Fluoroalkyl phosphates, method for their preparing and electrolytes based on thereof

FIELD: organic chemistry, chemical technology, electrolytes.

SUBSTANCE: invention relates to new fluoroalkyl phosphates that can be used as electrolytes in primary current sources, secondary current sources, capacitors, super capacitors and/or galvanic units. Invention describes fluoroalkyl phosphates of the general formula (I): Mn+[PFx(CyF2y+1-zHz)6-x]n wherein 1 ≤ x ≤ 6, 1 ≤ y ≤ 8, 0 ≤ z ≤ 2y + 1, 1 ≤ n ≤ 5 and Mn+ means a monovalent, bivalent or trivalent cation, in particular: NR1R2R3R4, PR1R2R3R4, P(NR1R2)kR3mR44-k-m (wherein k = 1-4; m = 0-3 and k + m ≤ 4), C(NR1R2)(NR3R4)(NR5R6), C(aryl)3, Rb or tropylium wherein R1-R8 mean hydrogen atom (H), alkyl or (C1-C8)-aryl that can be substituted partially for F, Cl or Br atoms and wherein Mn+ means Li+, Na+, Cs+, K+ and Ag+ are excluded. Except for, invention describes a method for preparing fluoroalkyl phosphates and electrolytes for primary current sources based on fluoroalkyl phosphates. Invention provides preparing new compounds possessing useful properties.

EFFECT: improved preparing method, valuable properties of compounds.

11 cl, 1 dwg, 7 ex

 

The invention relates to peralkylated, process for their preparation and to the use of these compounds as conductive salts in the current sources, capacitors, supercapacitors and galvanic elements.

In recent years, the world has dramatically increased the prevalence of portable electronic equipment, for example - the "road" and pocket computers, mobile phones and video cameras; accordingly, the demand for lightweight and highly efficient power sources.

Due to this sudden increase in demand and the attendant environmental problems becomes significant relevance development of rechargeable power sources with long life.

Current state of development presents lithium-ion power sources and Dolnoslaskie capacitors with very high capacitance (so-called super - or ultracondensed). Currently, both these systems as conductive salts are usually applied susceptible to hydrolysis and thermally unstable compounds LiPF6or N(C2H5)4BF4. When the contact of these substances with moist air or remaining in the solvent water, quickly formed HF. In addition to toxicity, HF has the property to have a very bad influence on the cyclical characteristics, and ultimately the way on the functioning of the electrochemical element.

As alternatives to these substances have been proposed imides, such as bis(trifloromethyl)imide, bis(pentafluoroethanesulfonyl)imide, or methanide, such as Tris(trifloromethyl)methane and its derivatives. For these salts is characterized by high stability with respect to the potential of the positive electrode, an organic aprotic solvent, they form a solution with a high electrical conductivity. However, imides not effectively Passepartout aluminum metal, which produces a current collector of the negative electrode in the current sources. On the other hand, the process of obtaining petanidou is very time-consuming (Turowsky, Seppelt, Inorg. Chem., 1988, 2135). In addition, the degree of purification of petanidou strongly depend on their electrochemical properties, such as stability against oxidation and the ability to passivation of aluminum.

The subject of this invention are electrically conductive salts, which are characterized by ease of access and electrochemical stability.

Another object of the invention is to increase the service life and improve the performance of the current sources, capacitors, supercapacitors and galvanic elements.

Discovered that the above objectives the achievement of which are stated by cooking peralkylated, described General formula (I)

Mn+[PFx(CyF2y+1-zHz)6-x]n-(I)

in which

1≤x≤6

1≤≤8

0≤z≤2U+1

1≤n≤5 and

Mn+denotes a monovalent or trivalent cation, in particular:

NR1R2R3R4,

PR1R2R3R4,

P(NRlR2)kR3mR44-k-m(where k=1-4, m=0-3 and k+m≤4),

C(NR1R2)(NR3R4)(NR5R6),

C(aryl)3, Rb or tropoli

where R1-R8denote H, alkyl or aryl group, (C1-C8), which can be partially substituted by F, Cl or Br,

and where Mn+=Li+, Na+Cs+To+and Ag+excluded.

