The composition is suitable as a solid electrolyte or separator for electrochemical elements

 

The proposed composition for electrode, a solid electrolyte or separator for electrochemical elements containing a mixture consisting of 1-95 wt.% solids, preferably inorganic solids with the size of the primary particles is from 5 nm to 20 μm and 5-99 wt.% polymer mass obtained by polymerization of 5-100 wt.%, in recalculation on weight of a condensation product of a polyhydric alcohol, at least one compound capable of reacting with the carboxylic or sulfonic acid, or their derivatives, or a mixture of two or more of them, and at least 1 mole per mole of the compounds of carboxylic or sulfonic acid, having at least one radically curable functional group, or its derivative, or a mixture of two or more of them, and 0-95 wt.%, in terms of the weight of one compound with an average (srednetsenovoj) molecular weight of at least 5000 and polyether segments in the main or side chain, and the mass fraction of the mixture in the composition is 1 to 100 wt.%. The technical result of the invention is to increase the mechanical strength, porosity of the obtained films and stamina in a short circuit. 3 S. and 2 C.p. f-crystals, 1 table.

what ectrolyte, containing lithium ions; for their use, for example, in solid electrolytes, separators and electrodes; solid electrolytes, separators, electrodes, sensors, electrochromic Windows, displays, capacitors and an ion-conductive films containing such compositions; to electrochemical elements such electrolytes, separators and/or electrodes; and also for use in the compositions of the solids in electrochemical elements to improve their resistance to cyclic charge/discharge.

Electrochemical elements, in particular elements of the battery, well-known, for example, from: "Ullmann''s Encyclopedia of Industrial Chemistry", 5th ed., including A3, VCH Verlagsgesellschaft mbH, Weinheim, 1985, page 343-397.

Among these elements, lithium and lithium-ion batteries take (in particular, as secondary elements) special position due to their high specific density of the stored energy.

Such elements contain a cathode, as described in the aforementioned monograph "Ullmann's", literaturnye mixed oxides of manganese, cobalt, vanadium or Nickel, which can be described for stoichiometric very simple case as LiMn2O4, LiCoO2, LiV2O5or LiNiO2.

With compounds, the cat is IDA react reversibly with the removal of lithium ions from the crystal lattice, moreover, it is the oxidation of metal ions such as ions of manganese, cobalt or Nickel. This reaction can be used in an electrochemical element for accumulating electric energy that connection, the receiving lithium ions (anode material) and literaturae mixed oxide (cathode material), separated by the electrolyte, through which lithium ions migrate from the mixed oxide in the anode material (charge process).

Compounds suitable for reversible accumulation of lithium ions, are usually on the discharge electrodes by means of a binder.

When the battery electrons through an external voltage source, and the lithium cations move through the electrolyte to the anode material. When using the item, on the contrary, the lithium cations through the electrolyte and electrons through the useful resistance to moving from the anode material to the cathode material.

Avoid short circuit inside the electrochemical cell between the two electrodes is electrically insulating, but permeable to cations lithium layer. This layer may be a so-called solid electrolyte or a conventional separator.

As you know, solid electrolytes and separators consist of mA the connection, containing lithium cations, and usually other additives, such as solvents.

As the substrate material in the American patent US-A 5296318 and US-And 5429891 available, for example, a copolymer of vinylidenefluoride and hexaferrite. However, the use of such high-resistance (co)polymers involves a number of disadvantages.

Polymers of this kind are not only expensive, but they also only work translated into the solution. Further, these polymers because of their relatively small conductivity of lithium cations increase the resistance element, so that upon receipt of the insulating layer is necessary to add an electrolyte, usually consisting of compounds containing lithium cations, such as LiPF6, LiAsF6or LiSbF6and an organic solvent such as ethylene carbonate resulting or propylene carbonate (US-A 5296318, US-A 5429891). In addition, the processing of such polymers is possible only in the presence of, for example, large quantities of plasticizers, such as di-n-butylphthalate, and pyrogenic silicic acids, which are added to ensure, on the one hand, a sufficient film formation and cohesion electrolyte layer and bonding with the electrode layers, and on the other hand, is uately batteries must be quantitatively removed from the multilayer composite element, consisting of a layer of anode layer, a solid electrolyte or separator layer and the cathode, by a very laborious and expensive in technical scale the extraction step.

In addition, the known solid electrolytes on the basis of polyalkyleneglycol, which are described, for example, in European patent applications EP-A 559317, EP-A 576686, EP-A 537930, EP-A 585072 and American patent US 5279910. Described in these documents, the polyesters modified in end, respectively, functional groups, for example, (meth)akrilovymi groups and before use as a solid electrolyte bound by energy supply (heat, light). Further, they contain, as a rule, salt conductivity, such as LiPF6to improve conductivity. The use of solids to improve the mechanical, thermal and dielectric strength of solid electrolyte in the scope of this document. In accordance with that described in this document system - despite stitching do not always have satisfactory properties with respect to mechanical strength, porosity of the obtained films and stamina in a short circuit.

Therefore, the present invention was based on the task of eliminating narutaru, but which can also be used in the manufacture of electrodes in electrochemical elements, and for other purposes described here.

The application of the proposed according to the invention compositions, in particular, due to the presence of solids III, as will be shown below, allows you to get solid electrolytes, separators or electrodes, which in comparison with known until now, systems have better resistance in the short circuit, high strength in compression, in particular at elevated temperatures (above 120oC) and higher porosity and, in addition, capable of long-term suppress the formation of lithium dendrites. In addition, the presence of solids leads to improved resistance to cyclic charge/discharge and increased load capacity current of the electrochemical element. Further, in a preferred application of the solids of the main character is binding, respectively neutralization of acids formed during operation of the electrochemical element.

