Dimer, trimer or polymer containing conjugated salt n - torpedine


C08F136/14 - containing elements other than carbon and hydrogen

 

(57) Abstract:

The invention relates to a material for rechargeable batteries, which is a conjugate dimer, trimer or polymer containing a salt of N-herperidin and having srednekamennogo MM not more than 500,000. Dimer, trimer or polymer is produced by the interaction of pyridine containing dimer, trimer or polymer with fluorine in the mixture of solvents in the presence of acid Bronsted or a salt thereof. This polymer receive a positive active material, the electrolyte material of the positive electrode of the battery. These materials have a high electromotive force, energy density and environmental acceptability, have low internal resistance during charging and discharging and high resilience electromotive force. The polymer is also used as a fluorinating agent. 11 C. and 6 C.p. f-crystals, 5 tab., 9 Il.

The invention relates to a material for rechargeable batteries having a high electromotive force, high energy density and high ecological acceptability, which have a low internal resistance when the electrical charging and discharging and are great for children to dimers, the trimers or polymers containing conjugated salt N-torpedine, as the material of rechargeable battery, the active material for the positive electrode, the electrolyte or the material of the rechargeable batteries used as the active material for the positive electrode and the electrolyte, which is obtained from a polymer containing conjugated salt N-torpedine; the battery, involving the use of such an active material for positive electrode, electrolyte, or material of the battery used as the active material for the positive electrode and the electrolyte; and fluorinating agent.

Rechargeable batteries are a necessary condition for the creation of sources of electrical energy, easily used as a national means of livelihood or as an important energy sources for complex devices. Been researched and developed various types of batteries depending on the required characteristics. Recently found wide spread of wireless electronic devices and, accordingly, took the battery having a high obhodimosti which is caused by the requirement of preserving the environment.

Of rechargeable batteries having a high energy density, are well known to those using lithium or lithium ions on the negative electrode. As a practical active materials for positive electrodes of such batteries are known inorganic compounds as the oxides of heavy metals, such as manganese dioxide, dioxide, cobalt, vanadium pentoxide, aluminum oxide, lithium manganese and lithium oxide of cobalt, iodine, thionyl chloride and fluorinated graphite, and organic polymers, such as polyaniline, polypyrrol and polythiophene. However, such inorganic compounds are associated with a number of problems from the point of view of production of rechargeable batteries, as they are toxic compounds and heavy metals are undesirable from the point of view of the General environment, and because of fluorinated graphite has neither ionic conductivity, electronic conductivity.

The disadvantage of fluorinated graphite is that it is not used for the production of rechargeable batteries. Further, the above-mentioned organic polymers cannot be used as such as materials for the positive electrode, which have a high energy charging.

For the synthesis of the polymer used as the material for the positive electrode, typically use polymerization by electrolysis, but with this method of polymerization of the polymer is formed only on the electrode, which causes great difficulty in the production of materials for the positive electrode of the battery.

In JP-A-178517/1989 described linear poly(pyridine-2,5-diyl), which can be used as the active material for rechargeable batteries. However, as in the case of the above-mentioned conventional organic polymeric materials, linear poly(pyridine-2,5-diyl) cannot be used per se as the active material for positive electrode, which has a high electromotive force, and need a separate phase doping and charging.

As mentioned above, any of the conventional active materials for the positive electrode, which has a high electromotive force and high energy, has a number of disadvantages, and there is therefore a need in the development of active materials for the positive electrode, which can be easily obtained and processed, and which would have a high electromotive, Vapiano, what salt-N-torpedine, represented by the following formula:

< / BR>
and a polymer containing as a suspension of the salt of N-herperidin and described by the following formula:

< / BR>
are excellent materials used as active material for the positive electrode (in the formulas, X-represents a conjugate base of the acid Bronsted). However, in the detailed study it was found that these materials have disadvantages, such as high internal resistance and lack of ability to recover electromotive force after application of the load (see comparative examples 1 and 2 and example 25). In addition, when these materials are used for rechargeable battery capable of charging and discharging, it turned out that the charging current is small due to the high internal resistance during charging (compare the battery of example 26 and comparative example 1). If the magnitude of the charging current is not large enough, charging takes a long time. Therefore there is an urgent need to develop an active material for positive electrode, which would ensure further improvement of performance characteristics of batteries pervi the th as a suspension of the salt of N-torpedine.

Connection, the so-called fluorinating agent, which Porirua chemical compound, is an important material to get used fluorine-containing compounds. However, the above-mentioned salt of N-torpedine or a polymer containing as a suspension of the salt of N-torpedine which is known as the fluorinating agent, unsatisfactory from the point of view of the fluorinating ability and fluorinating efficiency.

In order to solve these problems, the authors of the present invention have conducted extensive studies, based on a new concept of joining two or more structural parts of salt-N-torpedine, and as a result they were able to synthesize the dimers, trimers and polymers containing conjugate salt of N-torpedine, in which electrons can be paired. The result found that such dimers, trimers or polymers can solve the above problems and thus completed the development of the present invention.

The present invention relates to a dimer, trimer or polymer containing conjugated salt N-torpedine, which is an excellent material for the positive electrode of the rechargeable batteries with high nm is observed when charging and discharging and high ability to recover electromotive force; batteries primary cells or rechargeable batteries, providing for the use of such a dimer, trimer or polymer, and fluorinating agent.

In Fig. 1 presents a schematic view in partial section of the battery of the present invention obtained in examples 20-23.

In Fig. 2 presents a schematic view in partial section of the battery of the present invention obtained in example 24.

In Fig. 3 presents a graph showing the ability to recover electromotive force of the battery of example 20, which was measured in example 25.

In Fig. 4 presents a graph showing the ability to recover electromotive force of the battery of example 21, which was measured in example 25.

In Fig. 5 presents a graph showing the ability to recover electromotive force of the battery of example 22, which was measured in example 25.

In Fig. 6 presents a graph showing the ability to recover electromotive force of the battery of example 23, which was measured in example 25.

In Fig. 7 presents a graph showing the ability to recover electromotive force of the battery of comparative example 1, which was and is radieuse power of the battery of comparative example 2, which is measured in example 25.

In Fig. 9 presents a graph showing the change in battery voltage and charging current in one cycle of charging and discharging, which were measured in example 26.

Dimers, trimers or polymers containing conjugated salt N-torpedine, the present invention contain the repeating unit, represented by formula (I):

< / BR>
where adjacent radicals R1and R2, R2and R3, R3and R4or R4and R5can be connected to each other with the formation of CR6=CR7-CR8=CR9- and adjacent radicals R1'and R2'R2'and R3', R3'and R4'or R4'and R5'can be connected to each other with the formation of CR6'=CR7'-CR8'=CR9'- and one of the radicals R1- R9connected by a simple relationship with one of the radicals R1'- R9'and the rest of the radicals R1- R9, R1'- R9'are the same or different and each represents a simple bond, a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxy-carbonyl group, aryloxy different and each represents a conjugate base of the acid Bronsted, m = 1 or the number that provides the above srednecenovogo molecular weight, 1=0 or 1, provided that when m = 1, then 1 0.