Preference is given to peralkylated that are described by the formula

N(C2H5)4[PF3(C2F5)3],

N(CH3)4[PF3(C4F9)3],

[N(CH3)4][PF3(C4F9)3],

[N(C2H5)4][PF3(C2F5)3],

P[N(CH3)2]4[PF3(C2F5)3],

P[N(CH3)2]4][PF3(C4F9)3],

[P(CH3)4]+[PF3(C2F5)3/sub> ]-,

[P(C2H5)4]+[PF3(C2F5)3]-,

[P(CH3)4]+[PF3[C4F9]3]-,

[P(C2H5)4]+[PF3[C4F9]3]-,

With[N(CH3)2]3[PF3(C2F5)3]

With[N(CH3)2]3[PF3(C4F9)3].

Found that the compounds according to this invention are characterized by a very high electrochemical stability. Thus, according to this invention, peralkylated with the General formula (I) can be used both in pure form and in the form of their mixtures, as conductive salts in the primary and secondary current sources, capacitors, supercapacitors and galvanic elements. In addition, peralkylated according to this invention can be used as conductive salts in combination with other known in the field salts.

Peralkylated according to this invention as conductive salts preferably used in pure form, because in these cases is achieved particularly good reproducibility of electrochemical characteristics.

Peralkylated get from phosphoranes, the process of obtaining them are described in the application DE 19641138. Prepare 0,01-4-molar, preference is sustained fashion - 0,5-3-molar, particularly preferably 1.5 to 2.5-molar solution or suspension of these phosphoranes or peralkylated in solvents, preferably aprotic organic solvent, particularly preferably in solvents which are included in the group consisting of carbonates, esters, ethers, NITRILES, amides, ketones, esters, sulfonic acid, sulfonamide, sulfoxidov, esters of phosphoric acid, phosphoranes, chloroalkanes and mixtures thereof. Preferred are those solvents or mixtures thereof, which are directly suitable for use in primary or secondary power sources, capacitors, supercapacitors or galvanic elements, such as dimethylcarbonate, diethylcarbamyl, propylene carbonate, ethylene carbonate resulting, ethylmethylketone, methylpropylketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetate, γ-butyrolactone, ethyl acetate, methylpropionate, ethylpropane, methylbutyrate, ethyl butyrate, dimethylsulfoxide, dioxolane, sulfolane, acetonitrile, Acrylonitrile, tetrahydrofuran, 2-methyltetrahydrofuran or mixtures thereof.

For the reaction with peralkylated to the solution is added an equimolar amount or a slight excess of fluorides, chlorides, tetrafluoroborate or hexaphosphate metals or nonmetals, if it is desirable that their presence in the solution; prepost the sory choose connection members of the group [NR1R2R3R4]F, [NR1R2R3R4]Cl, [PR1R2R3R4]F, [PR1R2R3R4]Cl, [P(NR1R2)4]F, [P(NR1R2)4]Cl, [(NR1R2)3]Cl and [(NR1R2)3]F. For reaction with phosphorane add equimolar amount or a slight excess of N(CH3)4F, N(C2H5)4F, [R[(CH3)2]4]F or[N(CH3)2]3F. the Mixture prepared at the temperatures at which it is in a liquid state, preferably at temperatures between 0°s and 50°C, particularly preferably at room temperature. The composition is stirred for from 0.5 to 48 hours, preferably from 2 to 12 hours. If peralkylated according to this invention is obtained by carrying out the exchange reaction, the resulting by-product is separated by cooling the reaction mixture and subsequent filtration. If you use a reaction that is not accompanied by the formation of associated products, the reaction mixture can then be applied directly to the destination.

Thus obtained electrolytes suitable for use in primary power, secondary power sources, capacitors, supercapacitors and galvanic element is Oh, and also are the subject of the present invention.

In this invention the concentration of peralkylated in these electrolytes are preferably in the range from 0.01 to 4 M/l, particularly preferably from 0.5 to 3 M/L.