In accordance with the foregoing the present invention in one embodiment, the implementation relates to the composition Ia, containing a mixture of IIA consisting of (a) 1-95 mA is 20 μm and (b) 5-99 wt.% polymeric mass IV, obtained by polymerization B1) 5-100 wt.%, in terms of weight IV, V condensation of) at least one compound VI, capable of reacting with carboxylic or sulfonic acid, or their derivatives, or a mixture of two or more of them, and) at least 1 mole per mole of the compound VI, carboxylic or sulfonic acid VII having at least one radically curable functional group, or its derivative, or a mixture of two or more of them B2) 0-95 wt. % in terms of weight IV, another compound VIII with an average (srednetsenovoj) molecular weight of at least 5000 and polyether segments in the main or side chain, and the mass fraction of the mixture IIA in composition Ia is 1 to 100 wt.%.

The above composition Ia preferably contains a mixture of IIA consisting of (a) 1-95 wt.% solids III, preferably the primary solids III, with the size of the primary particles is from 5 nm to 20 μm and (b) 5-99 wt.% polymeric mass IV, obtained by polymerization B1) 5-100 wt.%, in terms of weight IV, V condensation of
) a polyhydric alcohol VI, containing in the main chain atoms of carbon and oxygen,
-unsaturated carboxylic acid VII
B2) 0 to 95 wt.%, in terms of weight IV, another compound VIII with an average (srednetsenovoj) molecular weight of at least 5000 and polyether segments in the main or side chain, and the mass fraction of the mixture IIA in composition Ia is 1 to 100 wt.%.

In yet another variant of its implementation the present invention relates to compositions Ib containing a mixture IIb, consisting of
a) 1-95 wt.% solids III, preferably the primary solids III, with the size of the primary particles is from 5 nm to 20 μm and
b) 5-99 wt.% polymer IX, obtained by polymerization
B1) 5-75 wt.%, in terms of the polymer IX, capable of radical polymerization of unsaturated compounds X, different from the above-mentioned carboxylic or sulfonic acid VII or its derivative, or a mixture of two or more of them
B2) 25-95 wt.%, in terms of the polymer IX, another compound VIII with an average (srednetsenovoj) molecular weight of at least 5000 and polyether segments in the main or side chain, and the mass fraction of the mixture IIb in the composition Ib is 1 to 100 wt.%.

As solids III, in the first place, applied inorganic solids, predpochtite is, is iliceto, sulfates, carbonates, phosphates, nitrides, amides, imides and carbides of the elements of the first, second, third or fourth main group or the fourth side group of the Periodic system of elements; a polymer selected from the group consisting of polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamides, polyimides; dispersion solids containing such polymer; and mixtures of two or more of them.

As an example, it should be mentioned, in particular: oxides, such as, for example, silicon dioxide, aluminum oxide, magnesium oxide or titanium oxide, mixed oxides, for example, of the elements silicon, calcium, aluminum, magnesium, titanium; silicates, such as, for example, wire, chain, layered and framework silicates; sulfates, such as, for example, sulfates of alkaline and alkaline-earth metals; carbonates, such as carbonates of alkali and alkaline-earth metals, such as calcium carbonate, magnesium or barium, or lithium carbonate, potassium or sodium phosphates such as Apatite; nitrides; amides; imides; carbides; polymers, such as, for example, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride; polyamides; polyimides; or other thermoplastics, thermosets or MESI two or more of the above solids.

Especially suitable for this basic solids. Under the main solids should be understood such substance, mixture with liquid, aqueous diluent, in which the maximum pH equal to 7, has a higher pH than that of the diluent.

Solids should preferably be practically insoluble in used as electrolyte fluid and to be electrochemically inert in the environment of the battery.

Particularly suitable solid substance having a primary particle size from 5 nm to 20 μm, preferably from 0.01 to 10 μm and in particular from 0.1 to 5 μm, and these particle sizes are determined using electron microscopy. The melting point solids preferably lies above the normal operating temperature of the electrochemical element, and the melting point above 120oC, in particular above 150oWith, proved to be particularly acceptable.

At this solids in terms of their appearance can be symmetric, i.e., to have a ratio of dimensions height:width:length ratio (external dimensions), is approximately equal to 1, and take the form of beads, granules, roughly circular formations, as well as any mnogogrannikakh, or to be distorted or unbalanced, i.e., to have a ratio of dimensions height:width:length ratio (external dimensions), is not equal to 1, and take the form of, for example, needles, asymmetrical tetrahedra, asymmetrical double pyramids, unbalanced hexahedron or octahedra, plates, circles or fibrous formations. For solids, having the form of asymmetric particles, above the upper boundary of the size of the primary particles refers to the smallest axis.

As VI compounds capable of reacting with carboxylic or sulfonic acid VII or their derivatives, or a mixture of two or more of them, fundamentally can be used all compounds that satisfy this criterion.

Compound VI is preferably selected from the group consisting of one - or polyhydric alcohol containing in the main chain exclusively carbon atoms; one or polyhydric alcohol containing in the main chain, along with at least two carbon atoms, at least one atom selected from the group consisting of oxygen, phosphorus and nitrogen; silicon compounds; amine containing at least one primary amino group; an amine containing at least one and at least one hydroxyl group; and a mixture of two or more of them.

Of these compounds, preferred compounds VI, which have two or more than two functional groups capable of reacting with carboxylic or sulfonic acid.

When using VI compounds, containing as functional groups, amino groups, it is preferable to use those with secondary amino groups, so that after the condensation/staple free NH-group in the composition Ia or absent, or present only in small quantities.