In particular, as the halogen atom may be fluorine atoms, chlorine, bromine and iodine. Among them, the fluorine atoms, chlorine and bromine are preferred. As the alkyl group may be an alkyl group containing from 1 to 15 carbon atoms, or the above-mentioned alkyl group, in which at least one hydrogen atom substituted by a hydroxyl group, CNS group having from 1 to 5 carbon atoms, alloctype containing from 6 to 10 carbon atoms, acyl group containing from 1 to 5 carbon atoms, alloctype containing from 1 to 5 carbon atoms, or aryl group containing from 6 to 10 carbon atoms;

as haloalkyl group may be an alkyl group containing from 1 to 15 carbon atoms, in which at least one hydrogen atom substituted by a hydrogen atom;

as the aryl group may be an aryl group containing from 6 to 15 carbon atoms, or the above-mentioned aryl group, in which at least one hydrogen atom substituted by a halogen atom, or an alkyl group containing from 1 to 5 carbon atoms;and the above-mentioned CNS group, in which at least one hydrogen atom substituted by a halogen atom, or aryl group containing from 6 to 10 carbon atoms;

as alloctype can be alloctype containing from 6 to 15 carbon atoms, or the above alloctype, in which at least one hydrogen atom substituted by a halogen atom, or an alkyl group containing from 1 to 5 carbon atoms;

as alkoxycarbonyl group can be alkoxycarbonyl group containing from 2 to 15 carbon atoms, or the above-mentioned alkoxycarbonyl group, in which at least one hydrogen atom substituted by a halogen atom or aryl group containing from 6 to 10 carbon atoms;

as aryloxyalkyl group can batteryaccessory group containing from 7 to 15 carbon atoms, or the above-mentioned aryloxyalkyl group, in which at least one hydrogen atom substituted by a halogen atom, or an alkyl group containing from 1 to 5 carbon atoms;

and as the acyl group may be an acyl group containing from 1 to 15 carbon atoms, or the above-mentioned acyl group, in which at least one hydrogen atom substituted by a halogen atom, which are the cation can be used, for example, compounds with a strong acid, e.g. sulfuric acid and its complex monetary, such as monomethylether and monoarticular; sulfonic acids such as methanesulfonate acid, econsultancy acid, chlorosulfonic acid, persulfonic acid, benzolsulfonat acid, toluensulfonate acid, nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, triftormetilfullerenov acid, trichloromethanesulfonate acid, performancelevel acid and cryptgetuserkey acid, carboxylic acids such as triperoxonane acid and trichloroacetic acid; or compounds of Lewis acids and hydrogen halides), such as HBF4, HPF6, HSbF4, HSbF6, HAsF6, HBC14, HBCl3F, Sb16and HSbCl5F.

The repeating unit represented by formula (I) may be the same or different.

Dimer, trimer or polymer containing conjugated salt N-torpedine, the present invention represent a dimer, trimer or polymer containing as a repeating element salt of N-torpedine represented by the above formula (I). From the point of view of high electric capacity (the Oba content of repeating units was not less than about 50 mol.%, preferably from 60 to 100 mol.%, especially approximately from 70 to 100 mol.%.

Examples of the other recurring units, for example, is the link of aromatic compounds, which are represented by formula (II):

< / BR>
where adjacent radicals R1and R2, R2and R3, R3and R4or R4and R5can be connected to each other with the formation of CR6=CR7-CR8=CR9- simultaneously two of the radicals R1- R9respectively represent a simple bond, and the remaining radicals are the same or different and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group, X-represents a conjugate base of the acid Bronsted, n = 2 or an integer, in which Brednikova molecular weight will not exceed 500000.

Dimer, trimer or polymer containing conjugated salt N-torpedine, the present invention has srednecenovogo molecular weight of not more than 500,000 and has the duplicate link, pricheski nitrile, containing from 2 to 5 carbon atoms, and aliphatic carboxylic acid containing from 1 to 5 carbon atoms, in the presence of acid Bronsted and/or its salts with pyridine containing a dimer, trimer or polymer comprising a repeating unit, of formula (III):

< / BR>
where two of the radicals R1- R5respectively represent a simple bond, and the remaining radicals are the same or different and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group with obtaining a dimer, trimer or polymer containing conjugated salt N-torpedine having a repeating element of the formula (II):

< / BR>
where R1- R5shall have the same meaning as above, X-represents a conjugate base of the acid Bronsted, n = 2 or an integer, wherein the molecular weight will not exceed 500000.

Peridiniaceae polymer which contains a repeating unit, represented by the above formula (III) is used in the quality scale, or connection, easily synthesized by a known method.

Dimer, trimer or polymer containing conjugated salt N-torpedine represented by the formula (I) having srednecenovogo molecular weight of not more than 500,000, can be obtained by the interaction of fluorine in the mixture of solvents, including aliphatic nitrile containing from 2 to 5 carbon atoms, and aliphatic carboxylic acid containing from 1 to 5 carbon atoms, in the presence of acid Bronsted and/or its salts with bipyridinium compound of formula (IV):

< / BR>
where one of the radicals R1- R5connected by a simple relationship with one of the radicals R1'- R5'and the rest of the radicals R1- R5, R1'- R5'are the same or different and each represents a simple bond, a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group, with the formation of dimer, trimer or polymer containing conjugated salt N-torpedine formula (I):

< / BR>
where R1- R9, R1'- R5'have the above znachenie acid Bronsted, m = 1 or the number that provides the above srednecenovogo molecular weight 1=0 or 1, provided that when m = 1, then 1 0.

Dimer, trimer or polymer of the present invention containing a conjugate salt of N-torpedine with srednecenovogo molecular weight of not more than 500,000 and having the repeating unit, represented by formula (II) can be obtained by the interaction of fluorine in the mixture of solvents, including aliphatic nitrile containing from 2 to 5 carbon atoms, and aliphatic carboxylic acid containing from 1 to 5 carbon atoms, in the presence of acid Bronsted and/or its salts with pyridine containing a dimer, trimer or polymer comprising a repeating unit, of formula (III):

< / BR>
where adjacent radicals R1and R2, R2and R3, R3and R4or R4and R5can be connected to each other with the formation of CR6=CR7-CR8=CR9- simultaneously two of the radicals R1- R9respectively represent a simple bond, and the remaining radicals are the same or different and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, alkoxyl is at or acyl group with the formation of the dimer, trimer or polymer containing conjugated salt N-torpedine formula (II):

< / BR>
where R1- R5have the above values, X-represents a conjugate base of the acid Bronsted, n = 2 or an integer, in which Brednikova molecular weight will not exceed 500000.

Dimer, trimer or polymer of the present invention containing a conjugate salt of N-torpedine represented by the formula (I) having srednecenovogo molecular weight of not more than 500,000, can be obtained by the interaction of fluorine in the mixture of solvents, including aliphatic nitrile containing from 2 to 5 carbon atoms and aliphatic carboxylic acid containing from 1 to 5 carbon atoms, in the presence of acid Bronsted and/or its salts with bipyridinium compound of formula (IV):

< / BR>
where the radicals R1and R2, R2and R3, R3and R4or R4and R5can be connected to each other with the formation of CR6=CR7-CR8=CR9- a radicals R1'and R2', R2'and R3', R3'and R4'or R4'and R5'connected to each other with the formation of CR6'= CR7'-CR8'= CR9'- and one of the radicals R1- R9, R1'- R9'are the same or different and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group with the formation of dimer, trimer or polymer containing conjugated salt N-torpedine formula (I):

< / BR>
where R1- R9, R1'- R9' have the above values, X-and X-'are the same or different and each represents a conjugate base of the acid Bronsted, m = 1 or the number that provides the above srednecenovogo molecular weight, 1=0 or 1, provided that when m = 1, then 1 0.

Peridiniaceae polymer can be obtained by polymerization of one or more types of compounds developedin or copolymerization of compounds developedin with copolymerizes with him monomer.

Examples of compounds developedin are, for example, 2,6-dichloropyridine, 2.5-dichloropyridine, 2,4-dichloropyridine, 3,5-dichloropyridine, 2,6-dibromopyridin, 3,5-dibromopyridin, 2.5-dibromopyridin, 2,6-diacritically, dichlorotrifluoroethane, dichloro(methyl)pyridine, dibromo(methyl)pyridine, dibromo(dimethyl)pyridine, dibromo(hexyl)pyridine, dichloro(trifluoromethyl)pyridine, dibromo(methoxy)pyridine, bromo(phenyl)pyridine, dibromo(phenoxy)pyridine, dibromo(methoxycarbonyl)pyridine, 5,8-dibromophenol, 5,8-dichlorohydrin, 4,7-dibromophenol, 1,4-dibromophenol, 1,4-dichlorethylene etc.

Examples copolymerizing monomers are halogen-substituted aromatic compounds that give the duplicate link aromatic compounds represented by the above formula (II) and which represents a benzene, naphthalene, pyrrole, thiophene or furan, which has at least two halogen atom and may be substituted by at least one alkyl group. Examples of halogen-substituted aromatic compounds are, for example, debrabant, dichlorobenzene, divodasa, dibromsalan, Dichlorotoluene, dibromsalan, dichloronaphthalene, debromination, depomedrol, dibromothiophene, dibromofuran etc.

The above-mentioned polymerization or copolymerization can be carried out in a known manner (cf., for example, Macromolecules, 27, 756(1994), J. Am. Chem. Soc. , 116, 4832(1994), Journal of Synthetic Organic Chemistry, Japan, 51, 795(1993), Synth. Met., 53, 1214(1993), J. Chem. Soc., Perkin Transactio 23(1983), Bull. Chem. Soc. Jpn., 51, 2091(1978)).

