JP2015512957A - A composite material, its production method and its use in a separator for an electrochemical cell. - Google Patents

Abstract

The present invention comprises at least one substrate comprising a nonwoven fabric as component (A), at least one nanocomposite material as component (B), at least one polyether or at least one polyether as component (C) The present invention relates to a novel composite material comprising a lithium salt as a group and optionally component (D). The invention further relates to a method for producing the novel composite material, its use in a separator for an electrochemical cell, and certain starting compounds that can be used to produce a nanocomposite material (B).

Description

The present invention comprises at least one base body comprising a nonwoven fabric as component (A), at least one nanocomposite as component (B), at least one polyether as component (C), or It relates to a novel composite material comprising at least one polyether-comprising radical and optionally a lithium salt as component (D).
The invention further relates to a method for the production of the novel composite material, its use in a separator for electrochemical cells, and certain starting compounds that can be used to produce a nanocomposite material (B).

  Energy storage has been a growing concern for a long time. For example, an electrochemical cell such as a battery or accumulator can serve to store electrical energy. In recent years, lithium ion batteries have become of particular interest. They are superior to conventional batteries in several technical aspects. They therefore make it possible to generate voltages that cannot be obtained using batteries based on aqueous electrolytes.

However, conventional lithium ion batteries having a carbon anode and a cathode based on a metal oxide are limited in their energy density. A new dimension in energy density is opened up by lithium-sulfur batteries. In a lithium-sulfur battery, sulfur is reduced at the sulfur cathode to S ²⁻ via polysulfide ions and reoxidized to form a sulfur-sulfur bond upon battery charging.

  In electrochemical cells, the positively and negatively charged electrode compositions are mechanically separated from each other by a non-conductive layer known as a separator to avoid internal discharge. Because of its porous structure, these separators allow ionic charge transport as a basic prerequisite for continuing current acquisition during battery operation. The basic requirement that the separator must meet is chemical and electrochemical stability for both the active electrode composition and the electrolyte. Furthermore, high mechanical strength must be ensured for the tension generated during the battery cell manufacturing process. At the structural level, a high porosity for electrolyte absorption is necessary to ensure high ionic conductivity. At the same time, as described in Journal Power Sources 2007, 164, 351-364, the pore size and channel structure must effectively inhibit the growth of metal dendrites to avoid short circuits. I must.

  The separator as the microporous layer often includes either a polymer film or a nonwoven fabric.

  Currently, polymer films based on polyethylene and polypropylene are usually used as separators in electrochemical cells, but these films do not have satisfactory stability at high temperatures of 130-150 ° C.

  As described in DE10255122 A1, DE10238941 A1, DE10208280 A1, DE10208277 A1 and WO 2005/038959 A1, commonly used polyolefin separator alternatives are filled with ceramic particles and additionally silicon, aluminum and / or zirconium A separator based on a nonwoven fabric fixed by an inorganic binder made of an oxide of an element. However, the nonwoven filled with the ceramic particles has an increased mass per unit area and a greater thickness compared to the unfilled nonwoven.

  WO 2009/033627 discloses layers that can be used as separators for lithium ion batteries. It comprises a nonwoven and particles incorporated into the nonwoven and comprising an organic polymer and optionally partially an inorganic material. Short circuits caused by metal dendrites are said to be avoided by such separators. However, WO2009 / 033627 does not disclose any long-term cycling experiments.

  WO 2009/103537 discloses a layer having a substrate with pores, the layer further comprising a crosslinked binder. In a preferred embodiment, the substrate is at least partially filled with particles. The disclosed layer can be used as a separator in a battery. However, WO 2009/103537 does not produce and test electrochemical cells having the disclosed layers.

  WO 2011/000858 discloses a porous membrane material that contains at least one carbon-containing metalloid oxide phase and can be used as a separator in a rechargeable lithium ion battery. As described in S. Spange et al. In Angew. Chem. Int Ed., 46 (2007) 628-632, the carbon-containing metalloid oxide phase is obtained by twin polymerization.

DE10255122 A1 DE10238941 A1 DE10208280 A1 DE10208277 A1 WO 2005/038959 A1 WO 2009/033627 WO 2009/103537 WO2011 / 000858

Journal Power Sources 2007, 164, 351-364.

S. Spange et al. In Angew. Chem. Int Ed., 46 (2007) 628-632.

  The separators known from the literature are one or more desired for the separator, eg thin thickness, small mass per unit area, eg excellent mechanical stability during manufacture such as high flexibility or low wear. In terms of the characteristics of the battery or in the operation of the battery, there are still defects in the growth of metal dendrites, excellent heat resistance, low shrinkage, high porosity, excellent ionic conductivity and excellent wettability with electrolyte liquid. Have. Some defects in the separator are ultimately responsible for the reduced lifetime of the electrochemical cell containing them. Furthermore, in principle, the separator must be chemically stable not only mechanically but also to the cathode material, anode material and electrolyte. In the field of lithium-sulfur batteries, separators are desired that also prevent premature cell death of lithium-sulfur batteries, especially caused by the migration of polysulfide ions from the cathode to the anode.

  The object of the present invention is therefore advantageous with respect to one or more properties of known separators and is an inexpensive separator for long-life electrochemical cells, in particular lithium-sulfur batteries, in particular excellent lithium. The object is to provide a separator exhibiting ion permeability, high thermal stability and excellent mechanical properties.

The purpose of this is to:
(A) a substrate made of at least one nonwoven fabric;
(B) (a) at least one inorganic or (semi) metal-organic phase (a) comprising at least one metal or metalloid M, and (b) at least one organic polymer phase (b). The organic polymer phase (b) and the inorganic or (semi) metal-organic phase (a) comprising an essentially co-continuous phase region, the average distance between two adjacent identical phase regions At least one nanocomposite material that is 100 nm or less,
(C) at least one polyether or at least one polyether-containing group (wherein the polyether-containing group is covalently bonded to the (semi) metal-organic phase (a) or the organic polymer phase (b)) And (D) optionally at least one lithium salt,
It is achieved by a composite material characterized in that

  The composites of the present invention are composite materials, also referred to as composite materials of the present invention, for the purposes of the present invention. In general, a composite material is a material that is a solid mixture that cannot be manually separated and has different properties than the individual components. Specifically, the composite material of the present invention is a fiber composite material.

  Depending on the ratio of the total volume of the substrate comprising the nonwoven fabric (A) to the total volume of the nanocomposite material (B) and depending on the method of contacting the component (A) with the component (B), comprising the nonwoven fabric (A) The substrate may be partially or completely penetrated by the nanocomposite material. Here, the substrate made of nonwoven fabric may be penetrated symmetrically or asymmetrically, ie the opposite sides of the substrate made of nonwoven fabric can be distinguished from each other.

  In one embodiment of the present invention, the substrate composed of the nonwoven fabric (A) in the composite material of the present invention is at least partly, preferably more than 50%, particularly completely penetrated by the nanocomposite material (B). May have been.

  The composite material of the present invention comprises, as component (A), a substrate composed of at least one nonwoven fabric, which is also referred to as nonwoven fabric (A) for short for the purpose of the present invention.

  Nonwoven fabrics and their manufacture are known to those skilled in the art. Many selectable nonwovens are commercially available. Thus, the nonwoven can be made from inorganic or organic materials, preferably organic materials.

  Examples of inorganic nonwoven fabrics include glass fiber nonwoven fabrics and ceramic fiber nonwoven fabrics.

  Examples of organic polymers for producing nonwovens include polyolefins, especially polyethylene or polypropylene, polymers of heteroatom-containing vinyl monomers, especially polyacrylonitrile, polyvinylpyrrolidone or polyvinylidene fluoride, polyesters, especially polybutyl terephthalate, polyethylene terephthalate. Or polyethylene naphthalate, polyamides, in particular PA6, PA11, PA12, PA6.6, PA6.10 or PA6.12, polyimide, polyetheretherketone, polysulfone or polyoxymethylene.

  In one embodiment of the present invention, the substrate comprising the nonwoven fabric (A) in the composite material of the present invention is a polyolefin, particularly polyethylene and polypropylene, a polymer of a heteroatom-containing vinyl monomer, particularly polyacrylonitrile, polyvinylpyrrolidone and polyvinylidene fluoride, polyester. , Especially polybutyl terephthalate, polyethylene terephthalate and polyethylene naphthalate, polyamide, especially PA6, PA11, PA12, PA6.6, PA6.10 and PA6.12, polyimide, polyetheretherketone, polysulfone and polyoxymethylene Made of an organic polymer selected from the group of polymers. Nonwoven fabric (A) made from polyester, in particular polyethylene terephthalate, is particularly preferred.

  The substrate made of non-woven fabric is preferably a sheet-like substrate, and for the purposes of the present invention the phrase “sheet-like” means that the described substrate is one of three spatial dimensions (extensions). That is, it means a three-dimensional body that is smaller in thickness than the other two dimensions, length and width. The thickness of the substrate is usually 1/5, preferably at least 1/10, particularly preferably at least 20 times smaller than the second largest dimension.

  As a result, the composite material containing the substrate (A) is also preferably a sheet-like body.

  In one embodiment of the invention, the composite material of the invention is a sheet.

  The substrate made of non-woven fabric preferably has a thickness in the range of 5 to 100 μm, particularly preferably 10 to 50 μm, especially 15 to 25 μm. The fibers from which the nonwoven is made usually have a fiber length that is preferably at least twice, preferably more than twice the average diameter of the fibers. The average diameter of at least 90% of the fibers contained in the nonwoven fabric is preferably 20 μm or less, particularly preferably 12 μm or less, particularly 4 to 6 μm. The porosity of the non-woven fabric substrate is preferably in the range of 50 to 80%, preferably in the range of 50 to 60%.

The composite material of the present invention is further referred to as a nanocomposite material (B) for the purposes of the present invention as component (B),
(A) at least one inorganic or (semi) metal-organic phase (a) comprising at least one metal or semi-metal M, and (b) at least one organic polymer phase (b), The organic polymer phase (b) and the inorganic or (semi) metal-organic phase (a) form an essentially cocontinuous phase region, the average distance between two adjacent identical phase regions Comprises at least one nanocomposite material of 100 nm or less, preferably 40 nm or less, particularly preferably 10 nm or less, in particular 5 nm or less.