The invention relates also to the primary power, secondary power sources, capacitors, supercapacitors and galvanic elements that contain at least one peralkylated with the General formula (I) according to this invention and may contain other salts and/or additives. These other salts and additives described in the literature, for example - Doron Aurbach: Nonaqueous Electrochemistry, Marc Dekker Inc., New York 1999; D.Linden: Handbook of Batteries, Second Edition, McGraw-Hill Inc., New York 1995, and G. Mamantov and A.I. Popov: Chemistry of Nonaqueous Solutions, Current Progress, VCH Verlagsgemeinschaft, Weinheim 1994. These works are included in the context of this description as a reference and, thus, are considered as part of the disclosure of this invention.

Peralkylated according to this invention can be applied with conventional electrolytes. Examples of suitable electrolytes are compounds, conductive salts which are LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, LiN(CF3SO2)2and LiC (CF3SO2)3as well as their mixtures. The electrolyte may also contain organic isocyanates (DE 19944603) to reduce the s content of the water. In addition, can be integrated lithium salts with the General formula (DE 19951804)

in which:

x and y are 1, 2, 3, 4, 5 or 6

Mx+denotes a metal ion

E - lisowska acid, which is part of the following groups:

BR1R2R3AIR1R2R3PR1R2R3R4R5AsR1R2R3R4R5and VR1R2R3R4R5where

R1-R5the same or different and may be connected directly to each other by single or double bonds, and each of them individually or together with others is a

halogen (F, Cl or Br),

alkyl or CNS radical (C1-C8), which may be partially or fully substituted by F, Cl or Br,

aromatic ring, which may be linked through oxygen linkages included in the following groups: phenyl, naphthyl, anthracene and phenanthrene, which may be unsubstituted, partially or hexosamine-alkyl (C1-C8) or F, Cl or Br,

aromatic heterocyclic ring, which may be linked through oxygen linkages included in the following groups: pyridyl, Persil and pyrimidyl, which may be unsubstituted, as well as the mono - or Tetra-substituted by alkyl (C 1-C8) or F, Cl or Br, and

Z denotes OR6, NR6R7, CR6R7R8, OSO2R6N(SO2R6) (SO2R7), C(SO2R6) (SO2R7) (SO2R8or OCOR6where

R6-R8the same or different and may be connected directly to each other by single or double bonds, and each of them individually or together with others is a

hydrogen, or compounds identified by the symbols R1-R5,

obtained in the reaction of the corresponding boric or phosphoric Lewis acid adduct solvent with lithium or imide of tetraalkylammonium, matanda or triflate.

In addition, there may be present borate salts (DE 19959722), which describes General formula

in which

M denotes a metal ion or a tetraalkylammonium,

x and y are 1, 2, 3, 4, 5 or 6,

R1-R4the same or different and represent CNS or carboxyl radicals (C1-C8), which can be linked directly to each other by single or double bonds. These borate salts get in the reaction of tetraalkoxysilane lithium or a mixture of 1:1 lithium alkoxide and a borate with a suitable hydroxyl or carboxyl compounds is observed in the ratio of 2:1 or 4:1 in an aprotic solvent.

May also be present additives such as silane compounds with the General formula

SiR1R2R3R4,

where R1-R4mean

N

CyF2y+1-zHz,

OCyF2y+1-zHz,

OC(0)CyF2y+1-zHz,

OSO2CyF2y+1-zHza

1≤x≤6,

1≤≤8,

0≤z≤2y+l and

R1-R4the same or different and each represents

the aromatic ring from the group consisting of phenyl and naphthyl which may be unsubstituted and monosubstituted or polyamideimide F, CyF2y+1-zHzOCyF2y+1-zHz, OS(O)CyF2y+1-zHz, OSO2CyF2y+1-zHzor N(CnF2n+1-zHz)2, or

heterocyclic aromatic ring from the group consisting of pyridyl, pirila and pyrimidyl, each of which can be monosubstituted or polyamidine F, CyF2y+1-zHzOCyF2y+1-zHz, OC(O)CyF2y+1-zHz, OSO2CyF2y+1-zHzor N (CnF2n+1-zHz)2(DE 10027626).