Among peridiniaceae polymers containing repeating unit, represented by the above formula (III), piperidinomethyl polymer containing a repeating unit, represented by formula (V)

< / BR>
where R1and R2, R2and R3or R3and R4can be connected to each other with the formation of CR5= CR6-CR7= CR8-, R1'and R2', R2'and R3'or R3'and R4'can be connected to each other with the formation of CR5'=CR6'-CR7'=CR8'- one of the radicals R1- R8and one of the radicals R1'- R8'at the same time represent a simple bond, respectively, and the remaining radicals have the same or different values and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group, can be obtained by polymerization, for example, one or more types of halogen-substituted compounds of bipyridyl represented by the formula (Va)

< / BR>
where the radicals R is of CR15=CR16-CR17=CR18- a radicals R11'and R12', R12'and R13'or R13'and R14'can be connected to each other with the formation of CR15'= CR16'-CR17'= CR18'- and at least one of the radicals R11- R18represents a halogen atom, and at least one of the radicals R11'- R18'represents a halogen atom, and the remaining radicals are identical or different and represent a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group. In another embodiment, piperidinomethyl polymer containing a repeating unit, represented by formula (V) may be obtained by copolymerization of at least one type of the above-mentioned halogen-substituted compounds of bipyridyl with at least one other type of the above-mentioned monomer copolymerization.

Examples of halogen-substituted compounds of bipyridyl represented by the above formula (Va) are, for example, compounds such as 5,5'-dichloro-2,2'-beerel, 5,5'-dibromo-2,2'-BIPM(hexyl)bipyridyl, dibromobiphenyl, dibromobis(trifluoromethyl)bipyridyl, dibromobiphenyl, 4,4'-dibromo-2,2'-biginelli, 6,6'-dibromo-2,2'-biginelli, 4,4'-dibromo-1,1'-biskinis etc.

In addition, from among pyridine containing polymers containing repeating unit, represented by formula (III), pyridine containing polymer which has a structure of CR6=CR7-CR8=CR9is formed in the connection of the radicals R1and R2, R2and R3, R3and R4or R4and R5can also be obtained by polymerization of one or more types of aniline derivatives represented by the formula (VI)

< / BR>
where the radicals R21and R22are the same or different and represent a halogen atom, alkyl group, haloalkyl group or aryl group, the radicals R23, R24and R25are the same or different and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, or alloctype. The polymerization process can be carried out in a known manner (cf Macromolecules, 14, 870(1981)).

The end part of the polymer chain, which contains the Holocene pyridine containing polymer, containing repeating unit, represented by formula (III), and piperidylidene polymer containing a repeating unit, represented by formula (V). For example, the end part of the polymer containing a repeating element of the formula (I) and synthesized using materials obtained by polymerization developedinto connection, usually represents a hydrogen atom or a halogen atom. In addition, the end part of the polymer containing a repeating element of the formula (I) and synthesized using materials obtained by copolymerization developedinto connection with decalarations compound capable of copolymerization with the first usually contains an aromatic group or haloaromatic group, in addition to hydrogen atom or halogen atom.

In addition, the end part of the polymer containing a repeating element of the formula (I) and synthesized using materials obtained by polycondensation aniline derivative represented by the formula (VI), contains an acyl group, an amino group or derived from the group. In the case when such polymerization using a catalyst or similar, there is also the case when the end gr duplicate link represented by formula (I) receive the result of the interaction of pyridine containing polymer containing a repeating unit, represented by formula (III), or piperidinomethyl polymer containing a repeating unit, represented by formula (V), fluorine (F2in the presence of acid Branstad, and/or salts of acid Branstad, and/or Lewis acid. Because fluorine, by its nature, is very reactive, there is a high probability of occurrence of side reactions, such as fluoridation, due to the high reactivity of fluorine. For this reason, the fluorine atom as a result of the reaction of fluorination may be substituted or may be attached not only to limit the group, but also to the structure of pyridine, forming the main chain of the polymer substitution group structure of pyridine or above the level of aromatic compounds contained as a repeating element.

Next, containing salt of N-torpedine polymer of the present invention may be such that it will be the lowest polymer represented by the formula (VII)

< / BR>
where the radicals R1and R2, R2and R3, R3and R4or R4and R5can/SUP>, R2'and R3', R3'and R4'or R4'and R5'can be connected to each other with the formation of CR6'= CR7'-CR8'= CR9'one of the radicals R1- R9connected by a simple relationship with one of the radicals R1'- R9'and the remaining radicals R1- R9, R1'- R9'are the same or different, and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group, X-and X'-are the same or different and each represents a conjugate base of the acid Branstad. The connection of bipyridyl, which is a starting material to obtain such a polymer represented by formula (VIIa)

< / BR>
where the radicals R1and R2, R2and R3, R3and R4or R4and R5can be connected to each other with the formation of CR6=CR7-CR8=CR9- a R1'and R2', R2'and R3', R3'and R4'or R4'and R5'can be connected to each other with education is one of the radicals R1'- R9'and the rest of the radicals R1- R9, R1'- R9'are the same or different and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group, can be obtained by the reaction of one or more types of compounds pyridine represented by the formula (VIIb):

< / BR>
where the radicals R1"and R2", R2"and R3", R3"and R4"or R4"and R5"can be connected to each other with the formation of CR6"=CR7"-CR8"=CR9"- no, at least one of the radicals R1- R9represents a hydrogen atom or halogen atom, and the others are the same or different and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group.

The process of dimerization can be carried out in a known way (for example, Synthesis, 73 is Eesa link represented by formula (III) or (V), and the connection of bipyridyl represented by formula (VIIa), can be transformed into another polymer containing a repeating unit, represented by formula (III) or (V), and another connection of bipyridyl represented by formula (VIIa), respectively, using one of the known methods of organic chemistry, such as halogenoalkane, alkylation, oxidation, nitration, acylation, alkoxysilane, aryloxyalkanoic, alkoxycarbonylmethyl or aryloxypropanolamine. Conversely, substitution group duplicate link represented by formula (III) or (V), or substitution group of the formula (VIIa) can be transformed into another substitution group as a result of transformation by ordinary chemical reactions (cf., for example, Synthetic Comm., 9, 497(1979), J. Am. hm. S. , 80, 2745(1958), J. Pharm. Soc. Jpn., 75, 731(1955), J. Pharm. Soc Jpn., 75, 733(1955).

Containing conjugated salt N-torpedine polymer represented by the above formula (VII) can be obtained by the interaction of compounds of bipyridyl formula (VIIa) with fluorine in the presence of acid and/or salt, for example, acid Bronsted and/or salts of acid Bronsted and/or Lewis acid.

Fluoride, use the link represented by formula (I), or containing a conjugate salt of N-torpedine polymer of the formula (VII) can be used without dilution. Usually, in order to regulate the intensity of the reaction it is preferable to use gaseous fluorine, diluted with any inert gas, so that the amount of inert gas amounted to 99.9-50%. Examples of such inert gases are nitrogen, helium, argon, terraformer, sulfur hexafluoride, etc.

Examples of the acid Bronsted used to retrieve containing conjugated salt N-torpedine polymer containing a repeating unit, represented by formula (I), or containing a conjugate salt of N-torpedine polymer of the formula (VII) are compounds having a high acidity, for example, sulfuric acid and its complex monoether, such as monomethylether and monoarticular; sulfonic acids such as methanesulfonate acid, econsultancy acid, chlorosulfonic acid, persulfonic acid, benzolsulfonat acid, toluensulfonate acid, nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, triftormetilfullerenov acid, trichloromethanesulfonate acid, performancelevel acid and triflora compounds of Lewis acids and hydrogen halides), such as HBF4, F6, HSbF4, SbF6, HAsF6, NWS4, NWS3F, HSbCl6and HSbCl5F. These acid Bronsted can also be used in the form of complex compounds with simple ether, sulfide, alcohol, water, nitrile, carboxylic acid, etc.