  The nanocomposite material (B) defined above is known in principle, and the microscopic structures of the phase (a) and the phase (b) match, that is, the phase (a) and the phase (b) are essential. Can be obtained in various macroscopic forms that form a co-continuous phase region and have an average distance between two adjacent identical phase regions of 100 nm or less. In WO2010 / 112581, pages 30-31, various nanocomposites (B) are described as solids. In WO2010 / 128144, page 38, line 1 to page 41, line 26, a nanocomposite material (B) of fine particles is described. In WO2011 / 000858, page 6, line 24 to page 12, line 28, a nanocomposite material (B) is described as a porous membrane material. With regard to the preferred embodiment of the nanocomposite (B) and the explanation of the terms “phase” and “phase region”, the above documents are fully incorporated by reference in the present specification.

  The metal or metalloid M in the inorganic or (semi) metal organic phase (a) is preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof. Selected from. In particular, M is selected from B, Al, Si, Ti, Zr and Sn, preferably from Al, Si, Ti and Zr, and in particular Si. It is particularly preferred that at least 90 mol%, in particular at least 99 mol%, or the total amount of all metals or metalloids M is silicon.

  In one embodiment of the present invention, the metal or semimetal M of the phase (a) in the composite material of the present invention is B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Selected from Bi and mixtures thereof, preferably selected from B, Al, Si, Ti, Zr and Sn, particularly preferably selected from Al, Si, Ti and Zr, especially as Si Selected.

  In a further embodiment of the invention, the metal or metalloid M in the composite material of the invention comprises at least 90 mol%, in particular at least 99 mol% silicon, based on the total amount of M.

  Furthermore, the composite material of the present invention comprises, as component (C), at least one polyether or at least one polyether-containing group (wherein the polyether-containing group is the (semi) metal-organic phase ( a) or an organic polymer phase (b).

Polyethers and their preparation are in principle known to those skilled in the art. Therefore, many polyethers are commercially available. Many of these polyethers preferably contain monomeric units of ethylene oxide or propylene oxide, especially ethylene oxide. Both cyclic and linear polyethers are known. An example of a defined cyclic polyether is 18-crown-6. Examples of linear polyesters include, among others, polyalkylene glycols, preferably poly-C ₁ -C ₄ -alkylene glycols, especially polyethylene glycol. The polyethylene glycol may contain up to 20 mol% of one or more C ₁ -C ₄ -alkylene glycols in the copolymerized form. The polyalkylene glycol is preferably a polyalkylene glycol having two methyl or ethyl end caps. The molecular weight M _w of a suitable polyalkylene glycol, in particular a suitable polyethylene glycol, can range from ≧ 200 g / mol to 100,000 g / mol, preferably from 400 g / mol to 10,000 g / mol. Preferred polyethers as component (C) are selected from the group consisting of polyethylene glycol, polypropylene glycol, and copolymers of ethylene oxide and propylene oxide.

  Polyether-containing groups, their preparation and handling are likewise known to those skilled in the art. Since polyether-containing groups are in principle derived from polyethers as described above, for example by hydrocarbon fragments of the corresponding polyethers or preferably by abstraction of hydrogen atoms from OH groups, polyether-containing groups are also in principle Based on ethylene oxide or propylene oxide, in particular ethylene oxide monomer building blocks.

  The polyether-containing group covalently bonded to the (semi) metal-organic phase (a) or the organic polymer phase (b) is preferably via the oxygen atom of the polyether-containing group or in particular a divalent hydrocarbon fragment For example, directly bonded to one of the two phases via a methylene group, an ethylene group, a propylene group or a phenylene group. Particularly preferably, the polyether-containing group comprising a monomer unit selected from the group consisting of ethylene oxide and propylene oxide is linked via a carbon atom to the (semi) metal-organic phase (a), in particular (semi) metal-organic. Bonds to the metal or metalloid M of phase (a), in particular to Si.

  The mass ratio of the total component (C), that is to say at least one polyether or at least one polyether-containing group, based on the total mass of the composite material is preferably 5 to 60% by weight, particularly preferably 30. -50 mass%. The mass ratio of the total nanocomposite material (B) based on the total mass of the composite material is preferably at least 20% by weight, particularly preferably at least 30% by weight, and may be 99% by weight or less, preferably 95% by weight or less. .

  The composite material of the present invention may optionally contain at least one lithium salt as component (D). The composite material of the present invention preferably contains at least one lithium salt as component (D).

  Component (D) is, in particular, a lithium salt usually used as an electrolyte salt in a lithium ion battery. The lithium salt (D) is particularly preferably lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, lithium bis (trifluoromethylsulfonyl) imide), and lithium tetrafluoroborate. Selected from the group consisting of

  In a further embodiment of the present invention, the lithium salt (D) in the composite material of the present invention comprises lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, lithium bis (trifluoro). Methylsulfonyl) imide), and lithium tetrafluoroborate.

In order to increase the thermal stability, the composite material according to the invention may comprise as a further component component (E) which is at least one inorganic (semi) metal oxide. Examples of such inorganic (semi) metal oxides include silicates, aluminates, titanium dioxide, barium titanate, zirconium dioxide and yttrium oxide.

The component (B) of the composite material of the present invention, that is, the nanocomposite material (B) is preferably
Having at least one first cationically polymerizable monomer unit A comprising a metal or metalloid M, and
Polymerization product of at least one monomer AB having at least one second cationically polymerizable organic monomer unit B bonded to the polymerizable monomer unit A via one or more covalent chemical bonds Because
The polymerization product is obtained by polymerizing both of the polymerizable monomer unit A and the polymerizable monomer unit B together with the breakage of the bond between A and B, and the monomer AB is the non-woven fabric substrate (A), the polyether Or a polymerizable organism obtained under cationic polymerization conditions wherein polymerization is carried out in the presence of the polyether-containing group (C) and optionally the lithium salt (D).

In a further embodiment of the invention, the nanocomposite material (B) in the composite material of the invention comprises
Having at least one first cationically polymerizable monomer unit A comprising a metal or metalloid M, and
Polymerization product of at least one monomer AB having at least one second cationically polymerizable organic monomer unit B bonded to the polymerizable monomer unit A via one or more covalent chemical bonds Because
The polymerization product is obtained by polymerizing both of the polymerizable monomer unit A and the polymerizable monomer unit B together with the breakage of the bond between A and B, and the monomer AB is the non-woven fabric substrate (A), the polyether Or a polymerization product obtained under cationic polymerization conditions where polymerization is carried out in the presence of the polyether-containing group (C) and optionally the lithium salt (D).

  The composite material of the present invention comprises a monomer AB, which will be described in detail below, a substrate (A) in which the monomer AB is the nonwoven fabric, the polyether or polyether-containing group (C), and optionally the lithium salt (D). Is produced by a process involving twin polymerization under cationic polymerization conditions that are polymerized in the presence of. Said components (A), (C) and (D) have been described above. The principle of twin polymerization of “twin monomer” is described, for example, in WO 2010/112581, 2 pages, 16 lines to 4 pages, 11 lines, or WO 2011/000858, 14 pages, 29 lines to 16 pages, 7 lines. The Twin polymerization of two different (twin) monomers is comprehensively described, for example, in WO 2011/000858, page 16, line 9 to page 24, line 11.

Therefore, the present invention
The following ingredients:
(A) a substrate made of at least one nonwoven fabric;
(B) (a) at least one inorganic or (semi) metal-organic phase (a) comprising at least one metal or metalloid M, and (b) at least one organic polymer phase (b). At least one nanocomposite material comprising,
In particular, the organic polymer phase (b) and the inorganic or (semi) metal-organic phase (a) form an essentially co-continuous phase region, the average distance between two adjacent identical phase regions Is a nanocomposite material of 100 nm or less,
(C) at least one polyether or at least one polyether-containing group (wherein the polyether-containing group is covalently bonded to the (semi) metal-organic phase (a) or the organic polymer phase (b)) And (D) optionally at least one lithium salt, a composite material comprising:
Having at least one first cationically polymerizable monomer unit A comprising a metal or metalloid M, and
At least one monomer AB having at least one second cationically polymerizable organic monomer unit B bonded to the polymerizable monomer unit A via one or more covalent chemical bonds,
A method of producing by polymerization under cationic polymerization conditions in which both of the polymerizable monomer unit A and the polymerizable monomer unit B are polymerized together with the breakage of the bond between A and B, wherein the polymerization is a substrate comprising the nonwoven fabric Also provided is a production process carried out in the presence of (A), the polyether or polyether-containing group (C) and optionally the lithium salt (D).

  The description of components (A), (B), (C) and (D) and the preferred embodiments in the method of the invention corresponds to the above description of these components for the composite material of the invention.

  The metal or metalloid M of the monomer unit A in the monomer AB is preferably selected from B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof. Is done. In particular, M is selected from B, Al, Si, Ti, Zr and Sn, preferably from Al, Si, Ti and Zr, and in particular Si. It is particularly preferred that at least 90 mol%, in particular at least 99 mol%, or the total amount of all metals or metalloids M is silicon.

  In one embodiment of the invention, the metal or metalloid M of the monomer unit A in the monomer AB used in the method of the invention for producing a composite material is B, Al, Si, Ti, Zr, Hf, Ge. , Sn, Pb, V, As, Sb, Bi and mixtures thereof, preferably selected from B, Al, Si, Ti, Zr, and Sn, particularly preferably Al, Si, Ti And Zr, particularly Si.

  In a further embodiment of the invention, the metal or metalloid M of the monomer unit A in the process of the invention for producing a composite material is at least 90 mol%, in particular at least 99 mol% silicon, based on the total amount of M. Including.

