at least one polymerisable functional group of the at least one silane compound can be polymerized or copolymerized by condensation reaction or by anionic polymerization. For example, the at least one polymerizable functional group of the at least one silane compound may have at least one polymerizable double bond, for example at least one carbon-carbon double bond, for example a vinyl group and / or a vinylidene group and / or a vinylene group and / or an acrylate group and / or a Methacrylate group, include or.

The at least one polymerization-initiating functional group of the at least one silane compound can be designed, for example, to start a free-radical polymerization, in particular for starting a living radical polymerization.

For example, the at least one polymerization initiating functional group of the at least one silane compound may be designed to initiate a living radical atom transfer (ATRP initiator) polymerization. The at least one polymerization-initiating functional group of the at least one silane compound may be, for example, in particular for a living free-radical radical polymerization (ATRP initiator), at least one halogen atom, for example chlorine (-Cl), bromine (-Br) or iodine (-I), preferably chlorine (-Cl) or bromine (-Br), for example one with at least one halogen atom, for example chlorine (-CI), bromine (-Br) or iodine (-I), preferably chlorine (-CI) or bromine (- Br), substituted alkyl group, include or be.

The at least one polymerization-initiating functional group, in particular for starting a living radical polymerization with atom transfer, the at least one silane compound can be used in particular in combination with at least one catalyst. The at least one catalyst may be in particular a transition metal halide, in particular a copper halide, for example copper chloride and / or copper bromide, for example copper (I) bromide, and optionally at least one ligand, for example at least one, in particular multidentate, nitrogen ligands (N-type ligand, English : N-type ligand), for example at least one amine, such as tris [2- (dimethylamino) ethyl] amine (Me6TREN) and / or tris (2-pyridylmethyl) amine (TPMA) and / or 2,2'-bipyridine and or N, N, N ', N ", N" -pentamethyldiethylenetriamine (PMDETA) and / or 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA). For example, the at least one catalyst may be a transition metal complex, especially a transition metal-nitrogen complex.

The radical buffer or the deactivated species can be formed from the at least one polymerization-initiating functional group of the at least one silane compound, the catalyst or complex and the monomer.

The at least one polymerization-controlling functional group of the at least one silane compound can be used, for example, for controlling a living radical polymerization, for example for controlling a stable free-radical polymerization (SFRP mediator), for example for controlling a nitroxide-mediated polymerization (NMP mediator) and / or for the control of a Verdazyl-mediated polymerization (VMP mediator), in particular for controlling a nitroxide-mediated polymerization (NMP mediator), and / or for controlling a reversible addition-fragmentation chain transfer polymerization (RAFT agent).

The at least one polymerization-controlling functional group, in particular for controlling a stable free-radical polymerization (SFRP mediator), for example for controlling a nitroxide-mediated polymerization (NMP mediator) and / or for controlling a verdazyl-mediated polymerization (VMP). Mediator), for example for controlling a nitroxide-mediated polymerization (NMP mediator), and / or for controlling a reversible addition-fragmentation chain transfer polymerization (RAFT agent), the at least one silane compound can be used in particular in combination with a the at least one polymerization initiator and / or with at least one polymerization initiating functional group of at least one silane compound, in particular which or for starting a stable free radical polymerization (SFRP), for example for starting a nitroxide-mediated polymerization (NMP) and / or for starting a Verdazyl mediated polymerization (VMP), in particular for initiating a nitroxide-mediated polymerization (NMP), and / or for starting a reversible addition-fragmentation chain transfer polymerization (RAFT), for example a radical initiator, for example an azoisobutyronitrile, such as azobis (isob utyronitrile) (AIBN), and / or a benzoyl peroxide such as dibenzoylperoxide (BPO), or a derivative thereof.

beziehungsweise eines Opferinitiators hiervon, wie:

und/oder auf 2,2,5-Trimethyl-4-phenyl-3-azahexan-3-oxyl (TIPNO):

beziehungsweise eines Opferinitiators hiervon, wie:

und/oder auf N-tertButyl-N-[1-diethylphosphono-(2-2-dimethylpropyl)nitroxid] (SG1*):

beziehungsweise eines Opferinitiators hiervon, und/oder, insbesondere für eine reversible Additions-Fragmentierungs-Kettenübertragungs-Polymerisation (RAFT-Agens), zum Beispiel eine Thiogruppe, beispielsweise eine Trithiocarbonatgruppe (-S-C=S-S-) oder eine Dithioestergruppe (-C=S-S-) oder eine Dithiocarbamatgruppe (-N-C=S-S-) oder eine Xanthatgruppe (-C=S-S^-), umfassen oder sein.The at least one polymerization-controlling functional group of the at least one silane compound, in particular for a nitroxide-mediated polymerization (NMP mediator), for example a, in particular linear or cyclic, nitroxide group and / or alkoxyamine group, for example based on 2,2,6, 6-tetramethylpiperidinyloxy (TEMPO):

or a victim initiator thereof, such as:

and / or 2,2,5-trimethyl-4-phenyl-3-azahexan-3-oxyl (TIPNO):

or a victim initiator thereof, such as:

and / or on N-tert-butyl-N- [1-diethylphosphono (2-2-dimethylpropyl) nitroxide] (SG1 *):

or a sacrificial initiator thereof, and / or, in particular for a reversible addition-fragmentation chain transfer polymerization (RAFT agent), for example a thio group, for example a trithiocarbonate group (-SC = SS-) or a dithioester group (-C = SS-) ), or a dithiocarbamate group (-NC = SS) or a xanthate group (-C = SS ^-) include, or be.

The radical buffer or the deactivated species can be formed in particular by reaction of the active species, namely free radicals, with stable radicals based on the nitroxide group and / or alkoxyamine group or the thio group.

In the context of a so-called graft-from design, for example, the at least one silane compound having at least one polymerizable and / or polymerization initiating and / or polymerization-controlling functional group, in particular before the addition of the at least one crown ether and / or Kronether derivative and / or of the at least one other monomer immobilized on the surface of the anode active material particles, in particular silicon particles. For example, the at least one silane compound can be immobilized by forming a, in particular covalent, chemical bond with surface material of the anode active material particles, in particular silicon particles. Then the at least one crown ether and / or the at least one crown ether derivative and / or the at least one further polymerizable monomer can be added. The immobilization can be carried out, for example, depending on the at least one silane compound in the presence or absence of at least one solvent.

The at least one crown ether and / or the at least one crown ether derivative and / or the at least one further polymerizable monomer may optionally react with the at least one immobilized silane compound by means of a free-radical polymerization. The radical polymerization can be a, in particular simple, radical polymerization, for example in the presence of only at least one radical initiator, such as AIBN and / or BPO, or in particular a living radical polymerization, for example an ATRP, SFRP, for example NMP, or RAFT. This may in particular involve a copolymerization, in particular of the at least one crown ether and / or crown ether derivative and the at least one polymerisable functional group of the at least one silane compound.

Insofar as the at least one, in particular adhesion-promoting, silane compound has a polymerisable functional group, in particular furthermore, if appropriate together with the at least one crown ether and / or crown ether derivative, at least one polymerization initiator, for example Free radical initiators, for example AIBN or BPO, - and / or possibly at least one solvent - are added. Thus, advantageously, the polymerization can be started.

Insofar as the at least one silane compound has a polymerization-initiating functional group, in particular for initiating a living radical polymerization with atom transfer (ATRP initiator), in particular, optionally together with the at least one crown ether and / or crown ether derivative, at least one catalyst, for example at least one transition metal halide, for example, a copper halide, and optionally at least one ligand, for example, a nitrogen ligand (N-type ligand), such as tris [2- (dimethylamino) ethyl] amine. Thus, advantageously, the polymerization can be started.

