JP2014522355A - Granular porous carbon material, method of using the granular porous carbon material in a lithium battery - Google Patents

Abstract

The carbon phase,
Including one or more pore phases disposed in the carbon phase,
The particulate carbon phase, together with the pore phase, forms a substantially co-continuous and irregular phase region, and the distance between adjacent regions of the pore phase is substantially 50 nm or less Porous carbon material.
[Selection] Figure 1

Description

  The present invention relates to a novel granular porous carbon material containing a carbon C phase and a pore phase, and a method of using the material in a lithium battery. The present invention also relates to a method for producing such a carbon material, and a composite material containing elemental sulfur and one or more granular porous carbon materials of the present invention.

  In the growing mobile society, mobile electrical devices have played a major role in the past. In recent years, batteries, particularly rechargeable batteries (so-called secondary batteries or accumulators) have been used in almost every part of daily life. Currently, secondary batteries are required to have complex characteristics with respect to electrical properties and mechanical properties. For example, in the electrical industry, there is a demand for new small and lightweight secondary batteries or accumulators with high capacity and high cycle stability to achieve a long life. Furthermore, the temperature sensitivity and self-discharge rate should be small to ensure high reliability and efficiency. At the same time, high safety standards are required for use. The lithium ion secondary battery having the above properties is particularly important for the automobile sector, and can be used, for example, as a power storage device in an electric vehicle or a hybrid vehicle.

  Furthermore, in this case, in order to realize a high current density, a storage battery having preferable electrokinetic characteristics is required. Also, when developing a new type of storage battery system, it is particularly important that a rechargeable storage battery can be manufactured in an inexpensive manner. Also, when developing new storage battery systems, the environmental perspective plays an increasingly important role.

Current positive electrodes of high energy lithium batteries nowadays typically include lithium transition metal oxides or spinel type complex oxides as electroactive materials. These _{examples, LiCoO 2, LiNiO 2, LiNi} 1-x-y Co x M y O 2 (0 <x <1, y <1, M is, for example, Al or Mn), or LiMn ₂ O _4, Or lithium iron phosphate. As for the structure of the negative electrode of the current lithium battery, it has been shown in recent years that a lithium graphite intercalation compound is used (Journal Electrochem. Soc. 1990, 2009). In addition, lithium silicon intercalation compounds, lithium alloys, and lithium titanates have been studied as negative electrode materials ("Next generation anodds for secondary Li-ion batteries" in High Energy Density Li-Batteries by KE Aifantis). , Wiley-VCH, 2010 ”, pages 129-162).

These two electrodes are coupled to each other in a lithium battery using a liquid electrolyte or a solid electrolyte. When (re) charging a lithium battery, the positive electrode material is oxidized (eg, according to the following formula: LiCoO ₂ → nLi ⁺ + Li _1-n CoO ₂ + ne ⁻ ). Thereby, lithium is desorbed from the positive electrode material and moves to the negative electrode in the form of lithium ions. In this negative electrode, lithium ions are bonded based on the reduction of the negative electrode material, and in the case of graphite, lithium ions are intercalated with the reduction of graphite. In this case, lithium occupies a portion of the intermediate layer in the graphite structure. When discharging the storage battery, lithium bonded to the negative electrode is released from the negative electrode in the form of lithium ions, and the negative electrode material is oxidized. Lithium ions move to the positive electrode through the electrolyte and are combined as the positive electrode is reduced. In the case of discharging the storage battery and in the case of recharging the storage battery, the lithium ions move through the separator.

In general, the main problem in storage batteries is the same for lithium batteries, but their limited capacity density or energy density. In recent years, lithium sulfur batteries (ie, lithium batteries in which the positive electrode material contains sulfur in the form of elemental or polymer bonds) are important. In a lithium-sulfur battery, polysulfide anions are formed at the positive electrode during the discharge process and discharged at the negative electrode. The chemical reaction and the positive electrode reaction can be expressed in a simplified form of 2Li ⁺ + S _x + 2e ⁻ → Li ⁺ ₂ S _x ²⁻ . The number of sulfur atoms decreases in the polysulfide anion formed in the progress of the discharge process. The theoretical energy density is about 2600 Wh / kg (assuming a complete reaction giving Li ₂ S. Refer to pages 2821 to 2826 of “Journal Material Chemistry, 2010, 20”), the lithium ion battery is a lithium transition metal. It has a theoretical energy density four times that of a conventional lithium ion battery using an oxide-based positive electrode material.

  However, in the case of lithium-sulfur batteries, it has been found that capacity loss is seen relatively rapidly due to repeated charging, which limits the battery life. This capacity loss is due to the loss of sulfur from the positive electrode material due to the production of polysulfide anions soluble in the electrolyte. Since elemental sulfur itself is insulating, it is necessary to use a large amount of conductive additive such as conductive carbon black or metal particles in the sulfur-based positive electrode material. However, due to the migration of sulfide, an insulating sulfur layer may be formed on the surface of the anode or in the region of the separator. As a result, the resistance and impedance of the battery increase.

  There are several basic approaches to prevent sulfur migration and concomitant sulfur loss in the cathode material.

  -For example, attaching sulfur atoms to a carbonaceous polymer backbone such as polycarbon sulfide (see, for example, US4833048, WO96 / 41387, US6117590, and US63030978). This method is difficult to manufacture and difficult to handle polymers There is a drawback of being.

  A method of using transition metal doped molybdenum sulfide, tungsten, sulfide, or titanium sulfide (see, for example, US6300009, US6319633, or US6376127). In this case, since the transition metal occupies a relatively high ratio in the positive electrode material, the specific capacity of the material is lowered.

  -The use of composites composed of sulfur or sulfur-containing electroactive materials and adsorbents with affinity for polysulfide anions such as porous carbon (aerogel), silica gel, eg aluminum oxides such as boehmite and pseudoboehmite (for example US5162175, WO99 / 33131, WO2009 / 114314).

US4833048 WO96 / 41387 US6117590 US6309778 US6300009 US6319633 US6376127 US5162175 WO99 / 33131 WO2009 / 114314

  B. Zhang et al., “Energy Environ. Sci. 2010, 3”, pages 1531-1537, includes carbon / sulfur as a positive electrode material for lithium-sulfur batteries in which sulfur is intercalated into the micropores of the microporous carbon material. The substance is listed. However, the composite material exhibits a sufficient discharge capacity only up to 42% sulfur content.

  In summary, with respect to the charge / discharge rates of carbon / sulfur based cathode materials known from the prior art to date, charge / discharge energy and / or cycle stability, eg capacity after multiple charge / discharge cycles. In terms of reduction and / or increase in impedance, it is insufficient. Particulate metalloids or metal phases and one or more carbon phases have recently been proposed to solve these problems, and these problems can be partially solved. Such quality of the composite material cannot be realized by a generally reproducible method. In general, the production is very complicated and cannot be used economically.

  An object of the present invention is to provide an electroactive material that is particularly suitable for the production of a positive electrode material for a lithium battery for a lithium-sulfur battery and that eliminates the disadvantages of the prior art. The positive electrode material produced using this electroactive material should have one or more, especially two or more of the following properties.

-High specific capacity,
-High cycle stability,
-Low self-discharge,
-Excellent mechanical stability.

  Furthermore, the material should be economical and particularly manufacturable with reproducible quality.

  It has surprisingly been found that the above object is achieved by a sulfur composite material comprising a carbon material as defined below.

  The carbon material of the present invention includes a carbon phase (hereinafter also referred to as carbon C phase or C phase) and one or more pore phases (hereinafter also referred to as pore phase P or P phase), Forming a pore phase that is a carbon phase of the particles and a substantially non-aligned co-continuous phase region, and the distance between adjacent pore phase regions is approximately 50 nm or less, preferably 20 nm or less, or 10 nm or less, For example, a granular porous carbon material of 0.5 to 50 nm, preferably 0.7 to 20 nm, and especially 1 to 10 nm.

  This carbon material is novel and forms the first part of the subject matter of the present invention.

  The granular carbon material of the present invention can be produced by a simple method including the following steps.

I. Supplying a granular composite material comprising one or more organic polymer phases and one or more inorganic (semi) metal oxide phases, wherein the organic polymer phase and the inorganic (semi) metal oxide phase are substantially co-continuous And the average distance between adjacent regions of the inorganic (semi) metal oxide phase is 50 nm or less, especially 20 nm or less, especially 10 nm or less, such as 1 to 50 nm, preferably 0.7 to 20 nm, and especially 1-10 nm,
II. Carbonizing the organic polymer phase of the composite material;
III. Removing the (semi) metal oxide phase by leaching.

  Such a process likewise forms part of the subject matter of the present invention.

  The granular carbon material of the present invention is particularly suitable for producing a sulfur-containing composite material containing elemental sulfur. This sulfur-containing composite material is particularly suitable for the production of a positive electrode material for a lithium-sulfur battery, which leads to not only high specific capacity, high mechanical stability, and good workability, but particularly to improved cycle stability, resulting in As a result, the life of the lithium-sulfur battery is improved.

  Furthermore, the present invention provides a composite material containing elemental sulfur and one or more porous carbon materials of the present invention.

  Furthermore, the present invention provides a method of using the composite material as an electroactive cathode material in a lithium sulfur material.

  Furthermore, the present invention provides a lithium sulfur battery in which the positive electrode comprises the composite material of the present invention (elemental sulfur and one or more porous carbon materials of the present invention).