［式中、
Ｍは、金属又は半金属であり、
Ｒ^１、Ｒ^２は、同一又は異なってもよく、それぞれ、基Ａｒ−Ｃ（Ｒ^ａ，Ｒ^ｂ）−（式中、Ａｒは、任意にハロゲン、ＣＮ、Ｃ_１−Ｃ_６−アルキル、Ｃ_１−Ｃ_６−アルコキシ、及びフェニルの中から選択される１個又は２個の置換基を有する芳香族環又は芳香族複素環であり、Ｒ^ａ、Ｒ^ｂは、それぞれ互いに独立して、水素もしくはメチルであるか、又は共に酸素原子もしくはメチリデン基（＝ＣＨ_２）を表す）であるか、
又はＲ^１Ｑ及びＲ^２Ｇ基が、共に式Ｉａ：

（式中、Ａは、二重結合上に縮合した芳香族環又は芳香族複素環であり、ｍは０、１又は２であり、基Ｒは、同一又は異なってもよく、ハロゲン、ＣＮ、Ｃ_１−Ｃ_６−アルキル、Ｃ_１−Ｃ_６−アルコキシ、及びフェニルの中から選択され、並びにＲ^ａ、Ｒ^ｂは、上記に規定した通りである）
の基を形成し、
Ｇは、Ｏ、Ｓ、又はＮＨであり、特にＯであり、
Ｑは、Ｏ、Ｓ、又はＮＨであり、特にＯであり、
ｑは、Ｍの原子価に従い、０、１、又は２であり、
Ｘ、Ｙは、同一又は異なってもよく、それぞれＯ、Ｓ、ＮＨ又は化学結合であり、
Ｒ^１’、Ｒ^２’は、同一又は異なってもよく、それぞれＣ_１−Ｃ_６−アルキル、Ｃ_３−Ｃ_６−シクロアルキル、エチレンオキシド及びプロピレンオキシドからなる群から選択されるモノマー単位を含むポリエーテル含有基又はアリール、又は基Ａｒ’−Ｃ（Ｒ^ａ’，Ｒ^ｂ’）−（式中、Ａｒ’は、Ａｒに提供された意味を有し、Ｒ^ａ’、Ｒ^ｂ’は、Ｒ^ａ、Ｒ^ｂに提供された意味を有する）であるか、Ｒ^１’、Ｒ^２’が、Ｘ及びＹと共に上記に規定した式Ｉａの基を形成するか、
又は、Ｘが酸素の場合、基Ｒ^１’は、式Ｉｂ：

（式中、ｑ、Ｒ^１、Ｒ^２、Ｒ^２’、Ｙ、Ｑ及びＧは上記に規定した通りであり、＃はＸとの結合を表す）の基であってもよい］
によって表されるモノマーＡＢを用いて実施される。 The process according to the invention for producing a composite material preferably has at least one monomer unit A and at least one monomer unit B, and has the general formula I:

[Where:
M is a metal or a semimetal,
R ¹ and R ² may be the same or different and each represents a group Ar—C (R ^a , R ^b ) — (wherein Ar is optionally halogen, CN, C ₁ -C ₆ -alkyl, C _1- C ₆ -alkoxy and an aromatic ring or aromatic heterocycle having one or two substituents selected from phenyl, wherein R ^a and R ^b are each independently hydrogen Or methyl, or both represent an oxygen atom or a methylidene group (= CH ₂ ),
Or the R ¹ Q and R ² G groups are both of formula Ia:

(In the formula, A is an aromatic ring or aromatic heterocyclic ring condensed on a double bond, m is 0, 1 or 2, and the groups R may be the same or different, and may be halogen, CN, Selected from C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl, and R ^a and R ^b are as defined above)
Form a group of
G is O, S or NH, in particular O,
Q is O, S or NH, in particular O,
q is 0, 1, or 2 according to the valence of M;
X and Y may be the same or different and are each O, S, NH or a chemical bond;
R ^{1 ′} and R ^{2 ′, which} may be the same or different, are each a poly-containing monomer unit selected from the group consisting of C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, ethylene oxide and propylene oxide. An ether-containing group or aryl, or a group Ar′-C (R ^{a ′} , R ^{b ′} ) — (wherein Ar ′ has the meaning provided for Ar, and R ^{a ′} , R ^{b ′} represents R ^a , having the meaning provided for R ^b ), or R ^{1 ′} , R ^{2 ′} together with X and Y form a group of formula Ia as defined above,
Or, when X is oxygen, the group R ^{1 ′} is of formula Ib:

(Wherein q, R ¹ , R ² , R ^{2 ′} , Y, Q and G are as defined above, and # represents a bond with X)]
Is carried out with the monomer AB represented by

In the monomer of formula I, part of the molecule corresponding to the group R ¹ and R ² G form the polymerizable unit (s) B. When X and Y are different from a chemical bond and R ^{1 ′} X and R ^{2 ′} are not an inert group such as C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl or aryl, then R ^{1 ′} X and R ^{2 ′} Y likewise form polymerizable unit (s) B. On the other hand, the metal atom M together with the groups Q and Y optionally forms the main component of the monomer unit A.

  For the purposes of the present invention, an aromatic group, or aryl, is a carbocyclic aromatic hydrocarbon group such as phenyl or naphthyl.

  For the purposes of the present invention, an aromatic heterocyclic group, or hetaryl, is generally a heterocyclic aromatic group having 5 or 6 ring atoms, one of the ring atoms being nitrogen, oxygen and sulfur. A heteroatom selected from the above, one or two further ring atoms may optionally be a nitrogen atom and the remaining ring atoms are carbon. Examples of aromatic heterocyclic groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, pyridyl, pyrimidyl, pyrazinyl or thiazolyl.

  For the purposes of the present invention, the fused aromatic group or ring is a carbocyclic aromatic divalent hydrocarbon group such as o-phenylene (benzo) or 1,2-naphthylene (naphtho).

  For the purposes of the present invention, a fused aromatic heterocyclic group or ring is a heterocycle as defined above in which two adjacent carbon atoms form a double bond as shown in formula Ia or in formulas II and III. Is an aromatic group of the formula.

  The metal or metalloid M in formula I is one of the embodiments of M that have been shown to be preferred, especially in the description of the composite material.

［式中、＃、ｍ、Ｒ^ａ及びＲ^ｂは、上記で規定した通りである。］で表される基を形成する。式Ｉａ及びＩａａにおいて、変数ｍは、特に０である。ｍが、１又は２の場合、Ｒは特にメチル又はメトキシ基である。式Ｉａ及びＩａａにおいて、Ｒ^ａ及びＲ^ｂは、特に水素である。式Ｉａにおいて、Ｑは特に酸素である。式Ｉａ及びＩａａにおいて、Ｇは、特に酸素又はＮＨであり、特に酸素である。 In a first embodiment of the monomer of formula 1, the groups R ¹ Q and R ² G are both groups of formula Ia as defined above, in particular of formula Iaa:

[Wherein, #, m, R ^a and R ^b are as defined above. ] Is formed. In the formulas Ia and Iaa, the variable m is especially 0. When m is 1 or 2, R is in particular a methyl or methoxy group. In formulas Ia and Iaa, R ^a and R ^b are in particular hydrogen. In formula Ia, Q is in particular oxygen. In the formulas Ia and Iaa, G is in particular oxygen or NH, in particular oxygen.

によって表され得る。 Among the monomers of the first embodiment, particularly those monomers of formula I in which q = 1 and the groups X—R ^{1 ′} and Y—R ^{2 ′} together form a group of formula Ia, in particular a group of formula Iaa preferable. Such monomers are represented by formulas II and IIa:

Can be represented by:

［式中、ｍ、Ａ、Ｒ、Ｒ^ａ、Ｒ^ｂ、Ｇ、Ｑ、Ｘ”、Ｙ、Ｒ^２’及びｑは上記で提供された意味を有し、特に好ましいと示された意味を有する。］で表される基である式Ｉのモノマーも好ましい。 Among the twin monomers of the first embodiment, q is 0 or 1 and X—R ^{1 ′} is of formula Ia ′ or Iaa ′:

Wherein m, A, R, R ^a , R ^b , G, Q, X ″, Y, R ^{2 ′} and q have the meanings provided above and have the meanings indicated as being particularly preferred. Also preferred are monomers of formula I which are groups represented by

によって表され得る。 Such monomers are of formula II ′ and formula IIa ′:

Can be represented by:

In formulas II and II ′, the variables have the following meanings:
M is a metal or metalloid, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si,
A and A ′ are each independently an aromatic ring or an aromatic heterocyclic ring condensed on a double bond,
m and n are each independently 0, 1 or 2, particularly 0;
G and G ′ are each independently of each other O, S or NH, in particular O or NH, in particular O,
Q and Q ′ are each independently O, S or NH, in particular O,
R, R ′ are independently selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl, in particular, independently of one another, methyl or methoxy;
R ^a , R ^b , R ^{a ′} and R ^{b ′} are independently selected from hydrogen and methyl, or R ^a and R ^b , and / or R ^{a ′} and R ^{b ′} are each Each represents an oxygen atom or ═CH ² , in particular, R ^a , R ^b , R ^{a ′} , R ^{b ′} are each hydrogen.
L is (Y—R ^{2 ′} ) _q , Y, R ^{2 ′} and q are as defined above;
X ″ is one of the meanings provided for Q, in particular oxygen.

In formulas IIa and IIa ′, the variables have the following meanings:
M is a metal or metalloid, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si,
m and n are each independently 0, 1 or 2, particularly 0;
G and G ′ are each independently of each other O, S or NH, in particular O or NH, in particular O,
R, R ′ are independently selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl, in particular methyl or methoxy;
R ^a , R ^b , R ^{a ′} and R ^{b ′} are independently selected from hydrogen and methyl, or R ^a and R ^b , and / or R ^{a ′} and R ^{b ′} are each Each represents an oxygen atom, in particular R ^a , R ^b , R ^{a ′} and R ^{b ′} are each hydrogen.
L is (Y—R ^{2 ′} ) _q , and Y, R ^{2 ′} and q are as defined above.

As examples of monomers of formula II or IIa, 2,2′-spirobis [4H-1,3,2-benzodioxacillin] (M = Si, m = n = 0, G = G ′ = O, R ^a = R ^b = R ^{a ′} = R ^{b ′} = Hydrogen compound of formula IIa). Such monomers are known from WO 2009/083082 and WO 2009/083083 or can be prepared by the methods described therein. As a further example of monomer IIa, 2,2-spirobis [4H-1,3,2-benzodioxaborin] (Bull. Chem. Soc. Jap. 51 (1978) 524) (M = B, m = n = 0, G = O, R ^a = R ^b = R ^{a ′} = R ^{b ′} = compound of formula IIa). Further examples of monomer IIa ′ include bis (4H-1,3,2-benzodioxaborin-2-yl) oxide (M = B, m = n = 0, L absent (q = 0), G = O, R ^a = R ^b = R ^{a '} = R ^b' = hydrogen, a compound of formula IIa ', Bull. Chem. Soc. Jap. 51 (1978) 524).