Examples of salt-based acid Bronsted used in the above process of obtaining, are various metal salts of the aforementioned acids Branstad and various ammonium salts and postname salts of the aforementioned acids Branstad. From the point of view of economy and efficiency of the reaction, alkali metal salts such as sodium salt, lithium salt and potassium salt, and various ammonium salts such as methylammonium salt, dimethylammonium salt, trimethylammonium salt, ethylammonium salt, triethylammonium salt, Tetramethylammonium salt, tetraethylammonium salt, butyl-ammonium salt, tetrabutylammonium salt and benzyltrimethylammonium salt are preferred.

Examples of the Lewis acid, it is acceptable to be used when retrieving containing conjugated salt N-torpedine polymer containing a repeating unit, represented by formula (I), or containing the SOP is, F3PF5, SbF3, SbF5, SbCl5, sF3, s13AsF5, AsCl5, SO3etc. These Lewis acid can also be used in the form of complex compounds with simple ether, sulfide, alcohol, water, nitrile, carboxylic acid, or etc.

If acid Bronsted, salt acid Bronsted or the Lewis acid used in the above process of obtaining, is a volatile liquid or can be prepared in the form of a volatile liquid, it can also be used as solvent, and in this case, the solvent is not always necessary. However, in order to obtain the target products in high yields under mild reaction conditions, it is generally preferable to use a solvent. Examples of solvents used for this purpose are, for example, NITRILES such as acetonitrile and propionitrile, fluorine-containing alcohols, such as triptorelin, tetrafluoropropanol, hexafluoroisopropanol and nonattitudinal; carboxylic acids such as formic acid, acetic acid and propionic acid, percarbonate acid, such as triperoxonane acid and pentafluoropropionic acid; Feria or Lewis acid will typically be selected so as to the number of molecules of acid or salt was not less than 0.5 of one nitrogen atom in the repeating part of the above formula (III) or a pyridine structure of formula (VIIa). To carry out the reaction with a high yield, it is preferable that the number of molecules of acid or salt was not less than 0.8, and in order to obtain the target product is more economical, it is preferable that the number of molecules of acid or salt lay in the range of 0.8 to 1.5. In the case of different combinations using acid Bronsted, salt acid Bronsted and the Lewis acid, the total number of molecules is the same as that described above.

With regard to the number of fluorine, it is generally preferable that it's made up of one or more molecules of fluorine on one nitrogen atom in the repeating part of the above formula (III) or a pyridine structure of formula (VIIa). The optimal number can not necessarily to choose, depending on conditions such as the method of introducing fluorine into the reactor, the reaction temperature, the type of reaction solvent and reactor from the point of view dissipation compounds in the reaction with fluorine.

When implementing the present invention as a method of obtaining containing conjugated salt N-torpedine di is agenoy salt N-torpedine polymer of the formula (VII) with a high degree of purity, high yield and high efficiency, it is preferable that the fluorine interacted with pyridine containing polymer containing a repeating element of the formula (III), or a combination of bipyridyl formula (VIIa) in the presence of acid and/or salt in a mixed solvent containing

aliphatic nitrile having from 2 to 5 carbon atoms, and aliphatic carboxylic acid having 1-5 carbon atoms.

Examples of aliphatic NITRILES containing from 2 to 5 carbon atoms, are, for example, acetonitrile, propio-nitrile, butyronitrile, valeronitrile, isovaleramide, etc., Particularly preferred is acetonitrile.

Examples of aliphatic carboxylic acids containing from 1 to 5 carbon atoms, are, for example, formic acid, acetic acid, propionic acid, butyric acid, somalina acid, valeric acid, trimethylhexane acid, Chloroacetic acid, dichloracetic acid, trichloroacetic acid, triperoxonane acid, etc. From them formic acid and acetic acid are particularly preferred.

Preferably, the volume ratio of aliphatic nitrile and aliphatic carboxylic acid (alipac the>Example of the acid or salt is the above-mentioned acid Bronsted, its salt or Lewis acid. Especially preferred is an acid Bronsted or Lewis acid. Preferably, the number of molecules of acid or salt ranged from 0.8 to 1.2, especially from 0.9 to 1.1, more preferably from 0.95 to 1.0 on one nitrogen atom in the repeating part of the formula (III) or a pyridine structure of formula (VIIa). In the case of joint use of acid and salt, the total number of molecules is the same as that described above.

The reaction temperature can be selected from the range in the range from -80oC to +40oC. From the viewpoint of improving the yield of the reaction range from -60oC to +30oWith is preferable, and from -30oWith up to room temperature - even more preferred.

In the above method of obtaining, when, for example, pyridine containing polymer containing the recurring element of the formula (III), coexists with acid Bronsted, as shown in the following formula, the acid Bronsted (HX) calls the acid-basic reaction occurring wholly or partially, according to the basicity of the pyridine nuclei, in which is formed an N-hydropyridine salt (see scheme I).

Therefore, as containing conjugated salt N-torpedine polymer containing a repeating element of the formula (I) receive the result of the interaction of pyridine containing polymer containing the recurring element of the formula (III), fluorine (F3in the presence of acid Branstad, and/or salts of acid Branstad, and/or Lewis acid, at a time when the reaction is not completed, the polymer contains the repeating unit formula (III) link, represented by the following formula (b):

< / BR>
or when using a Lewis acid (V), the polymer contains the repeating unit, represented by formula (III), the link of the formula (b) and/or link of the formula (C)

< / BR>
The present invention also relates to the battery, providing use containing conjugated N-ftorpirimidinu salt of a polymer containing a repeating unit, represented by formula (I), or containing a conjugate salt of N-torpedine polymer of the formula (VI link represented by formula (I), or containing a conjugate salt of N-torpedine polymer of the formula (VII) represents an excellent active material for positive electrode, which has a high electromotive force, high energy density and high environmental acceptability is low on the measure of internal resistance during charging and discharging, and has a good ability to recover electromotive force. In addition, the polymer of the present invention is used as the electrolyte because it has a salt structure and thus is also used as the material of the battery used as the active material for the positive electrode and the electrolyte.

Dimer, trimer or polymer of the present invention, being used as the active material for positive electrode, interacts with the negative electrode, such as lithium, zinc, magnesium, etc. and on its surface is formed a protective film comprising a metal fluoride. With such formed a protective film battery can stably be stored for a long time without short circuit and virtually no self-discharge. is th structure, and when flows electrochemical reaction with the active material (metal) of the negative electrode, metal ions diffuse into the polymer of the present invention to form an ion-conductive compound of the metal. Thus, even if the above electrochemical reaction proceeds, persists ionic conductivity. Therefore, the polymer of the present invention can also be used as an excellent solid electrolyte.

Next, an explanation of the preferred structures of the batteries requires the use of a containing a conjugate salt of N-torpedine dimer, trimer or polymer containing a repeating unit, represented by formula (I), or containing a conjugate salt of N-torpedine dimer, trimer or polymer of formula (VII), but the scope of the claims of the present invention is not limited to them.

(1) In the case of a battery, which is used containing a conjugate salt of N-torpedine dimer, trimer or polymer of the present invention as the active material for positive electrode.

[Preparation of positive electrode]

When the polymers of the present invention are in powder form, trebuia the resources and conductive agent and give them the necessary configuration together with tokenisation by pressing.

As a binder is preferably used, for example, a conventional binder, such as poly(tetrafluoroethylene) powder, carboxymethyl cellulose and poly(vinyl alcohol), and as a conductive agent preferably used, for example, powdered metals, such as powdered Nickel, powdered platinum; various thin metal fibers; various carbonaceous materials such as carbon fiber, pitch, tar, various types of carbon black such as acetylene carbon black, and graphite such as natural graphite, artificial graphite and primary graphite.

As econimies for the positive electrode is preferably used, for example, various carbon materials such as carbon fiber, pitch, tar, various types of carbon black such as acetylene carbon black, and graphite such as natural graphite, artificial graphite and primary graphite; mesh, perforated metal, expanded metal, mesh, metal fiber or similar, derived from platinum, gold, Nickel, stainless steel, iron, copper or similar to get a cheap battery with high aimery of the present invention is able to be molded in blankaartia materials, or when such polymers are capable of forming in plenkoobrazovatel material with a film-forming agent, of them as such receive a film or, if necessary, they are mixed with a binder and a conductive agent, or the ingredients listed below, and receive plenkoobrazovatel material, which is then processed in the positive electrode in combination with tokenisation. As film-forming agent are preferred, for example, such polymers as poly(ethylene oxide), poly(ethylene), poly(tetrafluoroethylene), poly(vinyl acetate), poly(Acrylonitrile) and poly(methyl acrylate) or gelatin.