In this respect, the at least one silane compound is a polymerization-controlling functional group, in particular for a stable free-radical polymerization (SFRP), for example for a nitroxide-mediated polymerization (NMP mediator) and / or for a Verdazyl-mediated polymerization (VMP mediator), or for a reversible addition-fragmentation chain transfer polymerization (RAFT agent), in particular further, optionally together with the at least one crown ether and / or crown ether derivative, at least one polymerization initiator, for example free-radical initiators, for example AIBN or BPO, can be added , Thus, advantageously, the polymerization can be started. In order to further improve the polymerization control, it is optionally also possible to use at least one polymerization-controlling agent, in particular for a stable free radical polymerization (SFRP), for example for a nitroxide-mediated polymerization (NMP mediator) and / or for a verdazyl-mediated polymerization (VMP polymerization). Mediator), and / or for a reversible addition-fragmentation chain transfer polymerization (RAFT agent), for example at least one nitroxide-based mediator, for example a sacrificial initiator in the form of an alkoxyamine, or at least one thio compound.

In the context of a, in particular so-called graft-to, embodiment, for example, the at least one crown ethers and / or at least one Kronether derivative and / or the at least one crown ethers and / or Kronether derivative comprehensive polymer with the at least one silane compound with at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group. Then, for example, anode active material particles, in particular silicon particles, can be added.

The reaction can be carried out, for example, by means of a free-radical polymerization. The radical polymerization can be a, in particular simple, radical polymerization, for example in the presence of only at least one radical initiator, such as AIBN and / or BPO, or in particular a living radical polymerization, for example an ATRP, NMP or RAFT. This may be a copolymerization, in particular of the at least one crown ether and / or crown ether derivative and the at least one polymerizable functional group of the at least one silane compound.

The reaction of the at least one crown ether and / or crown ether derivative and / or the at least one crown ether and / or crown ether derivative comprising polymer with the at least one silane compound having at least one polymerizable and / or polymerization initiating and / or polymerization-controlling functional group can be carried out, for example, in solution or carried out in at least one solvent and / or - in particular insofar as the reaction product formed in the reaction, for example (co-) polymer, should not be dissolved - the reaction product formed in the reaction, for example (co) polymer, dissolved in at least one solvent and / or be dissolved. After adding the anode active material particles, in particular silicon particles, in particular to the solution, the at least one solvent can then be removed again, for example by evaporation. Thus, the anode active material particles, in particular silicon particles, can advantageously be polymer-coated.

The silane function of the at least one silane compound or of the copolymer formed therefrom can advantageously be attached to the surface of the anode active material particles, in particular silicon particles, for example covalently. Thus, for example, the copolymer can be grafted onto the surface of the anode active material particles, in particular silicon particles.

For example, in particular insofar as the at least one, in particular adhesion-promoting, silane compound has a polymerizable functional group, the at least one crown ethers and / or the at least one crown ether derivative and / or the at least one crown ether and / or crown ether derivative comprising polymer with the at least one silane compound having at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group, for example with at least one, in particular adhesion-promoting, silane compound having at least one polymerizable functional group, for example a vinyl silane, such as trichlorovinylsilane, for example by adding at least one polymerization initiator, for example by adding at least one radical initiator, possibly in solution or in at least one solvent, converted into a copolymer, in particular copolymerized. Thus, it is advantageously possible to ensure a linkage, for example free-radical attachment, of the silane function to the polymer. Insofar as the co-polymer should not be dissolved, it can be solubilized. Then, for example, the anode active material particles, in particular silicon particles, can be added. In this case, advantageously, the silane function, for example trichlorosilane, of the at least one silane compound or the copolymer formed therefrom on the surface of the anode active material particles, in particular silicon particles, for example, covalently bond.

Or, for example, in particular insofar as the at least one, in particular adhesion-promoting, silane compound has a polymerisable functional group, the polymer may comprise at least one crown ether and / or the at least one crown ether derivative and / or the at least one crown ether and / or crown ether derivative. for example, by adding at least one polymerization initiator, for example by adding at least one radical initiator, possibly in solution or in at least one solvent, to form a polymer. Insofar as the polymer should not be dissolved, it can be solubilized. Then the polymer formed from the at least one crown ether and / or crown ether derivative and / or the polymer comprising at least one crown ether and / or crown ether derivative with the at least one silane compound having at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group , For example, with at least one, in particular adhesion-promoting, silane compound having at least one polymerizable functional group, for example a vinylsilane, such as trichlorovinylsilane, for example by re-addition of the at least one polymerization initiator, for example, radical initiator implemented. Thus, advantageously, the at least one silane compound having at least one polymerisable and / or polymerization-initiating and / or polymerization-controlling functional group can comprise the polymer formed from the at least one crown ether and / or crown ether derivative and / or the at least one crown ether and / or crown ether derivative Polymer are linked. Thus, it is advantageously possible to ensure a linkage, for example free-radical attachment, of the silane function to the polymer. Then, for example, the anode active material particles, in particular silicon particles, can be added. In this case, advantageously, the silane function, for example trichlorosilane, of the at least one silane compound or the copolymer formed therefrom on the surface of the anode active material particles, in particular silicon particles, for example, covalently bond.

Insofar as the at least one silane compound has a polymerization-initiating functional group, in particular for initiating a living radical polymerization with atom transfer (ATRP initiator), the reaction of the at least one crown ether and / or crown ether derivative and / or the at least one crown ether and / or A crown-ether derivative-comprising polymer having the at least one silane compound having the polymerization-initiating functional group, in particular in the presence of at least one catalyst, for example at least one transition metal halide, for example a copper halide, and optionally at least one ligand, for example a nitrogen ligand (N-type ligand), such as tris [2- (dimethylamino) ethyl] amine). Thus, advantageously, the polymerization can be started.

If the at least one silane compound has a polymerization-controlling functional group, in particular for a nitroxide-mediated polymerization (NMP mediator) or for a reversible addition-fragmentation chain transfer polymerization (RAFT agent), the reaction of the at least one crown ether and / or or Kronether derivatives and / or of the at least one crown ether and / or Kronether derivative comprising polymer with the at least one silane compound with the polymerization controlling functional group, in particular in the presence of at least one polymerization initiator, for example radical initiator, for example AIBN or BPO, performed. In order to further improve the polymerization control, optionally at least one polymerization-controlling agent, in particular for a nitroxide-mediated polymerization (NMP mediator), and / or for a reversible addition-fragmentation chain transfer polymerization (RAFT agent), for example at least one nitroxide-based mediator, for example a sacrificial initiator in the form of an alkoxyamine, or at least one thio compound, are added.

In a further embodiment, the at least one silane compound comprises at least one silane compound of the general chemical formula:

R 1, R _2, R ₃ may each, in each case independently of one another, denote a halogen atom, in particular chlorine (-CI), or an alkoxy group, in particular a methoxy group (-OCH ₃ ) or an ethoxy group (-OC ₂ H ₅ ), or an alkyl group, for example a linear alkyl group (- (CH ₂ ) _x -CH ₃ ) where x ≥ 0, in particular a methyl group (-CH ₃ ), or an amino group (-NH ₂ , -NH-) or a silazane group (-NH-Si) or a hydroxy group (-OH) or hydrogen (-H). For example, R1, R2 and R3 may be chlorine.

In particular, Y can stand for a linker, ie a bridging unit. In particular, Y may have at least one alkylene group (-C _n H _2n -) with n ≥ 1 and / or at least one alkylene oxide group (-C _n H _2n -O-) with n ≥ 1 and / or at least one carboxylic acid ester group (-C = OO-). ) and / or at least one phenylene group (-C ₆ H ₄ -).

A may in particular be a polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group.

A silane compound having at least one polymerizable functional group may advantageously serve as a coupling agent.