In monomers II and IIa, the unit MQQ ′ or MO ₂ forms the polymerizable unit A, while the remainder of monomers II and IIa, ie Q or Q ′ minus formula (Ia or Iaa (or Iaa) The group in which the oxygen atom is pulled forms the polymerizable unit B.

In formula III, the variables have the following meanings:
M is a metal or metalloid, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si,
A is an aromatic ring or an aromatic heterocycle condensed on a double bond,
m is 0, 1 or 2, in particular 0,
G is O, S or NH, in particular O or NH, in particular O,
Q is O, S or NH, in particular O,
q is 0, 1, or 2 according to the valence and charge of M;
R is independently selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl, in particular methyl or methoxy;
R ^a , R ^b are independently selected from among hydrogen and methyl, or R ^a and R ^b both represent an oxygen atom or ═CH ² , in particular, both are hydrogen,
R ^c and R ^d are the same or different and each comprise a polyether-containing group containing a monomer unit selected from the group consisting of C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, ethylene oxide and propylene oxide; Selected from among aryl, especially methyl.

In formula IIIa, the variables have the following meanings:
M is a metal or metalloid, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si,
m is 0, 1 or 2, in particular 0,
G is O, S or NH, in particular O or NH, in particular O,
For R, the group R is independently selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl, in particular methyl or methoxy,
R ^a , R ^b are independently selected from hydrogen and methyl, or R ^a and R ^b both represent an oxygen atom or ═CH ₂ , in particular both are hydrogen,
R ^c and R ^d are the same or different and each comprise a polyether-containing group containing a monomer unit selected from the group consisting of C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, ethylene oxide and propylene oxide; Selected from among aryl, especially methyl.

Examples of monomers of formula III or IIIa include 2,2-dimethyl-4H-1,3,2-benzodioxacillin (M = Si, q = 1, m = 0, G = O, R ^a = R ^b = Compound of formula IIIa, hydrogen, R ^c = R ^d = methyl), 2,2-dimethyl-4H-1,3,2-benzoxazacillin (M = Si, q = 1, m = 0, G = NH, R ^a = R ^b = hydrogen, R ^c = R ^d = methyl, compound of formula IIIa), 2,2-dimethyl-4-oxo-1,3,2-benzodioxacillin (M = Si , Q = 1, m = 0, G = O, R ^a + R ^b = O, R ^c = R ^d = methyl, the compound of formula IIIa), and 2,2-dimethyl-4-oxo-1,3 , 2-benzoxazine The cylinder (M = Si, q = 1 , m = 0, G = NH, R a + R b = O, R c Is R ^d = methyl, compound of formula IIIa) can be mentioned. Such monomers are known, for example, from Wieber et al. Journal of Organometallic Chemistry, 1, 1963, 93, 94. Further examples of monomer IIIa include 2,2-diphenyl [4H-1,3,2-benzodioxacillin] (J. Organomet. Chem. 71 (1974) 225), 2,2-di-n-butyl [ 4H-1,3,2-benzodioxastannin] (Bull. Soc. Chim. Belg. 97 (1988) 873), 2,2-dimethyl [4-methylidene-1,3,2-benzodioxacillin] ( J. Organomet. Chem., 244, C5-C8 (1983)), 2-methyl-2-vinyl [4-oxo-1,3,2-benzodioxazacillin].

  The monomers of formula III and IIIa are preferably not polymerized alone, but are copolymerized in combination with monomers of formula II or IIa.

［式中、
Ｍは、金属又は半金属、好ましくは、Ｂ、Ａｌ、Ｓｉ、Ｔｉ、Ｚｒ、Ｈｆ、Ｇｅ、Ｓｎ、Ｐｂ、Ｖ、Ａｓ、Ｓｂ又はＢｉであり、特に好ましくはＢ、Ａｌ、Ｓｉ、Ｔｉ、Ｚｒ又はＳｎであり、極めて特に好ましくはＡｌ、Ｓｉ、Ｔｉ又はＺｒであり、特にＳｉであり、
Ａｒ，Ａｒ’は、同一又は異なり、それぞれ、任意にハロゲン、ＣＮ、Ｃ_１−Ｃ_６−アルキル、Ｃ_１−Ｃ_６−アルコキシ、及びフェニルの中から選択される１個又は２個の置換基を有する芳香族環又は芳香族複素環であり、
Ｒ^ａ、Ｒ^ｂ、Ｒ^ａ’、Ｒ^ｂ’は、独立して、水素及びメチルの中から選択されるか、又はＲ^ａとＲ^ｂ、及び／又はＲ^ａ’とＲ^ｂ’が、それぞれの場合、共に酸素原子を表し、
ｑは、Ｍの原子価に従い、０、１、又は２であり、
Ｘ、Ｙは、同一又は異なってもよく、それぞれＯ、Ｓ、ＮＨ又は化学結合であり、
Ｒ^１’、Ｒ^２’は、同一又は異なってもよく、それぞれＣ_１−Ｃ_６−アルキル、Ｃ_３−Ｃ_６−シクロアルキル、エチレンオキシド及びプロピレンオキシドからなる群から選択されるモノマー単位を含むポリエーテル含有基又はアリール、又は基Ａｒ”−Ｃ（Ｒ^ａ”，Ｒ^ｂ”）−（式中、Ａｒ”は、Ａｒに提供された意味を有し、Ｒ^ａ”、Ｒ^ｂ”は、Ｒ^ａ、Ｒ^ｂに提供された意味を有する）であるか、Ｒ^１’、Ｒ^２’が、Ｘ及びＹと共に上記に規定した式Ａの基を形成する。］
によって表されるモノマーである。 In a further embodiment, the monomer AB of the general formula I has the general formula IV:

[Where:
M is a metal or metalloid, preferably B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb or Bi, particularly preferably B, Al, Si, Ti, Zr or Sn, very particularly preferably Al, Si, Ti or Zr, in particular Si,
Ar and Ar ′ are the same or different and are each optionally 1 or 2 substituents selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl An aromatic ring or an aromatic heterocycle having
R ^a , R ^b , R ^{a ′} and R ^{b ′} are independently selected from hydrogen and methyl, or R ^a and R ^b , and / or R ^{a ′} and R ^{b ′} are each Both represent oxygen atoms,
q is 0, 1, or 2 according to the valence of M;
X and Y may be the same or different and are each O, S, NH or a chemical bond;
R ^{1 ′} and R ^{2 ′, which} may be the same or different, are each a poly-containing monomer unit selected from the group consisting of C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, ethylene oxide and propylene oxide. An ether-containing group or aryl, or a group Ar ″ —C (R ^{a ″} , R ^{b ″} ) — (wherein Ar ″ has the meaning provided for Ar, and R ^{a ″} , R ^{b ″} represents R ^a , R ^b ) or R ^{1 ′} , R ^{2 ′} together with X and Y form a group of formula A as defined above. ]
Is a monomer represented by

In a preferred embodiment of the invention, the polymerization of at least one monomer AB in the process of the invention for producing a composite material comprises
Metal or semimetal M, and C ₁ -C 20 _- selected from alkyl, in particular methyl, and polyether-containing group, particularly ethylene oxide and propylene oxide, preferably from the group consisting of ethylene oxide _- hydrocarbon radical, preferably C ₁ -C 4 At least one first cationically polymerizable monomer unit A having at least one group covalently bonded to M via a carbon atom, selected from the group consisting of polyether-containing groups containing monomer units And at least one monomer AB having at least one second cationically polymerizable organic monomer unit B bonded to the polymerizable unit A via one or more covalent chemical bonds When,
At least one cationically polymerizable monomer unit A1 having a metal or metalloid and having at least one first monomer group A1 bonded to said polymerizable monomer unit A1 via one or more covalent chemical bonds. Copolymerization with at least one monomer A1B1 having two cationically polymerizable organic monomer units B1;
The copolymerization polymerizes both the polymerizable monomer units A and A1 and the polymerizable monomer units B and B1 with the breakage of the bond between A and B and the breakage of the bond between A1 and B1. It is carried out under cationic polymerization conditions.

  In a preferred embodiment, the metal or metalloid M in the monomer AB used in the copolymerization of the monomer AB and the monomer A1B1 and in the monomer A1B1 is independently of each other Si, Al, Ti or Zr, in particular The cation polymerizable monomer units B and B1 in Si and the corresponding monomers AB and A1B1 are covalently bonded to M via one or more oxygen atoms, respectively.

In a further preferred embodiment, the metal or metalloid M in the monomer AB used for the copolymerization of the monomer AB and the monomer A1B1 is Si and the monomer unit A is C ₁ -C ₁₈ -alkyl, vinyl, C 6 _-C 10 _- aryl, C 7 _-C 14 _- alkyl aryl, and ethylene oxide and propylene oxide, particularly selected from the group consisting of polyether-containing group containing monomer units selected from the group consisting of ethylene oxide, respectively carbon atoms With two identical or different groups bonded to Si.

  The monomer A1B1 is in principle defined in the same way as the monomer AB and can generally be represented by the general formula I as well.

  The monomer A1B1 particularly preferably has the general formula II or IIa described above.

  As monomer AB or monomer A1B1 of general formula I, 2,2′-spiro [4H-1,3,2-benzodioxacillin], 2,2-dimethyl [4H-1,3,2-benzodioxacillin], 2,2-diphenyl [4H-1,3,2-benzodioxacillin], 2,2-dialkyl [4H-1,3,2-benzodioxacillin], 2-alkyl-2-methyl [4H-1, 3,2-benzodioxacillin], 2-methyl-2-vinyl [4H-1,3,2-benzodioxacillin], or page 20 of WO2011 / 000858 in the polymerization process for producing the composite material of the present invention. The compounds described in lines 7 to 18 are preferably used. Methods for preparing the various monomers AB and A1B1 are described in the respective description and experimental part of the above publications WO2010 / 112581, WO2010 / 128144 and WO2011 / 000858.