In addition, these polymers can be used in a mixture with other known active materials for positive electrodes.

[Electrolyte]

The electrolyte may be used any conventional electrolyte, regardless of whether it is liquid or solid. Preferred liquid electrolytes are, for example, ethylene carbonate resulting, propylene carbonate, sulfolane, methylsulfone, dimethylsulfone, -butyrolactone, 1,3-dioxolane, 2-methyltetrahydrofuran, simple, diethyl ether, tetrahydrofuran, dimethoxyethane, acetonitrile, etc., Koya, hexafluoroantimonate lithium, hexaflurophosphate lithium triftorbyenzola lithium, etc., polymer electrolyte is, for example, vysokoosnovnymi nonaqueous gel electrolyte, and solid electrolytes are, for example, triftorbyenzola lithium, etc.

The battery requires the use of a liquid electrolyte, usually called a liquid electrolyte battery and a battery, in which, in particular, uses an organic solvent as a liquid electrolyte, is called non-aqueous liquid electrolyte battery. Battery using a solid electrolyte, called a solid electrolyte battery.

[Negative electrode]

As the negative electrode can be used, for example, lithium, aluminum, zinc, lithium alloy, magnesium and copper, which are used traditionally.

[Separator]

When using the separator, it is possible to approve, for example, the use of woven material, nonwoven material, etc., polyamide, polypropylene or similar, which are used traditionally.

The above elements can be assembled into the battery in the usual way.

(2) In the case of batteries, Pius solid electrolyte.

[Electrolyte]

Various forms of solid electrolyte can be obtained in the same manner as in the manufacture of the positive electrode in the above paragraph (1), except that it is not used with a conductive agent and economical.

[Positive electrode]

For the positive electrode can be used conventional active materials. This is, for example, oxides such as MnO2Ag2CrO4, SO2, ADO, PbO2, NiOOH, CuO2and V2O5simple substances, such as C12and Br2and halides, such as SOCl2and SO2Cl2. The positive electrodes produced in the usual way.

[Negative electrode]

The same as in paragraph(1) above.

[Separator]

In principle, the separator is not necessary. When the strength of molded parts made of a material of a battery used in the present invention, is insufficient, or when there are concerns about instability with long-term use, you can use the separator referred to in paragraph (1).

The battery can be assembled in the usual way, using the above positive electrode, negative ele is providing for the use of containing conjugated salt N-torpedine polymer of the present invention for the positive electrode, which is used as an active material for the positive electrode and the electrolyte.

[Positive electrode, which is used as an active material for positive electrode, and the electrolyte]

In the case when the same polymer of the present invention is used as the active material for the positive electrode and the electrolyte, the positive electrode may be made in accordance with the fact, as indicated above in paragraph (1). In this case, can be used with a conductive agent. Economical for the positive electrode is the same as described for the positive electrode in the above paragraph (1). When the positive electrode and the electrolyte used contains various mating salt N-torpedine polymers, the positive electrode can be obtained similarly as described in paragraph (1) or (2) above.

[Negative electrode]

Same as (1) described above.

[Separator]

Since the interface between the electrolyte of the present invention and the negative electrode does not occur under conditions of short circuit due to the formation of operator, referred to in paragraph (1).

When the same polymer of the present invention is used for the positive electrode, which was used both to obtain the active material for the positive electrode and the electrolyte, the battery can be collected in the usual way, without installing a separator between the electrolyte and the negative electrode and, if necessary, the separator can be installed. In the case where the polymer of the present invention, which is different from the polymer used as the active material for the positive electrode used for the manufacture of the electrolyte, the battery can be collected as described above in paragraph (2).

In any of paragraphs (1), (2) and (3) mentioned above, since the battery may be completely solid type, there are many cases when it can be used even at a temperature of, for example, not less than 100oWith no leaks.

In addition to containing conjugated salt N-torpedine polymers in the mixture can be introduced one or more types of polar compounds. Battery having low internal resistance, can be obtained by mixing 0.1 to 60% by weight, preferably 0.5 to 50% by weight, more predpochtitelnye connection is low or high melting point, the battery is used as the battery, keeping the battery features a completely solid type. As polar compounds can be used, for example, polar organic compounds, such as dimethyl sulfone, dimethylcarbonate, diphenylsulfone, methylphenylsulfonyl, 1,3-dioxolane, -butyrolactone, sulfolane, ethylene carbonate resulting, propylene carbonate, dimethyl simple broadcast tetraethyleneglycol, simple, dimethyl ether of triethylene glycol, simple, dimethyl ether of diethylene glycol, dimethoxyethane, ethylene glycol, ethanol, methanol, simple, diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, nitromethane, nitroethane, nitrobenzene, dinitrobenzene, trinitrobenzene, chlorodinitrobenzene, forminitrazole, acetonitrile, propionitrile, benzonitrile, triftorbyenzola pyridinium, tetrafluoroborate pyridinium, hexaflurophosphate pyridinium, hexafluoroarsenate pyridinium, hexafluoroantimonate pyridinium, tetrafluoroborate 2,6-dichloropyridine, tetrafluoroborate 3,5-dichloropyridine, tetrafluoroborate 2,4,5-trimethylpyridine, lithium methanesulfonate, bansilalpet lithium, toluensulfonate lithium methanesulfonate sodium, potassium methanesulfonate, polyphenylsulfone lithium polystyrenesulfonate lithium formate, lithium acetate if Torbert lithium hexaphosphate lithium, hexafluoroarsenate lithium hexafluoroantimonate lithium, lithium perchlorate, lithium chlorate, perbromic lithium, periodate lithium, lithium sulfate, acid sulfate, lithium, trichloracetic lithium, triptorelin lithium, lithium phosphate, lithium nitrate, lithium carbonate, acid lithium carbonate, tetrachloroaluminate lithium, lithium silicate, sodium perchlorate, potassium perchlorate, triftorbyenzola ammonium, tetrafluoroborate ammonium, ammonium chloride, triftorbyenzola sodium, triftorbyenzola potassium, triftorbyenzola zinc, tetrafluoroborate zinc, triftorbyenzola magnesium, tetrafluoroborate magnesium and water; and their mixtures.

The present invention also relates to the use of containing conjugated salt N-torpedine polymer of the present invention as a fluorinating agent. The connection is subject to fluoridation, can be an inorganic compound or organic compound, when this organic compound is preferred. Examples of organic compounds are, for example, compounds of any type, such as saturated aliphatic compounds, unsaturated aliphatic compounds, aromatic compounds, condensed aromaticheskiye, containing a heteroatom, an aromatic compound containing a heteroatom, organic metal compounds, organic polymers, etc., From them, particularly preferred are nucleophilic organic compounds.

Paired dimer, trimer or polymer of the present invention is obtained by fluorination of the corresponding dimer, trimer or polymer containing pyridine ring. To obtain a dimer, trimer or polymer containing a salt of N-torpedine, it is not necessary to polimerizuet monomer containing a salt of N-torpedine, and will polimerizuet pyridine containing monomer and further foryouth received dimer, trimer or polymer in accordance with the stated methods.

Further, the essence of the present invention is explained using the example of s, which do not limit the scope of its claims.

EXAMPLE 1

Bis(triftorbyenzola)-N, N'-debtor-4,4'-bipyridine (0.5 mmol) or triftorbyenzola N-torpedine (1 mmol) was added to a stirred solution of 2-acetylcyclohexanone (1 mmol) in acetonitrile (2 ml). Each reaction was carried out at the boiling temperature under reflux in a nitrogen atmosphere and the course of its flow was controlled by solution the dependence on reaction time are presented in table. 5. The values of the outputs of 2-acetyl-2-forcecoercion determined, spending19F-NMR of the reaction mixture using torbenson as an internal standard. The results are presented in table. 5.