Compounds according to this invention can also be used in electrolytes, which contain peralkylated lithium with the following formula

Li+[PFx(CyF2y+1-zHz)6-x ]-,

in which

1≤x≤5,

1≤≤8,

0≤z≤2y+1,

and the ligands (CyF2y+1-zHz) may be the same or different, and excluded compounds, which are described General formula

Li+[PFand(CHbFc,(CF3)d)e]-,

in which

but there is an integer from 2 to 5, b=0 or 1, C=0 or 1, d=2 and

e is an integer from 1 to 4, provided that b and C are not equal On simultaneously, and that the sum of a+e is equal to 6, and the ligands (CHbFwith(CF3)d) may be the same or different (DE 10008955). The process of obtaining peralkylated lithium characterized in that at least one of the compounds, which describes one of the General formulas

HmP(CnH2n+1)3-m

OP(CnH2n+1)3,

ClmP(CnH2n+1)3-m,

FmP(CnH2n+1)3-m

CloP(CnH2n+1)5-o,

FoP(CnH2n+1)5-o,

each of them

0≤m≤2, 3≤n≤8 and 0≤≤4,

foryouth by electrolysis in hydrogen fluoride, the mixture of products of fluorination separated by extraction, phase separation and/or distillation, and, excluding the access of moisture, conduct the reaction of the thus obtained fluorinated of alkylphosphine with lithium fluoride, mixed with an aprotic solvent is, next, the resulting salt is isolated and purified by conventional methods.

Compounds according to this invention can also be used in electrolytes, which contain salts with the General formula

Li[P(OR1)a(OR2)b(OR3)c(OR4)dFe],

in which 0<a+b+c+d<5 and a+b+c+d+e=6, a R1-R4, independently of one another, denote alkyl, aryl or heteroaryl radicals, and at least two of R1-R4can be connected directly to each other by single or double bonds (DE 10016801). Connections get in the reaction of phosphorus compounds(V), which describes General formula

P(OR1)a(OR2)b(0R3)c(OR4)dFe,

in which 0<a+b+c+d≤5 and a+b+c+d+e=5, a R1-R4meet defined above, with lithium fluoride in the presence of an organic solvent.

In addition, the compounds of this invention may also be present in ionic liquids, which are described General formula

To+And-,

in which

K+ is a cation of the group consisting of

where the same or different R1- R5can be connected directly to each other by single or double bonds, and each of them separately in the tee or in combination with others can have the following values:

- N,

- halogen,

is an alkyl radical (C-C8), which can be partially or completely substituted by the following groups: F, Cl, N (CnF(2n+1-x)Hx)2, O(CnF(2n+1-x)Hx, SO2(CnF(2n+1-x)Hxor CnF(2n+1-x)Hxwhere 1<n<6 and 0<x≤13,

and

And-there is one of the anions of the group consisting of [B(OR1)n(OR2)m(OR3)o(OR4)p]-,

where 0≤n, m, o, p≤4, and

m+n+o+p=4,

and R1-R4different or identical pairs can be connected directly to each other through odinary or double bond and each of them individually, or collectively with others, represents an aromatic ring from the group consisting of phenyl, naphthyl, anthracene and phenanthrene, which may be unsubstituted, monosubstituted or polyamidine CnF(2n+1-x)Hxwhere 1<n<6 and 0<x≤13, or halogen (F, Cl or Br),

aromatic heterocyclic ring from the group consisting of pyridyl, pirila and pyrimidyl, which may be unsubstituted, monosubstituted or polyamidine CnF(2n+1-x)Hxwhere 1<n<6 and 0<x≤13, or halogen (F, Cl or Br),

alkyl radical (C1-C8), which can be partially or completely substituted by the following group and, preferably F, Cl, N(CnF(2n+1-x)Hx)2, O(CnF(2n+1-x)Hx), SO2(CnF(2n+1-x)Hxor CnF(2n+1-x)Hxwhere 1 <n<6 and 0<x≤13,

or or1-OR4

individually or collectively with the other represents an aromatic or aliphatic carboxylic, dicarboxylic, oxysulphide or oxycarbonyl radical, which may be partially or fully substituted by the following groups, preferably F, Cl, N (CnF(2n+1-x)Hx)2, (CnF(2n+1-x)Hx), SO2(CnF(2n+1-x)Hxor CnF(2n+1-x)Hxwhere 1<n<6 and 0<x≤13 (DE 10026565). Compounds according to this invention may also be present in ionic liquids To+And-(DE 10027995), where K+corresponds above, and

And-the anion from the group which consists of

[PFx(CyF2y+1-zHz)6-x]-

1≤x≤<6

1≤≤8

0≤z≤2y+1.