  The pore phase (hereinafter referred to as P phase) and the carbon phase (hereinafter referred to as C phase) in the porous carbon material of the present invention form regions in a co-continuous arrangement characterized by the C phase and the P phase. The region in which the C and P phases are present in a substantially co-continuous arrangement generally comprises 80% by volume, in particular 90% by volume, of the inventive carbon material. Since the distance between the adjacent carbon phases is small, an arrangement mode of interconnected pores having a very small average pore diameter is formed. The pores penetrate the carbon skeleton in a sponge shape. The arrangement of the carbon phase and the pore phase is recognized using, for example, transmission electron microscopy (TEM), in particular HAADE-STEM (HAADF-STEM: high angle annular dark field scanning electron microscope).

  Similarly, in the composite material provided in step I according to the method of the invention, in a co-continuous arrangement over a large area, on the one hand the (semi) metal oxide phase (phase A) and on the other hand the organic polymer phase (phase B). ) Exists. In other words, phase A and phase B occupy most, that is, the non-insulating layer region is surrounded by an arbitrary continuous phase region over the entire region.

  Also, for example, one (semi) metal oxide as shown by analysis of materials using transmission electron microscopy (TEM), in particular HAADE-STEM (HAADF-STEM: high angle annular dark field scanning electron microscope). Phase A and the other polymer phase B form a continuous phase region that is spatially separated from one another and penetrates one another.

  For the terms “continuous phase or phase region”, “non-continuous phase or phase region”, and “co-continuous phase or phase region”, see W.W. J. et al. Work et al., “Definitions of Terms Related to Polymer Blends, Composites and Multiphase Polymeric Materials, (IUPAC Recommendations 2004), page 1987, page 7 to Pure Appl. Chem. According to this, the word “continuous” in relation to a phase is drawn within one range of a particular phase region, so that the continuous path to the boundary of all phase regions does not cross the phase region boundary. Means that Further, according to the above document, the co-continuous arrangement of the phase system composed of two or more phases means an arrangement mode in which a plurality of phases are phase-separated, and within one range of a specific phase region, It means that a continuous path to the boundary of all phase regions is drawn without crossing the boundary of the phase regions. Therefore, the phases in the co-continuous arrangement penetrate each other.

  In the carbon material of the present invention, the distance between adjacent C-phase regions is small, with an average of 300 nm or less, often 200 nm or less, or 100 nm or less, such as 0.5 to 300 nm, particularly 1 to 200 nm, or 1 to 100 nm. It is a range.

  In a preferred embodiment, the carbon material of the present invention has a region in which the distance between adjacent C phases is 5 nm or less, for example, 0.5 to 5 nm, particularly 1 to 5 nm. In addition, the carbon material of the present invention may have a region where the average distance between adjacent C phases is 5 nm or more, for example, 5 nm to 300 nm, particularly 10 nm to 200 nm, or 15 to 200 nm.

  In a specific embodiment, the carbon material according to the present invention has the above-mentioned region (average distance between adjacent C phases of about 80% by volume or more, particularly about 90% by volume or more based on the total volume of the carbon material. Exclusively in the range of 5 nm to 300 nm, for example in the range of 10 nm to 200 nm, or 15 to 200 nm.

  In a further embodiment, the carbon material of the present invention has a region where the average distance between adjacent C phases is less than 10 nm, such as 0.5-10 nm, or 0.5-5 nm, especially 1-5 nm, such as 10 nm. ˜300 nm, in particular 10 nm to 200 nm or 15 nm to 200 nm. In these regions, the volume ratio in the region where the distance between adjacent C phases is 10 nm or more, and particularly 5 nm or less is usually in the range of 5 to 70% by volume, and the distance between adjacent C phases is 10 nm or more, and particularly The volume ratio in the region of 15 nm or more is usually in the range of 30 to 95% by volume. The volume% standard is the total volume of the carbon material.

The granular carbon material of the present invention usually has fine pores. This means that the pores have an average pore diameter d (corresponding to twice the average pore radius r) of less than 10 nm, for example 1 to 5 nm. The specific volume of micropores, that is, the volume of micropores per gram of carbon material is generally 0.1 cm ³ / g or more, particularly 0.2 cm ³ / g or more, particularly 0.3 cm ³ / g or more, and usually 0.1-1.5 cm ³ / g, often 0.2-1.2 cm ³ / g, and especially 0.3-1.0 cm ³ / g. In certain embodiments of the present invention, the volume of micropores per 1g of carbon material is in the range of 0.5 to 1 cm ³ / g. The specific volume of the pores can be measured by the method of “Barrett, Joyner and Halenda” (BJH nitrogen adsorption) defined by German Industrial Standard DIN 66134. This specific volume is then the basis for the values reported here ("EP Barrett, LG Joyner, PP Halenda, J. Am. Chem. Soc. 73 (1951) 373). See also).

As in the case of micropores, the granular carbon material of the present invention may have mesopores. This is understood to be pores having an average pore diameter d in the range of 5 to 300 nm, in particular in the range of 10 to 200 nm, or 15 to 200 nm. The specific volume of mesopores, ie the volume of mesopores per gram of carbon material is generally 0.1 cm ³ / g or more, in particular 0.2 cm ³ / g or 0.3 cm ³ / g, for example 0.1~2.9cm ³ / g range, especially 0.2~2.7cm ³ / g range, or 0.3~2.5cm ranges from ³ / g. The specific volume of the mesopores is determined by BJH nitrogen adsorption according to the German industry standard DIN 66134 by the BJH nitrogen adsorption method.

Total pore specific volume of the carbon material of the present invention is usually in the range of 0.3~3cm ³ / g, and often ranges of 0.5~2.9cm ³ / g, and particularly 0.6～2.8Cm ³ This value is measured according to German Industrial Standard DIN 66134.

Because of the high micropores and any mesopore volume, the carbon material of the present invention is usually in the range of 200~3000m ² / g, and often ranges of 500~3000m ² / g, especially 800~1500m ² / g And a high BET specific surface area, especially in the range of 900 to 1400 m ² / g. The BET specific surface area is measured by the “Brunauer, Emmett and Teller” nitrogen adsorption method described in DIN ISO 69277.

  The carbon material of the present invention consists essentially of 85% by mass or more, often 95% by mass or more, in particular 98% by mass or more of elemental carbon, based on the total mass of the carbon material. Furthermore, the carbon material of the present invention may contain an element other than carbon, and here, it may contain a small amount of a foreign element. The proportion of this extraneous element is generally 15% by weight or less, often 5% by weight or less, in particular 2% by weight or less, and 1% by weight or less, based on the total weight of the carbon material. The heterogeneous elements are usually hydrogen and oxygen generated in the process of producing the carbon material, and optionally a transition metal or a halogen element. The hydrogen content is generally 1% by mass or less, in particular 0.5% by mass or less, based on the total mass of the carbon material. The halogen element content is 1% by mass or less, particularly 0.5% by mass or less, based on the total mass of the carbon material. The content of the transition metal is generally 1% by mass or less, particularly 0.5% by mass or less, based on the total mass of the carbon material. The oxygen content is generally not more than 15% by weight, often not more than 5% by weight, in particular not more than 2% by weight, in particular not more than 1% by weight, based on the total weight of the carbon material. The carbon content and the content of extraneous elements can themselves be measured by a known method by elemental analysis.

  The carbon material of the present invention is granular. The particles are regular or irregular in shape, and may have, for example, a symmetric shape, a spherical shape, a spheroidal shape, or an elliptical shape. However, the particles may have an irregular shape such as a spherical shape or an elliptical shape penetrating each other such as a raspberry shape. The particles are C-phase interpenetrating and several P-phases having substantially pores form the walls of the cavity, the interior of the cavity being formed by mesopores and completely hollow.

  Usually the weight average particle size of the particles is in the range of 20 nm to 50 μm, often 50 nm to 50 μm, preferably 200 nm to 20 μm, especially 1 μm to 20 μm. The particle size and particle size distribution reported here is based on the particle size determined by the mass ratio based on measurement by centrifugation at 23 ° C. This measurement is usually performed by standard methods using centrifugation. This method is described, for example, in H.H. “Analytical Ultracentrifugation of Nanoparticulates in Encyclopedia of Nanoscience and Nanotechnology, (American Scientific Pub. Machtle and L. Borger, “Analytical Ultracentrifugation of Polymers and Nanoparticles”, (Springer, Berlin, 2006).

  Moreover, this invention relates to the manufacturing method of the above-mentioned granular porous carbon material, and the granular porous carbon material obtained by this manufacturing method. The method according to the invention comprises the following steps.

  I. Providing a particulate composite material having one or more organic polymer phases and one or more inorganic (semi) metal oxide phases, wherein the organic polymer phase P and the inorganic (semi) metal oxide phase are substantially The distance between two adjacent regions of the (semi) metal oxide phase, including a continuous phase region, is 50 nm or less, in particular 20 nm, in particular 10 nm or less, for example 1 to 50 nm, in particular 0.7 to 20 nm, in particular 1 -10 nm.

II. Carbonizing the organic polymer phase of the composite material;
III. Removing the (semi) metal oxide phase by leaching.

  The composite material can be produced according to Step I according to the method of the present invention, using a known method called so-called twin polymerization. Twin polymerization is basically known, for example, “Angew. Chem. Int. Ed., 46 (2007)” by Spange et al., Pages 628 to 632, WO2009 / 083083, WO2009 / 133580, WO2010 / 112580, WO2010. / 112581, WO2010 / 128144, and WO2011 / 000858. The contents of these documents are referred to in this specification.