As preferred compounds should be mentioned, in particular: one - or polyhydric alcohols containing in the main chain exclusively carbon atoms, with 1 to 20, preferably 2 to 20 and, in particular, 2-10 alcohol HE-groups, in particular two-, three - and chetyrehtomnik alcohols, preferably 2-20 carbon atoms, such as, for example, ethylene glycol, propane-1,2 - or 1,3-diol, butane-1,2 - or 1,3-diol, butene-1,4 - or Butin-1,4-diol, hexane-1,6-diol, neopentylglycol, dodecane-1,2-diol, glycerol, trimethylolpropane, pentaerythritol or sugar alcohols, hydroquinone, novolak, bisphenol a, and, however, as follows from the above definition can also be applied monohydroxy alcohols, such cacciolfi, preferably those with two terminal hydroxyl groups, such as, for example,,-dihydroxyvitamin; polyether polyols such as are known from Ullmfnns Encyclopedic der technischen Chemie, 4th ed., volume 19, pages 62-65 and obtained, for example, through the interaction of a diatomic alcohols with polybasic, preferably dibasic, polycarboxylic acids;
one - or polyhydric alcohols containing in the main chain, along with at least two carbon atoms, at least one oxygen atom, preferably politicalparty, such as, for example, the polymerization products of alkylenediamines, such as isobutylene, propylene oxide, ethylene oxide, 1,2-epoxybutane, 1,2-epoxybutane, 1,2-epoxyhexane, tetrahydrofuran, stimulated, and can also be applied and modified in end groups politicalparty; these alcohols are predominantly molecular (srednecenovogo) weight of from 100 to 5000, preferably from 200 to 1000 and, in particular, from 300 to 800; such compounds are in themselves known and commercially available under the trade names Pluriolor Pluronic(the company BASF, Aktieri silicon, and in this case can be applied, in particular, polysiloxane, or copolymers of alkalinized with siloxane, or a mixture of polyepitopic with polysiloxane, as they are described, for example, in European patent applications EP-581296 and EP-A 525728, with relative molecular masses of these alcohols is really all of the above;
the alcohols according to the above definition, in particular politicalparty in which part or all of the carbon atoms are replaced by sulfur atoms, and the molecular weight of these alcohols is really above;
one - or polyhydric alcohols containing in the main chain, along with at least two carbon atoms, at least one phosphorus atom, or at least one nitrogen atom, such as, for example, diethanolamine and triethanolamine;
the lactones derived from compounds of the General formula HO-(CH2)z-COOH, where z is a number from 1 to 20, for example-caprolacton,-propiolactone or methyl-caprolacton;
silicon-containing compound, such as, for example, di - or trichlorosilane, intelligenceled, diphenyldichlorosilane, dimethyldichlorosilane;
silanol, such as, e.g the like, for example, butylamine, 2-ethylhexylamine, Ethylenediamine, hexamethylenediamine were, Diethylenetriamine, Tetraethylenepentamine, pentamethylenebis, aniline, phenylenediamine;
polyetherdiamine, such as, for example, 4,7-dioxideis-1,10-diamine, 4,11-dioxymethylene-1,14-diamine;
one - or polyhydric thiol, for example, aliphatic thiols, such as, for example, methyl, ethanthiol, cyclohexanethiol, dodecanthiol; aromatic thiols, such as, for example, thiophenol, 4-chlorothiophenol, 2-mercaptoacetic;
connection with at least one Tilney and at least one hydroxyl group, such as, for example, 4-hydroxythiophenol, and montypython the above polyhydric alcohols;
aminoalcohols, such as ethanolamine, N-methyl-ethanolamine, N-ethyl-ethanolamine, N-butyl-ethanolamine, 2-amino-1-propanol, 2-amino-phenylethanol, mono - or polyaminopropyl with more than two alifaticheskii bound hydroxyl groups, such as, for example, Tris(hydroxymethyl) methylamine, glucamine, N,N'-bis-(2-hydroxyethyl)-Ethylenediamine.

Can also be used a mixture of two or more of the above compounds VI.

The above-mentioned compounds VI according to the invention were condensed with carboxylic or sulfonic keys is output, or a mixture of two or more of them, and at least one, preferably all, free, able to condense groups within the compounds VI is subjected to condensation with the compound VII. As carboxylic or sulfonic acid VII in the context of the present invention can be applied to essentially all of the carboxylic and sulfonic acid containing at least one radically curable functional group, and derivatives thereof. When used here, the term "derived" encompasses both compounds derived from carboxylic or sulfonic acid-modified acid functions, such as, for example, esters, halides or anhydrides of the acids, and compounds derived from carboxylic or sulfonic acid-modified carbon chain carboxylic or sulfonic acids, such as, for example, halogenecarbonate or galogenarenov acid.

As compound VII here, in particular, should be called:
,-unsaturated carboxylic acid or,-unsaturated carboxylic acid.