In the context of one embodiment of this embodiment, A is a polymerizable functional group. In particular, A may be a polymerizable functional group having at least one polymerizable double bond. For example, A may be a polymerizable functional group having at least one carbon-carbon double bond. For example, A may represent a vinyl group or a vinylidene group or a vinylene group or an acrylate group or a methacrylate group.

aufweisen. Dabei können R1, R2, R3 insbesondere jeweils unabhängig voneinander für ein Halogenatom, insbesondere Chlor (-CI), oder eine Alkoxygruppe, insbesondere eine Methoxygruppe (-OCH₃) oder eine Ethoxygruppe (-OC₂H₅), oder eine Alkylgruppe, beispielsweise eine lineare Alkylgruppe (-(CH₂)_x-CH₃) mit x ≥ 0, insbesondere eine Methylgruppe (-CH₃), oder eine Aminogruppe (-NH₂, -NH-) oder Wasserstoff (-H) stehen. Beispielsweise kann SiR1R2R3 dabei für ein Mono-, Di- oder Trichlorsilan stehen. A kann dabei insbesondere für eine funktionelle Gruppe mit mindestens einer Kohlenstoff-Kohlenstoff-Doppelbindung, insbesondere für eine Vinylgruppe oder eine Acrylatgruppe oder eine Methacrylatgruppe, stehen. Dabei kann 1 ≤ n ≤ 20, vorzugsweise 1 ≤ n ≤ 5, insbesondere n = 2 oder 3, sein.A, in particular adhesion-promoting, silane compound having a polymerisable functional group can be, for example, the general chemical formula:

exhibit. In this case, R 1, R _2, R ₃ may each, in each case independently of one another, represent a halogen atom, in particular chlorine (--Cl), or an alkoxy group, in particular a methoxy group (-OCH ₃ ) or an ethoxy group (-OC ₂ H ₅ ), or an alkyl group, for example a linear alkyl group (- (CH ₂ ) _x -CH ₃ ) with x ≥ 0, in particular a methyl group (-CH ₃ ), or an amino group (-NH ₂ , -NH-) or hydrogen (-H). For example, SiR1R2R3 can stand for a mono-, di- or trichlorosilane. A may in particular stand for a functional group having at least one carbon-carbon double bond, in particular for a vinyl group or an acrylate group or a methacrylate group. In this case, 1 ≤ n ≤ 20, preferably 1 ≤ n ≤ 5, in particular n = 2 or 3, be.

insbesondere wobei R1, R2 und R3 für Chlor, A für Methacrylat stehen und n = 3 ist.An example of an especially adhesion-promoting silane compound having a polymerisable functional group is 3- (trichlorosilyl) propyl methacrylate:

in particular wherein R1, R2 and R3 are chlorine, A is methacrylate and n = 3.

In another embodiment of this embodiment, A is a polymerization-initiating functional group. In particular, A may represent a polymerization-initiating functional group for starting a living radical polymerization with atom transfer (ATRP initiator). A may be in particular a halogen atom, for example chlorine (-Cl) or bromine (-Br) or iodine (-I), in particular chlorine (-CI) or bromine (-Br).

aufweisen. Dabei können R1, R2, R3 insbesondere jeweils unabhängig voneinander für ein Halogenatom, insbesondere Chlor (-CI), oder eine Alkoxygruppe, insbesondere eine Methoxygruppe (-OCH₃) oder eine Ethoxygruppe (-OC₂H₅), oder Wasserstoff (-H) stehen. Beispielsweise kann SiR1R2R3 dabei für ein Mono-, Di- oder Trichlorsilan stehen. A kann dabei insbesondere für ein Halogenatom, beispielsweise Chlor (-CI), Brom (-Br) oder Iod (-I), vorzugsweise Chlor (-CI) oder Brom (-Br), stehen. Dabei kann 1 ≤ n ≤ 20, vorzugsweise 1 ≤ n ≤ 5, insbesondere n = 1 oder 2, und/oder 0 ≤ m ≤ 20, vorzugsweise 0 ≤ m ≤ 5, insbesondere m = 0 oder 1 oder 2, sein.A silane compound having a polymerization-initiating functional group, in particular for starting a living atom transfer radical polymerization (ATRP initiator), may be, for example, the general chemical formula:

exhibit. In particular, a methoxy group (-OCH ₃₎ or ethoxy (-OC ₂ H _5), or hydrogen, R1, R2, R3 particular in each case independently of one another a halogen atom, in particular chlorine (CI), or an alkoxy group (-H ) stand. For example, SiR1R2R3 can stand for a mono-, di- or trichlorosilane. A may be in particular a halogen atom, for example chlorine (-CI), bromine (-Br) or iodine (-I), preferably chlorine (-CI) or bromine (-Br). In this case, 1≤n≤20, preferably 1≤n≤5, in particular n = 1 or 2, and / or 0≤m≤20, preferably 0≤m≤5, in particular m = 0 or 1 or 2.

insbesondere wobei R1, R2 und R3 sowie A für Chlor stehen und n = 1 und m = 0 ist.An example of a silane compound having a polymerization initiating functional group, in particular for initiating a living radical atom transfer (ATRP initiator) polymerization, is trichloro [4- (chloromethyl) phenyl] silane or 4- (chloromethyl) phenyltrichlorosilane (CMPS):

in particular wherein R1, R2 and R3 and A stand for chlorine and n = 1 and m = 0.

In another embodiment of this embodiment, A is a polymerization-controlling functional group.

In one embodiment, A is a polymerization-controlling functional group for a nitroxide-mediated polymerization (NMP mediator). The polymerization-controlling functional group A can be in particular a nitroxide-based mediator. For example, it is possible for A to represent a nitroxide group and / or alkoxyamine group, for example based on 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) and / or 2,2,5-trimethyl-4-phenyl-3-azahexane-3 -oxyl (TIPNO) and / or N-tert-butyl-N- [1-diethylphosphono- (2-2-dimethylpropyl) nitroxides] (SG1 *).

und/oder

die 2,2,5-Trimethyl-4-phenyl-3-azahexane-3-oxyl-(TIPNO)-basierte Alkoxyamin-Silanverbindung der Formel:

und/oder die N-tertButyl-N-[1-diethylphosphono-(2-2-dimethylpropyl)nitroxid]-(SGl)-basierte Alkoxyamin-Silanverbindung der Formel:

Examples of silane compounds having a polymerization-controlling functional group, in particular for nitroxide-mediated polymerization (NMP mediator), are the 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) -based alkoxyamine-silane compound:

and or

the 2,2,5-trimethyl-4-phenyl-3-azahexane-3-oxyl (TIPNO) -based alkoxyamine silane compound of the formula:

and / or the N-tert-butyl-N- [1-diethylphosphono (2-2-dimethylpropyl) nitroxide] - (SGl) -based alkoxyamine-silane compound of the formula:

Instead of directly immobilizing at least one silane compound having at least one polymerization controlling functional group for nitroxide-mediated polymerization (NMP mediator), anode active material particles, particularly silicon particles, may be functionalized for nitroxide-mediated polymerization by (at least) containing at least one silane compound having at least a polymerisable functional group, for example 3- (trimethoxysilyl) propyl methacrylate, is immobilized on the surface of the anode active material particles, in particular silicon particles, and the at least one silane compound is then reacted with at least one nitroxide-based mediator, for example with at least one nitroxide or alkoxyamine compound, such as TEMPO, and reacted, for example, with at least one polymerization initiator, in particular radical initiator, such as AIBN.

In another embodiment, A is a polymerization-controlling functional group for reversible addition-fragmentation chain transfer polymerization (RAFT agent). The polymerization-controlling functional group may in particular be a thio group. For example, A may in this case for a trithiocarbonate (-S-C = SS) or a dithioester group (-C = SS), or a dithiocarbamate group (-NC = SS) or a xanthate group (-C = SS ^-) are provided.

For example, in the silane compound having a polymerization controlling functional group, in particular, for reversible addition-fragmentation chain transfer polymerization (RAFT agent), SiR 1 R 2 R 3 may be a chlorosilane, a methoxysilane, an ethoxysilane or a silazane and A is a dithioester or a dithiocarbamate or a Trithiocarbonate or a xanthate.

und/oder

und/oder

Examples of silane compounds having a polymerization-controlling functional group, in particular for reversible addition-fragmentation chain transfer polymerization (RAFT agent), are the trithiocarbonate or dithioester compound:

and or

and or

In a further embodiment, the at least one silane compound comprises at least one, in particular kronetherbasierte, silane compound of the general chemical formula:

In particular, Q1, Q2, Q3 and Qk may each independently of one another denote oxygen (O) or nitrogen (N) or an amine, for example a secondary amine (NH) and / or a tertiary amine, for example an alkyl- or arylamine, ( NR), stand.