EXAMPLE 2

After cooling mortar 937 mg (6 mmol) of 2,2'-bipyridyl, 2,08 ml (12 mmol) of complex simple ether and terraforming acid (85% HBF4Et2O) and 100 ml of acetonitrile in a bath to -20oWith a gaseous mixture consisting of 10% F2and 90% N2(% by volume) were added at 50 ml/min in the mortar mixture with intensive stirring. When the amount of the fluorine (F2) reached a total of 43.7 mmol, introduction of fluorine finished and missed only nitrogen gas to remove the remaining fluorine. Then the reaction system was heated to room temperature. After the condensation of a fallen precipitated crystals were filtered and got to 1.99 g (Yield: 90%) of bis-(tetrafluoroborate) N, N'-debtor-2,2'-bipyridine, which is then purified by means of recrystallization from a mixture of acetonitrile - simple broadcast and received 1.50 g (Yield: 68%) of crystals. The results of the study and the physical properties of the obtained product are shown in table. 1 and 2.

EXAMPLES 3-14

The same methodology as that described Soli acid Bronsted, the Lewis acid, solvent and fluorine, which are presented in the table. 1, resulting in a received various polymers containing conjugated salt N-torpedine. At the stage of further processing of the reaction, when the product is not knocked out of the reaction solution, the solvent of the reaction are condensed or evaporated to dryness under reduced pressure in the usual way or, if necessary, was carried out by crystallization or so on, resulting in a target product. The conditions of the reaction and the results obtained are presented in table.1, and the physical properties of the product are presented in table. 2.

Poly(pyridine-2,5-diyl), which is the material used in example 14 as a spin-off of pyridine containing polymer was synthesized from 2,5-dibromopyridine as follows.

The stirring of a mixture of 2,5-dibromopyridine (6,33 mmol), bis(1, 5cyclooctadiene) Nickel (0) (6,33 mmol), 1,5-cyclooctadiene (6,33 mmol) and triphenylphosphine 12.6 ml of N,N-dimethylformamide at 60oWith over 22 hours led to the formation of precipitates poly(2,5-pyridinyl) brown. The precipitates were washed sequentially with hot toluene, warm aqueous solution (pH 3) EDTA, warm water dissolve mg of poly(2,5-pyridinyl).

Poly(2,5-pyridinyl) (344 mg) and pentaploid antimony (968 mg, 4,47 mmol) in 50 ml of acetonitrile were placed in the flask of the apparatus for the fluorination. Downloaded the flask was purged with N2and placed in a cooling bath with a temperature of -20oC. a Gas mixture of 10%F2-90%N2(volume/volume) was injected directly above the surface of the rapidly stirred reaction mixture at a flow rate of 30 ml/min is Used, the number of F2was 22.5 mmol. After cessation F2through the flask for 10 minutes allow only N2at a flow rate of 20 ml/min. the Reaction mixture was evaporated to dryness under reduced pressure, and the residue was washed Et2O obtaining of 1.87 g of pure poly(N-torpedine hexafluoroantimonate-2,4-Diil).

EXAMPLE 15

After the introduction of 7.23 mmol of the complex of boron TRIFLUORIDE, acetonitrile (CH3NF3) in 7.4 ml of a solution of a mixture of acetonitrile and formic acid (volume ratio: 98/2) added 3,71 mmol 4,4'-bipyridyl. Then this solution the reaction mixture is cooled in a bath to 0oWith and introduced the gas mixture of 10% F2/90% N2(% by volume) at a rate of 30 ml/min under conditions sufficient mixing. When the amount of the fluorine (F2) DOS is brasego fluorine. Then the reaction system was returned to room temperature. The solvent was distilled from the solution of the reaction product under reduced pressure, then dried under vacuum and received bis(tetrafluoroborate) N,N'-debtor-4,4'-bipyridine having a purity not less than 99%, with a yield of 96%. As an impurity traces of bis-(tetrafluoroborate) N,N'-dihydro-4,4'-bipyridine. The identification and purity was carried out by comparing the spectrum of the obtained product with spectra of standard. The results obtained are presented in table. 3.

EXAMPLES 16-20

The same operations as described in example 15 was carried out using a polymer containing conjugated pyridine, acid, fluorine and mortar, which are presented in the table. 3. The crystals obtained by distillation of the solvent from the solution of the reaction product was washed with ethyl acetate and dried under reduced pressure. Reaction conditions and results are presented in table. 3. When the degree of purity of the product was less than 100%, as an impurity contained bis(tetrafluoroborate) N,N'-dihydro-4, 4'-bipyridine.

EXAMPLES 21-24

(Manufacturing of batteries using a polymer containing conjugated salt N-torpedine, as in the usual way using each of the components of the battery, shown in the table. 4, and Nickel mesh as econimies for the negative electrode.

In Fig.1 shows a schematic partial section of the obtained battery. The values of the electromotive force, the internal resistance and electric capacity of the battery are shown in table. 4.

In Fig. 1 number 1 is output to the negative electrode (stainless steel), the number 2 represents lithium (the active material for the negative electrode), the number 3 refers to the Nickel mesh, the number 4 represents an insulating gasket, the number 5 represents a separator and an electrolyte, the number 6 represents the container for the positive electrode (stainless steel), the number 7 represents the carbon plate, and the number 8 means the material of the positive electrode. Nickel mesh 3 (diameter 12 mm x 0.03 mm thickness) was installed between the carbon sheet 7 and the positive electrode container 6, to retain between them a high electrical conductivity.

COMPARATIVE EXAMPLES 1 and 2

Lithium button battery type was manufactured in the same manner as in example 21, in the form of a battery using salt N-torpedine, the options battery shown in the table. 4, and Nickel mesh as econimies for the negative electrode. The values of the electromotive force, the internal resistance and electric capacity of the battery are shown in table. 4. Comparing examples 21-24 with comparative examples 1 and 2, it was found that the battery using a polymer containing conjugated salt N-torpedine, has a lower internal resistance compared to the rechargeable battery, which used salt N-torpedine, which is a monomer, or poly[2-vinyl-(N-terpiridina salt], which is the lateral suspension of the polymer containing a salt of N-torpedine.

EXAMPLE 25

(Getting the battery using the material of the battery, comprising a polymer containing conjugated salt N-torpedine, which is used as an active material for the positive electrode and solid electrolyte)

Tablets with a diameter of 16 mm were obtained from 100 mg of a homogeneous mixture of bis(tetrafluoroborate) N, N'-debtor-4,4'-piperidine obtained in example 5, LiBF4and 3-methyl-sulfolane (the mass ratio of 6.6:3,4:1 on the molding press (1 t/cm2). Then made accumulates battery to the positive electrode, carbon as econimies for the positive electrode (14 mm diameter x 0.1 mm), lithium as the negative electrode (15 mm diameter x 0.38 mm) and Nickel mesh as econimies for the negative electrode (12mm diameter x 0.03 mm). Electromotive force obtained battery amounted to 3.58 B internal resistance of 26 ohms. In Fig. 2 presents a schematic view in partial section of this battery.

In Fig.2 number 1 means output for the negative electrode (stainless steel), the number 2 means lithium (the active material for the negative electrode), the number 3 refers to the Nickel mesh, number 4 denotes an insulating gasket, the number 6 indicates a container, a positive electrode (stainless steel), the number 7 means a carbon plate and the number 9 means the material of the battery to the positive electrode. Nickel mesh 3 (12 mm diameter x 0.03 mm thickness) was installed between the carbon plate 7 and the positive electrode container 6, to retain between them a high conductivity.

EXAMPLE 26

(Comparison of recoverability electromotive force)

As shown in Fig. scientists in examples 21-24, implemented a discharge at a load of 10 kω for 1 min (Fig. 3-8). Then the circuit is again opened (Fig .3-8), and traced the voltage changes approximately every 2 C. Similarly, tests were carried out of the rechargeable batteries obtained in comparative examples 1 and 2. The obtained results are presented graphically (Fig. 3-8).

As can be seen from Fig. 3-8, the ability to recover electromotive force after discharge significantly better with rechargeable batteries that use a polymer containing conjugated salt N-torpedine compared with the rechargeable battery, which used salt N-torpedine, which is a monomer, or a polymer containing as a side pendants salt N-torpedine.

EXAMPLE 27

Experiments on charging and discharging was performed on the batteries of example 22 and comparative example 1. Repeated discharge under conditions of constant resistance at 110 kω for 5 h, and then charge at the constant voltage of 4.3 and 4.5 B, respectively (charging was performed at a constant current of 140 mA until the voltage of 4.3 or 4.5 (B). In Fig.9 shows one such cycle.