  In the case of copolymerization of the monomers AB and A1B1, the molar ratio of the two monomers can be varied within a wide range. The molar ratio of monomers AB and A1B1 to each other is usually in the range of 5:95 to 9: 1, often in the range of 1: 9 to 4: 1 or 1: 4 to 2: 1, in particular 1: 2 The range is 6: 4. In particular, when AB is a monomer containing a polyether-containing group, not more than 50% by weight of AB and simultaneously at least 50% by weight of monomer A1B1 of the general formula II or IIa are used, based on the total weight of the monomers used .

  Polymerization of at least one monomer AB, or copolymerization of at least one monomer AB with at least one monomer A1B1, component (C) contained in the composite material corresponds to the polyether used in the method As a result, it has been found that it can be advantageously carried out in the presence of polyethers. In this case, monomer AB need not contain a polyether-containing group. Polyethers that can be used as component (C), and preferred embodiments thereof, are described above in the description of component (C) of the composite material of the present invention.

  In a further embodiment of the present invention, component (C) used in the method of the present invention for producing a composite material is selected from the group consisting of polyethylene glycol, polypropylene glycol, and a copolymer of ethylene oxide and propylene oxide. Polyether.

  In a further embodiment of the invention, the polymerization in the process of the invention for producing a composite material is in the presence of a further component (E), which is an inorganic (semi) metal oxide in the form of at least one particle. Will be implemented. Examples of such particles are described above in the description of component (E) of the composite material of the present invention.

  The polymerization conditions in the method of the present invention are as follows: in the copolymerization of the monomers AB and A1B1, monomer units that form the inorganic or (semi) metal-organic phase (a) and monomer units that form the organic polymer phase (b), Cationic polymerizable organic units are selected to polymerize synchronously. The term “synchronously” does not necessarily mean that the polymerization of the first monomer unit and the second monomer unit proceeds at the same rate. Rather “synchronously” means that the polymerization of the first monomer unit and the second monomer unit is kinetically coupled and initiated by the same polymerization conditions.

In the case of monomers AB and A1B1, synchronous polymerization is ensured when the copolymerization is carried out under cationic polymerization conditions. The copolymerization of the monomers AB and A1B1, in particular the copolymerization of the monomers of the general formulas III and IIIa defined above with the general formulas II and IIa, in particular in the presence of a protic catalyst or in the presence of an aprotic Lewis acid Implemented below. Preferred catalysts here are Bronsted acids, such as trifluoroacetic acid, trichloroacetic acid, formic acid, chloroacetic acid, dichloroacetic acid, hydroxyacetic acid (glycolic acid), lactic acid, cyanoacetic acid, 2-chloropropanoic acid, 2,3- Examples also include organic carboxylic acids such as bishydroxypropanoic acid, malic acid, tartaric acid, mandelic acid, benzoic acid or o-hydroxybenzoic acid, and organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and toluenesulfonic acid. Inorganic Bronsted acids such as HCl, H ₂ SO ₄ or HClO ₄ are equally suitable. As the Lewis acid, for example, BF ₃ , BCl ₃ , SnCl ₄ , TiCl ₄ or AlCl ₃ can be used, complex Lewis acids or Lewis acids dissolved in ionic liquids are also possible. The acid is usually used in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the total weight of the monomers.

  Preferred catalysts are organic carboxylic acids, in particular organic carboxylic acids having a pKa (25 ° C.) in the range 0-5, especially 1-4, such as trifluoroacetic acid, trichloroacetic acid, formic acid, chloroacetic acid, dichloro Acetic acid, hydroxyacetic acid (glycolic acid), lactic acid, cyanoacetic acid, 2-chloropropanoic acid, 2,3-bishydroxypropanoic acid, malic acid, tartaric acid, or o-hydroxybenzoic acid.

  The polymerization or copolymerization carried out under cationic conditions comprises a substrate (A) comprising a nonwoven fabric, a polyether or polyether-containing group (C), optionally a lithium salt (D), and optionally inorganic (semi-) in the form of particles. It is carried out in the presence of metal oxide (E).

  The polymerization can in principle be carried out in bulk, or preferably at least partially in an inert solvent or diluent. Suitable solvents or diluents are organic solvents, for example halogenated hydrocarbons such as dichloromethane, trichloromethane, dichloroethane, chlorobutane or chlorobenzene, aromatic hydrocarbons such as toluene, xylene, cumene or tert-butylbenzene, Aliphatic and alicyclic hydrocarbons such as cyclohexane or hexane, cyclic or alicyclic ethers such as tetrahydrofuran, dioxane, diethyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, diisopropyl ether, and mixtures of the above organic solvents Is mentioned. Preference is given to organic solvents in which the monomers AB and A1B1 are sufficiently soluble under the polymerization conditions (solubility at 25 ° C. of at least 10% by weight). These include in particular aromatic hydrocarbons, cyclic and alicyclic ethers and mixtures of these solvents.

  The polymerization of monomer AB or the copolymerization of monomers AB and A1B1 is preferably carried out under conditions that are substantially free of water, that is, under conditions where the concentration of water at the start of polymerization is less than 0.1% by weight. It is therefore preferred to use monomers that do not discharge water under the polymerization conditions as monomers AB and A1B1 or as monomers of formula I. These include in particular monomers of the formulas II, IIa, III and IIIa.

  The polymerization can in principle be carried out in a wide temperature range, preferably in the range from 0 to 200 ° C., in particular in the range from 20 to 120 ° C.

  In a further embodiment of the invention, the polymerization in the process of the invention for producing a composite material is carried out at a temperature in the range of 0-200 ° C.

  The inventive method for producing a composite material is preferably carried out in such a way that the composite material formed in the polymerization is obtained directly in the form of a thin layer.

  In a first embodiment, the substrate consisting of a nonwoven is first of all a starting compound for further components, ie in particular monomer AB or monomers AB and A1B1, and optionally a polyether as component (C), and an electrolyte. In the second process step loaded with salt (D) and / or inorganic (semi) metal oxide particles (E), monomer AB or monomers AB and A1B1 are components (C), (D) and (E). Is converted into a nanocomposite (B) that is incorporated in a chemically unchanged form.

  Methods for producing filled nonwovens are in principle known to those skilled in the art. Thus, the nonwoven fabric can be partially or fully loaded or filled with the necessary starting components, for example, by impregnation, painting, doctor blade method, calendering, or combinations thereof. Nonwoven fabrics filled in this manner are subsequently subjected to conditions that cause polymerization or copolymerization.

  The composite material obtained in this way is particularly suitable as a separator or as a constituent of a separator in an electrochemical cell.

  For the purposes of the present invention, the term electrochemical cell or battery encompasses any type of battery, capacitor and accumulator (secondary battery), in particular lithium, lithium ion, lithium-sulfur, And storage batteries including alkaline metal cells or batteries, such as alkaline earth metal batteries, and high-energy or high-power system forms, as well as electrolytic capacitors and double-layer capacitor forms known as Supercaps, Goldcaps, BoostCaps or Ultracaps To do.

  The present invention further provides a method of using the above-described composite material of the present invention as a separator or as a constituent of a separator in an electrochemical cell, a fuel cell or a supercapacitor.

  The invention likewise provides a separator for an electrochemical cell comprising the composite material of the invention as described above, in particular comprising the composite material of the invention as described above.

  The invention likewise provides a fuel cell, battery or capacitor comprising at least one separator according to the invention as described above.

  The composite material of the present invention is preferably suitable for electrochemical cells based on the migration of alkali metal ions, especially suitable for lithium metal, lithium-sulfur and lithium ion cells or batteries, especially lithium ion secondary cells or batteries. Suitable for secondary batteries. The composite material of the present invention is particularly suitable for electrochemical cells from the group of lithium-sulfur cells.

The present invention provides an electrochemical cell comprising at least one separator according to the invention as described above, and (X) at least one cathode and (Y) at least one anode.

  The electrochemical cell of the present invention, in particular the rechargeable electrochemical cell, is preferably a cell in which charge transport in the cell is mainly caused by lithium cations.

  Thus, a particularly preferred electrochemical cell is a lithium ion cell, in particular a lithium ion secondary cell, having at least one separator layer made of the composite material of the present invention. Such a cell is generally at least one anode suitable for a lithium ion cell, a cathode suitable for a lithium ion cell, an electrolyte, and at least one anode comprising the composite material of the present invention. It has a separator layer.

  For suitable cathode materials, suitable anode materials, suitable electrolytes, and possible arrangements, reference is made to relevant prior art, such as suitable research literature and references, for example Wakihara et al. ): Lithium ion Batteries, 1st Edition, Wiley VCH, Weinheim, 1998, David Linden: Handbook of Batteries (McGraw-Hill Handbooks), 3rd Edition, McGraw-Hill Handbooks, McGraw-Hillbooks. of Battery Materials. Wiley-VCH, 1998, and the like.

Possible cathodes are, in particular, cathode materials whose electroactive component is, for example, a lithium-transition metal oxide such as lithium-cobalt oxide, lithium-nickel oxide, lithium-cobalt-nickel oxide or lithium-vanadium oxide, Lithium sulfide or polysulfide such as Li ₂ S, Li ₂ S ₈ , Li ₂ S ₆ , Li ₂ S ₄ or Li ₂ S ₃ , or a lithium-transition metal phosphate such as lithium-iron phosphate The cathode. Also suitable are cathode materials that contain iodine, oxygen, sulfur, etc. as electroactivation components. However, when materials containing polymers containing sulfur or polysulfide bridges are used as cathode materials, ensure that the anode is charged with Li ⁰ before such electrochemical cells can be discharged and charged. Must.

  The electrochemical cell of the present invention further includes at least one anode (Y) in addition to the separator and the cathode (X) of the present invention.