Compounds according to this invention can also be present in the electrolytes, which contain compounds with the following formula:

NR1R2R3,

in which

R1and R2denote H, CyF2y+1-zHzor (CnF2n-mHm)X, where X is an aromatic or heterocycle is ical radical, and

R3means (CnF2n-mHm)Y, where Y is a heterocyclic radical or

(CoF2o-pHp)Z, where Z is an aromatic radical, and where n, m, o, R, u and z satisfy the following conditions:

0≤n≤6,

0≤m≤2n,

2≤o≤6,

0≤R≤2O,

1≤≤8, and

0≤z≤2y+1,

for reducing the amount of acid in aprotic electrolytic systems in electrochemical elements.

The electrolyte may also contain a mixture of the following components:

a) at least one salt of peralkylated lithium with the General formula

Li+[PFx(CyF2y+1-zHz)6-x]-

1≤x≤5

1≤≤8, and

0≤z≤2y+1,

and the ligands (CyF2y+1-zHzin each case, may be the same or different, and

b) at least one polymer (DE 10058264).

The electrolyte may also contain tetranitroaniline salts with the General formula

Mn+([BR4]-)n,

in which

Mn+represents a monovalent, divalent or trivalent cation,

the ligands R in each case identical and represent a (CxF2x+1), where 1≤x≤8,

and n=1, 2, or 3 (DE 10055811). The process of obtaining tetranitroaniline salts characterized in that at least one connection with a total of four who uloi M n+[B(CN)4]-)nin which Mn+and n correspond to defined above, foryouth in the reaction with at least one fluorinating agent, in at least one solvent, and the obtained fluorinated compound is isolated and purified using conventional methods.

The electrolyte may also contain borate salts with the General formula

Mn+[BFxCyF2y+1-zHz)4-x]n-,

in which

1<x<3, 1≤≤8 and 0≤2≤2U+1, and

Mn+monovalent, divalent or trivalent cation (1≤n≤3)addition of potassium and barium, in particular:

Li,

NR1R2R3R4PR5R6R7R8P(NR5R6)kR7mR84-k-m(where k=1-4, m=0-3 and k+m≤4), or

C(NR5R6)(NR7R8)(NR9R10), where

R1-R4denote CyF2y+1-zHz

and

R5-R10represent N or CyF2y+1-zHzor

aromatic heterocyclic cation, in particular nitrogen and/or oxygen and/or sulfur-containing aromatic heterocyclic cation (DE 10103189). The process of obtaining these compounds is characterized by the fact that

a) when cooled conduct the reaction in a mixture of 1:1 complexes BF3/solvent with an organolithium the the group then the main part of the solvent is removed by gradual heating, after which the solid is filtered off and washed with a suitable solvent, or

b) conducting the reaction in 1:1-mixture of lithium salts in a suitable solvent and salts(CF3)F3then the mixture is stirred at elevated temperature and remove the solvent, after which the reaction mixture is added aprotic non-aqueous solvents, preferably solvents which are used in electrochemical elements, then the mixture is dried, or

c) at elevated temperatures carry out the reaction in the mixture composition is from 1:1 to 1:1,5 salts(CF3)F3and lithium salts in the water, then the mixture is heated to boiling point and kept at this temperature for from 0.5 to 2 hours to remove water, then add aprotic non-aqueous solvents, preferably solvents which are used in electrochemical elements, after which the mixture is dried.