In the present invention, twin polymerization is understood to mean the polymerization of monomer M (referred to as twin monomer),
a) one or more generally cationically polymerizable first organic monomer units;
b) Usually having one or more metals or (semi) metals that bond via oxygen to monomer units polymerizable under cationic polymerization conditions to form (semi) metal oxides. In the cationic polymerization, the polymerizable monomer unit A and the polymerizable monomer unit B are polymerized in synchronism so as to break the bond between A and B. In addition, the polymerization is optionally performed in the presence of a particulate metal oxide or metalloid oxide.

  These processes yield good nanocomposites with high yields and good reproducibility. The polymerization product is obtained by polymerization of the inorganic (semi) metal oxide phase containing the (semi) metal present in the monomer and optionally present in the (semi) metal oxide particles, and the monomer unit A. It has both organic polymer phases. Within the particles, the different phases take a co-continuous form, and the phase region of the same phase usually has an average spacing of 50 nm or less, in particular 20 nm or less, in particular 10 nm or less, for example 0.5-50 nm, in particular 0.7-20 nm, in particular 1-10 nm. The average distance between adjacent regions of the (semi) metal oxide phase, ie the average distance between regions of the (semi) metal oxide phase separated by a single region of the organic polymer phase is typically 50 nm. Hereinafter, it is 20 nm or less, particularly 10 nm or less. Similarly, the average distance between adjacent regions of the organic polymer phase, ie, the average distance between regions of the (semi) metal oxide phase separated by a single region of the organic polymer phase is typically 50 nm. Hereinafter, it is 20 nm or less, particularly 10 nm or less. However, in some examples, the average distance between adjacent regions of the organic polymer phase may be 300 nm or 100 nm. The average distance between the same phases can be measured by the method described above for measuring the dimensions of the C phase. This measuring method is for example by small-angle X-ray scattering (SAXS) or by transmission electron microscopy (TEM), in particular HAADF-STEM.

  Regarding the removal of the (semi) metal oxide phase required in step (III), the (semi) metal present in the monomer M or in the (semi) metal oxide particles is Si, Sn, Al, B, Ti, and It has been found desirable to select from Zr. More preferably, the (semi) metal is silicon or aluminum, especially silicon.

  Monomers suitable as the twin monomer M are known or can be prepared by methods similar to those described above. Examples include the publications cited at the beginning and the following publications.

Silyl enol ether (Chem. Ber. 119, 3394 (1986); J. Organomet. Chem. 244, 381 (1981); JACS 112, 6965 (1990))
Cycloboroxan (Bull. Chem. Jap. 51, 524 (1978); Can. J. Chem. 67, 1384 (1989); J. Organomet. Chem. 590, 52 (1999))
Cyclosilicate (Chemistry of Heterocyclic Compounds, 42, 1518, (2006); Eur. J. Inorg. Chem. (2002), 1025; J. Organomet. Chem. 1, 93 (1963); 212, 301 (1981); J. Org. Chem. 34.2496 (1968); Tetrahedron 57, 3997 (2001), and WO2009 / 083082 and WO2009 / 083083).
・ Cyclostannane (J. Organomet. Chem. 1, 328 (1963))
・ Cyclozirconate (JACS 82,3495 (1960))
Suitable monomers M can be represented by the general formula I:

However, in the formula:
M is a metal or metalloid, preferably a metal or metalloid of Group 3, Group 4 or Group 4 of the periodic table, in particular B, Al, Ti, Zr or Si, more preferably B, Si or Ti, in particular Si;
R ¹ and R ² may be the same or different and are each an Ar—C (R ^a , R ^b ) -radical. However, in this case, Ar is optionally halogen, _CN, aromatic or heteroaromatic ring having C 1 -C _{6 alkyl,} C 1 -C ₆ alkoxy, and 1 or 2 substituents selected from phenyl R ^a and R ^b are each independently hydrogen or a methyl group, or they are both an oxygen atom or a methylidene group (═CH ₂ ), and particularly both are hydrogen, or R ¹ O And R ² O are both radicals of formula A.

In the above formula, A is an aromatic or heteroaromatic ring bonded to a double bond, m represents 0, 1 or 2, and the radicals R may be the same or different. Selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl, R ^a and R ^b are as defined above.

  q represents the valence or charge of M, and is 0, 1, or 2, especially 1.

  X and Y may be the same or different, and each is O or a chemical bond, particularly O.

R ^{1 ′} and R ^{2 ′} may be the same or different, and each is C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, aryl, or Ar′-C (R ^{a ′} , R ^{b '} )-radical. Here, Ar ′ is defined as Ar, R ^{a ′} and R ^{b ′} are mutually defined as R ^a and R ^b , particularly hydrogen, and R ^{1 ′} and R ^{2 ′} together with X and Y , As described above, a radical of formula A.

Suitable for twin polymerization is the monomer of formula 1. Where M, R ¹ , R ² , q, Y, and R ^{2 ′} are mutually defined as described above, and the R ^{1 ′} radical has the following formula:

のラジカルである。

The radical of

In the formula, R ¹ , R ² , R ^{2 ′} , and Y are defined as described above, and # means a bond to M. Among these, M, R ¹ , R ² , q, Y, and R ^{2 ′} are monomers such as those having the definitions specified as preferred, in particular R ¹ O and R ² O radicals, of formula A It is a radical.

  Also suitable for twin copolymerization are the monomers of formula I. However, M is Ti or Zr, and q = 1. In particular, these monomers are μ-oxide cross-linked oligomers such as tetramers.

In the monomer of formula I, the part of the molecule corresponding to R ¹ and R ² O constitutes a polymerizable organic monomer unit. Similarly, when X and Y are not chemical bonds, and R ^{1 ′} X and R ^{2 ′} are not inert radicals such as C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, or aryl, The R ^{1 ′} X and R ^{2 ′} radicals constitute a polymerizable organic monomer unit A.

  In the present invention, an aromatic radical, or aryl, is understood to mean an aromatic carboxylic hydrocarbon radical, such as, for example, phenyl or naphthyl.

  In the present invention, a heteroaromatic radical or heteroaryl refers to a heteroaromatic radical that is generally 5- to 6-membered, one of the rings being nitrogen, oxygen, and sulfur, and being a heteroatom. Understood. Moreover, the other ring member of 1 or 2 may be a nitrogen atom, and the remaining ring members may be carbon. Examples of heteroaromatic groups are funyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, pyridyl, pyrimidinyl, pyridazinyl or thiazolyl.

  In the context of the present invention, bonded aromatic radicals or rings are understood as meaning the above-mentioned heterocyclic aromatic compounds. In this heteroaromatic compound, two adjacent carbon atoms form a double bond as shown in Formula A or Formulas II and III.

In a first embodiment of the monomer of formula I, the R ¹ O group and the R ² O group are both radicals of the above-mentioned formula A, in particular the radical of formula Aa.

Here, #, m, R, R ^a , and R ^b are defined as described above. In the expressions A and Aa, the variable m is 0. When m is 1 or 2, R is in particular a methyl or methoxy group. In the formulas A and Aa, R ^a and R ^b are in particular hydrogen with respect to each other.

In the monomer of the first embodiment, especially in the monomer of formula I, q = 1, and the X—R ^{1 ′} and Y—R ^{2 ′} groups are each a radical of the formula A, in particular a radical of the formula Aa It is. Such monomers can be represented by Formulas II and IIa.

Of the twin monomers of the first embodiment, preferred are those of formula I, q is 0 or 1, and the X—R ¹ group is a radical of formula A ′ or Aa ′. .

In the formula, m, A, R, R ^a , R ^b , Y, R ^{2 ′} , and q are each as defined above, and are particularly preferably defined clearly.

  Such a monomer can be represented by the following formula II 'or IIa'.

  In Formulas II and II ', each variable is defined as follows:

  M is a metal or metalloid, preferably the third or fourth main group of the periodic table, or a metal or metalloid that is a fourth transition element, in particular B, Al, Ti, Zr or Si, more preferably B, Si or Ti, in particular Si.

  A and A ′ are each independently an aromatic or heteroaromatic ring bonded to a double bond moiety.

m and n are each independently 0, 1 or 2, especially 0;
R, R ′ are each independently selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl, in particular each is methyl or methoxy;
R ^a , R ^b , R ^{a ′} and R ^{b ′} are each selected from hydrogen and methyl, or R ^a and / or R ^b and / or R ^{a ′} and R ^{b ′} are each an oxygen atom Or = CH ₂ , in particular R ^a , R ^b , R ^{a ′} , R ^{b ′} are each hydrogen,
L is a (Y—R ^{2 ′} ) _q group (where Y, R ^{2 ′} and q are each defined as described above, and in particular, q is 1).

In Formula IIa and Formula IIa ′, the variables are defined as follows:
M is a metal or metalloid, preferably a metal, or the third or fourth main group of the periodic table, or a fourth transition metal, in particular B, Al, Ti, Zr, or Si, preferably B, Si, or Ti, especially Si;
m and n are each independently 0, 1 or 2, especially 0;
R, R ′ are each independently selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl, in particular each methyl or methoxy;
R ^a , R ^b , R ^{a ′} and R ^{b ′} are each selected from hydrogen and methyl, or R ^a and / or R ^b and / or R ^{a ′} and R ^{b ′} are each an oxygen atom Or = CH ₂ , in particular R ^a , R ^b , R ^{a ′} , R ^{b ′} are each hydrogen;
L is a (Y—R ^{2 ′} ) _q group (where Y, R ^{2 ′} and q are each defined as above, particularly q is 1);
An example of a monomer of formula IIa and formula IIa ′ is 2,2′-spirobis [4H-1,3,2-benzodioxaline] (M = Si, m = n = 0, R ^a = R ^b = R ^a compound of formula IIa wherein ^{a ′} = R ^{b ′} = hydrogen). Such monomers are known from the prior art international patent applications WO2009 / 083082 and PCT / EP2008 / 010169 (WO2009 / 083083). Moreover, this monomer can be manufactured by the method described in these literatures. Another example of monomer IIa is 2,2-spirobi [4H-1,3,2-benzodioxaline] (M = B, m = n = 0, R ^a = R ^b = R ^{a ′} = R ^{b 'is} a compound of formula IIa) is (Bull.Chem.Soc.Jap.51 (1978) refer to 524). Other examples of monomers of formula IIa ′ are bis [4H-1,3,2-benzodioxalin-2-yl] oxide (M = B, m = n = 0, R ^a = R ^b = R ^{a ′} = R ^{b ′} = a compound of formula IIa ′ in which hydrogen (see Bull. Chem. Soc. Jap. 51 (1978) 524).