In one embodiment of the present invention, the anode (Y) is an anode made of carbon, an anode containing Sn or Si, and a formula: Li _{4 + x} Ti ₅ O ₁₂ (wherein x is a numerical value of> 0 to 3). May be selected from among anodes comprising lithium titanate. The anode made of carbon can be selected, for example, from hard carbon, soft carbon, graphene, graphite and in particular from graphite, intercalated graphite and a mixture of two or more of the above carbons. The anode comprising Sn or Si can be selected, for example, from nanoparticulate Si or Sn powder, Si or Sn fibers, carbon-Si or carbon-Sn composites, and Si-metals or Sn-metal alloys.

In a further embodiment of the present invention, the electrochemical cell of the present invention comprises an anode comprising carbon, an anode comprising Sn or Si, and a formula: Li _{4 + x} Ti ₅ O ₁₂ , wherein x is a numerical value> 0-3. The anode (Y) selected from among the anodes comprising lithium titanate.

Apart from the electroactive component, the anode and cathode are further components, for example
Conductive or electroactive components such as carbon black, graphite, carbon fiber, carbon nanofiber, carbon nanotube or conductive polymer,
Polyethylene oxide (PEO), cellulose, carboxymethyl cellulose (CMC), polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, polytetrafluoroethylene, styrene-butadiene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer Polymer, polyvinylidene difluoride (PVdF), polyvinylidene difluoride-hexafluoropropylene copolymer (PVdF-HFP), tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene, perfluoroalkyl-vinyl ether copolymer , Vinylidene fluoride-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, vinylidene fluoride-chloro Trifluoroethylene copolymer, ethylene-chlorofluoroethylene copolymer, ethylene-acrylic acid copolymer (with and without sodium ion), ethylene-methacrylic acid copolymer (with and without sodium ion), Ethylene-methacrylic acid ester copolymers (with and without sodium ions), polyimide, and binders such as polyisobutene may be included.

  The two electrodes, ie the anode and the cathode, are connected to each other in a manner known per se, using a separator according to the invention and a liquid or solid electrolyte. For this purpose, for example, the composite material according to the present invention is laminated on one of two electrodes (anode or cathode) provided with a power output lead, and is impregnated with an electrolyte, followed by It is possible to attach an oppositely charged electrode with a power output lead and optionally roll up the sandwich obtained by this method and introduce it into the battery housing. Also, a power output lead, cathode, separator, anode, and power output lead of layers or membrane-like constituent materials are laminated to form a sandwich-like material, and optionally a sandwich-like material is wound around the battery casing. It is also possible to subsequently impregnate the laminate with an electrolyte.

  Possible liquid electrolytes are in particular non-aqueous solutions of lithium and molten Li salts (water content, generally <20 ppm), for example lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoro Methyl sulfonate, lithium bis (trifluoromethylsulfonyl) imide, or lithium tetrafluoroborate, etc., especially ethylene carbonate, propylene carbonate, and the following solvents such as lithium hexafluorophosphate or lithium tetrafluoroborate: dimethyl A mixture of carbonate, diethyl carbonate, dimethoxyethane, methyl propionate, ethyl propionate, butyrolactone, acetonitrile, ethyl acetate, methyl acetate, toluene and xylene with one or more solvents, etc. Switching aprotic solvent, especially in a mixture of ethylene carbonate and diethyl carbonate, and the solution.

  In general, a separator layer according to the invention impregnated with a liquid electrolyte, in particular a liquid organic electrolyte, is arranged between the electrodes.

  The present invention further provides a method of using the electrochemical cell according to the present invention in a lithium ion battery. The present invention further provides a lithium ion battery comprising at least one electrochemical cell according to the present invention. The electrochemical cells according to the present invention can be coupled to each other, for example, connected in series or in parallel in a lithium ion battery according to the present invention. A series connection is preferred.

  The invention further provides a method of using the electrochemical cell according to the invention as described above in a motor vehicle, a bicycle equipped with an electric motor, an aircraft, a ship or a stationary energy storage.

  The present invention also provides a method for using the lithium ion battery according to the present invention in an electrical device, particularly a mobile electrical device. Examples of mobile electrical devices include vehicles such as automobiles, bicycles, aircraft, or water vehicles such as boats and ships. Examples of other mobile electrical devices are for example manually moved such as computers, in particular laptops, telephones or power tools, in particular drills, rechargeable battery drivers or rechargeable battery tuckers, for example in the construction sector Things.

  The use of the lithium-ion battery according to the present invention, including the separator according to the present invention, in electrical equipment is caused by increased long-term operation before charging, dose loss during lower long-term operation, and short circuits and cell destruction. Provide reduced risk of spontaneous discharge. If the same service life is to be achieved using electrochemical cells with lower energy density, heavier mass electrochemical cells would have to be tolerated.

  Monomers AB comprising at least one polyether-containing group that can be used in the process according to the invention for producing the composite material according to the invention are novel. Such specific monomers AB are known by known methods that can also be used to prepare monomers AB, with the introduction of polyether-containing groups carried out by methods known to those skilled in the art, in particular organic chemists. Can be prepared.

The present invention also provides
Having at least one first cationically polymerizable monomer unit A comprising a metal or metalloid M, and
A monomer AB having at least one second cationically polymerizable organic monomer unit B bonded to the metal or metalloid M of the polymerizable monomer unit A via one or more covalent chemical bonds ,
Monomers AB comprising at least one polyether-containing group are also provided.

In the monomer AB according to the present invention, M is Si, the cationically polymerizable organic monomer unit B is covalently bonded to M via two oxygen atoms, and the monomer unit A is C ₁ -C _18. - alkyl, vinyl, C 6 _-C 10 _- aryl, C 7 _-C 14 _- alkyl aryl, and is selected from the group consisting of polyether-containing group containing monomer units selected from the group consisting of ethylene oxide and propylene oxide, respectively Having two identical or different groups bonded to Si via a carbon atom, wherein at least one of the two groups bonded to Si via a carbon atom is a polyether-containing group Certain monomers AB are preferred.

［式中、
Ｒは、同一又は異なってもよく、ハロゲン、ＣＮ、Ｃ_１−Ｃ_６−アルキル、Ｃ_１−Ｃ_６−アルコキシ、及びフェニルの中から選択され、
ｍは、０、１又は２であり、特に０であり、
Ｒ^ａ、Ｒ^ｂは、それぞれ互いに独立して、水素又はメチルであり、特に水素であり、
Ｒ^１’は、Ｃ_１−Ｃ_６−アルキル、Ｃ_３−Ｃ_６−シクロアルキル、エチレンオキシド及びプロピレンオキシドからなる群から選択されるモノマー単位を含み、炭素原子を介して結合しているポリエーテル含有基、又はアリール、又は基Ａｒ’−Ｃ（Ｒ^ａ’，Ｒ^ｂ’）−（式中、Ａｒ’は、Ａｒに提供された意味を有し、Ｒ^ａ’、Ｒ^ｂ’は、Ｒ^ａ、Ｒ^ｂに提供された意味を有する）であり、
Ｒ^２’は、エチレンオキシド及びプロピレンオキシドからなる群から、特にエチレンオキシドから選択されるモノマー単位を含み、炭素原子を介して結合しているポリエーテル含有基である］
で表される化合物の中から選択される。 In one embodiment of the present invention, monomer AB has the general formula IIIa ′:
Formula IIIa ′:

[Where:
R may be the same or different and is selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl;
m is 0, 1 or 2, in particular 0,
R ^a and R ^b are each independently of each other hydrogen or methyl, in particular hydrogen,
R ^{1 ′} includes a polyether unit that includes a monomer unit selected from the group consisting of C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, ethylene oxide, and propylene oxide, and is bonded via a carbon atom. A group, or aryl, or a group Ar′-C (R ^{a ′} , R ^{b ′} ) — (wherein Ar ′ has the meaning provided for Ar, and R ^{a ′} , R ^{b ′} represents R ^a , R ^b has the meaning provided),
R ^{2 ′} is a polyether-containing group comprising a monomer unit selected from the group consisting of ethylene oxide and propylene oxide, particularly selected from ethylene oxide, and bonded via a carbon atom]
Is selected from the compounds represented by:

In formula IIIa ′, R ^{1 ′} is preferably C ₁ -C ₆ -alkyl, in particular methyl.

［式中、
ｏは、０又は１〜１８の整数であり、好ましくは１〜６の整数であり、特に１であり、及び
ｎは、１〜１００の整数であり、好ましくは５〜５０の整数であり、特に８〜３０の整数である］
で表される基である。 In a particularly preferred embodiment of the present invention, in said preferred monomer AB, said polyether-containing group which is bonded to Si via a carbon atom has the formula C-PEG:

[Where:
o is 0 or an integer from 1 to 18, preferably an integer from 1 to 6, in particular 1, and n is an integer from 1 to 100, preferably an integer from 5 to 50; Especially an integer of 8 to 30]
It is group represented by these.

  The invention is illustrated by the following examples, which are not intended to limit the invention.

  Unless indicated otherwise,% is in each case mass%.

I. Preparation of monomers containing polyether-containing groups 1 Synthesis of 2-methyl-2- (3- (polyethylene glycol 500 ω-methyl ether) propanediyl-1) [4H-1,3,2-benzodioxacillin]

  I. 1. a Hydrosilylation of polyethylene glycol α-allyl ether ω-methyl ether with dichloromethylsilane

To remove water, 250 g (0.46 mol) of polyethylene glycol α-allyl ether ω-methyl ether (commercially available from NOF Corporation as Uniox-MA 500; n = 11, M = 540 g / mol, residual water content, 0.26% by mass (Karl Fischer titration method)) was dissolved in 200 ml of water-free toluene under a nitrogen protective gas atmosphere, and 10 g (0.09 mol) of trimethylchlorosilane (M = 108.64 g / mol) Were mixed. The mixture was heated at 120 ° C. for 3 hours. After cooling to 20 ° C., other volatile compounds such as toluene and hexamethyldisiloxane ((CH ₃ ) ₃ SiOSi (CH ₃ ) ₃ ) were removed at 80 ° C./5 mbar.

0.8 μl of a solution of 205 mg hexachloroplatinum (IV) acid hydrate (H ₂ PtCl ₆ ^* 6 H ₂ O) in 0.5 ml isopropanol was added to the dried allyl ether. 58.6 g (0.51 mol) of dichloromethylsilane (Cl ₂ SiH (CH ₃ ), M = 115 g / mol) was added dropwise at 50 ° C. over 1 hour and the reaction mixture was Stir for 2 hours. 301 g of product (M = 655 g / mol) was obtained in quantitative yield.