G may in particular be at least one polymerisable functional group, for example with which one of the carbon atoms and / or Q1 and / or Q2 and / or Q3 and / or Qk is substituted.

In particular, G may have at least one polymerisable double bond, for example at least one carbon-carbon double bond, for example at least one vinyl group and / or vinylidene group and / or vinylene group and / or allyl group, for example allyloxyalkyl group, for example allyloxymethyl group, and / or at least one hydroxy group, for example Alkylene hydroxy group, for example methylene hydroxy group.

Furthermore, G may, for example, one or more other groups, for example, which serve as a linker - ie a bridging unit or as a bridge segment - include. For example, G may further include at least one benzo group and / or cyclohexano group.

g may be in particular for the number of polymerisable functional groups G and in particular 1 ≦ g, for example 1 ≦ g ≦ 5, for example 1 ≦ g ≦ 2.

In particular, k can stand for the number of units in parentheses, and in particular 1 ≦ k, for example 1 ≦ k ≦ 3, for example 1 ≦ k ≦ 2.

Y 'can in particular stand for a linker, ie a bridging unit. For example, Y 'can be at least one alkylene group (-C _n H _2n -) with n ≥ 0, in particular n ≥ 1, and / or at least one alkylene oxide group (-C _n H _2n -O-) with n ≥ 1 and / or at least one Carboxylic ester group (-C = OO-) and / or at least one phenylene group (-C ₆ H ₄ -) include. For example, Y 'may here stand for an alkylene group -C _n H _2n - where 0 ≦ _n ≦ 5, for example n = 1 or 2 or 3.

s may be in particular for the number of silane groups (-SiR1R2R3), in particular via linker Y ', and in particular 1≤s, for example 1≤S≤5, for example 1≤S≤2.

R 1, R _2, R ₃ may each, in each case independently of one another, denote a halogen atom, in particular chlorine (-CI), or an alkoxy group, in particular a methoxy group (-OCH ₃ ) or an ethoxy group (-OC ₂ H ₅ ), or an alkyl group, for example a linear alkyl group (- (CH ₂ ) _x -CH ₃ ) where x ≥ 0, in particular a methyl group (-CH ₃ ), or an amino group (-NH ₂ , -NH-) or a silazane group (-NH-Si) or a hydroxy group (-OH) or hydrogen (-H). For example, R1, R2 and R3 may be chlorine.

umfassen. In particular, Q1, Q2, Q3 and Qk may be oxygen. For example, the at least one silane compound may contain at least one, in particular kronetherbasierte, silane compound of the general chemical formula:

include.

und/oder

Examples of such, especially kronetherbasierte, silane compounds are:

and or

Such, in particular kronetherbasierte, silane compounds can advantageously via the silane group, in particular covalently, and for example additionally via van der Waals and / or hydrogen bonds, on the surface of the anode active material particles, in particular silicon particles, tie and serve, for example, as a silane-based adhesion promoter.

Within the scope of a further embodiment, the polymerization or reaction of the at least one crown ether and / or crown ether derivative takes place in at least one solvent. By solvent polymerization or solution polymerization, advantageously, the molecular weight of the polymer to be formed can be better controlled. After the polymerization or conversion of the at least one crown ether and / or crown ether derivative, the at least one solvent can be removed, in particular again.

In a further embodiment, the method for producing an anode for a lithium cell and / or lithium battery, in particular for a lithium-ion cell and / or lithium-ion battery, designed.

Within the scope of a further embodiment - especially in the context of which the polymerization of the at least one crown ether and / or crown ether derivative takes place homogeneously with the anode active material particles, in particular silicon particles, but separately from further electrode components (method 1) - those with which by the polymerization or Implement trained polymer provided, in particular coated, anode active material particles, in particular silicon particles, mixed with at least one further electrode component and, for example by doctoring, processed into an anode. So Advantageously, the artificial SEI layer can be specifically formed on the anode active material particles, in particular silicon particles, and, for example, the amount of the at least one crown ether and / or crown ether derivative required for coating the anode active material particles, in particular silicon particles, minimized.

1. a) Mischen der Anodenaktivmaterialpartikel, insbesondere Siliciumpartikel, und des mindestens einen Kronethers und/oder Kronether-Derivates,
2. b) Starten der Polymerisation des mindestens einen Kronethers und/oder Kronether-Derivates mittels, beispielsweise durch Zugabe, des mindestens eines Polymerisationsinitiators,
3. c) Mischen der, mit dem durch die Polymerisation ausgebildeten Polymer versehenen, insbesondere beschichteten, Anodenaktivmaterialpartikel, insbesondere Siliciumpartikel, mit mindestens einer weiteren Elektrodenkomponente, und
4. d) Verarbeiten, beispielsweise durch Rakeln, der Mischung zu einer Anode.

Within the scope of an embodiment of this embodiment, the method comprises the method steps:

1. a) mixing the anode active material particles, in particular silicon particles, and the at least one crown ether and / or crown ether derivative,
2. b) starting the polymerization of the at least one crown ether and / or crown ether derivative by means, for example by addition, of the at least one polymerization initiator,
3. c) mixing the, provided with the polymerization formed by the polymer, in particular coated, anode active material particles, in particular silicon particles, with at least one further electrode component, and
4. d) processing, for example by knife coating, the mixture to an anode.

The mixing in process step a) and the polymerization in process step b) can optionally be carried out in at least one solvent. After the polymerization or after process step b), for example before process step c) or during or after process step d), the at least one solvent can then be removed again.

In the context of another embodiment, in particular within the framework of which the polymerization of the at least one crown ether and / or crown ether derivative takes place homogeneously with the anode active material particles, in particular silicon particles, and also further electrode components (method 2), the anode active material particles, in particular silicon particles, are provided with at least one another electrode component and mixed with the at least one crown ether and / or crown ether derivative. In this way, the polymerization can be carried out in situ, in particular directly during the mixing, for example of a slurry, to form an anode. In this case, the anode active material particles, in particular silicon particles, the at least one further electrode component and the at least one crown ether and / or the at least one crown ether derivative can be mixed together at the same time. Optionally, however, first the anode active material particles, in particular silicon particles, and the at least one electrode component can be mixed with one another and then the at least one crown ether and / or the at least one crown ether derivative can be added to the mixture.

Within the scope of one embodiment of this embodiment, after the mixing, the polymerization is started by means of, for example, addition of, the at least one polymerization initiator. In particular, the polymerization can be started by means of, for example, adding, the at least one polymerization initiator and the at least one catalyst and / or the at least one polymerization-controlling agent, for example the at least one nitroxide-based mediator and / or the at least one thio compound. After the polymerization of the at least one crown ether and / or crown ether derivative, the mixture can then be processed to an anode, for example by doctoring. Thus, advantageously, the number of process steps can be reduced and in this way the process can be simplified. In addition, in this case, the polymer formed from the at least one crown ether and / or crown ether derivative can also serve as a binder for the anode to be produced. Optionally, this can be dispensed with the addition of an additional binder as a further electrode component.