  In principle, monomer M comprises monomers of the following formulas III and IIIa:

In formula III, the variables are defined as follows:
M is a metal or metalloid, preferably a metal, or a third or fourth group of the periodic table, or a fourth transition metal, particularly B, Al, Ti, Zr, or Si, preferably B, Si, or Ti , Especially Si;
A is an aromatic or heteroaromatic ring bonded to a double bond moiety;
m is 0, 1 or 2, especially 0;
q is 0, 1 or 2 depending on the valence and charge of M;
R is selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl, in particular each methyl or methoxy;
R ^a , R ^b are each selected from hydrogen and methyl, or R ^a and R ^b are both oxygen atoms or ═CH ₂ , especially both are hydrogen;
R ^c and R ^d are each independently selected from C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, and anneal, and in particular are each methyl.

In formula IIIa, the variables are defined as follows:
M is a metal or metalloid, preferably a metal, or the third or fourth main group of the periodic table, or a fourth transition metal, in particular B, Al, Ti, Zr, or Si, preferably B, Si, or Ti, especially Si;
m is 0, 1 or 2, especially 0;
q is 0, 1 or 2 depending on the valence and charge of M;
R radicals are independently selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy and phenyl, in particular each methyl or methoxy;
R ^a , R ^b are each selected from hydrogen and methyl, or R ^a and R ^b are each an oxygen atom or ═CH ₂ , especially both are hydrogen;
R ^c and R ^d may be the same or different and are selected from C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, and anneal, and in particular are each methyl.

Examples of monomers of formula III or IIIa include 2,2-dimethyl-4H-1,3,2-benzadioxacillin (M = Si, q = 1, m = 0, R ^a = R ^b = hydrogen, R ^c = R ^d = methyl compound of formula IIIa), 2,2-dimethyl-4H-1,3,2-benzoxazacillin (where M = Si, q = 1, m = 0, G = NH A compound of formula IIIa wherein R ^a = R ^b = hydrogen, R ^c = R ^d = methyl), 2,2-dimethyl-4-oxo-1,3,2-benzodioxacillin where M = Si, a compound of formula IIIa wherein q = 1, m = 0, R ^a + R ^b = O, R ^c = R ^d = methyl), and 2,2-dimethyl-4-oxo-1,3,2-benzoxaza Syrin (where M = Si, q = 1, m = 0, G = NH, R ^a + R ^b = O, R ^c = R ^d = methyl compound of formula IIIa). Such monomers are known, for example, from “Journal of Organometallic Chemistry; 1, 1963, 93, 94” by Wieber et al. Other examples of monomer IIIa are 2,2-diphenyl [4H-1,3,2-benzodioxacillin] (see “J. Organomet. Chem. 71 (1974) 225”); 2,2-di-n -Butyl [4H-1,3,2-benzodioxastannin] (see "Bull. Soc. Chim. Belg. 97 (1988) 873"); 2,2-dimethyl [4-methylidene-1,3,2] -Benzodioxacillin] (see “J. Organomet. Chem., 244, C5-C8 (1983)”); 2-methyl-2-vinyl [4-oxo-1,3,2-benzodioxazacillin] It is.

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

  In a further preferred embodiment, the monomer of formula I is of the formula IV, V, Va, VI or VIa.

  In Formula IV, each variable is defined as follows:

M is a metal or metalloid, preferably a metal, or the third or fourth main group of the periodic table, or a fourth transition metal, in particular B, Al, Ti, Zr, or Si, preferably B, Si, or Ti, especially Si;
Ar and Ar ′ are the same or different and each is an aromatic ring or an aromatic heterocycle, especially 2-funyl or phenyl, and the aromatic ring or aromatic heterocycle is optionally halogen, CN, C ₁ -C ₆ - _alkyl, C 1 -C ₆ - have alkoxy, and one or two substituents selected from phenyl;
R ^a , R ^b , R ^{a ′} and R ^{b ′} are each selected from hydrogen and methyl, or R ^a and / or R ^b and / or R ^{a ′} and R ^{b ′} are each an oxygen atom Or = CH ₂ , in particular R ^a , R ^b , R ^{a ′} , R ^{b ′} are each hydrogen;
q is 0, 1 or 2, depending on the valence of M, in particular 1;
X and Y are the same or different and are O or a chemical bond;
R ^{1 ′} and R ^{2 ′} are the same or different and are each C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, annealed, or Ar ″ -C (R ^a ″). , R ^b ″) -radical (where Ar ″ is defined as Ar and R ′, and R ^a ″, R ^b ″ is R ^a , R ^b or R ^a ′, R ^b ′). Or R ^{1 ′} , R ^{2 ′} together with X and Y are defined as radicals of formula A, in particular radicals of formula Aa as described above).

Particularly preferred among the monomers of formula IV are q = 0, 1 or 2, especially q = 1, wherein the X—R ^{1 ′} and Y—R ^{2 ′} groups are the same or different, each Ar ′ '—C (R ^a ″, R ^b ″) O group, preferably Ar ″ —CH ₂ O group (R ^a = R ^b = hydrogen), respectively. Here, Ar ″ is defined as described above, in particular, selected from funyl, thienyl, pyrrolyl, and phenyl, and the four rings described above are unsubstituted or halogen, CN, C ₁ — It has 1 or 2 substituents selected from C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl. Such monomers can be described by the following formulas V and Va.

In equations V and Va, the variables are defined as follows:
M is a metal or metalloid, preferably a metal, or the third or fourth main group of the periodic table, or a fourth transition metal, in particular B, Al, Ti, Zr, or Si, preferably B, Si, or Ti, especially Si;
Ar and Ar ′ are the same or different and each is an aromatic ring or an aromatic heterocycle, especially 2-funyl or phenyl, and the aromatic ring or aromatic heterocycle is optionally halogen, CN, C ₁ -C ₆ - _alkyl, C 1 -C ₆ - have alkoxy, and one or two substituents selected from phenyl;
R ^a , R ^b , R ^{a ′} and R ^{b ′} are each selected from hydrogen and methyl, or R ^a and / or R ^b and / or R ^{a ′} and R ^{b ′} are both oxygen atoms Or = CH ₂ , in particular R ^a , R ^b , R ^{a ′} , R ^{b ′} are each hydrogen;
q is 0, 1 or 2, depending on the valence of M, and is especially 1.

In the formula Va, m is 0, 1 or 2, in particular 0, R is selected from halogen, CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy and phenyl, in particular methyl and methoxy It is.

An example of a monomer of formula V or Va is tetraflufuryloxysilane (compound of formula Va wherein M = Si, q = 1, m = 0, R ^a = R ^b = hydrogen) (“Angew. Chem. Int. Ed , 46 (2007) 628). Another example of a monomer of formula V or Va is tetraflufurirotitanate (see “Adv. Mater. 2008, 20, 4113”). This compound is tetramerized to (μ ⁴ -oxide) -hexakis (m-furfuryloxo) octakis (furfuriroxo) tetratitanium. This is used as a twin monomer. An example of monomer V or Va is trifluorofuryloxyborane (compound of formula Va where M = B, q = 0, m = 0, R ^a = R ^b = hydrogen).

Also, the monomer of formula IV has the same or different X—R ^{1 ′} and Y—R ^{2 ′} groups, each group being C ₁ -C ₄ -alkyl, especially methyl, C ₃ -C ₆ -cyclo Selected from alkyl and aryl, for example phenyl, ie X and Y are each a chemical bond. This type of monomer is represented by the following formulas VI and Via.

In formulas VI and VIA, the variables are defined as follows:
MM is a metal or metalloid, preferably a metal, or the third or fourth main group of the periodic table, or a fourth transition metal, in particular B, Al, Ti, Zr or Si, more preferably B, Si, Or Ti, in particular Si;
Ar and Ar ′ are the same or different in the formula (VI) and each is an aromatic ring or an aromatic heterocycle, in particular 2-funyl or phenyl, and the aromatic ring or aromatic heterocycle is optionally halogenated 1 or 2 substituents selected from: CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, and phenyl;
R ^a , R ^b , R ^{a ′} and R ^{b ′} are each selected from hydrogen and methyl, or R ^a and / or R ^b and / or R ^{a ′} and R ^{b ′} are each an oxygen atom Or = CH ₂ , in particular R ^a , R ^b , R ^{a ′} , R ^{b ′} are each hydrogen;
q is 0, 1 or 2, depending on the valence of M, in particular 1;
R ^c and R ^d may be the same or different and are selected from C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, and anneal, and in particular are each methyl.

In formula VIa, m is 0, 1 or 2, in particular 0, R is selected from CN, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy and phenyl, in particular each of methyl or methoxy is there.

An example of a monomer of formula VI or VIa is a compound of formula VIa where bis (furfuryloxy) dimethylsilane (M = Si, q = 1, m = 0, R ^a = R ^b = hydrogen, R ^c = R ^d = methyl) ).