Particularly suitable,
in which R1, R2and R3denote hydrogen or alkyl residues with 1 to 4 carbon atoms, and among them, preferred are acrylic and methacrylic acid; further, suitable cinnamic acid, maleic acid, fumaric acid, taconova acid or p-vinylbenzoic acid, and their derivatives, such as anhydrides, for example maleic anhydride or itacademy anhydride;
halides, in particular acid chlorides such as acrylic acid chloride or methacrylic kilty;
esters, such as, for example, (cyclo)alkyl(meth)acrylate with the carbon atoms to 20 in the alkyl residue, such as, for example, methyl-, ethyl-, propyl-, butyl-, hexyl-, 2-ethylhexyl-, stearyl-, lauryl-, cyclohexyl-, benzyl-, trifluoromethyl-, hexaferrites, tetrafluoropropyl(meth)acrylate, polypropyleneglycol(meth)acrylates, poliatilenglikole(meth)acrylates, poly(meth)acrylates of polyols, such as, for example, glycerine(meth)acrylate, trimethylolpropane(meth)acrylate, PENTAERYTHRITE or three(meth)acrylate, diethyleneglycol(mono-(2-aryloxy)ethyl)carbonate, poly(meth)acrylates of alcohols, which have radically curable group such as, for example, esters of (meth)achromaticity carboxylic acid, such as, for example, vinyl acetate, finalproject, vinylboronate, vanillacream, vinylacetat, benildeans, ministart, vinylacetat, vinylketones, divinisation, divinylbenzene, 2-vinyl-2-ethylhexanoate, vinyltrifluoroborate;
complex allyl esters of other aliphatic or aromatic carboxylic acids, such as, for example, ZIOC scientists, arylpropionate, allylmalonate, allergiccontact, allelectric, allidina, AllStart, allylacetate, allylmalonate, allylchloride, allylacetate, diallylamine, diallylmalonate, cialisonline, diallylphthalate, diallylamine, diallylamine, cialiscanadianpharmacy, alliterated, allylphosphonate, allimportant;
,-unsaturated carboxylic acids or their derivatives, such feniluksousna acid, 2-methylvinylketone acid, isobutyl-3-butenoate, allyl-3-butenoate, allyl-2-hydroxy-3-butenoate, diketene;
sulfonic acids, such as, for example, vinylsulfonic acid, allyl - and medicalinsurance acid, and their esters and halides, vinyl ether of benzosulfimide acid amide 4-vinylbenzenesulfonic acid.

Can PR is osobogo to radical polymerization compounds X, used for obtaining the polymer IX, should, in particular, to include the following:
olefinic hydrocarbons, such as, for example, ethylene, propylene, butylene, isobutylene, hexene or higher homologues and vinylcyclohexane;
(meth)Acrylonitrile;
halogenated olefinic compounds, such as, for example, vinylidenefluoride, vinylidenechloride, viniferin, vinyl chloride, hexaferrites, cryptochrome, 1,2-dichloroethylene, 1,2-defloration and tetrafluoroethylene; vinyl alcohol, vinyl acetate, N-vinyl pyrrolidone, N-vinylimidazole, vinylformamide;
nitrocharge phosphorus, such as, for example, dechlorinated phosphorus, hexachlor(triphosphate), and their partially or completely substituted alkoxy, phenoxy-, amino - and forelcosure derivatives, i.e. compounds which can be polymerized with the formation of polyphosphazene;
aromatic, olefinic compounds, such as, for example, styrene,-methylsterol;
vinyl ether, such as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, oktilovom, decroly. dodecyloxy, 2-ethylhexyloxy, cyclohexyloxy, benzyl, triptoreline, geksaftorpropilenom, tetrafluoropropylene ether.

These compounds X as well as products V condensation will polimerizuet conventional, well-known specialist way, preferably radically, and in the obtained molecular masses really described below for compound VIII.

As compound VIII in the first place can be considered the connection medium (srednetsenovoj) molecular weight of at least 5000, preferably from 5000 to 20000000, in particular from 100,000 to 6000000, which can solutionat the lithium cations and act as a binder. Suitable compounds VIII are, for example, polyesters and copolymers that contain at least 30 wt. % the following structural level, in terms of the total weight of compounds VIII:

and R1, R2, R3and R4represent aryl, alkyl groups, preferably methyl groups, or hydrogen, are the same or different and may contain heteroatoms, such as oxygen, nitrogen, sulfur or silicon.

Such compounds are described, for example, in M. C. Armand et al. Fast Ion Transport in Solids, Elsevier, New York, 1979, pages 131-any.

The above polymeric mass IV, respectively, the polymer IX, may also exist in the form of a foam, and in this case, the solid II distributed it as such. A mixture of IIA according to the invention should consist of 1-95 wt.%, preferably 25-90 wt.% and, in particular, 30-70 wt.% of solids III and 5-99 wt.%, preferably 10-75 wt.% and, in particular, 30-70 wt.% of the polymeric mass IV, but it is desirable that the compound VIII polymeric mass IV had a medium (srednecenovogo) molecular weight of from 5,000 to 100000000, preferably from 50,000 to 8000000. Polymeric mass IV may be obtained by interaction of 5-100 wt. %, preferably 30-70 wt.%, in terms of polymer weight IV, compound V with 0-95 wt.%, in particular 30-70 wt.%, in terms of polymer weight IV, with the compound VIII.

The mixture IIb according to the invention should consist of 1-95 wt.%, preferably 25-90 wt.% and, in particular, 30-70 wt.% of solids III and 5-99 wt.%, preferably 10-75 wt.% and, in particular, 30-70 wt. % of polymer IX, but it is desirable that the compound VIII polymer IX had a medium (srednecenovogo) molecular weight of from 5,000 to 100000000, preferably from 50,000 to 8000000. Polymer IX can be obtained by reacting the eschete on the polymer IX, with compound VIII.

Below are proposed according to the invention composition Ia and Ib, respectively, a mixture of IIA and IIb are discussed together and are referred to as "the composition according to the invention, respectively the mixture according to the invention".

To obtain the composition according to the invention, which should contain a mixture according to the invention in an amount of from 1 to 100 wt.%, preferably from 35 to 100 wt. % and in particular from 30 to 70 wt.%, in terms of the composition according to the invention can be obtained a mixture of solids III, V condensation, if necessary, compounds VIII, respectively, the mixture of solids III, compound X and compound VIII and the usual additives, such as plasticizers, preferably polyethylene oxide or polypropyleneoxide plasticizers.

As plasticizers can be used aprotic solvents, preferably such that solutionwhat lithium ions, such as dimethylcarbonate, diethylcarbamyl, dipropylamine, Diisopropylamine, dibutylamine, ethylene carbonate resulting, propylene carbonate; oligoanilines, such as, for example, disutility ether, di-tert-butyl ether, daintily ether, directroy ether, deceptively ether, dioctyloxy epilobii ether, 1-tert-butoxy-2-methoxyethane, 1-tert-butoxy-2-ethoxyethane, 1,2-dimethoxypropane, 2-methoxyethylamine ether, 2-ethoxyethyl ether, dietilenglikoluretan ether, diethyleneglycol-tert-butyl methyl ether, triethylenemelamine ether, tetraethylethylenediamine ether-butyrolactone, dimethylformamide; hydrocarbons with the General formula CnH2n+27<n<50; organic phosphorus compounds, in particular phosphates and phosphonates, such as, for example, trimethylphosphate, triethyl phosphate, tripropyltin, tributyl phosphate, triisobutylene, triphenylphosphate, trihexalon, trick-Telfast, Tris(2-ethylhexyl)phosphate, tredecimpunctata, diethyl-n-butylphosphine, Tris(butoxyethyl)phosphate, Tris(2-methoxyethyl)phosphate, Tris(tetrahydrofuryl)phosphate, Tris(1H, 1H,5H-octafluoropentyl)phosphate, Tris(1H, 1H-tiptoety)phosphate, Tris(2-diethylamino)phosphate, diethylaminophenyl, depropylpropafenone, demotivational, direktinvestitionen, dioctyladipate, ethyldimethylammonium, metiltiofosfonata, triethylphosphate, dimethyl(2-oxopropyl)phosphonate, diethyl(2-oxopropyl)phosphonate, dipropyl(2-oxopropyl)phosphonate, ethyldimethylammonium, trimethylphosphate, triethylphosphate ulfate, the sulfonates, sulfoxidov, sulfones and sulphites, such as, for example, dimethylsulfate, diethylsulfate, picosulfate, dimethyl sulfone, diethylsulfate, diethylproprion, dibutyltin, tetramethylarsonium, methylsulfone, dimethylsulfoxide, diethylsulfoxide, dipropylacetamide, dibutylsebacate, tetramethylsilane, ethylmethanesulfonate, 1,4-butanediol bis(methanesulfonate), diethylsulfate, dipropylacetate, diotisalvi, vexillologist, dioctyladipate, SO2ClF;
NITRILES, such as Acrylonitrile;
the dispersant, in particular, with the structure of a surfactant;
as well as mixtures thereof.

The composition of the invention can be dissolved or dispersed in the inorganic, preferably organic, liquid diluent, but it is desirable that the composition according to the invention have a viscosity of preferably from 100 to 50,000 MPawith, and then it is applied on the substrate material in a known manner, such as spraying, pouring, dipping, centrifuging, using a roll printing method, high, deep or flat printing screen and method. Further processing can be carried out, as usual, for example, by removal of the diluent is particularly detailreturn and dioxane, hydrocarbons, in particular mixtures of hydrocarbons, such as benzene, toluene and xylene, complex aliphatic esters, in particular ethyl acetate and butyl acetate, and ketones, in particular acetone, ethylmethylketone and cyclohexanone. You can also use combinations of these diluents.

As the substrate material can be treated materials commonly used for the electrodes, preferably metals such as aluminum and copper. Can also be used temporary intermediate substrates, such as films, in particular films of polyester, such as films of polyethylene terephthalate. It is reasonable to provide such films as a separating layer, preferably from polysiloxanes.

Preparation of solid electrolytes and separators may also be termoplasticheskie, for example by injection molding, casting from the melt, pressing, plasticities or extrusion, optionally followed by a stage of calendering the composition of the invention.

After the film forming composition according to the invention of volatile components such as solvents or plasticizers, can be removed. The crosslinking of the compositions according to the invention can be carried out in a known manner, for example, by obleceni is In and absorbed radiation dose from 5 to 50 Mrad, ultraviolet or visible light, and usually it is advisable to add an initiator, such as benzyldimethylamine or 1,3,5-trimethylbenzenesulfonamide, in quantities, in particular not more than 1 wt.%, in terms of polymer weight IV, respectively, on the polymer IX, and to carry out the crosslinking in the course of, as a rule, from 0.5 to 15 minutes, preferably in an atmosphere of inert gas, for example nitrogen or argon; by thermal radical polymerization, preferably at temperatures over 60oWith, but it is desirable to add an initiator, such as azobisisobutyronitrile, in amounts generally not more than 5 wt.%, preferably from 0.05 to 1 wt.%, in terms of polymer weight IV, respectively, on the polymer IX; by electrochemically induced polymerization; or by ionic polymerization, for example, acid-catalyzed cationic polymerization, and as a catalyst in the first place can be considered acid, preferably a Lewis acid such as F3or LiBF4or LiF6. It is reasonable to catalysts containing lithium ions, such as LiBF4or LiPF6remained in the solid electrolyte or separator in the form of salts provodimosti.lechenie cell in the composition administered can dissociate containing cations of lithium compound, the so-called salt conductivity, and optionally other additives, such as organic solvents, so-called electrolyte.

These substances can be partially or completely mixed with the receiving layer composition or introduced into it after receiving layer. As salts conductivity can be used are well known and are described, for example, in European patent application EP-A 96629 salt conductivity. It is particularly suitable such compounds as, for example, LiF6, LiAsF6, LiSbF6, LiClO4, LiN(CF3SO2)2, LiBF4or LiCF3SO3as well as mixtures of such compounds. These salts conductivity are used in quantities of from 0.1 to 50 wt.%, preferably from 0.1 to 20 wt.%, in particular from 1 to 10 wt.%, in terms of the mixture according to the invention.

As organic electrolytes can be seen above when discussing the "plasticizers" connections, and apply conventional organic electrolytes, preferably esters such as ethylene carbonate resulting, propylene carbonate, dimethylcarbonate, diethylcarbamyl or mixture of such compounds.

It is advisable to offer according to the present invention is a solid electrolyte, Sep is t 10 to 500 μm, even more preferably from 10 to 200 μm and in particular from 20 to 100 μm.

Since the composition according to the invention is intended for use as a cathode, respectively, to obtain a cathode, it is usually introduced applied to the cathode electrochemically active connection with electronic conductivity (cathodic compound), preferably the compound of lithium. In particular, such compounds are:
LiCoO2, LiNiO2, LixMnO2(0<x1), LixMn2O4(0<x2), LixMoO2(0<x2), LixMnO3(0<x1), LixMnO2(0<x2), LixMn2O4(0<x2), LixV2O4
(0<x2,5), LixV2O3(0<x3,5), LixVO2(0<x1), LixWO2(0<x1), LixWO3
(0<x1), LixTiO2(0<x1), LixTi2O4(0<x2), LixRUO Li2(0<x1), LixFe2O3
(0<x2), LixFe3O4 (0<x3,8), LixV3S5(0<x1,8), LixTa2S2(0<x1), LixFeS (0<x1), LixFeS2(0<x1), LixNbS2
(0<x2,4), LixMoS2(0<x3), LixTiS2(0<x2), LixZrS2(0<x2), LixNbSe2
(0<x3), LixVSe2(0<x1), LixNiPS2(0<x1,5), LixFePS2(0<x1,5).

When used as anode in the composition according to the invention is introduced as the anode material commonly used and known in the prior art, the electrochemically active connection with electronic conductivity (anode connection), and such compounds are, in particular, the following connections:
Li, laisteridge metal alloys, micronized carbon black, natural and synthetic graphite, synthetic graphitized coal dust and carbon fiber, oxides such as titanium oxide, zinc oxide, tin oxide, molybdenum oxide, tungsten oxide, carbonate as the anode in the composition according to the invention is added to 20 wt.% in terms of the total weight of the composition, soot conductivity and, if necessary, the above-mentioned conventional additives. When applying to obtain the cathode or the cathode composition contains, calculated on the total weight of from 0.1 to 20 wt.% conductive carbon black.

The composition of the invention can be used in electrochemical elements as the only solid electrolyte, and/or separator, and/or electrode, or in a mixture with other solid electrolytes, separators and/or electrodes.

Further, the present invention relates to suitable for use, in particular in electrochemical elements, multi-layer composite element, preferably in the form of a film, more preferably in the form of a film with a total thickness of from 15 to 1500 μm, in particular, with a total thickness of from 50 to 500 μm, comprising at least one first layer containing electrochemically active connection with electronic conductivity, and at least one second layer containing the above composition according to the invention and not containing electrochemically active compounds with electronic conductivity.

Further, the present invention describes a method of obtaining such a multilayer composite element, comprising the following stages:
(the showing of the layer, specified above; and
(III) subsequent combining at least one first layer and at least one second layer in the usual way coating.

Preferably, at least one second layer is applied to the temporary substrate. According to the invention using commonly used temporary substrate, such as, for example, the separator film of polymer or paper, preferably coated paper, such as, for example, siliconized polyester film. The receipt of this second layer, however, it is also possible on a continuous substrate, such as, for example, a discharge electrode or no substrate.

The combination, respectively, the manufacture of the above layers is carried out by means of coating, respectively, for the films, without applying pressure, such as, for example, films irrigation or coating using a doctor blade, and means applying pressure, such as, for example, extrusion, laminating, lamination, calendering or extrusion. If necessary, the thus obtained multi-layer composite element can be sewn, respectively overiden, radiation, electrochemical Elenio may also contain the above-mentioned first layer.

As follows from the above, the multi-layer composite element can be easily performed with the components of release film/separator (second layer)/electrode (first layer).

Next, by applying a double-sided coating may be running multi-layer composite element with the components of the anode/separator/cathode.

When you do this, proceed as follows:
First anode material, such as tin oxide, conductive carbon black, the composition according to the invention, salt conductivity and a plasticizer such as propylene carbonate, mixed together and the obtained mixture is then poured onto the electrode, and then irradiated with UV light (component 1). Then on the discharge electrode, covered with soot conductivity, causing the cathode material, for example LiMn2O4and then pour the mixture consisting of the composition according to the invention, salts of the conductivity and the plasticizer. Then this multilayered composite element is irradiated with UV light (component 2). By combining both of the above components receive the multi-layer composite element, which can be used in conjunction with any solid and/or liquid electrolyte in the electrochemical element.

The above mniki, accordingly, the discharge electrodes, since the resulting multi-layer composite element consisting, as above, from a first and a second layer itself has a mechanical strength sufficient for use in electrochemical cells.

Filling such a multilayer composite electrolyte and salt conductivity can be carried out both before merging layers, if necessary, after contact with suitable discharge electrodes, such as metal foil, and even after installing the multi-layer composite element in a battery case, and a special microporous structure of the layers in the application of the composition according to the invention is due, in particular, the presence of above solids in the separator, and, possibly, the electrodes facilitates the absorption of the electrolyte and salt conductivity and the displacement of air in the pores. The filling can be carried out at temperatures from 0oC to about 100oWith depending on the used electrolyte.

Proposed according to the present invention, the electrochemical cell can be used as automotive, instrument or flat battery.

Further, the present invention relates to an electrochemical element containing a solid electrolyte, the separator or the electrode, as defined above, or a combination of two or more of them, as well as to the application of the aforementioned electrochemical element as automotive, instrument or flat battery.

In addition, the present invention relates to the use of solids III with the size of the primary particles is from 5 nm to 20 μm in the solid electrolyte, the separator or the electrode to increase the stability of the electrochemical elements to cyclic charge/discharge, as when carrying out the present invention it was found that the addition of such solids exceptionally positive effect on the electrochemical properties of the elements.