• a') Mischen der Anodenaktivmaterialpartikel, insbesondere Siliciumpartikel, und mindestens einer weiteren Elektrodenkomponente und des mindestens einen Kronethers und/oder Kronether-Derivates,
• b') Starten der Polymerisation des mindestens einen Kronethers und/oder Kronether-Derivates mittels, beispielsweise durch Zugabe, des mindestens eines Polymerisationsinitiators, zum Beispiel mittels, beispielsweise durch Zugabe, des mindestens einen Polymerisationsinitiators und/oder des mindestens einen Katalysators und/oder des mindestens einen polymerisationskontrollierenden Mittels, beispielsweise des mindestens einen nitroxidbasierten Mediators und/oder der mindestens einen Thioverbindung, und
• c') Verarbeiten, beispielsweise durch Rakeln, der Mischung zu einer Anode, umfassen. Gegebenenfalls kann in Verfahrensschritt a') der mindestens eine Kronether und/oder das mindestens eine Kronether-Derivat zu der Mischung aus Anodenaktivmaterialpartikeln, insbesondere Siliciumpartikeln, und der mindestens einen weiteren Elektrodenkomponente zugegeben werden.

For example, the method may include the method steps:

• a ') mixing the anode active material particles, in particular silicon particles, and at least one further electrode component and the at least one crown ether and / or crown ether derivative,
• b ') starting the polymerization of the at least one crown ether and / or crown ether derivative by means, for example by addition, of the at least one polymerization initiator, for example by means of, for example, addition of the at least one polymerization initiator and / or the at least one catalyst and / or at least one polymerization-controlling agent, for example the at least one nitroxide-based mediator and / or the at least one thio compound, and
• c ') processing, for example by knife coating, mixing to an anode. Optionally, in process step a '), the at least one crown ether and / or the at least one crown ether derivative can be added to the mixture of anode active material particles, in particular silicon particles, and the at least one further electrode component.

The mixing in process step a ') and the polymerization in process step b') can be carried out in particular in at least one solvent. After the polymerization or after process step b '), for example before or during or after process step c'), then the at least one solvent can be removed again.

Within the scope of another embodiment, the anode active material particles, in particular silicon particles, are mixed with at least one further electrode component and with the at least one crown ether and / or crown ether derivative and the at least one polymerization initiator, and the mixture is processed to form an anode, for example by doctoring. The mixing and processing is preferably carried out under conditions such as at one, in particular low, temperature and / or in the absence of light, in which the at least one polymerization initiator does not start the polymerization reaction, in particular at least substantially. After the mixture has been processed into an anode, the polymerization is then started, in particular by irradiation, for example with ultraviolet radiation, for example a UV lamp, and / or by heating or heating the mixture.

Thus, advantageously, the number of process steps can be further reduced and the process further simplified. In addition, in this case the polymer formed from the at least one crown ether and / or crown ether derivative can likewise serve as a binder for the anode to be produced. If appropriate, it is therefore also possible to dispense with the addition of an additional binder as further electrode component. In addition, the polymer can thus be formed in the already processed form and advantageously a curing in the already processed form can be achieved.

• a") Mischen der Anodenaktivmaterialpartikel, insbesondere Siliciumpartikel, mindestens einer weiteren Elektrodenkomponente, des mindestens einen Kronethers und/oder Kronether-Derivates und des mindestens einen Polymerisationsinitiators, insbesondere Mischen der Anodenaktivmaterialpartikel, insbesondere Siliciumpartikel, mindestens einer weiteren Elektrodenkomponente, des mindestens einen Kronethers und/oder Kronether-Derivates und des mindestens einen Polymerisationsinitiators und beispielsweise des mindestens einen Katalysators und/oder des mindestens einen polymerisationskontrollierenden Mittels, beispielsweise des mindestens einen nitroxidbasierten Mediators und/oder der mindestens einen Thioverbindung;
• b") Verarbeiten, beispielsweise Rakeln, der Mischung zu einer Anode; und
• c") Starten der Polymerisation des mindestens einen Kronethers und/oder Kronether-Derivates durch Bestrahlen, insbesondere mit Ultravioletterstrahlung und/oder durch Erwärmen beziehungsweise Erhitzen der Mischung.

umfassen. Beispielsweise kann in Verfahrensschritt a"), zum Beispiel zunächst, der mindestens eine Kronether und/oder das mindestens eine Kronether-Derivat und, zum Beispiel dann, der mindestens eine Polymerisationsinitiator zu einer Mischung aus Anodenaktivmaterialpartikeln, insbesondere Siliciumpartikeln, und der mindestens einen weiteren Elektrodenkomponente zugegeben werden.For example, the method may include the method steps:

• a) mixing the anode active material particles, in particular silicon particles, at least one further electrode component, the at least one crown ether and / or crown ether derivative and the at least one polymerization initiator, in particular mixing the anode active material particles, in particular silicon particles, at least one further electrode component, the at least one crown ether and / or Kronether derivative and the at least one polymerization initiator and for example the at least one catalyst and / or the at least one polymerization controlling agent, for example the at least one nitroxide-based mediator and / or the at least one thio compound;
• b ") processing, for example doctoring, mixing to an anode;
• c ") starting the polymerization of the at least one crown ether and / or crown ether derivative by irradiation, in particular with ultraviolet radiation and / or by heating or heating of the mixture.

include. For example, in process step a "), for example initially, the at least one crown ether and / or the at least one crown ether derivative and, for example, the at least one polymerization initiator to a mixture of anode active material particles, in particular silicon particles, and the at least one further electrode component be added.

The mixing in process step a "), the processing in process step b") and the polymerization in process step c ") can be carried out in particular in at least one solvent After polymerization or after process step c") then the at least one solvent can be removed again ,

In the context of the above embodiments, the at least one further electrode component may comprise at least one carbon component, for example graphite and / or conductive carbon black, and / or at least one, optionally additional, for example compatible, binder, for example carboxymethylcellulose (CMC) and / or carboxymethylcellulose salts, such as Lithium carboxymethyl cellulose (LiCMC) and / or sodium carboxymethyl cellulose (NaCMC) and / or potassium carboxymethyl cellulose (KCMC), and / or polyacrylic acid (PAA) and / or polyacrylic acid salts, such as lithium polyacrylic acid (LiPAA) and / or sodium polyacrylic acid (NaPAA) and / or potassium polyacrylic acid (KPAA), and / or polyvinyl alcohol (PVAL) and / or styrene-butadiene rubber (SBR), and / or at least one solvent.

In particular, the at least one, optionally additional, binder may have carboxylic acid groups (-COOH) and / or hydroxyl groups (-OH). For example, the at least one, optionally additional, binder may comprise or be polyacrylic acid (PAA) and / or carboxymethyl cellulose (CMC) and / or polyvinyl alcohol (PVAL).

In particular, the at least one crown ether and / or the at least one crown ether derivative and / or the polymer comprising at least one crown ether and / or crown ether derivative can have carboxylic acid groups (-COOH) and / or hydroxyl groups (-OH).

Insofar as both the at least one, if appropriate additional, binder and the at least one crown ether and / or the at least one crown ether derivative and / or the at least one crown ether and / or crown ether derivative comprising polymer carboxylic acid groups (-COOH) and / or hydroxyl groups (- OH), advantageously provided with the polymer, for example, coated, anode active material particles, in particular silicon particles, are covalently connected via a condensation reaction with the at least one binder. In this case, an anhydride compound can be achieved by a condensation reaction between two carboxylic acid groups. In this case, an ester compound can be achieved by a condensation reaction between a carboxylic acid group and a hydroxy group. By a condensation reaction between two hydroxy groups while an ether compound can be achieved.

For example, silicon particles (Si-PAA) provided with a polymer based on polyacrylic acid can be covalently bonded with polyacrylic acid (PAA) and / or carboxymethylcellulose (CMC) and / or polyvinyl alcohol (PVAL) as a binder via a condensation reaction according to the following schemes: Si-PAA + PAA: -COOH + -COOH → anhydride compound Si-PAA + CMC: -COOH + -COOH → anhydride compound Si-PAA + PVAL: -COOH + -OH → ester compound

Optionally - in particular in the context of the above-described embodiments, within which the polymer formed from the at least one crown ether and / or crown ether derivative can also serve as a binder - can be omitted as the addition of at least one, in particular additional, binder as a further electrode component or the If appropriate, at least one further electrode component can also be made binder-free.