The electrolyte may also contain foruminformation salt, which describes General formula

Mn+([PFx(CyF2y+1-zHz)6-x]-)n

in which

1≤x≤5,

1≤≤8 and

0≤z≤2y+1, n=1, 2, or 3, and the ligands (CyF2y+1-zHzin each case the same or different when that foruminformation salt, kotoryj n+is a lithium cation and a salt

M+[PF4(CF3)2]-), where M+=Cs+Ag+or+,

M+[PF4(C2F5)2]-), where M+=Cs+,

M+[PF3(C2F5)3]-), where M+=Cs+.K+, Na+or para-Cl (C6H4N2+,

M+[PF3(C3F7)3]-), where M+=Cs+, K+, Na+pair-Cl (C6H4N2+or a pair of O2N (C6H4N2+- excluded (DE 10055812). The process of obtaining these peralkylated salts characterized in that at least one of the compounds with the General formula

HrP(CsH2s+1)3-r,

OP(CsH2s+1)3,

ClrP(CsH2s+1)3-r,

FrP(CsH2s+1)3-r,

CltP(CsH2s+l)s-tand/or

FtP(CsH2s+1)5-t,

where in each case,

0≤r≤2

3≤s≤8 and

0≤t≤4,

foryouth by electrolysis in hydrogen fluoride, the mixture of products of fluorination share, then in an aprotic solvent or mixture of solvents with the exclusion of moisture carry out the reaction of the obtained fluorinated organophosphorus compounds with what Obedinenie, which is described by the General formula Mn+(F-)nin which Mn+and n correspond to defined above, and received forumilpopolo salt is isolated and purified by conventional methods.

Compounds according to this invention may be present in electrolytes, which contain foruminformation salt (DE 10109032) with the formula

(Ma+)b[(CnF2n+1-mHm)yPF5-y(CR1R2)xPF5-y(CnF2n+1-mHm)y](2-)(a*b/2)

in which

Ma+there is monovalent, divalent or trivalent cation,

a=1, 2, or 3, b=2 when a=1, b=2 if a=3, b=1 when a=2

and in each case

1≤n≤8,

0≤m≤2 if n=1 or 2

0≤m≤4 3≤n≤8,

1≤x≤12,

0≤≤2,

where R1and R2in each case the same or different and included in the group of substituents consisting of fluorine, hydrogen, alkyl, foralkyl and perfluoroalkyl, and

where in each case the substituents (CnF2n+1-mHm) may be the same or different. These compounds are obtained when conducting the reaction solution at least one fluorine-α,ωbis(alkylphosphate)alkane with at least one fluoride salt with General formula (Ma+)[F-]awhere (Ma+and meet defined above, which which allows to obtain forumilpopolo salt, and then, if required, allocate the past and/or produce clean using conventional methods.

Compounds according to this invention can be used in electrolytes for electrochemical elements, in which the material of the positive electrode is a metal substrate with a coating, and the metal included in the group consisting of Sb, Bi, Cd, In, Pb, Ga and tin and their alloys (DE 10016024). The process of obtaining these materials for positive electrodes differs in that

a) prepare a suspension or Sol of a metal or alloy substrate in urotropine,

b) suspension emuleret with hydrocarbon, C5-C12,

c) the emulsion is precipitated on a substrate of metal or alloy, and

d) hydroxides or oxyhydroxides metal is transformed into the corresponding oxides by heating system.

Compounds according to this invention can also be used in electrolytes for electrochemical elements with negative electrodes, which are made of ordinary substituted and intercalation of lithium compounds, and also in cases, when the material of the negative electrode is a mixture of lithium oxide particles which have a coating of one or more metal oxides (DE 19922522). The material of the negative electrode may consist of a mixture of lithium oxide particles, which have aircraft the Oia from one or more polymers (DE 19946066). Compounds according to this invention can also be applied in systems in which the negative electrode consists of a mixture of lithium oxide particles which have a coating of one or more compounds of alkali metals and metal oxides (DE 10014884). The process of obtaining these materials is characterized by the fact that the particles suspension in an organic solvent, then add a suspension of alkali metal salts in an organic solvent, then add a solution of metal oxides in an organic solvent, after which the suspension add gidrolizuemye solution, then particles with a coating agent is dried and calicivirus. Compounds according to this invention can also be applied in systems in which the material of the positive electrode contains an additive-doped tin oxide (DE 10025761). This positive electrode material was obtained as follows:

a) add urea to the solution of chloride of tin,

b) adding to the resulting solution methenamine and suitable alloying connection

c) emuleret Sol obtained in petroleum ether,

d) wash the obtained gel and remove the solvent by vacuum, and

e) is dried and heated gel.