Examples
Example 1
75 g gidrofobizirovannogo epoxysilane of wollastonite (Wollastonit) Treminpense which has a pH of 8.5, was dispersed using a high speed stirrer in 300 g of toluene. Then added to the mixture of 12.5 g of polyethylene oxide with average (srednetsenovoj) molecular weight 2000000 (Polyoxthe company Union Carbide), 12.5 g of methacrylic diafora the propylene oxide-ethylene oxide-blockpolymers (PluriolPE600, the company BASF Aktiengesellschaft) and 0.02 g of UV photoinitiator (LucirinBDK, firm BASF Aktiengesellschaft).

The mixture is then put squeegee with injection molding gap of 300 μm on silikonizirovannaya dividing the paper at 60oWith over 5 minutes to remove the solvent after removal of the dried coating will receive a film thickness of 40 μm, which is subjected to photostructurable in an argon atmosphere by a 10-minute exposure from a distance of 5 cm from overactivity fluorescent lamps (TL 09, firm Philipps).

The flexible film has an excellent bending strength. It doesn't break when you bend it with bending radii, much less 1 mm

Even after two weeks storage at room temperature, the film does not contain spiriticheskij crystals of polyethylene oxide and shows high resistance to swelling in fisheye salt conductivity, absorbed in sufficient quantities as a result of spontaneous diffusion within a few minutes by increasing the mass in the result of swelling of less than 50 wt.%.

The swollen film has high strength. The results are presented in the table.

Example 2
60 g of wollastonite with an average particle size of 3 μm, aqueous suspension which has a pH of 8.5, was dispersed using a high speed stirrer in 200 g of tetrahydrofuran (THF). Then added to the mixture of 13.3 g of polyethylene oxide with average (srednetsenovoj) molecular weight 2000000 (Polyoxthe company Union Carbide), 13.3 g of methacrylic diafora the propylene oxide-ethylene oxide-blockpolymers (PluriolPR600, the company BASF Aktiengesellschaft), 13.3 g soluble in THF copolymer vinylidenefluoride with geksaftorpropena (Kynarflex2850, the company ELF Atochem) and 0.02 g of UV photoinitiator (LucirinBDK, firm BASF Aktiengesellschaft).

The mixture is then put squeegee with injection slit 500 μm on silikonizirovannaya dividing the paper at 60oWith over 5 minutes to remove the solvent after removal of the dried coating produces the deposits from a distance of 5 cm from superactivity fluorescent lamps (TL 09, the firm Philipps).

The flexible film has an excellent bending strength. It doesn't break when you bend it with bending radii, much less 1 mm

Even after two weeks storage at room temperature, the film does not contain spiriticheskij crystals of polyethylene oxide and shows high resistance to swelling in the above-mentioned organic electrolytes containing salt conductivity.

Organic electrolytes containing salt conductivity, absorbed in sufficient quantities as a result of spontaneous diffusion within a few minutes by increasing the mass in the result of swelling of less than 50 wt.%.

The swollen film has high strength. The results are presented in the table.

Example 3
60 g of silica flour (Silbond800 EST, firm Quarzwerke Frechen) with an average particle size of 3 μm, aqueous suspension which has a pH of 7.5, was dispersed using a high speed stirrer in 250 g of tetrahydrofuran (THF). Then added to the mixture of 13.3 g of polyethylene oxide with average (srednetsenovoj) molecular weight 3000000 (Polyoxthe company Union Carbide), 13.3 g of methacrylic diafora the propylene oxide-ethylene oxide-Blackpool the th in THF copolymer vinylidenefluoride with geksaftorpropena (Kynarflex2850, the company ELF Atochem).

The mixture is then put squeegee with injection slit 500 μm on silikonizirovannaya dividing the paper at 60oWith over 5 minutes to remove the solvent after removal of the dried coatings are produced film thickness of 50 μm, which is subjected to photostructurable in nitrogen atmosphere by electrons at the acceleration voltage of 150 kV with absorbed radiation dose of 30 Mrad.

The flexible film has an excellent bending strength. It doesn't break when you bend it with bending radii, much less 1 mm

Even after two weeks storage at room temperature, the film does not contain spiriticheskij crystals of polyethylene oxide and shows high resistance to swelling in the above-mentioned organic electrolytes containing salt conductivity.

Organic electrolytes containing salt conductivity, absorbed in sufficient quantities as a result of spontaneous diffusion within a few minutes by increasing the mass in the result of swelling of less than 50 wt.%.

The swollen film has high strength. The results are presented in the table.

Example 4
60 g gidrofobizirovannogo metacriticism of wollastonite with an average R is 200 g of tetrahydrofuran (THF). Then added to the mixture of 13.3 g of polyethylene oxide with average (srednetsenovoj) molecular weight 2000000 (Polyoxthe company Union Carbide), 13.3 g of methacrylic diapir acid propylene oxide-ethylene oxide-blockpolymers (PluriolPE600, the company BASF Aktiengesellschaft), 13.3 g soluble in THF copolymer vinylidenefluoride with geksaftorpropena (Kynarflex2850, the company ELF Atochem) and 0.02 g of azobisisobutyronitrile.

The mixture is then put squeegee with injection slit 500 μm on silikonizirovannaya dividing the paper at 60oWith over 5 minutes to remove the solvent after removal of the dried coatings are produced film thickness of 50 μm, which is subjected to photostructurable in nitrogen atmosphere by a 10-minute exposure from a distance of 5 cm from overactivity fluorescent lamps (TL 09, firm Philipps).

The flexible film has an excellent bending strength. It does not break when bending it with bending radii, much less 1 mm

Even after two weeks storage at room temperature, the film does not contain spiriticheskij crystals of polyethylene oxide and shows high resistance to abujanigeria salt conductivity, absorbed in sufficient quantities as a result of spontaneous diffusion within a few minutes by increasing the mass in the result of swelling of less than 50 wt.%.

The swollen film has high strength. The results are presented in the table.

Example 5
Example 5 is essentially the same as example 1, but with the following changes:
Instead Tremin600 EST use Tremin939-600 MST, gidrofobizirovannym metallicana needle-like wollastonite with an average particle size of 3.5 μm; instead of PluriolPE600 use PluriolE600, polymerizat of ethylene oxide, respectively, in the same quantities as in example 1; the blade, is used for applying the resulting mixture on silikonizirovannaya separating paper, has a casting gap of 200 μm.

The results of the film obtained and processed in accordance with example 1, are presented in the table.

Comparative example 1
12.5 g of polyethylene oxide with average (srednetsenovoj) molecular weight 2000000 (Pluriolthe company Union Carbide), 12.5 g IU the , PE600, the company BASF Aktiengesellschaft) and 0.02 g of UV photoinitiator (LucirinBDK, firm BASF Aktiengesellschaft) was dissolved in 200 g of THF.

The mixture is then put squeegee with injection slit 750 μm on silikonizirovannaya dividing the paper at 60oWith over 5 minutes to remove the solvent after removal of the dried coating will receive a film thickness of 40 μm, which is subjected to photostructurable in an argon atmosphere by a 10-minute exposure from a distance of 5 cm from overactivity fluorescent lamps (TL 09, firm Philipps).

The flexible film has an excellent bending strength. It doesn't break when you bend it with bending radii, much less 1 mm, Even after two-week storage at room temperature, the film does not contain spiriticheskij crystals of polyethylene oxide and shows high resistance to swelling in the above-mentioned organic electrolytes containing salt conductivity.

Organic electrolytes containing salt conductivity, absorbed in sufficient quantities as a result of spontaneous diffusion within a few minutes by increasing the mass in the result of swelling of less than 150 wt.%, moreover, there is a significant changed igodit in all cases, to the failure of the electrochemical element as a result of too high speeds of discharge or microconidia closures.

The results are presented in the table.

Comparative example 2
75 g gidrofobizirovannogo epoxysilane of wollastonite (Tremin800 EST, firm Quarzwerke Frechen) with an average particle size of 3 μm, aqueous suspension which has a pH of 8.5, was dispersed using a high speed stirrer in 300 g of toluene. Then added to the mixture of 12.5 g of polyethylene oxide with average (srednetsenovoj) molecular weight 2000000 (Polyoxthe company Union Carbide), 12.5 g of methacrylic diafora the propylene oxide-ethylene oxide-blockpolymers (PluriolPE600, the company BASF Aktiengesellschaft) and 0.02 g of UV photoinitiator (LucirinBDK, firm BASF Aktiengesellschaft).

The mixture is then put squeegee with injection molding gap of 300 μm on silikonizirovannaya dividing the paper at 60oWith over 5 minutes to remove the solvent after removal of the dried coating will receive a film thickness of 40 microns.

The flexible film has an excellent bending strength. It doesn't break when you bend it with bending radii, much less 1 mm

After two weeks storage at room temperature the film is not content the above-mentioned organic electrolytes, containing salt conductivity. After a few minutes the swelling on the film cracks or she sticks together, making it impossible for her to use.

The results are presented in the table.

Comparative example 3
According to US-A 5429891, example 1 (F), to a mixture of 30 g of the copolymer vinylidene-fluoride with geksaftorpropena (Kynarflex2822, the company ELF Atochem), 20 g silanizing pyrogenic silicic acid (Aerosil R974, the company Degussa), suspension in water which has a pH of 7, 50 g of dibutyl phthalate (Palatinol With the firm BASF Aktiengesellschaft) and 200 g of acetone add 5 wt.% in terms of dibutyl phthalate, trimethylolpropane.

The mixture is then put squeegee with injection slit 750 μm on a glass plate, dried for 15 minutes in the air stream and are buried between layers of Mylarthe thickness of 0.075 mm, Then the film layer thickness of 100 μm structured by irradiation by electrons with an energy of 4.5 MeV to the absorbed dose of 5 mrad, and the dose in a single pass exposure is 2.5 Mrad.

The flexible film has an excellent bending strength.

Before applying film in lithium-ion batteries require time-consuming odellodom achieved resistance to cyclic charge/discharge is unsatisfactory. Removal of the plasticizer film five times in 10 minutes, extracted at room temperature in diethyl ether, which are taken in the quantity equal to 50-fold weight of the film. After removal of the plasticizer, the film becomes fragile and breaks easily when bent.

The film containing no plasticizer, shows high resistance to swelling in the above-mentioned organic electrolytes containing salt conductivity.

Organic electrolytes containing salt conductivity, absorbed in sufficient quantities as a result of spontaneous diffusion within a few minutes.

The swollen film has high strength. The results are presented in the table.


Claims

1. Composition to obtain electrodes used in electrochemical elements, solid electrolytes and separators containing inorganic solid substance and a polymer weight, wherein as the polymer mass contains mass, obtained by polymerization of 5-100 wt. % in recalculation on weight of a condensation product of a polyhydric alcohol containing in the main chain atoms of carbon and oxygen, and at least 1 mole per mole of polyhydric alcohol

2. The composition according to p. 1, characterized in that it further comprises a copolymer of vinylidenefluoride and hexaferrite.

3. Composition under item 1 or 2, characterized in that it contains gidrofobizirovannogo inorganic solid substance.

4. The multi-layer composite element that includes at least one first layer containing electrochemically active connection with electronic conductivity, and at least one second layer made of a composition comprising an inorganic solid substance and a polymer weight, wherein the second layer is made of the composition according to one of paragraphs. 1-3.

5. The use of inorganic solids with the size of the primary particles is from 5 nm to 20 μm as an additive to the solid electrolyte, separator and e

 

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