Nevertheless, it is possible-for example in order to improve the mechanical stability and / or conductivity of the anode to be formed-to use at least one binder, for example additional binder, in particular different from the polymer formed from the polymerizable monomer, as a further electrode component.

Optionally, the at least one solvent used in the polymerization can also serve as an electrode component, for example for the formation of an electrode slip. Thus, it may be possible to dispense with the addition of an additional solvent as a further electrode component.

In particular, for example insofar as the at least one solvent is removed again after the polymerization, at least one solvent, in particular different from the solvent of the polymerization, can be used as further electrode component.

With regard to further technical features and advantages of the method according to the invention, reference is hereby explicitly made to the explanations in connection with the anode active material according to the invention, the anode according to the invention, the electrolyte according to the invention, the electrolyte additive according to the invention and the cell and / or battery according to the invention and to the figures and the description of the figures.

Further objects of the present invention are an anode active material and / or an anode and / or an electrolyte, in particular anolyte, for a lithium cell and / or lithium battery, in particular for a lithium-ion cell and / or lithium-ion battery which is produced by a method according to the invention and / or wherein the anode active material and / or the anode are anode active material particles, for example silicon particles and / or graphite particles and / or tin particles, in particular Silicon particles, which are provided with at least one polymer, in particular coated, which is formed for example of at least one crown ether and / or Kronether derivative having at least one polymerizable functional group, and / or wherein the electrolyte, in particular anolyte, at least one crown ether and / or at least one crown-ether derivative having at least one polymerizable functional group, for example as an electrolyte additive, for example Anolytadditiv, comprises, in particular contains.

An anode active material according to the invention or produced according to the invention, for example the polymer comprising at least one crown ether and / or crown ether derivative, and / or an anode produced according to the invention and / or an electrolyte prepared according to the invention and / or an electrolyte additive according to the invention can be prepared, for example, by nuclear magnetic resonance spectroscopy ( NMR) and / or infrared spectroscopy (IR) and / or Raman spectroscopy (Raman). In addition, an anode active material according to the invention or produced according to the invention and / or an anode produced according to the invention can be prepared, for example, by surface analysis methods such as Auger electron spectroscopy (AES) and / or X-ray photoelectron spectroscopy (XPS) and / or time-of-flight secondary ion mass spectrometry ( TOF-SIMS, Time-of-Flight Secondary Ion Mass Spectrometry) and / or Energy Dispersive X-Ray Spectroscopy (EDX) and / or Wavelength Dispersive X-Ray Spectroscopy (WDX), for example EDX / WDX, and / or by means of structural investigation methods, such as transmission electron microscopy (TEM), and / or cross-sectional investigations, such as Scanning Electron Microscopy (SEM) and / or Energy Dispersive X-ray Spectroscopy (EDX, English: Energy Dispersive X-ray). ray spectroscopy), for example, SEM-EDX, and / or transmission electron microscopy (TEM) and / or electron energy loss spectroscopy (EELS; Electron Energy Loss Spectroscopy), for example TEM-EELS. For example, transition metals contained in an ATRP catalyst and / or nitroxide-based mediators such as TEMPO, and / or RAFT chemicals may be detectable, among others.

With regard to further technical features and advantages of the anode active material according to the invention, the electrolyte according to the invention and the anode according to the invention, reference is hereby explicitly made to the explanations in connection with the process according to the invention, the electrolyte additive according to the invention and the cell and / or battery according to the invention and to the figures and the description of the figures.

In addition, the invention relates to an electrolyte additive, in particular anolyte additive, for a lithium cell and / or lithium battery, in particular for a lithium-ion cell and / or lithium-ion battery, which comprises at least one crown ether and / or at least one crown ether -Derivat having at least one polymerizable functional group comprises or the use of a Kronethers and / or Kronether derivative having at least one polymerizable functional group as electrolyte additive, in particular Anolytadditiv.

With regard to further technical features and advantages of the electrolyte additive according to the invention, reference is hereby explicitly made to the explanations in connection with the process according to the invention, the anode active material according to the invention, the electrolyte according to the invention, the anode according to the invention and the cell and / or battery according to the invention and to the figures and the description of the figures.

Furthermore, the invention relates to a lithium cell and / or lithium battery, in particular a lithium-ion cell and / or lithium-ion battery, which is produced by a method according to the invention and / or an anode active material according to the invention and / or an anode according to the invention and / or an electrolyte according to the invention and / or an electrolyte additive according to the invention.

With regard to further technical features and advantages of the cell and / or battery according to the invention, reference is hereby explicitly made to the explanations in connection with the method according to the invention, the anode active material according to the invention, the anode according to the invention, the electrolyte according to the invention, the electrolyte additive according to the invention and to the figures and the description of the figures.

list of figures

• 1a ein Flussdiagramm zur Veranschaulichung einer Ausführungsform des erfindungsgemäßen Herstellungsverfahrens;
• 1b einen schematischen Querschnitt durch eine Anode, welche gemäß der in 1a gezeigten Ausführungsform des erfindungsgemäßen Verfahrens hergestellt ist;
• 2a ein Flussdiagramm zur Veranschaulichung einer weiteren
• Ausführungsform des erfindungsgemäßen Herstellungsverfahrens; und 2b einen schematischen Querschnitt durch eine Anode, welche gemäß der in 2a gezeigten, weiteren Ausführungsform des erfindungsgemäßen Verfahrens hergestellt ist,
• 3a ein Flussdiagramm zur Veranschaulichung einer weiteren Ausführungsform des erfindungsgemäßen Herstellungsverfahrens;
• 3b ein Reaktionsschema zur Veranschaulichung der in 3a gezeigten weiteren Ausführungsform des erfindungsgemäßen Herstellungsverfahrens; und
• 4 ein Flussdiagramm zur Veranschaulichung einer weiteren Ausführungsform des erfindungsgemäßen Herstellungsverfahrens.

Further advantages and advantageous embodiments of the objects according to the invention are illustrated by the drawings and exemplary embodiments and explained in the following description. It should be noted that the drawings and embodiments have only descriptive character and are not intended to limit the invention in any way. Show it

• 1a a flow diagram illustrating an embodiment of the manufacturing method according to the invention;
• 1b a schematic cross section through an anode, which according to the in 1a shown embodiment of the method according to the invention is produced;
• 2a a flow chart illustrating another
• Embodiment of the production method according to the invention; and 2 B a schematic cross section through an anode, which according to the in 2a shown, another embodiment of the method according to the invention is produced,
• 3a a flowchart illustrating a further embodiment of the manufacturing method according to the invention;
• 3b a reaction scheme illustrating the in 3a shown further embodiment of the manufacturing method according to the invention; and
• 4 a flowchart illustrating a further embodiment of the manufacturing method according to the invention.

The 1a and 2a illustrate that in the inventive method for producing an anode active material or an anode 100 '100' for a lithium cell and / or lithium battery, in particular for a lithium-ion cell and / or lithium-ion battery, anode active material particles, in particular silicon particles, 1 and at least one crown ether and / or crown ether derivative 2 be mixed with at least one polymerizable functional group and the polymerization of at least one polymerizable functional group of the at least one crown ether and / or crown ether derivative 2 optionally by means of at least one polymerization initiator 3 , is started. The polymerization can be for example a living radical polymerization, for example, a living radical atom transfer (ATRP) or a stable free radical polymerization (SFRP), for example, a nitroxide-mediated polymerization (NMP), or a reversible addition fragmentation chain transfer Polymerization (RAFT), be.