When comparing the curve of the charging-razradi-4,4'-bipyridine, which is a polymer containing a conjugated salt N-torpedine, the charging voltage is lower and the degree of charging more than monomer: tetrafluoroborate N-torpedine. High voltage charging causes the decomposition of the electrolyte and significantly shortens the life of the battery as the battery. Therefore, the polymer containing conjugated salt N-torpedine, the present invention becomes excellent material for rechargeable batteries than monomer: salt N-torpedine.

EXAMPLE 28 and COMPARATIVE EXAMPLE 3

The connection shown in the table. 5, ferromoly under the reaction conditions shown in the same table, when using a fluorinating agent, shown in the same table. The output obtained fluorinated product and the value of the chemical shift19F-NMR (internal standard F13in CD3CN) are presented in table. 5.

As can be seen from the table. 5, the fluorinating agent of the present invention can provide a fluorination process with a high yield and short duration of response compared with comparative example 3, and is excellent in its fluorinating ability and effectiveness of fluoridation.

1. Dimer, trimer or polymer containing conjugated salt N-torpedine with srednecenovogo molecular weight of not more than 500,000; and specified dimer, trimer or polymer contains a conjugate salt of N-torpedine, comprising, essentially, a recurring element of the formula (I)

< / BR>
where adjacent radicals R1and R2, R2and R3, R3and R4or R4and R5can be connected to each other with the formation of CR6= CR7-CR8= CR9- and adjacent radicals R1'and R2', R2'and R3', R3'and R4'or R4'and R5'can be connected to each other with the formation of CR6'= CR7'-CR8'= CR9'- and one of the radicals R1-R9connected by a simple relationship with one of the radicals R1'-R9'and the rest of the radicals R1-R9, R1'-R9'are the same or different and each represents prlog group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group;

X-and X-'are the same or different and each represents a conjugate base of the acid Bronsted;

m represents 1 or number that provides the above srednecenovogo molecular weight;

l = 0 or 1, provided that when m= 1, then l 0.

2. Dimer, trimer or polymer under item 1, characterized in that the dimer, trimer or polymer consists essentially of at least one repeating unit, represented by formula (II)

< / BR>
where adjacent radicals R1and R2, R2and R3, R3and R4or R4and R5can be connected to each other with the formation of CR6= CR7-CR8= CR9- simultaneously two of the radicals R1-R9respectively represent a simple bond, and the remaining radicals are the same or different and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, cyanograea number, when Brednikova molecular weight will not exceed 500000.

3. A method of obtaining a dimer, trimer or polymer containing conjugated salt N-torpedine with srednecenovogo molecular weight of not more than 500,000 and has a recurring element of the formula (II), namely, that the fluorine interacts in a mixture of solvents, including aliphatic nitrile containing 2 to 5 carbon atoms, and aliphatic carboxylic acid containing 1 to 5 carbon atoms, in the presence of acid Bronsted and/or its salts with pyridine containing a dimer, trimer or polymer that includes a recurring element of the formula (III)

< / BR>
where two of the radicals R1-R5respectively represent a simple bond, and the remaining radicals are the same or different and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group,

obtaining dimer, trimer or polymer containing conjugated salt N-torpedine having duplicate link formosana acid Bronsted;

n= 2 or an integer, wherein the molecular weight will not exceed 500000.

4. A method of obtaining a dimer, trimer or polymer containing conjugated salt N-torpedine represented by the formula (I) having srednecenovogo molecular weight of not more than 500,000, which consists in the fact that the fluoride interacts in a mixture of solvents, including aliphatic nitrile containing 2 to 5 carbon atoms and aliphatic carboxylic acid containing 1 to 5 carbon atoms, in the presence of acid Bronsted and/or its salts with bipyridinium compound of formula (IV)

< / BR>
where one of the radicals R1-R5connected by a simple relationship with one of the radicals R1'-R5'and the rest of the radicals R1-R5, R1'-R5'are the same or different and each represents a simple bond, a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group,

with the formation of dimer, trimer or polymer containing conjugated salt N-torpedine formula (I)

< / BR>
where R1-R9
m= 1 or the number that provides the above srednecenovogo molecular weight;

l= 0 or 1, provided that when m= 1, then l0.

5. A method of obtaining a dimer, trimer or polymer containing conjugated salt N-torpedine with srednecenovogo molecular weight of not more than 500,000 and has a recurring element of the formula (II), namely, that the fluorine interacts in a mixture of solvents, including aliphatic nitrile containing 2 to 5 carbon atoms, and aliphatic carboxylic acid containing 1 to 5 carbon atoms, in the presence of acid Bronsted and/or its salts with pyridine containing a dimer, trimer or polymer that includes a recurring element of the formula (III):

< / BR>
where adjacent radicals R1and R2, R2and R3, R3and R4or R4and R5can be connected to each other with the formation of CR6= CR7-CR8= CR9- simultaneously two of the radicals R1-R9respectively represent a simple bond, and the remaining radicals are the same or different and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, aou group

with the formation of dimer, trimer or polymer containing conjugated salt N-torpedine formula (II)

< / BR>
where R1-R5have the above values;

X-- the conjugate base of the acid Bronsted;

n= 2 or an integer, in which Brednikova molecular weight will not exceed 500000.

6. A method of obtaining a dimer, trimer or polymer containing conjugated salt N-torpedine represented by the formula (I) having srednecenovogo molecular weight of not more than 500,000, which consists in the fact that the fluoride interacts in a mixture of solvents, including aliphatic nitrile containing 2 to 5 carbon atoms, and aliphatic carboxylic acid containing 1 to 5 carbon atoms, in the presence of acid Bronsted and/or its salts with bipyridinium compound of formula (IV)

< / BR>
where the radicals R1and R2, R2and R3, R3and R4or R4and R5can be connected to each other with the formation of CR6= CR7-CR8= CR9-, and the radicals R1'and R2', R2and R3', R3and R4'or R4'and R5'connected to each other with the formation of CR6'= CR7'-CR8'= CR9'- and E of the radicals R1-R9, R1'-R9'are the same or different and each represents a hydrogen atom, halogen atom, alkyl group, haloalkyl group, aryl group, CNS group, alloctype, alkoxycarbonyl group, aryloxyalkyl group, a cyano, a nitro-group or acyl group,

with the formation of dimer, trimer or polymer containing conjugated salt N-torpedine formula (I)

< / BR>
where R1-R9, R1'-R9'have the above values;

X-and X-'are the same or different and each represents a conjugate base of the acid Bronsted;

m= 1 or the number that provides the above srednecenovogo molecular weight;

l= 0 or 1, provided that when m= 1, then l0.

7. The active material for positive electrode that contains a dimer, trimer or polymer containing conjugated salt N-torpedine, under item 1 or 2.

8. The active material for the positive electrode under item 7, characterized in that it further adds polar connection.

9. The electrolyte containing dimer, trimer or polymer containing conjugated salt of N-Perper is unity.

11. Material batteries primary cells, which contains a dimer, trimer or polymer containing conjugated salt N-torpedine, under item 1 or 2, and is used as an active material for the positive electrode and the electrolyte.

12. Material battery on p. 11, characterized in that it further adds polar connection.

13. Battery primary cells, which use an active material for positive electrode under item 7 or 8, the electrolyte under item 9 or 10 or the material of the battery under item 11 or 12.

14. Fluorinating agent, including dimer, trimer or polymer containing conjugated salt N-torpedine, under item 1 or 2.

15. Method of fluorination connection with use of a fluorinating agent under item 14.

16. The method according to p. 15, in which connection, subject to fluoridation, is an organic compound.

17. The method according to p. 16 in which the organic compound is a nucleophilic organic compound.

 

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The invention relates to a method of manufacturing an electric energy to the device for implementing the method, the compound with N-F-communication and making electrical energy, and to the battery using the same connection, provides the solution of the problem of production of electrical energy by the use of the materials as the active material for battery, electrolyte, etc. that are easy to use and are acceptable from the point of view of environmental protection

The invention relates to chemical current sources, in particular for lead batteries

The invention relates to a new method of obtaining perphosphate lithium General formula (I), where a = 1, 2, 3, 4, or 5, b = 0 or 1, C = 0, 1, 2 or 3, d = 0, 1, 2 or 3; e = 1, 2, 3, or 4, provided that the sum of a+e = 6, the sum of b+c+d = 3, and b and C are not simultaneously denote 0, provided the ligands (CHbFc(CF3)d) can be different, and monochlor - or fluorine-, dichloro - or debtor, chlortetracycline, hormone, HARDI-, Hartry or chlortetracycline, formano, Ferdi-, fortri or fortetracycline or cryptomonadales subjected to electrochemical fluorination in an inert solvent, the resulting mixture of products if necessary, divide by distillation at various fluorinated products and the fluorinated alkylphosphine, put in an aprotic, polar solvent at from -35 to 60oWith interaction with lithium fluoride
The invention relates to the field of electrical engineering, in particular for lead-acid batteries

The invention relates to electrical engineering and can be used in the manufacture of chemical current sources (CCS), namely in the preparation of electrolytes

The invention relates to electrical engineering and can be used in the manufacture and treatment" failed due to sulfate crystallization of lead batteries

The invention relates to the production of hydrocarbon oligomers with reactive end groups and can be used in the synthetic rubber industry

FIELD: chemical current supplies; electrolytes used for lead-acid batteries.