¹ H-NMR (CDCl ₃ , 500 MHz): δ = 0.7 ppm (3H, CH ₃ SiCl ₂ —R), 1.1-1.2 ppm (2H, m, RCl ₂ Si CH ₂ CH ₂ CH ₂ OR _{), 1.6-1.7ppm (2H, m,} RCl 2 SiCH 2 CH 2 CH 2 OR), 3.3ppm (3H, s, -OCH 3), 3.4-3.5ppm (2H, dd, _{RCl 2 SiCH 2 CH 2 CH 2} OR), 3.5-3.7 (44H, m, R (O CH 2 CH 2) 11 OCH 3).

  I. 1. b Synthesis of 2-methyl-2- (3- (polyethylene glycol 500 ω-methyl ether) propanediyl-1) [4H-1,3,2-benzodioxacillin]

  Diisopropylethylamine (Hunig base, M = 129) previously distilled by calcium hydride with 28 g (0.22 mol) of 2-hydroxybenzyl alcohol (saligenin, M = 124.1 g / mol) in 150 ml of water-free toluene. 0.24 g / mol) was charged into the reaction vessel under a nitrogen atmosphere. Example I.1. 1. 147 g (0.23 mol) of the dichlorosilane obtained in a (n = 11, M = 655 g / mol) is dissolved in 150 ml of water-free toluene and poured into the first mixture for 75 minutes, the temperature exceeding 40 ° C. It was added dropwise. The reaction mixture was subsequently heated to 80 ° C. and stirred at this temperature for 1 hour. After cooling to 20 ° C., the diisopropylamine hydrochloride was removed by filtration and the solvent was removed at 80 ° C. and 5 mbar. 140 g of the desired product (87%, M = 707 g / mol) was obtained.

¹ H-NMR (CDCl ₃ , 500 MHz): δ = 0.15 ppm (3H, CH ₃ Si—R), 0.55-0.65 (2 H, m, R ₃ Si CH ₂ CH ₂ CH ₂ OR _{), 1.4-1.5ppm (2 H, m} , R 3 SiCH 2 CH 2 CH 2 OR), 3.15ppm (3H, s, -OCH 3), 3.2-3.3ppm (2H, dd , R ₃ SiCH ₂ CH ₂ CH ₂ OR), 3.3-3.5 (44H, m, R (O CH ₂ CH ₂ ) ₁₁ OCH ₃ ), 4.75 ppm (2 H, s, Ar— CH _{2 - OR), 6.7-7.1ppm (4H,} m, Ar-H).

  I. 2 Synthesis of 2-methyl-2- (3- (polyethylene glycol 1000 ω-methyl ether) propanediyl-1) [4H-1,3,2-benzodioxacillin]

  I. 2. a Allylation of polyethylene glycol methyl ether with allyl chloride

  Under a nitrogen atmosphere, 300 g (0.3 mol) of polyethylene glycol methyl ether (commercially available as Pluriol 1020 from BASF SE; M = 1000 g / mol) was dissolved in 350 ml of water free tetrahydrofuran. A total amount of 13.2 g (0.33 mol) of sodium hydride (M = 24.0 g / mol) was added in small portions over 45 minutes as a 60% strength by weight dispersion in oil. To complete the reaction, the reaction mixture was subsequently stirred at 60 ° C. for 75 minutes. Solvent THF was removed on a rotary evaporator and dichloromethane was added to the residue. The organic phase was washed twice with water and dichloromethane was removed by distillation. 247 g of allylated polyethylene glycol (78%, M = 1040 g / mol) were obtained.

¹ H-NMR (CDCl ₃ , 500 Mhz): δ = 3.3 ppm (3H, s, —OCH ₃ ), 3.4-3.6 (88H, m, CH ₂ ═CH—CH ₂ (O CH ₂ CH ₂ ) ₂₂ OCH ₃ ), 3.9 ppm (2H, d, CH ₂ ═CH— CH ₂ (OCH ₂ CH ₂ ) ₂₂ OCH ₃ ), 5.1, 5.2 ppm (2H, d, CH ₂ ═CH— _{CH 2 (OCH 2 CH 2)} 22 OCH 3), 5.9ppm (1H, m, CH 2 = CH -CH 2 (OCH 2 CH 2) 22 OCH 3).

  I. 2. b Hydrosilylation of polyethylene glycol α allyl ether ω methyl ether with dichloromethylsilane

In a nitrogen atmosphere, Example I.I. 2. 242 g (0.23 mol) of polyethylene glycol α-allyl ether ω-methyl ether obtained in a (n = 22, M = 1040 g / mol, residual water content, 0.26% by mass (Karl Fischer titration method)) Together with 6 g (0.06 mol) of trimethylchlorosilane (M = 108.64 g / mol) and 200 ml of dry toluene, the reaction vessel was charged and heated at 120 ° C. for 3 hours. After cooling to 20 ° C., other volatile compounds such as toluene and hexamethyldisiloxane ((CH ₃ ) ₃ SiOSi (CH ₃ ) ₃ ) were removed at 80 ° C./4 mbar.

0.5 μl of a solution of 205 mg hexachloroplatinum (IV) acid hydrate (H ₂ PtCl ₆ ^* 6 H ₂ O) in 0.5 ml isopropanol was added to the dried allyl ether. 29.7 g (0.26 mol) of dichloromethylsilane (Cl ₂ SiH (CH ₃ ), M = 115 g / mol) was added dropwise at 50 ° C. over 1 hour and the reaction mixture was then further added at 80 ° C. Stir for 2 hours. 272 g of product (M = 1155 g / mol) was obtained in quantitative yield.

¹ H-NMR (CDCl _3, 500 Mhz): δ = 0.7 ppm (3H, CH ₃ SiCl ₂ —R), 1.1-1.2 ppm (2 H, m, RCl ₂ Si CH ₂ CH ₂ CH ₂ OR _{), 1.6-1.7ppm (2H, m,} RCl 2 SiCH 2 CH 2 CH 2 OR), 3.3ppm (3H, s, -OCH 3), 3.4-3.5ppm (2H, dd, _{RCl 2 SiCH 2 CH 2 CH 2} OR), 3.5- 3.7 (88H, m, R (O CH 2 CH 2) 22 OCH 3).

  I. 2. c Synthesis of 2-methyl-2- (3- (polyethylene glycol 1000 ω-methyl ether) propanediyl-1) [4H-1,3,2-benzodioxacillin]

  Diisopropylethylamine (Hunig's base, M = 129.) Previously distilled by calcium hydride with 29 g (0.224 mol) of 2-hydroxybenzyl alcohol (saligenin, M = 124.1 g / mol) and 160 ml of water-free toluene. (24 g / mol) 60.4 g (0.47 mol) was charged into the reaction vessel under a nitrogen atmosphere. Example I.1. 2. Dichlorosilane (n = 22, M = 1155 g / mol) 270.9 g (0.234 mol) obtained in a was dissolved in 100 ml of water-free toluene, poured into the first mixture for 30 minutes, temperature 40 ° C. Was added dropwise so as not to exceed. The reaction mixture was subsequently heated to 80 ° C. and stirred at this temperature for 1 hour. After cooling to 20 ° C., the diisopropylamine hydrochloride was removed by filtration and the solvent was removed at 80 ° C. and 5 mbar. 231 g of the desired product (82%, M = 1207 g / mol) was obtained.

¹ H-NMR (CDCl _3, 500 Mhz): δ = 0.05 ppm (3H, CH ₃ SiCl ₂ —R), 0.55-0.65 (2 H, m, R ₃ Si CH ₂ CH ₂ CH ₂ OR _{), 1.3-1.4ppm (2H, m,} R 3 SiCH 2 CH 2 CH 2 OR), 3.05ppm (3H, s, -OCH 3), 3.1-3.2ppm (2H, dd, _{R 3 SiCH 2 CH 2 CH 2} OR), 3.3- 3.5 (88H, m, R (O CH 2 CH 2) 22 OCH 3), 4.6ppm (2 H, s, Ar- CH 2 - OR), 6.5-6.9 ppm (4H, m, Ar-H).

II. Production of composite materials according to the invention II. 1 General process for the production of composites according to the invention Polyethylene glycol methyl ether (commercially available from BASF-SE as Pluriol® A 500E) and lithium trifluorosulfonimide (LiTFSI) with a molecular weight of about 500 g / mol Was homogenized at 85 ° C. 266 mg (1.6 mmol) of 2,2-dimethyl [4H-1,3,2-benzodioxacillin] (prepared as described in Tetrahedron Lett. 24 (1983) 1273) was added thereto. Subsequently, the mixture was prepared as described in 436 mg (1.6 mmol) of molten 2,2′-spirobi [4H-1,3,2-benzodioxacillin] (WO 2011/000858, page 28, lines 9-19). Moved to). To initiate the polymerization, d-chloroform (CDCl ₃₎ of 56mg was added starting solution containing tin tetrachloride 5.45mg in.

The reactive monomer mixture was polymerized at 95 ° C. for 10 minutes, partially transferred to a metal plate preheated at 95 ° C. in a dryer, and PET non-woven fabric (commercially available from APODIS Filtertechnik OHG as non-woven fabric “PES20”, m ² , 20 μm thick, 5 × 3.5 cm area) was placed so as to obtain a sheet-like composite material having a layer thickness of 30-90 μm. Subsequently, polymerization was carried out in a dryer under nitrogen flow at 95 ° C. for 3 hours, and then the sample was further heated under reduced pressure at 195 ° C. for 30 minutes.