As part of the in 1a In an embodiment illustrated, in a method step a) anode active material particles, in particular silicon particles, 1 and at least one crown ether and / or crown ether derivative 2 mixed. The polymerization of the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative 2 can thereby, for example by addition of a polymerization initiator 3 be started in a process step b). To the molecular weight of the resulting polymer 20 To better control, the polymerization can be carried out in a solvent (solution polymerization), for example, which is removed again after the polymerization. It will be - as well as in 1b FIG. 2 illustrates the anode active material particles, in particular silicon particles, 1 with the polymer formed by the polymerization 20 coated. The coated anode active material particles, in particular silicon particles, 1.20 are then in one process step c ) with one or more, further electrode components, such as graphite and / or Leitruß 4 and binder 5 and / or solvent mixed. As in 1b illustrated here may serve as the further electrode component binder 5 in particular different from that from the at least one crown ether and / or crown ether derivative 2 trained polymer 20 be. In a process step d) then the mixture is 1,20,4,5 to an anode 100 processed, for example, gerakelt.

1b illustrates that an appropriately prepared anode 100 with polymer 20 Coated anode active material particles, in particular silicon particles, 1 and graphite and / or Leitruß particles 4 which may be included in an additional binder 5 are embedded.

As part of the in 2a illustrated embodiment - in the course of mixing a slurry to form an anode 100 ' - In a process step a ') anode active material particles, in particular silicon particles, 1 and at least one further electrode component, such as graphite and / or Leitruß 4 and optionally binder, mixed in a solvent. To the mix of the Anode active material particles, in particular silicon particles, 1 and the at least one further electrode component 4 then at least one Kronether and / or Kronether derivative 2 with at least one polymerizable functional group added. Subsequently, in a process step b ' ) the polymerization of the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative 2 to a polymer 20 , for example by means of at least one polymerization initiator 3 , started directly during the slip mixing (in-situ polymerization) and the resulting slurry 1,4,20 then in one process step c '), for example, doctored, and directly and to an anode 100 ' processed.

2 B illustrates that from the at least one Kronether and / or Kronether derivative 2 formed polymer 20 in the context of this embodiment also as a binder 20 can serve, in which 20 at a correspondingly prepared anode 100 ' Anodenaktivmaterialpartikel, in particular silicon particles, 1 and graphite and / or Leitruß particles 4 are embedded.

3a illustrates that within the scope of a further embodiment of the method according to the invention, for example in a method step A ), at least one silane compound 2 * having at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group is immobilized on the surface of anode active material particles, in particular silicon particles. The at least one silane compound 2 * may, for example, be a vinyl silane or a silane-based ATRP initiator or a silane-based NMP mediator or a silane-based RAFT agent.

To the reaction product 12 * is then, for example in a process step B ), at least one crown ether and / or crown ether derivative 2 with at least one polymerizable functional group added. In this case, starting from the surface of the anode active material particles, in particular silicon particles, a (co) polymer 12 * 2 is formed and the anode active material particles, in particular silicon particles, 1 are coated in this manner.

The coated anode active material particles, in particular silicon particles, 12 * 2 can then, for example, in one process step C ), with one or more further electrode components, such as graphite and / or Leitruß 4 and binder 5 and / or solvent, mixed and the mixture 12 * 2,4,5, for example in one process step D ), to an anode 100 ' processed, for example, be doctored. An appropriately prepared anode 100 ' can one to the in 1a shown, have similar schematic cross section and polymer 2 * 2 (20) coated anode active material particles, in particular silicon particles, 1 and graphite and / or Leitruß particles 4 which may be included in an additional binder 5 are embedded.

3b illustrates that in this case the at least one silane compound 2 *, for example 4- (chloromethyl) phenyltrichlorosilane, for example by condensation reaction with hydroxyl groups, in particular silicon hydroxide groups or silanol groups (Si-OH), on the surface of the anode active material particles, in particular silicon particles, 1 a, in particular covalent , Bonding with the anode active material particles, in particular silicon particles, 1 and enter a starting from the surface of the anode active material particles, in particular silicon particles, 1 polymerization of the at least one polymerizable functional group of the at least one crown ether and / or crown ether derivative 2 can start.

4 illustrates that within the scope of a further embodiment of the method according to the invention, for example in a method step A '), at least one crown ether and / or crown ether derivative 2 with at least one polymerizable functional group and / or at least one, from the at least one crown ether and / or crown ether derivative 2 polymer formed with at least one silane compound 2 * is reacted with at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group. The at least one silane compound 2 * may, for example, be a vinyl silane or a silane-based ATRP initiator or a silane-based NMP mediator or a silane-based RAFT agent.

In this case, a (co) polymer 22 * is formed, to which 22 * then, for example in one process step B ' ), Anode active material particles, in particular silicon particles, 1 are added. The silane function of the (co) polymer 22 * formed during the reaction, for example by condensation reaction, for example with hydroxy groups, in particular silicon hydroxide groups or silanol groups (Si-OH), on the surface of the anode active material particles, in particular silicon particles, 1 one, in particular covalent , Binding with the anode active material particles, in particular silicon particles, 1 and the anode active material particles, in particular silicon particles, 1 are coated in this manner.

The coated anode active material particles, in particular silicon particles, 122 * can then, for example, in one process step C '), with one or more further electrode components, such as graphite and / or Leitruß 4 and binder 5 and / or solvent, mixed and the mixture 122 *, 4.5, for example in one process step D ') are processed to an anode 100''', for example, doctored. An appropriately prepared anode 100 '''may be one to that in 1a shown, have similar schematic cross-section and polymer 22 * (20) coated anode active material particles, in particular silicon particles, 1 and graphite and / or Leitruß particles 4 which may be included in an additional binder 5 are embedded.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 2014/0248543 A1 [0004, 0005]
• US 2015/0072246 A1 [0006]
• US 2010/0273066 A1 [0007]
• US 2012/0007028 A1 [0008]
• CN 104362300 [0009]
• US 2014/0342222 Al [0010]
• WO 2015/107581 [0013]

Cited non-patent literature

• H. Zhao et al., J. Power Sources, 263, 2014, pp. 288-295 [0011]
• J.-H. Min et al. In Bull. Korean. Chem. Soc., 2013, Vol. 34, no. 4th, p. 1296-1299 [0012]

Claims (25)

Method for producing an anode active material and / or an anode (100, 100 ', 100 ", 100'") and / or an electrolyte for a lithium cell and / or lithium battery, in particular for a lithium-ion cell and / or Lithium-ion battery, and / or for producing a lithium cell and / or lithium battery, in particular a lithium-ion cell and / or lithium-ion battery, in the anode active material particles (1) and / or an electrolyte at least one crown ether and / or crown ether derivative (2) are provided with at least one polymerizable functional group and / or polymer comprising at least one crown ether and / or crown ether derivative. Method according to Claim 1 in which the at least one crown ether and / or the at least one crown ether derivative (2) is polymerized and / or the polymer comprising at least one crown ether and / or crown ether derivative is prepared by polymerization of the at least one crown ether and / or crown ether derivative (2) is or will be trained. Method according to Claim 1 or 2 wherein the anode active material particles (1) and / or the electrolyte further provided with at least one further polymerizable monomer and / or with at least one polymer formed by polymerization of the at least one crown ether and / or crown ether derivative (2) and at least one further polymerizable monomer become. Method according to one of Claims 1 to 3 in which the anode active material particles (1) are coated with at least one polymer formed by polymerization of the at least one crown ether and / or crown ether derivative (2) and / or the electrolyte is mixed with the at least one crown ether and / or crown ether derivative (2) in particular where anode active material particles (1) are coated with at least one polymer formed by polymerization of the at least one crown ether and / or crown ether derivative (2) and the at least one further polymerizable monomer and / or the electrolyte with the at least one crown ether and / or or Kronether derivative (2) and with the at least one further polymerizable monomer is added. Method according to one of Claims 1 to 4 wherein the at least one crown ether and / or the at least one crown ether derivative (2) and / or the at least one further polymerizable monomer by a living radical polymerization, in particular by a living radical polymerization with atom transfer or by a stable free radical polymerization, for example by a nitroxide-mediated polymerization, or by a reversible addition-fragmentation chain transfer polymerization, is polymerizable and / or polymerized. Method according to one of Claims 1 to 5 wherein the anode active material particles (1) comprise or are silicon particles and / or graphite particles and / or tin particles, in particular silicon particles. Method according to one of Claims 1 to 6 wherein the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative (2) comprises or is at least one polymerizable double bond and / or at least one hydroxy group. Method according to one of Claims 1 to 7 in which the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative (2) and / or the at least one further polymerizable monomer has at least one vinyl group and / or at least one vinylidene group and / or at least one vinylene group and / or at least one Allylgruppe, in particular allyloxyalkyl group, and / or at least one acrylate group and / or at least one methacrylate group and / or at least one hydroxy group, in particular alkylene hydroxy group, comprises or is. Method according to one of Claims 1 to 8th wherein the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative (2) and / or the at least one further polymerizable monomer comprises or is at least one carbon-carbon double bond. Method according to one of Claims 1 to 9 wherein the at least one crown ether and / or the at least one crown ether derivative (2) comprises a crown ether or a crown ether derivative of the general chemical formula:

wherein Q1, Q2, Q3 and Qk are each independently oxygen or nitrogen or an amine, especially oxygen, where k is the number of units in parentheses, G being at least one polymerisable functional group and g stands for the number of polymerizable functional groups G. Method according to Claim 10 in which G comprises at least one vinyl group and / or at least one vinylidene group and / or at least one vinylene group and / or at least one allyl group, in particular allyloxyalkyl group, and / or at least one hydroxy group, in particular alkylene hydroxy group. Method according to Claim 10 or 11 where G furthermore comprises at least one benzo group and / or cyclohexano group. Method according to one of Claims 1 to 12 wherein the at least one crown ether and / or the at least one crown ether derivative (2) comprises a crown ether or a crown ether derivative of the general chemical formula:

wherein G 'is at least one polymerisable functional group, in particular at least one vinyl group and / or at least one vinylidene group and / or at least one vinylene group and / or at least one allyl group and / or at least one hydroxy group, and wherein 1 ≤ g' , Method according to one of Claims 1 to 13 in which the at least one crown ether and / or the at least one crown ether derivative (2) and / or the polymer comprising at least one crown ether and / or crown ether derivative furthermore has at least one silane group and / or at least one silane compound (2 *) at least one polymerizable and / or polymerization-initiating and / or polymerization-controlling functional group is used. Method according to one of Claims 1 to 14 wherein the at least one crown ether and / or the at least one crown ether derivative (2) comprises a crown ether or a crown ether derivative of the general chemical formula:

wherein R1, R2, R3 each independently represents a halogen atom or an alkoxy group or an alkyl group or an amino group or a silazane group or a hydroxy group or hydrogen, Q1, Q2, Q3 and Qk each independently represent oxygen or nitrogen or an amine , in particular oxygen, k is the number of the unit in parentheses, G is at least one polymerisable functional group, g is the number of polymerisable functional groups G, Y 'is a linker, in particular -C _n H _2n - With n = 1 or 2 or 3, and s stands for the number of, in particular via the linker Y 'attached, silane groups. Method according to one of Claims 3 to 15 wherein the at least one further polymerizable monomer (2): at least one polymerizable carboxylic acid and / or at least one polymerizable carboxylic acid derivative, in particular at least polymerizable organic carbonate and / or anhydride, and / or at least one carboxylic acid ester, and / or at least one carbonitrile, and / or at least one ether, in particular at least one further crown ether and / or at least one further crown ether derivative and / or at least one vinyl ether, and / or at least one, in particular aliphatic or aromatic, unsaturated hydrocarbon , Method according to one of Claims 3 to 16 in which the at least one further polymerisable monomer (2) is acrylic acid and / or methacrylic acid and / or vinylene carbonate and / or vinylethylene carbonate and / or maleic anhydride and / or poly (ethylene glycol) methyl ether acrylate and / or methyl methacrylate and / or vinyl acetate and / or acrylonitrile and / or at least one further crown ether and / or at least one further Kronether derivative having at least one polymerizable functional group, in particular having at least one polymerizable double bond, and / or having at least one hydroxy group, and / or a trifluorovinyl ether and / or 1,1-difluoroethene and / or hexafluoropropene and / or 3,3,4,4,5,5,6,6,6-nonafluorhexene and / or 2,3,4,5,6-pentafluorophenylethene and / or 4- (trifluoromethyl) phenylethene and / or styrene and / or a derivative thereof. Method according to one of Claims 1 to 17 wherein the anode active material particles (1) are mixed and polymerized with at least one crown ether and / or crown ether derivative having at least one polymerizable functional group. Method according to one of Claims 1 to 18 in which the at least one silane group of the at least one crown ether and / or crown ether derivative is immobilized on the surface of the anode active material particles (1), in particular silicon particles, and the at least one polymerisable functional group of the at least one crown ether and / or crown ether derivative is polymerized, or - wherein at least one silane compound (2 *) having at least one polymerizable and / or polymerization initiating and / or polymerization-controlling functional group immobilized on the surface of the anode active material particles (1), in particular silicon particles, and the at least one crown ether and / or the at least one crown ether Derivative (2) is added and polymerized. Method according to one of Claims 1 to 19 in which the at least one crown ether and / or the at least one crown ether derivative (2), in particular in at least one solvent, is polymerized and anode active material particles, in particular silicon particles, in particular to the solution, are added, and / or - wherein the at least one Kronether and / or Kronether derivative polymer is dissolved in at least one solvent and to the solution anode active material particles, in particular silicon particles, are added, wherein the at least one solvent is removed again. Method according to Claim 20 in which the at least one crown ether and / or the at least one crown ether derivative (2) and / or the polymer comprising at least one crown ether and / or crown ether derivative has at least one silane group and / or with at least one silane compound (2 *) with at least a polymerizable and / or polymerization initiating and / or polymerization-controlling functional group reacted, in particular polymerized, is. Method according to one of Claims 14 to 21 wherein the at least one silane compound comprises at least one silane compound of the general chemical formula:

wherein R1, R2, R3 each independently represent a halogen atom or an alkoxy group or an alkyl group or an amino group or a silazane group or a hydroxy group or hydrogen, Y is a linker, in particular wherein Y is at least one alkylene group and / or at least one Alkylene oxide group and / or at least one carboxylic acid ester group and / or at least one phenylene group, and A is a polymerizable and / or polymerization initiating and / or polymerization controlling functional group, in particular where A is a polymerizable functional group having at least one polymerizable double bond, in particular for a vinyl group or a vinylidene group or a vinylene group or an acrylate group or a methacrylate group, or wherein A represents a polymerization-initiating functional group for starting a living radical polymerization under atom transfer, in particular e represents bromine or chlorine, or wherein A is a polymerization-controlling functional group for a nitroxide-mediated polymerization, in particular for a nitroxide group and / or alkoxyamine group, or for a polymerization-controlling functional group for a reversible addition-fragmentation chain transfer polymerization, in particular for a thio group, stands. Anode active material and / or anode (100, 100 ', 100 ", 100''') and / or electrolyte for a lithium cell and / or lithium battery, in particular for a lithium-ion cell and / or lithium-ion battery, produced by a method according to one of Claims 1 to 21 and / or wherein the anode active material and / or the anode (100, 100 ', 00 ", 100''') comprises anode active material particles (1), in particular silicon particles, which are provided with at least one polymer which comprises at least one crown ether and / or crown ether -Derivat is formed with at least one polymerizable functional group, and / or wherein the electrolyte contains at least one Kronether and / or at least one Kronether derivative having at least one polymerizable functional group. Electrolyte additive for a lithium cell and / or lithium battery, in particular for a lithium-ion cell and / or lithium-ion battery, comprising at least one crown ether and / or at least one crown ether derivative (2) having at least one polymerizable functional Group. Lithium cell and / or lithium battery, in particular lithium-ion cell and / or lithium-ion battery, produced by a method according to one of Claims 1 to 22 and / or comprising an anode active material and / or an anode (100, 100 ', 100 ", 100'") and / or an electrolyte Claim 23 and / or an electrolyte additive Claim 24 ,

Images