  Such monomers of formulas IV, V, Va, VI and VIa are known, for example, from the prior art described in the papers by Spange et al. Or can be prepared in a similar manner.

  The monomer of formula VI or VIa is preferably not polymerized alone and is combined with the monomer of formula V and formula Va.

In a further embodiment of the invention, the twin monomer M is an aromatic having on average an identical or different aryl group, in particular two or more trialkylsilyloxymethyl groups and / or aryldialkylsilyloxymethyl groups bonded to the benzene ring. Selected from compounds. As used herein, alkyl is alkyl having 1 to 4 carbon atoms, particularly methyl or ethyl. As used herein, aryl is phenyl or naphthyl, particularly phenyl. One example of a trialkylsilyloxymethyl group is trimethylsilyloxymethyl ((H ₃ C) ₃ Si—O—CH ₂ —). The aryldialkylsilyloxymethyl group is, for example, a dimethylphenylsilyloxymethyl group (phenyl (H ₃ C) ₃ Si—O—CH ₂ —). In this case, the aryl ring bonded to the trialkylsiloxymethyl group and / or the aryldialkylsiloxymethyl group is, for example, C ₁ -C ₄ -alkoxy such as methoxy, C ₁ -C ₄ -alkyl, trialkylsiloxy, Or it has other substituents, such as aryl dialkyl silyloxy. More preferably, such a twin monomer is a phenolic compound having two or more trialkylsilyloxymethyl groups and / or aryldialkylsilyloxymethyl groups bonded to the phenyl ring of the phenol compound. The OH group of this phenolic compound may be etherified with a trialkylsilyl group and / or an aryldialkylsilyl group. Such a compound can be produced by hydroxymethylating an aromatic compound, particularly a phenol compound, and reacting with a trialkylhalosilane or aryldialkylhalosilane. In the case of phenolic starting materials, not only hydroxymethyl groups but also phenolic OH groups are converted into the corresponding silyl ethers. Examples of aromatic compounds are in particular phenolic compounds such as phenol, cresol and bisphenol A (= 2,2-bis- (4-hydroxyphenyl) propane).

  The aromatic compounds having on average the same or different aryl groups, in particular two or more trialkylsilyloxymethyl groups and / or aryldialkylsilyloxymethyl groups bonded to the benzene ring, are themselves homopolymerized or copolymerized. can do. Aromatic compounds having, on average, two or more trialkylsilyloxymethyl groups and / or aryldialkylsilyloxymethyl groups bonded to the same or different aryl groups, in particular a benzene ring, can be represented by the formula II, IIa, II ′, or II ′. It is preferred to copolymerize with the monomer of a or the compound of formula IV, V or Va.

  Preferred monomers M according to the invention are selected from monomers of the formulas II, IIa, II 'and II'a, in particular monomers of the formula IIa. These monomers of formula II, IIa, II 'or II'a, wherein M is preferably Si, are most preferred monomers of formula IIa where M is Si.

  Monomer M is typically polymerized in an organic aprotic solvent or solvent mixture. The produced nanocomposite material is preferably an aprotic solvent insoluble (solubility at 25 ° C. of less than 1 g / liter). As a result, particularly small particles of polymeric material are formed under polymerization conditions.

  By using an aprotic solvent that does not dissolve the nanocomposite material produced during polymerization, the production of particles is basically promoted. If the polymerization is carried out in the presence of a particulate inorganic material, the production of particles can be controlled by the presence of the particulate inorganic material. This prevents the generation of coarse particulate material.

  The aprotic solvent is preferably selected so that the monomer is at least partially soluble. This means that the solubility of the monomer in the solvent under the polymerization conditions is 50 g / liter or more, in particular 100 g / liter or more. In general, the organic solvent is selected such that the solubility of the monomer at 20 ° C. is 50 g / liter, in particular 100 g / liter. More particularly, the solvent is selected such that the monomer is almost or completely dissolved. That is, the ratio of the solvent to the monomer is selected so that 80% or more, particularly 90% or more, of the monomer MM is completely dissolved under the polymerization conditions.

  “Aprotic” includes solvents in which the polymer used in the polymerization substantially contains one or more protons attached to a heteroatom such as O, S, or N (and is therefore more or less acidic). Means no. Therefore, the proportion of the protic solvent in the solvent or solvent mixture used for the polymerization is less than 10% by volume, in particular less than 1% by volume, in particular less than 0.1% by volume, based on the total amount of the organic solvent.

  The polymerization of the monomer M is preferably performed in a state in which almost no water is present, that is, the water content at the start of polymerization is preferably less than 500 ppm based on the amount of solvent used.

  The solvent may be inorganic or organic, or a mixture of an inorganic solvent and an organic solvent. Preferably, it is an organic solvent.

  Suitable aprotic organic solvents are, for example, halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, trichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1-chlorobutane, chlorobenzene, dichlorobenzene, fluorobenzene and the like. And pure hydrocarbons that are aliphatic, cycloaliphatic or aromatic, and mixtures of these hydrocarbons and halogenated hydrocarbons. Examples of pure hydrocarbons are generally acyclic aliphatic hydrocarbons having 2-8, preferably 3-8 carbon atoms, in particular ethane, iso- and n-propane, n-butane, and isomers thereof. , N-pentane and its isomers, n-hexane and its isomers, n-heptane and its isomers, and alkanes such as n-octane and its isomers, cyclopentane having 5 to 8 carbon atoms, Alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, and cycloalkanes such as cycloheptane, and benzene, toluene, xylene, mesitylene, ethylbenzene, cumene (2-propylbenzene), and isocumene (1-propylbenzene) And aromatic hydrocarbons such as tert-butylbenzene.

  Preferably, it is a mixture of the above-mentioned hydrocarbons and halogenated hydrocarbons, such as halogens such as chloromethane, dichloromethane, trichloromethane, chloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, and 1-chlorobutane. And halogenated aromatic hydrocarbons such as chlorobenzene, 1,2-dichlorobenzene, and fluorobenzene.

  Examples of inorganic protic solvents are in particular supercritical carbon dioxide, carbon oxysulfide, carbon disulfide, nitrogen dioxide, thionyl chloride, sulfuryl chloride, and liquid sulfur dioxide, and the latter acting as a polymerization initiator. Three solvents.

  The monomer M is usually polymerized in the presence of a polymerization initiator or a catalyst. The polymerization initiator is selected such that cationic polymerization of monomer M (ie, monomer unit A) is initiated, and the catalyst is selected to act as a catalyst for the formation of the (semi) metal oxide phase. Therefore, in the course of the polymerization of the monomer M, the monomer unit A is polymerized, and a (semi) metal oxide phase is generated synchronously.

  Note that the term “synchronous” does not necessarily mean that the polymerization of the monomer unit A and the generation of the (semi) metal oxide phase proceed at the same rate. However, “synchronous” means that these processes are combined kinetically and caused by cationic polymerization conditions.

In principle, suitable polymerization initiators or catalysts are all substances known to act as catalysts in cationic polymerization. Such materials include protic acids (Bronsted acids) and aprotic Lewis acids. Preferred protic catalysts are Bronsted acids, for example organic carboxylic acids such as trifluoroacetic acid or lactic acid, in particular organic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid or toluenesulfonic acid. Similarly, inorganic Bronsted acids such as HCl, H ₂ SO ₄ or HClO ₄ are also preferred. The Lewis acid used may be, for example, BF ₃ , BCl ₃ , SnCl ₄ , TiCl ₄ , or AlCl ₃ . It is also possible to use Lewis acids that are complexly bound or dissolved in an ionic liquid. The polymerization initiator or catalyst is usually used in an amount of 0.1 to 10% by mass, preferably 0.5 to 5% by mass, based on the monomer M.

  The temperature required in the polymerization of the monomer M is usually in the range of 0 to 150 ° C, particularly in the range of 10 to 120 ° C. In the case of polymerization of an acid catalyst, the polymerization temperature is in the range of 0 to 100 ° C, particularly in the range of 10 to 80 ° C.

  In one embodiment of the invention, the polymerization of the monomer M is carried out in the presence of one or more particulate materials. With regard to step (III) of the method of the invention, the material is an inorganic oxide material, preferably a (semi) metal oxide. Of these, preferred are titanium oxide, silicon oxide, tin oxide, aluminum oxide, or boron oxide, particularly silicon dioxide and aluminum oxide.

  The particulate material generally has a particle size of 5 μm or less, preferably 1 μm or less, in particular 0.5 μm or less. When the particles are aggregates of primary particles, the particle size is understood to mean the size of the primary particles (primary particle diameter) forming the aggregates. The particulate inorganic material has an average particle size (weight average particle size), which in the case of aggregates of primary particles (weight average primary particle size) is 5 to 5000 nm, often 5 to 1000 nm, especially 10 to 500 nm. Or 15 to 200 nm. Here, the average particle diameter is based on a mass average or a weight average measured by a method known per se using light scattering or an ultracentrifuge.

  Preferred granular (semi) metal oxides are titanium dioxide powder (especially exothermic titanium dioxide), aluminum oxide powder (especially exothermic aluminum oxide), and silica powder (especially finely divided silica such as fumed silica or precipitated silica). In this case, the particles preferably have a particle size or a primary particle size determined as described above. Such materials are under the trade names Aerosil® and Aeroxide® (Evonik), Cab-O-Sil® (Cabot), or Syloid® (Grace). It is commercially available. In a particularly preferred embodiment of the invention, the inorganic particulate material is finely divided silica, in particular fumed silica. Further preferred are zeolites, especially those having an acidic active moiety.

  In a preferred configuration of the present embodiment, the granular (semi) metal oxide contains at least a part of a polymerization initiator or a catalyst. This can be done, for example, by treating the particulate (semi-) polymerization initiator or catalyst metal oxide, and also for example in the solution of the polymerization initiator or catalyst (e.g. a solution in the organic solvent used for the polymerization) into the particles (semi-solid). This is achieved by suspending the metal oxide.

  When the polymerization is carried out in the presence of a particulate (semi) metal oxide, the oxide is usually 0.01-100 parts by weight, in particular 0.05-50 parts by weight, based on 1 part by weight of monomer A. Used in an amount of 10000 parts by weight (based on the total amount of monomer A, in particular 5 to 5000% by weight, or the ratio of the amount of particles (semi) metal oxide to monomer A is 100: 1 1: 100, especially 50: 1 to 1:20).

  In a preferred embodiment of the invention, the particulate (semi) metal oxide is used in an amount of 0.01 to 1 part by weight, in particular 0.055 to 0.5 part by weight, based on 1 part by weight of monomer A. Is done. In another preferred embodiment, the particulate material is used in an amount of 1-100 parts by weight, in particular 1.5-50 parts by weight, based on 1 part by weight of monomer A. On the other hand, first, the properties of the resulting granular composite material are determined by the components produced in the polymerization, and secondly, the particles obtained in the polymerization consist of granular (semi) metal oxides used in the polymerization. A core and a shell composed of a composite material disposed in the core and obtained by polymerization of the monomer M;

  Prior to further processing, the composite material thus obtained is washed with an organic solvent or solvent mixture to remove impurities. It is also preferred that the composite material be dried and / or ground prior to further processing.

  In the second step (II) of the method according to the present invention, the granular composite material produced in step (I) is carbonized.

In order to perform this carbonization, the granular composite material obtained in step (I) is
Usually, heating is performed to a temperature exceeding 500 ° C., in particular, exceeding 700 ° C., for example, a temperature in the range of 500 to 1500 ° C., particularly a temperature in the range of 700 to 1200 ° C., with almost oxygen excluded. By “substantially excluded oxygen” is meant that the partial pressure of oxygen in the reaction zone where carbonization is carried out is low, preferably 20 mbar or less, in particular 10 mbar. Carbonization is preferably performed in an inert gas atmosphere, for example, in a nitrogen or argon atmosphere. The inert gas atmosphere preferably contains less than 1% by volume, especially less than 0.1% by volume oxygen.

  The granular composite material is preferably used for carbonization in a dry state, that is, a powder state substantially free of a solvent. In the following, “substantially free of solvent” means that the solvent content of the composite material is less than 1% by mass, particularly less than 0.1% by mass.

  Optionally, carbonization may be carried out in the presence of an oxidant that promotes the formation of graphite, for example a transition metal halide such as iron trichloride. As a result, the carbon in the carbon material of the present invention is all in the form of graphite or graphene units (that is, a polycyclic form bonded to a structural unit, and each carbon is commonly bonded to the other three carbons. Effect). The amount of such an oxidizing agent is generally 1 to 20% by mass based on the composite material. When this type of oxidizing agent is used in carbonization, the composite material and the oxidizing agent are usually mixed with each other and the mixture is carbonized in the form of a powder substantially free of solvent. Optionally, after the carbonization, the oxidizing agent may be removed by extraction cleaning of the oxidizing agent, for example. In this removal, a solvent or a solvent mixture in which the oxidizing agent and its reaction product are soluble may be used, or a vaporization method may be used.

  In this way, in step (II), a material composed of carbon and (semi) metal oxide is obtained. This material has one or more carbon phases (C phase) and one or more inorganic (semi) metal oxide phases. The C phase and the inorganic (semi) metal oxide phase form a substantially co-continuous phase region with an irregular arrangement. The distance between two adjacent regions of the (semi) metal oxide phase is 50 nm or less, in particular 20 nm or less, preferably 10 nm or less, for example in the range of 0.5 to 50 nm, in particular 0.7 to 20 nm, in particular It is in the range of 1 to 10 nm. Regarding the measurement of the distance between two adjacent regions of the (semi) metal oxide phase, the method described above for the composite material obtained in step (I) can be applied as well. The particle size of the material is the same as that of the carbon material.

  In step (III) of the method according to the invention, one or more (semi) metal oxide phases are squeezed out of the particulate material obtained in step (II).

  Surprisingly, in the process of carbonization in step (II) and in the process of squeezing out the (semi) metal oxide phase, the phase structure of the composite material obtained in step (I) is almost retained. The granular porous carbon material of the present invention is formed by squeezing the (semi) metal oxide phase from the carbon and (semi) metal oxide composite material obtained in step (II). The pores in the carbon material may be formed in regions where one or more (semi) metal oxide phases are present in the composite material composed of carbon and (semi) metal oxide obtained in step (II). high.

  Exploitation of one or more (semi) metal oxide phases from the particulate material obtained in step (II) is to treat the particulate material obtained in step (II) with an aqueous solution of a non-oxidizing acid. It can be done in a simple way. This non-oxidizing acid is suitable for dissolving the (semi) metal oxide in the aqueous medium. Preferable examples are alkali metal hydroxide solutions such as sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, or acidic aqueous solutions such as hydrochloric acid aqueous solution or hydrofluoric acid. In particular, when the (semi) metal oxide phase is silicon dioxide, gas phase HF is preferred. When the alkali metal hydroxide aqueous solution is used, the content of the alkali metal hydroxide is in the range of 1 to 50% by mass. When an aqueous non-oxidizing acid such as aqueous hydrochloric acid or hydrofluoric acid is used, the acid content is usually in the range of 1 to 60% by mass. Exploitation of the (semi) metal oxide phase is usually performed using aqueous HF at a temperature in the range of 10 to 150 ° C, for example in the range of 20 to 25 ° C. The time required to extract the (semi) metal oxide phase can be measured by a person skilled in the art by a predetermined experiment. Of course, this time depends on the type and temperature of the solvent used, but is usually in the range of 1 to 24 hours.

  The granular porous carbon material of the present invention thus obtained may be washed before use. This washing is, for example, removal of impurities using a solvent such as water or a mixture of water and a water-miscible organic solvent or a solvent mixture. Moreover, it is preferable to dry and / or grind | pulverize before the other use of the granular porous carbon material of this invention.

  By the method according to the present invention, the granular porous carbon material of the present invention can be produced easily and in large quantities. Furthermore, this material is suitable for many applications such as gas storage materials, filter materials, and catalyst carriers, anode materials for supercapacitors, lithium ion batteries, solar cells, or water purification.

  The granular porous carbon material thus obtained is particularly suitable as a constituent element of an electrode material in an electrochemical cell (particularly a lithium battery).

  As used herein, an electrochemical cell or battery refers to any type of battery, capacitor, and accumulator (secondary battery), particularly an alkali metal battery or battery, such as lithium, lithium ion, lithium-sulfur, and alkaline earth. Metal batteries and accumulators are meant and include those used in the aspects of high energy or high efficiency systems known under the names Supercaps, Goldcaps, BoostCaps, or Ultracaps.

  More specifically, the granular porous carbon material of the present invention is suitable for an electrochemical cell based on the movement of alkali metal ions. This electrochemical cell is in particular a lithium metal battery, a sodium-sulfur metal battery, a lithium-sulfur battery, and a lithium ion battery. The porous carbon material of the present invention is particularly suitable for electrochemical cells from the group consisting of alkali metal-sulfur batteries such as sodium-sulfur batteries or lithium-sulfur batteries.

  In lithium-sulfur batteries, the granular porous carbon material of the present invention is used in particular in the form of a sulfur-containing composite material. Such sulfur-containing composite materials include elemental sulfur and one or more particulate porous carbon materials of the present invention. Such a composite material is electrically active and is suitable as a positive electrode material for an alkali metal-sulfur battery (particularly a lithium-sulfur battery). It is also suitable as a positive electrode material for sodium-sulfur batteries.

  In the sulfur-containing composite material, a small amount of the porous carbon material of the present invention is sufficient to bring about a significant improvement in the properties of the positive electrode material. The sulfur-containing composite material of the present invention is generally 1 to 45% by mass, particularly 2 to 30% by mass, particularly 3 to 20% by mass, and especially 3 to 20% by mass of the carbon material of the present invention, based on the entire sulfur-containing composite material. In particular, it is contained in an amount of 3 to 20% by mass. The amount of elemental sulfur is usually 55 to 99% by weight, in particular 70 to 98% by weight, and in particular 80 to 97% by weight, based on the sulfur-containing composite material.

  A portion of the porous carbon material of the present invention can be replaced with a conventional carbon material such as conductive carbon black or an inorganic filler.

  The production of the sulfur-containing composite material of the present invention can be easily performed by melting elemental sulfur by incorporating a desired amount of the porous carbon material of the present invention. The temperature required to do this is in the temperature range of 120-300 ° C, and preferably 120-150 ° C. Alternatively, the porous carbon material of the present invention may be taken into a solution of elemental sulfur in a suitable organic solvent, and then the solvent may be removed. Examples of suitable solvents are in particular aromatic and halogenated aromatic hydrocarbons such as toluene, xylene and chlorobenzene, and carbon disulfide and carbon dibromide.

  The sulfur-containing composite material of the present invention is particularly suitable as an electroactive element for a positive electrode in an alkali metal sulfur battery (particularly a lithium sulfur battery). Therefore, the present invention provides a positive electrode for an alkali metal sulfur battery (particularly a lithium sulfur battery, particularly a lithium sulfur secondary battery) and a lithium sulfur battery (particularly a lithium sulfur secondary battery) containing the sulfur-containing composite material of the present invention. A method of using a sulfur-containing composite material is provided.

  In addition to the sulfur-containing composite material of the present invention, the positive electrode typically includes one or more binders for bonding the electroactive element of the sulfur-containing composite material and other electro-optic conductive or electroactive elements. The positive electrode generally has electrical contacts for supplying and removing charges. The amount of the sulfur-containing composite material of the present invention is usually 20% by mass or more, often 30% by mass or more, particularly 40% by mass or more, based on the total mass of the positive electrode material, subtracting the current collector and the electrical contacts. For example 20 to 80% by weight, often 30 to 70% by weight, in particular 40 to 65% by weight, and in particular 50 to 60% by weight.

  Further, suitable conductive or electroactive elements are described in the opening prior art and related research papers (see, for example, “ME Spahr, Carbon Conductives for Lithium-Ion Batteries, in M. Yoshio et al. (Eds. ) Lithium Ion Batteries, Springer Science + Business Media, New York 2009, ”described on pages 117 to 154). Other useful conductive or electroactive materials in the positive electrode of the present invention include carbon black, graphite, carbon fiber, carbon nanofiber, carbon nanotube, or conductive polymer. Usually, the conductive material used for the negative electrode is about 2.5 to 40% by mass, after subtracting the current collector and the electrical contact, based on the total mass of the negative electrode material. Used with 50-97.5 wt%, often 60-95 wt% of the sulfur-containing composite material of the present invention.

  In principle, binders suitable for the production of positive electrodes using the above-mentioned electroactive materials include all conventional binders suitable for positive electrode materials. This conventional binder is disclosed in the prior art and related research papers (for example, “A. Nagai, Applications of PVdF-Related Materials for Lithium-Ion Batteries, in M. Yoshio et al. (Eds.) Ith. 155-162 of Batteries, Springer Science + Business Media, New York 2009, and "H. Yamamoto and H. Mori, SBR Binder (for negative electrode) See page 180 ") It is.

  Useful binders include in particular: polyethylene oxide (PEO), cellulose, carboxymethyl cellulose (CMC), polyethylene, polypropylene, polytetrafluoroethylene, polyacrylonitrile-methyl methacrylate, polytetrafluoroethylene, styrene- Butadiene copolymer, tetrafluoroethylene-hexafluoroethylene copolymer, polyvinylidene fluoride (PVDF), polyvinylidene fluoride hexafluoropropylene copolymer (PVDF-HFP), tetrafluoroethylene hexafluoropropylene copolymer, tetrafluoroethylene, perfluoroalkyl-vinyl ether copolymer, Vinylidene fluoride-hexafluoropropylene copolymer, ethylene-tetraf Oroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, ethylene-chloro-fluoroethylene copolymer, ethylene-acrylic acid copolymer (with or without sodium ion), ethylene-methacrylic acid copolymer (with sodium ion) With or without), ethylene-methacrylic acid ester copolymers (with or without sodium ions), polyimide, and polyisobutene.

  The binder is optionally selected taking into account the nature of any solvent used in the production. The binder is generally 1-10% by weight, based on the total mixture of positive electrode material, i.e. sulfur-containing composite material and any other electroactive or conductive material. Preferably, it is 2 to 8% by mass, particularly 3 to 7% by mass.

  The positive electrode itself has the prior art and research papers shown at the beginning (for example, “RJ Brodd, M. Yoshio, Production processes for Fabrication of Lithium-Ion Batteries, in M. Yoshi et al. (Eds. ) Lithium Ion Batteries, Springer Science + Business Media, New York 2009, ”pages 181 to 194)). For example, the positive electrode optionally uses an organic solvent or solvent mixture (eg, N-methylpyrrolidinone, or a hydrocarbon solvent) to connect the sulfur-containing composite material of the present invention to other components of the positive electrode material (other electroactive or Mixed with a conductive element and / or organic binder) and optionally subjected to a molding step or an application step of an inert metal foil (eg, Au, Ag, or Cu foil). Then, you may dry as needed. Drying is performed at a temperature of 80 to 150 ° C., for example. The drying operation is continued for 3 to 48 hours under reduced pressure. Optionally, a melting step or a sintering step may be performed for molding.

  The present invention also provides an alkali metal sulfur battery, particularly a lithium sulfur battery, particularly a lithium sulfur secondary battery, comprising one or more positive electrodes containing the electroactive material of the present invention.

  Such a battery typically includes one or more positive electrodes of the present invention, a negative electrode suitable for a lithium sulfur battery, an electrolyte, and optionally a separator.

Concerning suitable negative electrode materials, suitable electrolytes and separators are constructed in possible arrangements and possible shapes. Possible arrangements are known, for example, in the prior art shown at the beginning. The possible shapes, for example, ^{"Wakihara et al (editor) in Lithium} Ion Batteries, 1 st edition, Wiley VCH, Weinheim, 1998; David Linden:. Handbook of Batteries (McGraw-Hill Handbooks), 3 rd edition, McGraw -Hill Professional, New York 2008; J. O. Besenhard: Handbook of Battery Materials. Wiley-VCH, 1998; M. Yoshio et al. (Ed.) Lithium Ion Bet. rk 2009;. K.E Aifantis, S.A.Hackney, R.V.Kumar, are described in, High Energy Density Lithium Batteries, Wiley-VCH, 2010 "(ed.).

Useful negative electrodes include graphite, metallic lithium, lithium-graphite compounds, lithium alloys (eg, lithium-silicon alloys), nanocrystalline silicon, or lithium metal oxides (such as lithium titanate (eg, Li ₄ Ti ₅ O ₁₂ )). ) As an electrode active element.

The negative electrode may contain further elements in addition to the electroactive elements. Further elements are, for example, conductive or electroactive elements such as carbon black, graphite, carbon fibers, carbon nanofibers, carbon nanotubes or conductive polymers, and binders associated with the positive electrodes described above.

  The electrodes are disposed between separators impregnated with electrolyte. Examples of separators are in particular glass fiber nonwoven fabrics and polyethylene porous films such as polypropylene and PVdF. Moreover, it is also possible to use a polymer electrolyte instead of the electrolyte and the separator.

  The two electrodes (ie, negative electrode and positive electrode) are connected to each other in a manner known per se using a liquid or other solid electrolyte and optionally a suitable separator. For this purpose, for example, a separator is laminated in one of two electrodes having an output conductor (negative electrode or positive electrode), impregnated with an electrolyte, and the reverse charge provided by the output conductor is applied. A separator is applied to the charged electrode, and the obtained sandwich structure is arbitrarily wound and introduced into the battery housing.

  Useful liquid electrolytes include non-aqueous solutions of lithium and molten lithium salts (usually water content <20 ppm). For example, lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, trifluoromethyl sulfonate, lithium bis (trifluoromethylsulfonyl) imide, or lithium tetrafluoroborate, especially hexafluoride. Lithium phosphate or lithium tetrafluoroborate is replaced with a suitable aprotic solvent such as ethylene carbonate, propylene carbonate, dioxolane, and mixtures thereof, and one or more of the following mixtures: dimethyl carbonate, diethyl carbonate, dimethoxy Ethane, methyl propionate, ethyl propionate, butyrolactone, acetonitrile, ethyl acetate, methyl acetate, toluene, and xylene, especially those contained in a mixture of ethylene carbonate and diethyl carbonate. The solid electrolyte used may be, for example, an ion conductive polymer.

  The lithium sulfur battery of the present invention may have a prism thin film structure. In this prism thin film structure, the solid electrolyte thin film is disposed between the film constituting the negative electrode and the film constituting the positive electrode. A central cathode output conductor is disposed between each positive electrode film to form a double-sided cell configuration. Other embodiments may use a single-sided cell configuration in which a single positive output conductor is assigned to a single negative / separator / positive element combination. In this configuration, the insulating film is typically disposed between the individual negative electrode / separator / positive electrode / output conductor element combinations.

TEM analysis of the sample of Example 7.3 (bar is 50 nm) Thermogravimetric analysis of the samples of Examples 9a and 9b

  The following drawings and examples illustrate the invention, but should not be understood as being limited to each of these embodiments.

  TEM analysis and HAADF-STEM analysis were performed at 200 kV operating voltage using the Tecnai F20 transmission electron microscope (FEI, Eindhoven, the Netherlands) by the thin layer method (embedding the sample in a synthetic resin as a matrix). .

  Specific surface area and pore size distribution were analyzed by measuring nitrogen adsorption / desorption isotherms based on the German Industrial Standard DIN 66134 by the “Barret, Joyner and Halender” method. The BET surface area was measured according to DINISO 9277 using nitrogen adsorption.

  The thermogravimetric analysis test was performed with a TGA7 thermogravimetric analyzer (Perkin Elmer) using a platinum crucible at a heating rate of 40 K / min.

Starting material:
2,2′-spirobi [4H-1,3,2-benzodioxacillin] was produced by the method defined in WO2010 / 112580.

  The particulate material used was fumed silica with Aerosil® 300 (primary particle size 7 nm) and Aerosil® OX50 (primary particle size 40 nm).

  Toluene and dichloromethane were added p. a. Used in quality.

Examples 1 to 7: Method for producing general carbon material using granular material 1) 1 g of granular material shown in Table 1 was suspended in 200 ml of dichloromethane. 240 mg of methanesulfonic acid was added thereto, and the resulting dispersion was stirred at 22 ° C. for 15 minutes. The solvent was then removed under reduced pressure. The solid thus obtained was dissolved in 200 ml of toluene. On the other hand, a solution in which 2 g of 2,2′-spirobi [4H-1,3,2-benzodioxacillin] was dissolved in 50 ml of toluene was dropped, and the mixture was stirred at 22 ° C. for 15 minutes. Subsequently, the powdered solid was filtered and dried under reduced pressure at 40 ° C. until a constant mass was reached.

  2) Next, the powder obtained in step (i) was calcined in a tubular furnace with an argon flow at 800 ° C. or 1100 ° C. for 2 hours. A black powder was thus obtained.

  3) Thereafter, the powder obtained in Step 1 was stored in a 40% HF aqueous solution for 3 days. Next, the remaining powder was filtered off, washed with water and ethanol, and dried at 40 ° C. under reduced pressure until a constant mass was reached.

Example 8: General method for the production of carbon material without using particulate material 1) 240 mg of methanesulfonic acid was dissolved in 200 ml of toluene. On the other hand, a solution in which 2 g of 2,2′-spirobi [4H-1,3,2-benzodioxacillin] was dissolved in 50 ml of toluene was dropped, and the mixture was stirred at 22 ° C. for 15 minutes. Subsequently, the powdered solid was filtered and dried under reduced pressure at 40 ° C. until a constant mass was reached.

  2) Next, the powder obtained in step (i) was calcined in a tubular furnace with an argon flow at 800 ° C. or 1100 ° C. for 2 hours. A black powder was thus obtained.

  3) Thereafter, the powder obtained in Step 1 was stored in a 40% HF aqueous solution for 3 days. Next, the remaining powder was filtered off, washed with water and ethanol, and dried at 40 ° C. under reduced pressure until a constant mass was reached.

  According to elemental analysis, the powder thus obtained had a carbon content of greater than 84% by mass and a silicon content of less than 2% by mass. The oxygen content was less than 15% and the hydrogen content was less than 1.5%.

  The TEM image in FIG. 1 shows the hollow carbon particles obtained from Step 3 of Example 7 (Example 7.3). This figure shows that the carbon material of the hollow carbon particles is porous.

  Table 1 shows the production of the carbonaceous material.

Example 9a: Production of a sulfur-containing composite material from sulfur and the carbon material of the invention:
1 g of the powder from Example 7.3 was melted with 6 g of elemental sulfur at a temperature of 140 ° C. and left at this temperature for 5 hours. The solid obtained in the cooling process was pulverized into powder using a mortar and pestle.

Example 9b: Sulfur-containing composite material consisting of sulfur and carbon and silicon dioxide Production of sulfur-containing composite material from carbon 1 g of powder from Example 7.2 was melted with 6 g of elemental sulfur at a temperature of 140 ° C. It was left at this temperature for 5 hours. The solid obtained in the cooling process was pulverized into powder using a mortar and pestle.

  The materials of the examples of Examples 9a and 9b were analyzed using a thermogravimetric analyzer (see FIG. 2).

  As can be seen with reference to the curve in FIG. 2, the carbon material from Example 7.3, ie, the material after the removal of the inorganic (semi) metal oxide phase, is the material of Example 7.2. In comparison, the binding performance of sulfur is significantly increased. This is explained by the increased sulfur sublimation temperature compared to the composite of carbon and silicon dioxide (Example 9b). This indicates that sulfur in the sulfur carbon composite material (Example 9a) was inserted into the pores of the carbon material of Example 7.3.

Example 10: Production of positive electrode using the sulfur-containing composite material according to Example 9a First, an ink of a sulfur-containing composite material was produced in a water / isopropanol mixture. For this purpose, 0.02 g of polyvinyl alcohol was dissolved in 16.0 g of water / isopropanol (10: 1 v / v) in a laboratory glass bottle. To this solution, 0.47 g of conductive black (Super P 6743 Bodio from Timcal, Switzerland), 0.07 g of synthetic graphite (KS6 6743 Bodio from Timcal, Switzerland), and 1.71 g of Example 9 Of sulfur-containing composite material was added and the mixture was stirred until a uniform suspension was obtained. For dispersion, the suspension was transferred into a stainless steel vessel and then ground using a ball mill (Pulversette, manufactured by Fritsch) with stirring at 300 rpm for 30 minutes in a stainless steel ball. This dispersion produced a creamy, very uniform ink.

This ink was sprayed onto an aluminum foil using an air brush method on a vacuum table (temperature is 60 ° C.). Nitrogen was used for spraying. A solids amount of 2.5 mg / cm ² was realized.

Reference Example 10 Production of Positive Electrode Using Sulfur A positive electrode was produced in the same manner as described in Example 10 except that the positive electrode was produced by producing the following suspension.

  In a laboratory glass bottle, 0.02 g of polyvinyl alcohol was dissolved in 16.0 g of water / isopropanol (10: 1, v / v). To this solution was added 1.25 g of conductive black (Super P 6743 Bodio from Timcal, Switzerland), 0.07 g of synthetic graphite (KS6 6743 Bodio from Timcal, Switzerland), and 0.93 g of the sulfur example. 9 sulfur was added and the mixture was stirred until a uniform suspension was obtained. Further, the step of supplying ink and the step of manufacturing the electrode were performed by the same method as described in Example 10.

Example 11:
In order to evaluate the electrochemical properties of the electrodes of Examples 10 and 10a, an electrochemical cell was constructed. Negative electrode: lithium foil having a thickness of 50 μm, separator: Celgard 2340 having a thickness of 38 μm, and the positive electrodes of Examples 10 and 10a described above.

An electrolyte 1M LiTFSI (LiN (SO ₂ CF ₃ ) ₂ ) dissolved in a 1: 1 (v / v) mixture of dioxolane and dimethoxyethane. The battery was charged and discharged using a current of 7.50 mA at a voltage between 1.8 and 2.5. The results are shown in Table 2.

Claims (23)

The carbon phase,
Including one or more pore phases disposed in the carbon phase,
The carbon phase of the particle forms a plurality of substantially co-continuous and irregular phase regions together with the pore phase, and the distance between adjacent phase regions of the pore phase is substantially 50 nm or less. A granular porous carbon material. 0.1 cm ³ / g or more, particularly pores in the proportion of 0.2~1cm ³ / g are as defined in claim 1 having a pore size in the range of 1~5nm measured by BJH nitrogen adsorption method in accordance with DIN66134 Carbon material. Further, 0.1 cm ³ / g or more, claim particular pore ratio of 0.3~2.7cm ³ / g is, with pore diameters in the range of 5~300nm measured by BJH nitrogen adsorption method in accordance with DIN66134 2. The carbon material according to 2. Any one of claims 1 to 3 having a total pore volume in the range of 0.3 to ³ cm ³ / g, particularly 0.5 to 2.9 cm ³ / g, as measured by the BJH nitrogen adsorption method according to DIN 66134. The carbon material according to item. As determined by the nitrogen adsorption method according to DIN ISO 9277, the carbon material according to claim 1 having a BET specific surface area of 200~3000m ² / g.   The carbon material according to any one of claims 1 to 5, which has a weight average particle diameter in a range of 20 nm to 50 µm.   The carbon material according to any one of claims 1 to 6, which has a carbon content of 95% by mass or more based on the total mass of the carbon material. I. A particulate composite material comprising one or more organic polymer phases and one or more inorganic (semi) metal oxide phases, wherein the organic polymer phase P and the inorganic (semi) metal oxide phase are substantially co-continuous. Forming a phase region and supplying a granular composite material having an average distance between adjacent phase regions of the inorganic (semi) metal oxide phase of 50 nm or less;
II. Carbonizing the organic polymer phase of the composite material;
III. Removing the (semi) metal oxide phase by leaching;
The manufacturing method of the granular carbon material characterized by having. In the supply step of the granular composite material in step I,
a) one or more cationically polymerizable organic monomer units;
b) one or more (semi) metals bonded to the cationically polymerizable monomer units via oxygen to form (semi) metal oxides;
The manufacturing method of Claim 8 in which the superposition | polymerization process under cationic polymerization conditions of the 1 or more types of monomer M which has this is included.   The manufacturing method according to claim 9, wherein the (semi) metal is silicon.   The production method according to claim 9 or 10, wherein the one or more monomers M are polymerized in the presence of a particulate (semi) metal oxide.   The production method according to claim 11, wherein the granular (semi) metal oxide is silicon dioxide.   The production method according to claim 11 or 12, wherein the granular (semi) metal oxide has an average particle diameter in the range of 5 nm to 5000 nm.   The method according to any one of claims 11 to 13, wherein the granular (semi) metal oxide is treated with an acid before polymerization.   The granular carbon material obtained by the manufacturing method of any one of Claims 8-14.   The granular carbon material according to claim 15 having the characteristics according to any one of claims 1 to 7.   The method to use the carbon material of any one of Claims 1-7, 15, or 16 for manufacture of an electrochemical cell.   A composite material comprising elemental sulfur and one or more carbon materials according to any one of claims 1 to 7, 15, or 16.   19. A composite material according to claim 18 comprising 1 to 45% by weight of carbon and 55 to 99% by weight of sulfur, based on the total weight of the composite material. Supplying the granular carbon material according to any one of claims 1 to 7, 15, or 16;
Introducing a granular carbon material into a melt of elemental sulfur;
The manufacturing method of the composite material which has this.   The method of using the composite material of Claim 18 or 19 as a positive electrode material in an alkali metal sulfur battery, especially a lithium sulfur battery.   A positive electrode for an alkali metal sulfur battery, in particular a lithium sulfur battery, comprising one or more composite materials according to claim 18.   An alkali metal sulfur battery comprising one or more positive electrodes according to claim 22.

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