SUBSTANCE: electrolyte is doped with polyacrylamide in the amount of 0.001 to 6.0 mass percent per amount of electrolyte. Polyacrylamide added to electrolyte depends for its action on its coagulating properties and on increase of electrolyte viscosity which holds powdered active masses and products of reaction on electrolyte surface thereby preventing their fall-down, creeping, and wash-out. Polyacrylamide is introduced in the form of its aqueous solution before or after battery is filled with electrolyte to function as its additive.

EFFECT: improved operating characteristics and enhanced service life of batteries.

2 cl

FIELD: electrical engineering; chemical current sources; production of lead-acid cells, additives for sulfuric-acid electrolytes in particular.

SUBSTANCE: proposed additive is made from mixture of sulfate of metal with phosphonocarboxylic acids and aminoalkylphosphonic or hydroxyalkylene diphosphonous acids in diluted sulfuric-acid medium at pH no more than 0.8 and total content of phosphonous acids equal to 0.001-0.015 mass-% and metal sulfate of 10-18 mass-%. Additive may additionally include fluorine-containing surfactants in the amount of 0.01-0.1 mass-%. Proposed additive is used for excluding sulfitation of plates of lead-acid cells and restoration of sulfated storage batteries.

EFFECT: enhanced efficiency.

5 cl, 3 ex

FIELD: electrical engineering; lead battery manufacture.

SUBSTANCE: proposed lead battery has strengthened active material on its positive plate thereby enhancing its utilization efficiency at low internal resistance of battery. Novelty is that only positive plates hold in their voids gel-like sulfuric-acid electrolyte and remaining space of battery is filled with liquid sulfuric acid electrolyte.

EFFECT: enlarged service life of battery.

1 cl, 1 tbl

FIELD: electrical engineering.

SUBSTANCE: proposed method for preparing electrolyte aqueous component for chemical current supply includes magnetization of distilled water for which purpose permanent magnet is immersed in the latter, then water is heated to boiling temperature, and boiling water is doped with animal-origin substrate in the amount of 5 to 8 g per 1 liter of water and boiled for 20 - 30 minutes, whereupon vegetable-origin oil in the amount of 15 - 20 ml per 1 liter of water and vegetable-origin resin in the amount of 20 - 25 ml per 1 liter of water are added thereto, and boiling is continued for 5 - 10 minutes; then solution obtained is cooled down and filtered off.

EFFECT: enhanced power characteristics of battery.

4 cl, 1 tbl

FIELD: electrical engineering.

SUBSTANCE: proposed method is used for reconditioning lead battery cells filled with sulfuric acid based electrolyte using additive based on aqueous solution of hydrogen peroxide, saccharides, and/or aldehydes, or their derivatives. Novelty is that lead battery is alternately or periodically charged and discharged in the course of electrochemical reconditioning of cells upon its treatment with some reconditioning additives based on aqueous solution of hydrogen peroxide and after main charge. Battery is charged to full possible level by current amounting to 1.1-4% of rated value and its discharge is conducted with current of 0.01-5% of rated capacity of cell or battery; as an alternative, battery is charged in two phases by current of constant magnitude. Discharge below admissible value is conducted by current amounting to 1 to 4% of rated capacity followed by charging with current amounting to 3-10% of battery capacity until voltage per cell or per any cell of battery is reduced to 1.6 V. In the process battery acquires 10-15% of its rated capacity; entire procedure is repeated two to five times. Reconditioning additive has 1 to 70 ml of sulfuric acid at density of 1 to 1.32 g·cm-3, 0.1 to 10 g of saccharides in the form of solid material and/or aldehydes, or their derivatives, 0.1 to 10 g of sodium and/or potassium bicarbonate, and/or at least one hydroxide out of group of alkali metals in the form of solid material, and 0.1 to 20 g (better 0.5 to 2 g) of disulfonic acid dinaphthyl methane disodium salt per every liter of hydrogen peroxide aqueous solution. Reconditioning additive can also incorporate 0.1 to 10 g of sodium perborate and/or tetraborate, and/or pyrophosphate in the form of solid material.

EFFECT: enhanced battery capacity exceeding primary rated value.

11 cl, 5 ex

FIELD: electricity.

SUBSTANCE: invention is attributed to lead batteries (AB). In this invention lead AB contains group of plates fitted into accumulator jar and ionogen introduced in it for plate group saturating with ionogen with simultaneous forming processing. Here lead AB is adapted to be used partly charged when charge condition is limited within interval from exceeding 70% to less than 100%. Plate group is formed by package consisting of large number of negative electrode bases including grid bases filled with active material of negative electrodes, of large number of positive electrode bases including grid bases filled with active material of positive electrodes and porous separator located between negative electrode bases and positive electrode bases. Ionogen contains at least one kind of ions selected from group consisting of aluminium ions, selenium ions and titanium ions.

EFFECT: creation of lead battery suitable to be used in partly charged condition.

23 cl, 9 tbl, 71 ex

FIELD: chemistry.

SUBSTANCE: invention relates to compounds of formula I, production and use thereof to obtain corresponding organophosphinates [Kt]z+ z[(CnHmF2n+1-m)xPCIyF6.x.y]- (I) where [Kt]z+ is an organic cation of formula (1) [NR4]' (1) where R is an optionally phenyl-substituted linear C1-4-alkyl; formula (2) [PR24]+ (2) where R2 is independently C6-14-alkyl; or formula (6) [HetN]z+ (6), where HetNz+ is a heterocyclic cation selected from a group comprising imidazolium, pyrazolium, dihydroimidazolium, pyrrolidinium, triazolium, pyridinium, pyridazinium, pyrimidinium, piperidinium, piperazinium, pyrazinium, R1,-R4, denote H or C1-10-alkyl; n=1-4, m=0 to 2n+1, x=1-4, y=1, z=1-2, under the condition that x+y<5.

EFFECT: novel compounds, a method of producing said compounds and use of said compounds to obtain valuable compounds are disclosed.

12 cl, 10 ex

FIELD: electricity.

SUBSTANCE: as halogenide of another element, potassium bromide is taken at the following ratio of components (wt %): lithium nitrate 76.5…73.5; potassium bromide 23.5…26.5.

EFFECT: reduced temperature of melting and specific enthalpy of melting, which reduces power inputs for putting electrolyte into working condition and expands temperature range of electrolyte usage.

5 ex

FIELD: electricity.

SUBSTANCE: invention relates to chemical current sources, particularly to compositions of electrolytes, used in lead-acid accumulators, and can be used for production of accumulator batteries for electric vehicles, automobiles with combined power plant, as well as for vehicles with traditional petrol engine. Electrolyte contains, wt %: borate methylphosphite 0.6-0.8, perfluoropolyether acids flouranhydrides with molecular weight of 800-1,000 0.1-0.3, Chitosan 0.1-0.3, sulphuric acid 20.0-30.0, and distilled water up to 100.

EFFECT: technical result is improved electrical and operating characteristics of lead accumulator, as well as increasing its service life.

1 cl, 2 tbl, 5 ex

FIELD: power cell electrolytes.

SUBSTANCE: invention provides lithium fluoroalkyl phosphates, method for preparation thereof, and their use as electrolyte salts in batteries, condensers, supercondensers, and chemical power sources.

EFFECT: achieved good reproducibility of electrochemical properties.

17 cl, 3 tbl

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