Compounds according to this invention can also be applied in systems in which the materials of the positive electrodes contain is at the restored tin oxide (DE 10025762). This positive electrode material was obtained as follows:

a) add urea to the solution of chloride of tin,

b) adding to the resulting solution methenamine,

c) emuleret Sol obtained in petroleum ether,

d) wash the obtained gel and remove the solvent by vacuum,

e) is dried and heated gel, and

f) process the received SnO2the flow of the reducing gas in aerated oven.

The advantage of peralkylated according to this invention is their electrochemical stability. This property allows the use of conductive salts, which contain compounds according to this invention, current sources, capacitors, supercapacitors and galvanic elements.

Examples

Below is the meaning of the invention is illustrated by examples. These examples are illustrative and not limiting of the invention.

Example 1

Obtain N(C2H5)4[PF3(C2F5)3] after Li[PF3(C2F5)3]

Equimolar amounts of N(C2H5)4X (X=F or Cl) in methylene chloride is added to from 1.5 to 2.5 molar solution of Li[PF3(C2F5)3]. The solution was stirred at room temperature for several hours, during which is formed in small amounts, the creation of sediment LiX. Then the reaction mixture in the next two hours, maintained at a temperature of from -30°-10°With, then the precipitate at a temperature of from -30°-10°With filtered off under reduced pressure. The solvent is removed by distillation. After drying at 100°and under reduced pressure to obtain the target product as a colorless granules.

The results of the spectroscopic analysis19F-NMR (CD3CN; reference: CCl3F):

- 43,6 DM (1F)

- 79,7 m (3F)

- 81,3 M (6F)

- 87,0 DM (2F)

- 115,3 M (4F)

- by 115.7 M (2F)

Example 2

Obtaining N(CH3)4[PF3(C2F5)3] through PF2(C2F5)3

Equimolar amount of N(CH3)4F -40°added to 10 g PF2(C2F5)3(obtained by the method DE 19846636) in dichloromethane. This mixture for several hours is stirred and warmed to room temperature. Then the solvent is removed by distillation and allocate N(CH3)4[PF3(C2F5)3].

The results of the spectroscopic analysis19F-NMR (CD3CN; reference: CCl3F):

- 44,0 DM (1F)

- 80,0 m (3F)

- 82 m (6F)

to 87.5 DM (2F)

- 115, 8mm m (4F)

for 116.2 m (2F)

Example 3

Obtaining N(CH3)4[PF3(C4F9)3] through PF2(C4F9)3

P is the receiving is carried out by the same way, as in Example 2, starting from PF2(C4F9)3. As a source of cations is applied N(CH3)4F.

Example 4

Obtain P[N(CH3)2]4[PF3(C2F5)3] and P[N(CH3)2]4[PF3(C4F9)3]

Receiving is carried out by the same method as in Example 2. As a source of cations used P[N(CH3)2]4F.

Example 5

Obtain P[N(CH3)2]4[PF3(C4F9)3] and P[N(CH3)2]4[PF3(C2F5)3]

Receiving is carried out by the same method as in Example 1. As a source of cations used P[N(CH3)2]4Cl.

Example 6

Getting With[N(CH3)2]3[PF3(C2F5)3] and[N(CH3)2]3[PF3(C4F9)3]

Receiving is carried out by the same method as in Example 1. As a source of cations is used With[N(CH3)2]Cl.

Example 7

The electrochemical stability of the electrolytes

The measurements were carried out in a cell with a working electrode made of stainless steel, platinum or gold, lithium counter-electrode and a lithium reference electrode; in each case successively removed 5 cyclovertical. Sweat is ncial first increased at a rate of 10 mV or 20 mV/s from rest potential to 6V relative to Li/Li +, then returned back to the resting potential. In order to expand the measurement range, the solvent used a mixture of 1:1 EC and DMC (ethylene carbonate resulting and dimethylcarbonate).

All described electrolytes were stable at the potentials of the positive electrode more than 5 Century. In figure 1 this is shown by the example of the electrolyte containing the compound [PF3(C2F5)3]-.

1. Peralkylated described General formula (I)

Mn+[PFx(CyF2y+1-zHz)6-x]n-(I)

in which 1≤x≤6;

1≤≤8;

0≤z≤2U+1;

1≤n≤5 and

Mn+denotes a monovalent, divalent or trivalent cation, in particular

NR1R2R3R4;

PR1R2R3R4;

P(NRlR2)kR3mR44-k-m(where k=1-4, m=0-3 and k+m≤4);

C(NR1R2) (NR3R4) (NR5R6);

C(aryl)3, Rb or tropoli where R1-R8denote H, alkyl or aryl (C1-C8), which can be partially substituted by F, Cl or Br, and where Mn+=Li+, Na+Cs+, K+and Ag+excluded.

2. Peralkylated according to claim 1

a) N(C2 H5)4)PF3(C2F5)3],

b) N(CH3)4[PF3(C4F9)3],

(C) [N(CH3)4)[PF3(C4F9)3],

d) [N(C2H5)4][PF3(C2F5)3],

e) P[N(CH3)2]4[PF3(C2F5)3],

f) P[N(CH3)2]4[PF3(C4F9)3],

g) [P(CH3)4]+[PF3(C2F5)3]-,

h) [P(C2H5)4]+[PF3(C2F5)3]-,

i) [P(CH3)4]+[PF3[C4F9]3]-,

k) [P(C2H5)4]+[PF3[C4F9]3]-,

l) [N(CH3)2]3[PF3(C2F5)3]

m) [N(CH3)2]3[PF3(C4F9)3].

3. The method of producing peralkylated according to claim 1, characterized in that the reaction is carried out phosphoranes with fluoride salt or the reaction of peralkylated salt with the cation Mn+and fluoride, chloride, tetrafluoroborate, hexaphosphate or other anions in the solvent, preferably in aprotic organic solvents.

4. The method of producing peralkylated according to claim 3, the tives such as those what is the reaction of peralkylated [NR1R2R3R4]X, [P(NR1R2)4]X [PR1R2R3R4]X or [C(NR1R2)3]X, where X Is F-, Cl-BF4-or PF6-and R1-4correspond to the definitions given above.

5. The method of producing peralkylated according to claim 3, characterized in that the reaction is carried out phosphoranes with N(CH3)4F, N(C2H5)4F, [P[N(CH3)2]4]F or[N(CH3)2]3F.

6. The method of producing foruminformation on PP 5, characterized in that the reaction of the fluorinated alkylphosphines in a solvent or mixture of solvents, which are directly suitable for use in the primary and secondary current sources, capacitors, supercapacitors or galvanic elements.

7. The method of producing foruminformation on p-6, characterized in that the aprotic organic solvents are selected from the group consisting of carbonates, esters, ethers, NITRILES, amides, ketones, esters, sulfonic acid, sulfonamide, sulfoxidov, esters of phosphoric acid, phosphoranes, chloroalkanes and mixtures thereof.

8. The method according to p-7, characterized in that the used solvents are dimethylcarbonate, diethylcarbamyl, impregnated incarbone, the ethylene carbonate resulting, ethylmethylketone, methylpropylketone, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetate, γ-butyrolactone, ethyl acetate, methylpropionate, ethylpropane, methylbutyrate, ethyl butyrate, dimethylsulfoxide, dioxolane, sulfolane, acetonitrile, Acrylonitrile, tetrahydrofuran, 2-methyltetrahydrofuran or mixtures thereof.

9. Peralkylated, which can be obtained in the process according to any one of p-8.

10. Electrolytes for primary current, secondary current sources, capacitors, supercapacitors and/or galvanic cells containing at least one peralkylated according to any one of claims 1 to 9.

11. The electrolyte of claim 10, characterized in that the concentration of peralkylated(s) in the electrolyte is in the range from 0.01 to 4 mol/l, preferably from 0.5 to 3 mol/l, particularly preferably from 1.5 to 2.5 mol/L.



 

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