Claims (28)

The following ingredients:
(A) a substrate made of at least one nonwoven fabric;
(B) (a) at least one inorganic or (semi) metal-organic phase (a) comprising at least one metal or semi-metal M, and (b) at least one organic polymer phase (b) Including
The organic polymer phase (b) and the inorganic- or (semi) metal-organic phase (a) form a substantially co-continuous phase region, and the average distance between two adjacent identical phase regions is At least one nanocomposite material that is 100 nm or less,
(C) at least one polyether or at least one polyether-containing group (wherein the polyether-containing group is covalently bonded to the (semi) metal-organic phase (a) or the organic polymer phase (b)) And (D) optionally at least one lithium salt,
A composite material comprising:   The composite material according to claim 1, wherein the substrate made of the nonwoven fabric (A) is at least partially infiltrated with the nanocomposite material (B).   The non-woven fabric substrate (A) is made of an organic polymer selected from the group consisting of polyolefins, polymers of heteroatom-containing vinyl monomers, polyesters, polyamides, polyimides, polyether ether ketones, polysulfones and polyoxymethylenes. The composite material according to claim 1 or 2.   The metal or metalloid M of the phase (a) is selected from among B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof. Item 4. The composite material according to any one of Items 1 to 3.   5. The composite material according to claim 1, wherein the metal or metalloid M of the phase (a) contains at least 90 mol% of silicon, based on the total amount of M. 6.   The lithium salt (D) is a group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethylsulfonate, lithium bis (trifluoromethylsulfonyl) imide, and lithium tetrafluoroborate. The composite material according to any one of claims 1 to 5, which is selected from: The nanocomposite material (B) is
At least one first cationically polymerizable monomer unit A comprising a metal or metalloid M, and at least bonded to the polymerizable monomer unit A via one or more covalent chemical bonds A polymerization product of at least one monomer AB having one second cationically polymerizable organic monomer unit B,
The polymerized product is polymerized under cationic polymerization conditions, in which both the polymerizable monomer unit A and the polymerizable monomer unit B are polymerized together with the bond breakage between A and B, and the monomer AB is made of the nonwoven fabric ( The composite according to any one of claims 1 to 6, which is obtained by polymerization in the presence of A), the polyether or the polyether-containing group (C) and optionally the lithium salt (D). material. The following ingredients:
(A) a substrate made of at least one nonwoven fabric;
(B) (a) at least one inorganic or (semi) metal-organic phase (a) comprising at least one metal or semi-metal M, and (b) at least one organic polymer phase (b) At least one nanocomposite material comprising
(C) at least one polyether or at least one polyether-containing group (wherein the polyether-containing group is covalently bonded to the (semi) metal-organic phase (a) or the organic polymer phase (b)) And (D) optionally at least one lithium salt, comprising:
Having at least one first cationically polymerizable monomer unit A comprising a metal or metalloid M and bonded to said polymerizable monomer unit A via one or more covalent chemical bonds At least one monomer AB having at least one second cationically polymerizable organic monomer unit B,
Under cationic polymerization conditions, both the polymerizable monomer unit A and the polymerizable monomer unit B are polymerized together with the breakage of the bond between A and B, and the polymerization is performed on the substrate (A) made of the nonwoven fabric, the poly A production process characterized in that it is carried out in the presence of an ether or polyether-containing group (C) and optionally the lithium salt (D).   The metal or metalloid M of the monomer unit A in the monomer AB is selected from B, Al, Si, Ti, Zr, Hf, Ge, Sn, Pb, V, As, Sb, Bi and mixtures thereof. The method according to claim 8.   The method according to claim 9, wherein the metal or metalloid M of the monomer unit A contains at least 90 mol% of silicon, based on the total amount of M. Said monomer AB having at least one monomer unit A and at least one monomer unit B is represented by the general formula I:

[Where:
M is a metal or a semimetal,
R ¹ and R ² may be the same or different and each represents a group Ar—C (R ^a , R ^b ) — (wherein Ar is optionally halogen, CN, C ₁ -C ₆ -alkyl, C An aromatic ring or an aromatic heterocyclic ring having 1 or 2 substituents selected from _1- C ₆ -alkoxy and phenyl, wherein R ^a and R ^b are each independently hydrogen or methyl; Or are both an oxygen atom or a methylidene group (= CH ₂ ),
Or R ¹ Q and R ² G groups taken together to form Formula Ia:

(In the formula, A is an aromatic ring or aromatic heterocyclic ring condensed on a double bond, m is 0, 1 or 2, and the groups R may be the same or different, and may be halogen, CN, C ₁ -C ₆ - _alkyl, C 1 -C ₆ - is selected from alkoxy and phenyl, and ^R a, ^{R b} are as defined above)
Form a group of
G is O, S, or NH;
Q is O, S, or NH;
q is 0, 1, or 2 according to the valence of M;
X and Y may be the same or different and are each O, S, NH or a chemical bond;
R ^{1 ′} and R ^{2 ′, which} may be the same or different, are each a poly-containing monomer unit selected from the group consisting of C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, ethylene oxide and propylene oxide. An ether-containing group, or aryl, or a group Ar′-C (R ^{a ′} , R ^{b ′} ) — (wherein Ar ′ has the meaning defined for Ar, and R ^{a ′} and R ^{b ′} are R ^a , R ^b have the meanings provided), or R ^{1 ′} , R ^{2 ′} together with X and Y form a group of formula Ia as defined above,
Or, when X is oxygen, the group R ^{1 ′} is of formula Ib:

(Wherein q, R ¹ , R ² , R ^{2 ′} , Y, Q and G are as defined above, and # represents a bond with X)]
The method of any one of claims 8 to 10 represented by: Polymerization of at least one monomer AB,
Metal or metalloid M, and at least 1 having at least one group selected from the group consisting of C ₁ -C ₂₀ -hydrocarbon groups and polyether-containing groups and covalently bonded to M via a carbon atom At least one second cationically polymerizable organic having a first cationically polymerizable monomer unit A and bonded to said polymerizable unit A via one or more covalent chemical bonds At least one monomer AB having monomer unit B;
At least one cationically polymerizable monomer unit A1 having a metal or metalloid and having at least one first monomer group A1 bonded to said polymerizable monomer unit A1 via one or more covalent chemical bonds. Copolymerization with at least one monomer A1B1 having two cationically polymerizable organic monomer units B1;
When the copolymerization is under cationic polymerization conditions, both polymerizable monomer units A and A1 and polymerizable monomer units B and B1 likewise break the bond between A and B, and between A1 and B1. The method according to any one of claims 8 to 11, which is carried out by polymerizing together with bond breaking.   The metal or metalloid M in the monomer AB and the monomer A1B1 is independently of each other Si, Al, Ti or Zr, and the corresponding cationically polymerizable organic monomer units B and B1 in the monomers AB and A1B1 are 13. The method of claim 12, wherein each is covalently bonded to M via one or more oxygen atoms. The metal or semimetal M in the monomer AB is a Si, and the monomer unit A _is C 1 _{-C 18} - alkyl, _vinyl, C 6 _{-C 10} - _aryl, C 7 _{-C 14} - alkyl aryl, and 13. A group selected from the group consisting of polyether-containing groups comprising monomer units selected from the group consisting of ethylene oxide and propylene oxide, each having two identical or different groups bonded to Si via a carbon atom. Or the method of 13.   The method according to any one of claims 8 to 14, wherein the component (C) is a polyether selected from the group consisting of polyethylene glycol, polypropylene glycol, and a copolymer of ethylene oxide and propylene oxide.   The process according to any one of claims 8 to 15, wherein the polymerization is carried out in the presence of a further component (E), which is an inorganic (semi) metal oxide in at least one particle form.   The process according to any one of claims 8 to 16, wherein the polymerization is carried out at a temperature in the range of 0 to 200 ° C.   Use of the composite material according to any one of claims 1 to 7 as a separator or as a constituent of a separator in an electrochemical cell, a fuel cell or a supercapacitor.   The separator for electrochemical cells containing the composite material of any one of Claims 1-7. 20. An electrochemical cell comprising at least one separator according to claim 19, and (X) at least one cathode, and (Y) at least one anode. An anode (Y) from an anode comprising carbon, an anode comprising Sn or Si, and an anode comprising lithium titanate of the formula Li _{4 + x} Ti ₅ O ₁₂ (where x is a number> 0-3) 21. The electrochemical cell according to claim 20, which is selected.   A method for using the electrochemical cell according to claim 20 or 21 in a lithium ion battery.   A lithium ion battery comprising at least one electrochemical cell according to claim 20 or 21.   Use of the electrochemical cell according to claim 20 or 21 in a motor vehicle, a bicycle equipped with an electric motor, an aircraft, a ship or a stationary energy storage. Having at least one first cationically polymerizable monomer unit A comprising a metal or metalloid M;
A monomer AB having at least one second cationically polymerizable organic monomer unit B bonded to the metal or metalloid M of the polymerizable monomer unit A via one or more covalent chemical bonds. And
Monomer AB characterized in that it comprises at least one polyether-containing group. M is Si;
The cationically polymerizable organic monomer unit B is covalently bonded to M via two oxygen atoms;
A polyether in which the monomer unit A comprises C ₁ -C ₁₈ -alkyl, vinyl, C ₆ -C ₁₀ -aryl, C ₇ -C ₁₄ -alkylaryl, and monomer units selected from the group consisting of ethylene oxide and propylene oxide Selected from the group consisting of containing groups, each having two identical or different groups bonded to Si via a carbon atom, and two bonded to Si via the carbon atom 26. A monomer according to claim 25, wherein at least one of the groups is a polyether-containing group. Formula IIIa ′:

[Where:
R may be the same or different and is selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl;
m is 0, 1 or 2;
R ^a and R ^b are each independently hydrogen or methyl,
R ^{1 ′} contains a polyether unit containing a monomer unit selected from the group consisting of C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, ethylene oxide and propylene oxide and bonded via a carbon atom Group, aryl, or group Ar′-C (R ^{a ′} , R ^{b ′} ) — (wherein Ar ′ has the meaning defined for Ar, and R ^{a ′} , R ^{b ′} represents R ^a , R ^b have the meaning defined),
R ^{2 ′} is a polyether-containing group containing a monomer unit selected from the group consisting of ethylene oxide and propylene oxide and bonded via a carbon atom]
A monomer AB selected from the compounds represented by: Said polyether-containing group bonded to Si via a carbon atom is represented by the formula C-PEG:

[Where:
o is 0 or an integer from 1 to 18, and n is an integer from 1 to 100]
The monomer AB according to claim 26 or 27, which is a group represented by the formula: