TW388998B - Mixtures suitable as solid electrolyte or separator for electrochemical cells and having specific plasticizers - Google Patents

Description

Printed by A7 __B7 of the Consumers' Cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs V. Description of the Invention (1) The present invention relates to a mixture particularly suitable for electrochemical cells having a lithium ion-containing electrolyte; it is used in, for example, solid electrolytes, separators, and electrodes Applications: solid electrolytes, separators, electrodes, body sensors, electrochromic windows, displays, capacitors, and ion-conducting films containing this type of mixture; electrochemical cells with such solid electrolytes, separators, and / or electrodes ; And the use of solids present in this mixture to improve cycle stability on electrochemical cells. Electrochemical cells, especially rechargeable, are conventional, for example from UlLmann's Encyclopedia of Industrial Chemistry, 5th edition, volume A3, VCH VerlagsgesellschafitmbH, Weinheim, 1985, pages 343-397. Due to the high specific energy storage density of lithium battery packs and lithium ion battery packs, they occupy a special place in these batteries, especially as secondary batteries. As mentioned, in particular the excerpt from "Ullmann " above, the cathode of this battery contains a lithium compound oxide of manganese, cobalt, vanadium, or nickel; the simplest case in terms of stoichiometry is described as LiMn2 04, LiCo02, LiV2 05 or LiNi02. These compound oxides react reversibly with substances such as graphite, which enables lithium ions to be incorporated into their crystal lattice, lithium ions are removed from the crystal lattice, and metal ions such as manganese therein , Cobalt, or nickel ion oxidation. In an electrochemical cell, this reaction can be used to store electrical energy by using a compound that accepts lithium ions, meaning an anode material, and a lithium-containing compound oxide, meaning a cathode material, using an electrolyte. Separated, lithium ions from the compound oxide can sneak into the anode material (charge) during the process. Compounds suitable for reversible storage of lithium ions are usually fixed with an adhesive -4-This paper's standard applies to Chinese National Standards (CNS) Λ4 «ί 格 （210Χ 297,: Μί) I 、 1τ ------- ^ *-(Please read the precautions on the back before filling in ft? This page) A7 B7 The Central Bureau of Standards of the Ministry of Economic Affairs only consumes Cooperative printed five. Description of the invention (2 to the collector. During battery charging, the electron system flows through an external voltage source, and the ion system passes through the electrolyte toward the anode material. When the battery is used, the plutonium ion system flows through the electrolyte, but the electronic system From the anode material to the cathode material through a load 0 In order to avoid short circuits in electrochemical cells, a thin layer that is electrically insulating but can pass through lithium cations is located between the two electrodes. This can be called a solid electrolyte Or conventional separators. As is generally known, solid electrolytes and separators are composed of a carrier material, which is incorporated into a dissociable compound that contains lithium cations and is used to increase lithium ion conductivity, and generally Incorporation of other additives, such as solvents. Polyoxyalkylene-based solid electrolytes are known and described in, for example, EP-A559 317, EP-A576 686, EP-A537 930, EP-A585 072 and US 5 279 910. The polyethers described in these references are modified at their terminal or functional groups, such as using (meth) acrylfluorenyl, and in Before being used as a solid electrolyte, it is crosslinked by introducing energy (heat or light). It usually also contains a conductive salt such as LiPF6 to improve its electrical conductivity. Use solids to improve the mechanical and thermal properties of solid electrolytes And electrical strength are not described in these references. Therefore, although the systems described in these references have been crosslinked, the mechanical strength and porosity of the formed films, and short-circuit protection are not necessarily Has satisfactory properties. So far the solvents used in Li batteries are mainly alkyl ethers, such as dimethyl ether, and olefinic carbonates, such as vinyl carbonate (EC) and propylene carbonate: private clothing — ^ -----. 玎 ------ line-- (Please read the notes on the back before filling out this page) tThe paper scale is applicable to China National Standards (CNS), \ 4 坎 _ 格 （ 210X 297 films) A7 B7 printed by employees of the Central Standards Bureau of the Ministry of Economic Affairs. Fifth, the description of the invention (3) Ester (PC). Such systems are described in particular in JP 08 273 700 and JP 09 115 548. Electrolyte solutions based on various esters are also known. For example, WO 97/16862 describes an electrolyte solution containing boric acid esters of the following formulae (A) to (D): *, -o, " l-〇

Where X is halogen, R1, R2, R3, and R4 are straight or branched aliphatic or aromatic alkyl groups, which may be substituted with different anionic groups, and Z is straight or branched aliphatic Or aromatic alkyl or siloxane. J. Electrochem. Soc., 143, 1996, pp. 4047-4053, describes an electrolyte solvent for rechargeable lithium and lithium-ion batteries, based on borate, called BEG-1, and It has the following formula (E) and is used in combination with EC and / or PC.

ΕΡ-Β-0 599 534 is a description of the carbonate compound R1 -CH2 -0-C0-0-CH2 R2 (F) of the following formula (F) _- 6 -_ This paper applies the Chinese National Standard (CNS) A4iUi grid ( 2 丨 Ox Gong Ling) -----.-- J--Private Clothing -------- ΪΤ ------. ^ (Please read the notes on the back before filling this page) A7 V. Description of the invention (4) wherein R1 is hydrogen, alkynyl or fluorenyl substituted by one or more _ atoms, and R2 is a tiger group which does not have gas at the position, or does not have chlorine at the π position and is Or multiple atom-substituted alkyl groups, with the proviso that the fish and 2 are not the same, the compound Q ^ -o-cao-CHHCF2) 4 ^-, except for, and its use in non-aqueous electrolyte solutions . EP-A0698 933 relates to a non-aqueous battery, which contains a special electrolyte solution, which in particular contains a phosphate triester of formula (R0) 3PK), wherein each of the radicals R is the same or different, and is a calcined radical, or two Each fluorene group can form a ring with the phosphorus atom to which they are bound. Alkyl phosphates of this type, and their use in non-aqueous electrolyte solutions and in batteries, are also described in EP-A 0 696 077. Formula 0 = P (-0- (CH2CH20) qR2) 3 phosphate ester 'wherein 丨 to 忉, and 圮 is q-C4-alkyl, and its use as an electrolyte in a zinc battery is described in JP 07 161 357. Other phosphoric acid esters having a nicotinic base and their use as electrolytes in lithium ion batteries are described in jp 58 206 078. JP 61 256 573 describes an electrolyte based on a phosphorous vinegar polymer containing at least one polymerizable group. 3 An object of the present invention is to overcome the above disadvantages and provide a solid electrolyte and a separator particularly suitable for manufacturing the same. Mixtures, and can be used to make electrodes in electrochemical cells and other applications described herein. I have found that this project is achieved using a novel mixture, which contains the solid melon as described below; the use of this novel mixture is to obtain a solid electrolyte 'separator or electrode, which is compared with the systems known so far, f please First read the notes on the back of 59 before filling out this page > Central Standard of the Ministry of Economic Affairs "

Paper size 14 ^ 1 Medium_ ^: material (CNS) (210X297 inscription) Printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs, printed on the paper. The paper size is applicable to Chinese national standards (CNS) Λ4ίϋΰ ^ Α7 Β7 V. Description of the invention (5) With improved short-circuit protection, increased compressive strength, especially at higher than UCTC, and larger porosity, and can continue to suppress the formation of Li dendritic crystals "The existence of this solid also provides the improved cycle safety. Qualitative and higher current capacity electrochemical cells. If a better alkaline animal is used, the acid system formed during the operation of the electrochemical cell is further removed or neutralized. "Using the compounds (E1) to (E5) <vinegar as defined herein exists in the mixture The mechanical properties of the films made from this mixture, as well as the ease with which they can be peeled from the temporary carrier, are improved. At the same time, the esters used also have electrolyte properties. Therefore, a specific embodiment of the present invention is to provide a mixture la 'which contains a mixture Ha, which is composed of the following materials: a) 1 to 95% by weight of solid m, preferably alkaline solid rhenium, having a primary particle size 5 to 20 microns, and b) 5 to 99% by weight of the polymer composition JY, which can be obtained by polymerizing

bl) based on composition IV, a condensation product V α to 5 to 100% by weight of the following: a) at least one compound VI ′ which is capable of reacting with picoric acid or with phosphonic acid or a derivative thereof or a mixture of two or more thereof, And Lu) per mole of compound VI, at least 1 mole of folic acid or dicarboxylic acid VII 'having at least one functional group capable of radical polymerization, or a derivative thereof or a mixture of two or more thereof, and b2) 0 to 95 weight based on Composition IV. /. Another compound vm '-8-(210χ 297λ \ ^ ~ Ρ ~: · —, — equipment ---- ^ --- order ---- --- line (please read the precautions on the back before filling in the tips (This page) A7 B7 V. Description of the invention (6) It has an average molecular weight (average number) of at least 5,000 on its main chain or side. The chain has polyether segments, and at least one formula (E1) to (E5) Ester ORl B— OR2 \ 0 OR3 (E1) .-- (Please read the precautions on the back before filling this page)

O = C

O = P Ο Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

S ο .ORl OR2 ORl -OR2, OR3 / ORl, 〇2 (E2) (E3) (E4) -9 This paper size applies to Chinese National Standard (CNS) Λ 4% grid (210X297 total) A7 B7 V. Description of the invention (7 Printed by the Central Bureau of Standards, Ministry of Economic Affairs, Consumer Cooperatives, r4o or 1 \ / Si R30 ^ GR2 (H5) where each of R1, R2, R3, and R4 is the same as or different from the other, and has nothing to do with each other. Linear or branched chain qC: 4-alkyl, (_CH2_CH2_〇) n_CH3, where η is 1 to 3, C3_c0_cycloalkyl or aromatic hydrocarbon group, which can be substituted sequentially, with the condition that the group 囷 Ri, At least one of r2, R3, or R4 is (_CH2_CH2_Q) n-CH3, where η is 1 to 3. The above-mentioned mixture 乜 preferably contains the mixture Da, which is composed of a) 1 to 95% by weight The solid ffl, preferably alkaline solid rhenium, has a primary particle size of 5 nm to 20 microns, and b) 5 to 99% by weight of the polymer composition IV, which can be obtained by polymerizing the following materials called composition IV As a benchmark, the condensation product V α) of 5 to 100% by weight of the following substances: polyol α, which contains carbon and oxygen and cold in its main chain) per mole of polyol VI, at least 1 mole of α 々 · Unsaturated carboxylic acids νπ and b2) Based on Composition IV, 0 to 95% by weight of another compound, which has an average molecular weight (number average) of at least 5000, and has a puzzle on its main chain or side chain Chain segment. In another specific embodiment, the present invention provides a mixture of calendars. Please read the items on the back before filling in this page. Line -10 This paper size applies to the Chinese national standard (CNS grid (2l0x 297〇y) A7

A7 B 5. Description of the invention (8) It contains the compound nb, which is composed of the following materials: a) 1 to 95% by weight solid rhenium, preferably alkaline solid rhenium, having a primordial size of 5 nm to 20 microns, And b) 5 to 99% by weight of the polymer composition, can be obtained by polymerizing the following and M) based on polymer IX, 5 to 75% by weight. /. Compound X 'capable of radical polymerization and which is different from the acid or acid νπ or its derivative, or a mixture of two or more thereof, and b2) based on the polymer DC' 25 to 95% by weight of another compound νίΠ, which has an average fraction (average number) of at least 5000, a polyether segment on its main chain or side chain, and at least one ester of formula (E1) to (E5) ORl OR2 OR3 (E1) Ministry of Economic Affairs ORL printed by the Central Bureau of Standards Consumer Cooperatives

O = C \ 〇R2 (E2) -11-The paper scale is applicable to the Chinese National Standard (CNS) A4ML 枋 (2 丨 0x297) A7 B7 Five 'Explanation of the invention (

Each of R1, R2, R3, and R4 is the same or different from the other, and has nothing to do with each other. Each is a linear or branched CrQp alkyl group, (-CH2-CH2-0) n-CH3, where η is 1 To 3 ′ C3 -C6 -cyclohexyl or aromatic hydrocarbon group, which may be substituted in turn, with the proviso that at least one of the groups 圏 Ri, R2, R3 or R4 is 0) n-CH3, where n is 1 to 3 . The solid m used is mainly an inorganic solid, preferably an inorganic alkaline solid, the type of which is selected from the group consisting of oxides, chemical oxidations of elements of the main group of the periodic table, the second, the third, or the fourth subgroup or the fourth subgroup. Compounds, silicate sulfates, carbonates, phosphates, nitrides, amides, imides, and carbides, and hydrates, the type of which is selected from the group consisting of polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, Polydifluoroethylene, polyimide, and polyimide; this paper is included in this paper and is suitable for printing by the Central Bureau of Standards of the Ministry of Economic Affairs of the Ministry of Economic Affairs of China. Industrial and consumer cooperatives Yinu V. Description of the invention (10) Type polymer I solid dispersion; or a mixture of two or more of them β Specific examples are: oxides, such as silica, calcium oxide, aluminum oxide, magnesium oxide and Dioxin 'combined oxides' such as the oxides of the elements silicon, calcium, aluminum, magnesium and titanium; silicates, such as ladder silicates, fiber _, leaf-, and structural fragment salts '' are preferably dreams 'Greystone' is especially hydrophobized wollastonite; Acid salts such as sulfates of alkali metals and alkaline earth metals; carbonates such as carbonates of metal and earth metals such as calcium, magnesium, barium, lithium, sodium or sodium carbonate; phosphates such as apatite ; Nitrides; amines; imides; carbides; polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, and polydifluoroethylene; polyfluorene; polyfluorene; And other thermoplastic plastics, thermosetting materials and microbody gels, as well as solid teaching materials, especially those containing the aforementioned polymers, and mixtures of two or more of the aforementioned solids. According to the present invention, the solid m that is preferentially used is an inorganic Li-ion conductive solid, more preferably an inorganic basic Li-ion conductive solid. 3 Lithium borate, such as Li4B6〇ii3 (txH 〇Li3 (B02) 3, Li2 B4 07 * xH2 0, LiB02, where X can be a number of 0 to 2; bell salt, such as Li2〇 * Al2〇3 * H2〇, Li2Al2 04, LiAl. 2; lithium aluminosilicates, such as lithium-containing zeolites, feldspar, feldspar-like, leaf _ and fiber silicates, and especially LiAiSi2a6 (spodumene), LiAlSiA. (Leaf feldspar), LiAiSi04 (faceted stone), mica For example, the code [継] 4〇], OH) 2, / K {Li, Al, Fe] 3 [AlSi] 4〇10 (F-OH) 2; lithium zeolite, especially its form is fibrous, Lamellar or cube-shaped, especially those with the formula Li2 / zO * Al2〇3 * xSi〇2 * yH20, where the redundancy is related to the valence bond, 乂 is 18 _____- 13- This paper size applies to Chinese national standards (CNS ) 8 4 grids (2 丨 0X297) 筇-Binding --- line (please read. Read the notes on the back before filling out this page) Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy ¾ A7 B7 Note (11) to about 12, and y is 0 to about 8; lithium broken compounds, such as Li2C2, Li4C; Li3 N; oxides and compound bell oxides, such as LiA102, Li2Mn03, Li2 0, Li202, Li2Mn04, Li2Ti03 Li2NH; LiNH2; Lithium phosphates, such as Li3 P04, LiP03, LiAlFP04, LiAl (0H) P04, LiFeP04, LiMnP04; Li2C03; lithium silicates, ladder-shaped silicates, fibers-, leaves- and groups Lithium silicates, such as Li2Si03, Li2Si04 &Li6Si2; lithium sulfates, such as Li2S04, LiHS04, LiKS04; Li compounds indicated during the discussion of cathode compounds, when used as solid II, the presence of conductive carbon black Excluded from this corpse: and mixtures of two or more of the Li-ion conductive solids mentioned above. Basic solids are particularly suitable here. For the purpose of the present invention, an alkaline solid is a mixture with a liquid and an aqueous diluent. The diluent itself has a pH 値 not greater than 7, and the mixture has a higher pH 比 than this diluent. This solid should advantageously be substantially insoluble in liquids used as electrolytes and be electrochemically inert in the battery medium. Particularly suitable solids are those with primary particle size _ small _ 5 nanometers to 20 micrometers, preferably 0.01 to 10 micrometers, and especially 0.1 to 5 micrometers. The particle size given is by electron microscope Measured. The melting point of this solid is preferably higher than the normal operating temperature of electrochemical cells, and the melting point is higher than 120 ° C, especially higher than 15 ° C, which has proven to be particularly advantageous. The solids here can be in their external shape Symmetrical, meaning that it has height ... Width: The size ratio (aspect ratio) of length is about 1, and is made into a sphere or pellet, which is roughly circular in shape, or in the shape of any desired polyhedron, such as a cube , Tetrahedron, hexahedron, octahedron, or bipyramid, or _-14 -__ This paper size applies to the Chinese National Standard (CNS) eight 4 grids (210κ 297,: ,, &gt; 1Π ~ ~. Γ — I Gutter (please read the notes on the back before filling out this page) A7 A7 Printed by BEIJING Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs B7 V. Description of Invention (12) It can be skewed or asymmetric, which means that it has height Width: The size ratio (aspect ratio) of the length is not equal to 1, and it is in the form of a needle, an asymmetric tetrahedron, an asymmetric double pyramid, an asymmetric hexa or octahedron, a sheet or a plate, or a fiber shape. If these solids are asymmetric particles, then The upper limit given to the size of the nascent particles in each case refers to the smallest axis. Compounds that can be used as compounds VI can react with carboxylic acids or acids yjj or their derivatives or mixtures of two or more thereof, It is, in principle, any compound that meets this standard. Compound VI is preferably selected from the group consisting of: mono- or polyhydric alcohols, which have only carbon in their main chain; mono- or polyhydric alcohols, in their main In addition to at least two carbon atoms in the chain, at least one atom is selected from the group consisting of oxygen, scale, and nitrogen 'containing wonderful compounds; amines having at least one primary amine group; amines having at least one secondary amine group Amine alcohols; mono- or multi-pentameric thiols; compounds having at least one thiol group and at least one warp group; and mixtures of two or more thereof, where 'the preferred user is therefore A compound VI having two or more functional groups capable of reacting with a carboxylic acid or a sulfonic acid. When a compound containing an amine group as a functional group is used, it is preferable to use a compound having a secondary amine group, so that it is condensed / crosslinked. after that Mixture Ia is complete. It does not contain free NH groups, or contains only a small number of such groups. Some of the preferred compounds that can be pointed out are: early- or multiple-fermentation species, which have only one on their main chain, and Having from 1 to alcoholic OH groups, preferably from 2 to 20 alcoholic OH groups, and especially from 2 to 10 alcoholic OH groups, especially di-, tri- and tetra-light alcohols, Better system __ -15- This paper size is applicable to Chinese National Standard (CNS) Λ4 grid (210X297 male ITi 1ί ----: 丨 丨-丨 installation ------ order ------ (Please read the precautions on the back before filling this page) A7 ------- B7 V. Description of the invention (13) '— It has 2 to 20 carbon atoms, such as ethylene glycol, 12 propylene glycol, 13 propylene — Alcohol, butanediol U-diol, butylene glycol, butanediol, W-hexanediol, neopentyl glycol, dodecadiol, glycerine trikimethylpropane, isoprene tetraol , Sugar alcohols, terephthalylene, varnishes and ^ A, but as is clear from the definition above, monohydric alcohols such as methanol, ethanol, propanol, n-butanol, Second_ butanol and third-butanol; further 'can also be used Hydroxyolefins, preferably those having two ends, such as α, ω-dihydroxybutadiene; oligomeric polyester polyols, as known from, for example, the Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, No. Pages 62-65, and obtained by, for example, reacting a dihydric alcohol with a multivalent, preferably dibasic, polyacid; a mono- or polyhydric alcohol printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs In addition to at least two carbon atoms in its main chain, it contains at least one oxygen atom, preferably a polyether alcohol, such as an epoxidized alkylene &lt; polymerization product. Propylene oxide, ethylene oxide, 1,2, butylene oxide, ι, 2-epoxide, u-hexane oxide, tetrahydrofuran, and styrene oxide. Polyethers modified at the terminal group can also be used. Alcohols, such as polyether alcohols modified with Nik end groups; these alcohols preferably have a molecular weight (number average) of 100 to 5000, more preferably 2000 to 10,000, and particularly J00 Up to 800; compounds of this type are known in nature and are commercially available, e.g. under the trademarks Pluriol® or Pururic® (B ASFAktiengesellschaft) obtained ♦ Alcohols, as defined above, in which some or all of the carbon atoms have been replaced by silicon, in particular polysiloxanes or alkylene oxide / siloxane copolymers, or polyether alcohols and polysiloxanes The mixture is, for example, EP-B 581 2% and EP-A 525 728 -16. This paper size is applicable to the Chinese standard (CNS) Λ4 condition (public / Γ Α7 Β7) The Central Bureau of Standards of the Five Ministry of Economic Affairs only consumes Cooperatives printed invention descriptions (wherein those described in '14 are applicable to these alcohols at their molecular weights; alcohols as defined above, especially polyether alcohols' part of or All oxygen atoms have been replaced by sulfur atoms, of which the same applies to the molecular weight of these alcohols; mono- or polyhydric alcohols, in addition to at least two carbon atoms in their main chain, contain At least one phosphorus atom or at least one nitrogen atom, such as diethanolamine and triethanolamine; lactones derived from the formula HO- (CH2) z-COOH, where 2 is a number from 1 to 20, such as ε-caprolactone, 0 _ Propiolactone, r_butyrolactone and methyl 4_caprolactone; silicon-containing compounds, such as Di- and tri-gas silane, phenyl tri-gas silyl di-epoxy and dimethyl ethyl .. alkenyl gas stone burn; silanols, such as trimethyl silanol; have at least one primary and / or Secondary amine amines, such as butylamine, 2-ethylhexylamine, ethylenediamine, hexamethylenediamine, [ethylenetriamine, tetraethylpentylamine, pentaethylenehexaamine, aniline, and phenylenediamine; Ether diamines, such as 4,7-dioxydecane_u〇_ diamine, and-tetradecyl-1,14-diamine; '-mono- or polyfunctional thiols, such as Aliphatic thiols, such as methylpyridine, fluorene hexane thiol and dodecane thiol; aromatic thiols: *,, 4-aminosulfanyl, and 2-supported aniline; σ &amp; A compound containing at least one thiol group and at least one hydroxyl group, Thiophan, and a single post-base sulfone 4--17-f paper as defined above is applicable to Chinese National Standards (CNS) (CNS) } / \ 4 叱 格 （2] 〇χ 297 public tears --------- install ------ 1τ ------ ^ (谙 Please read the notes on the back first and fill in this five 、 Explanation of invention (15 Α7 Β7 Central Samples Bureau of Ministry of Economic Affairs Classes such as ethanolamine, N-methylethanolamine, N · ethylethanolamine N-butylethanolamine, 2-amino small propanol, 2 • amino_ 丨 · phenylethanol, and eight or more g Mono- or polyamine-based polyols in a family manner such as ginsyl (hydroxymethyl) -methylamine, glucosamine, and NN | _bis (2 • hydroxymethyl) ethyl— • amine 0 1 Or a mixture of compounds VJ as defined above. According to the present invention, the above-mentioned compound W is condensed with a few or continuous acids having at least one radically polymerizable functional group, or condensed with a mole or a mixture of two or more thereof. At least one and preferably all of the free groups in W can be condensed with the compound ^. For the purpose of the present invention, the carboxylic acid or sulfonic acid M used may in principle be any carboxylic acid or sulfonic acid having at least one functional group capable of free-radical polymerization, or it may be a derivative thereof. The term "derivative" as used herein encompasses compounds derived from a few acids or acids modified on an acid functional group, such as esters, phosphonium halides, and anhydrides, as well as those derived from compounds that have been modified on their carbon backbone. Modified compounds of several acids or sulfonic acids, such as carboxylic acids and sulphonic acids. The compounds ΥΠ indicated here, in particular: α, /?-Unsaturated carboxylic acids and cold, r-unsaturated Carboxylic acids. Α, / 5-unsaturated carboxylic acids which are particularly suitable here are those having the following formula

The scale of this paper is stabbed to the Chinese National Standard (CNS) Λϋ7210 × 2. {Please read 85. Please read the notes on the back before filling in this page) .Shang ------ Printed by the staff of the Central Standardization Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (16) where R1, R2, and R3 are hydrogen or C4_carbon of the C plant, and the preferred users are thus propionic acid and methyldienoic acid; users can also successfully prepare From cinnamic acid, maleic acid, fumaric acid, decomposed aconitic acid, or p-vinylformic acid 'and other street organisms, such as wild species, such as maleic acid or decomposed aconitic anhydride; halide 'Especially chlorides, such as vaporized propionate or gaseous methylpropionate. Fermented; vinegars', such as (cyclo) (fluorenyl) acrylic acid appearance, in this appearance base has up to 20 carbons Atoms such as methyl, ethyl, propyl, butyl '(meth) acrylic acid, 2-ethylhexyl, stearyl, lauryl, cyclohexyl, hexyl, difluoromethyl, hexafluoropropyl And tetrafluoropropyl esters, polypropylene glycol mono (meth) propionate, polyethylene glycol mono (meth) acrylate, polyether alcohols (Meth) acrylates, such as glyceryl di (meth) acrylate, trimethylolpropane di (meth) propionate, iso-pentaerythritol di- and tri (fluorenyl) propionate, bis (Mono (2-propenyloxy) ethyl) diethylene glycol, and poly (meth) acrylates having alcohols capable of radically polymerizing in turn, such as (meth) acrylic acid and vinyl alcohol And / or allyl alcohol esters; other aliphatic or aromatic acetic acid vinyl vinegars, such as vinegar, ethyl acetate, ethyl propionate, ethyl butyrate, vinyl hexanoate Vinegar, Ethyl Caprylate, Vinyl Decanoate, Vinyl Stearate, Vinyl Palmitate, Ethyl Crotonate, Diethyl Acetate, Divinyl Sebacate, 2-ethyl Vinyl hexanoate and vinyl difluoroacetate; feminyl esters of other aliphatic or aromatic polyacids, such as allyl acetate, allyl propionate, allyl butyrate, hexanoate Propyl vinegar, allyl octanoate, allyl decanoate octanoate, stearic acid. Allyl-19- This paper size applies to Chinese National Standard (CNS) Λ4% grid (2IOX 297 Gong) --------_-- install --- ^ ---- 1T ------ ^ (Please read the notes on the back before filling this page) 4,-扃 Working Consumers' Cooperative Association ^ A7 ______ B7 _ V. Description of the invention (17) Ester, allyl palmitate, allyl crotonic acid, allyl vinegar, allyl lactate , Diallyl oxalate, diallyl malonate, diallyl succinate, diallyl glutarate, diallyl adipate, diallyl pimelate Base ester, diallyl cinnamate, diallyl maleate, diallyl phthalate, diallyl isophthalate, benzene-1,3,5- Triallyl tricarboxylic acid, allyl tricarboxylic acid cassia tricarboxylic acid, allyl trifluoroacetate, allyl perfluorobutyrate, and allyl perfluorooctanoate; dot, r-unsaturated defect Acids or their derivatives, such as ethylene acetic acid, 2-methyl vinyl acetic acid, isobutyl 3-butyrate, allyl 3-butenoate, allyl 2-hydroxy-3-butenoate Esters and diketenes; sulfonic acids, such as acetic acid, allyl- and methallylic acid, to Halides and esters thereof, vinyl acetate item benzene with 4-yl acetate Xi stupid cross-stuffed amine. Mixtures of two or more of the above mentioned acids and / or acids may also be used. The following individual compounds X can be pointed out, which can be radically polymerized and used to prepare polymers IX: olefins, such as ethylene, propylene, butene, isobutylamidine, hexene and high-carbon homologues, and vinyl cyclohexane, · (Meth) propionitrile; halogen-containing olefin compounds, such as difluoroethylene fluorene, divinylidene, fluoroethylene, ethylene gas, hexafluoropropane, trifluoropropylene, dichloroacetamidine, 1,2- Difluoroethylene and tetrafluoroethylene; vinyl alcohol, vinyl acetate, N-ethylfluorenyltetrahydropyrrolidone, N_vinylmethylene, and ethylene methylformamide; 20- The standard of this paper applies Chinese gardener standards ( CNS) Λ4 ^ lattice (210x2970; ^ llII ------ M ** (Please read the note on the back before filling in this F-kl B7 V. Description of the invention (18) The Central Bureau of Standards, Ministry of Economic Affairs Industrial and consumer cooperatives print f-nitrile vapors, such as digassed phosphazene and hexagas (triphosphazene), and they are substituted to some extent by &amp; oxy, phenoxy, amine or fluoroalkoxy Completely substituted I derivatives, meaning compounds that can be polymerized to give polyphosphazene; aromatic olefin compounds such as styrene and fluorenylbenzene Ethylene; ethyl ethers, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2ethylhexyl, cyclohexyl Group, trifluoromethyl, hexafluoropropyl and tetrafluoropropyl vinyl ethers. Of course, it is also possible to use a mixture of the above-mentioned compound X, so this will result in the copolymer 'depending on the preparation method' whose content is randomly distributed. Monomers, or block copolymers. These compounds X, like the condensation product V, are polymerized in a manner known to those skilled in the art, preferably by free radical polymerization; regarding the molecular weight obtained, The following applies to the compounds vm. The compounds νιπ are mainly those having an average molecular weight (number average) of at least, preferably 5,000 to 20,000,000 ', especially 10,000 to 6,000,000. And can be. Compounds that are sufficient to dissolve bell cations and act as binders. Examples of suitable compounds νζΗ are polyethers, and copolymers with at least 30% by weight of the following structural units based on the total weight of compound vm R, X -c—c—o—

R1, R2, R3, and R4 are aryl or alkyl, preferably methyl or hydrogen, and may be the same or different, and may contain heteroatoms, such as oxygen, nitrogen J, sulfur, or sand 3 21 Applicable to China National Standards (CNS) Λ4 specifications (2 丨 0X 297A ^) m · (Please read the precautions on the back before filling out the wooden pages --- Ordered by an industrial and consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Cleavage A7 B7 V. Description of the invention (19) This type of compound is described, for example, in MB Armand et al., Fast ion transport in solids, Elsevier, New Yorkj 1979, pages 131-136 'and FR-A 7832976. The compound ν] π may also consist of a mixture of two or more compounds of this type. The polymer composition IV and / or polymer κ as defined above may also be a foam, so the solid π is distributed in itself According to the present invention, the mixture na should be from 1 to 95% by weight, preferably from 25 to 90% by weight, and especially from 30 to 70% by weight, solid m, and from 5 to 99% by weight, preferably It is 10 to 75% by weight, and especially 30 to 70% by weight of the party composition IV, which The compound vm in the polymer composition IV should advantageously have an average molecular weight (number average) of 5000 to 100,000,000, preferably 50,000 to 8,000,000. The polymer composition IV can be made by weight of 5 to 100. The compound V is preferably 30 to 70% by weight, based on the polymer composition IV, and 0 to 95% by weight, and particularly 30 to 70% by weight of the compound vm is combined by the polymer. The substance iv is obtained based on the reaction. According to the present invention, the mixture nb should be 1 to 95% by weight, preferably 25 to 90% by weight, and especially 30 to 70% by weight of solid m, and 5 to 99% by weight, preferably 10 to 75% by weight, and especially 30 to 70% by weight of polymer IX, where the compound vm in polymer IX can advantageously have an average molecular weight (number average) of 5000 to 100,000,000, preferably 50,000 to 8,000,000. Polymer IX can be used in an amount of 5 to 75 children, preferably 30 to 70 weight. Compound X, based on polymer IX, and 25 to 95 Weight _-22-_ This paper size is in accordance with China's standard ((milk) 8 4 grid (210 &gt; &lt; 297 Public Therapy); ----- ^ ------ 11 ------ Huan: (阅读 Read the notes on the back before filling in this 1) Special 疋 30 to 70 weight. The compound is based on polymer IX. 5. Description of the invention (2,070). The novel mixture obtained by the reaction also contains at least one (E1) to (E5) ester as described at the beginning of this article. Among the esters of the formulae (I5) to (E5) mentioned above, the formulate phosphate is preferably used. Examples of the groups R1 and R2 and, if present, R3 and / or Rule 4 are methyl, ethyl, n-propyl, isopropyl, n-butyl, third butyl, cyclopentyl, Ring. Hexyl and radicals' and (-&lt; ^ 2-〇12-0) 11-〇13, where 11 is 1 to 3, but it should be noted when pointed out above that the groups R1, R2, R3 Or at least one of R4 is (-CH2-CH2-0) n-CH3 'where η is 1 to 3, preferably 1 or 2. It is also preferred to use esters of the formulae (E1) to (E5), where Ri, R2 and, if present, R3 and / or R4, are the same and are -CH2-CH20-CH3 or (-CH2-CH,- 0) 2-CH3, the corresponding phosphate of which is once again preferred here. Examples of compounds that are particularly preferred are the formulae (Ela) to (E5a): I,... -------------- 1T (Please read the precautions on the back before filling this page)

B 00¾ 0 = C (

(E1a) (E2a) Printed by the Consumer Standards Cooperative of the Central Standards Bureau of Didi 〇 = P (-0-CtL ^-CHj -0 -CHj (E3a) and 0 o \ s CHjOCH ^ (E4a) -23 -The size of this paper is applicable to the Chinese National Standard (CNS) M Pig (210x 297) Printed on the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 —______________ B7 V. Description of the Invention (21) &quot; —

Si (-0-CH2 -CH2 -OCH3) 4 (E5a) Due to its nature, the esters used here are very suitable as plasticizers in the mixtures according to the invention and usually have a viscosity at room temperature It contains 10 mPas, preferably s 5 mPas, and especially g 3 can tart. It usually has a stagnation point of about 200 ° C or higher, preferably about 250 ° C or higher, and especially about 300 ° C or higher. In each case, it is measured under atmospheric pressure, and in its use At a temperature of about -50 ° C to about 150 ° C, it has a sufficiently low vapor pressure of about 10-5 to about 10. Aiba. Its southern point means that it can be steamed and can therefore be made with high purity. Furthermore, these esters cover a wide temperature range as liquids under atmospheric pressure, usually falling to about -30 ° C, preferably down to about _4 ° C, and still remain liquid. The esters can be used as a solvent in the electrolyte system of Li-ion batteries, at least about 80 ° C, preferably at least about 12CTC, and more preferably at least about 150 C. Of course, according to The esters used in the present invention are used together with the plasticizers mentioned below to make mixtures. It is preferred to use a solvent combination, which has a sufficiently low viscosity and can be strong and powerful; the ions of the glutamate conductive salt cover a wide temperature range It is liquid and has sufficient stability electrochemically and chemically, and is resistant to hydrolysis. The content of esters in this novel mixture is usually 1 to 200% by weight, preferably 2 to 100% by weight. And more preferably 2 to 70% by weight, in each case based on the compound na / IIb. The esters used according to the present invention are prepared by conventional methods, such as K Mura Kami in Chem. High Polymer (Japanese version), 7, pp. 188-193 (1950 ) _______- 24 -__ This paper music scale is applicable to the Chinese National Standard (CNS) Λ4ί〇Μ 210X297 male i;;) ~~------ called --.-- installation ------ 1Τ ------- ^ (Please read the notes on the back before filling out this page) Printed A7 ________B7 by the Central Standardization Bureau of Ministry of Economic Affairs, Consumers and Consumers Cooperatives V. Description of the invention (22) '' and in H. Steinberg Organic Boron Chemistry, Chapter 5, J. Wiley &amp; Sons, NY ,, 1964. The starting materials here are usually acids, anhydrides or gaseous hydrazones, and esters are based on them, such as boric acid, c (o) ci2, p0ci3, so2a2, and SiCl4 'and they are known in a known manner from them. The corresponding mono- or polyhydric alcohols or ether alcohols react. The novel mixtures la and lb, and the individual mixtures na and Hb, are discussed together below, and are individually referred to as, the novel mixtures &quot; and &quot; the novel mixture &quot;. This novel mixture contains novel compounds and esters in an amount of 1 to 100% by weight, compared to 35 to 100% by weight. Based on the novel mixture in each case. To prepare this novel mixture, a mixture can be used: Guli m, the condensation product v and the compound vm if needed, or a mixture 'made from: solid m, compound X and compound νπι, and at least An ester of the formulae (E1) to (E5), and the usual additives used if necessary, such as other plasticizers, preferably those containing polyethylene oxide or polypropylene oxide. Other plasticizers used can be aprotic solvents, preferably those that can dissolve Li ions, such as diacid diacid, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, carbonic acid Dibutyl ester, ethylene carbonate and propylene carbonate; oligomeric osmium oxides such as dibutyl ether, di-third-butyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl Ether, dinonyl ether, didecyl ether, di (dodecyl) ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1-third-butoxymethoxyethane,丨 _Third-butoxy-2-ethoxyacetamidine, 1,2-dimethoxypropane, 2-acetoxyethyl ether, 2-ethoxyethyl ether 'diethylene glycol di Butyl ether, dimethylene tertiary-butylmethyl mystery, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, butyrolactone and --____ -25- _ paper size Applicable to China Standard (CNS) Λ4 · (21QX2 (^ u -----;-·-^ ------ 11 ------ iron: (Please wash and read the precautions on the back) Refill. ¾ This page) A7

Printed by the Employees' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Ⅴ. Description of the Invention (23) Dimethylformamide; hydrocarbons of the formula CnH2n + 2, of which 7 &lt; n &lt;50; organic conversion compounds, especially phosphates and phosphonic acids Esters, such as trimethyl acetate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, tripentyl phosphate, trihexyl phosphate, trioctyl phosphate, and ginseng phosphate (2_ Ethylhexyl), tridecyl phosphate, diethyl n-butyl phosphate, ginseng (butoxyethyl) phosphate, ginseng (2-methoxyethyl) phosphate, phosphoric acid Ginseng (tetrahydroanyl), Ginseng phosphate (1H, 1H, 5H-octafluoropentyl), Ginseng phosphate (1H, m-trifluoroethyl), Ginseng phosphate-(2- (diethylamine) ) Ethyl) Ester, Diethyl Ethyl Phosphonate, Dipropyl Propyl Phosphonate, Dibutyl Butyl Phosphonate, Dihexyl Hexyl Phosphonate, Dioctyl Octyl Phosphonate, Winter Methyl Phosphine Ethyl Acetate, Diethyllinate Methyl Acetate, Triethyl Phosphonate Acetate, Dimethyl 2-oxopropylphosphonate, Diethyl 2-oxopropylphosphonate, 2-oxopropyl Dipropylphosphonic acid, diethoxy Ethyl formate, trimethyl phosphonate, triethyl phosphonate, tripropyl phosphonate and tributyl phosphonate; organic sulfur compounds such as sulfate, sulfonate, Phosphonium, amidines, and sulfites, such as dioxin, diethyl sulfoxide, diol sulfite, dimethylfluorene, diethylfluorene, diethylpropylfluorene, Butylpyrene, tetramethylenepyrene, methylcyclobutene I-, dimethylmethylene, diethyl: dimethylmethylene, dipropylammonium, dibutylmethylene, tetramethylenemethylene, methane Acid ethyl ester, bis (methanesulfonic acid) 1,4-butanalcohol ester, diethyl sulfate, dipropyl tellurate, sulfuric acid; butyl vinegar, dihexyl sulfate, dioctyl sulfate and S02cif; and nitriles , Such as acrylonitrile; 'dispersants, especially those with a surfactant structure; and "00" mixtures of these. The mixture according to the present invention can be dispersed or dissolved in inorganic compounds. It is better to have -26- This paper size is applicable to China National Standards (CNS) 8 4 grid (210X297) ------------ equipment — I · (Please read the precautions on the back before filling this page) Thread A7 B7 V. Description of the invention (24 In the liquid thinner of the printing machine of the Central Bureau of Standards of the Ministry of Economic Affairs, Bei Gong Xiao F Cooperative, which is based on the present invention The mixture should have a viscosity of preferably 100 to 50,000 mPas, and can then be applied to the carrier material in a manner known per se, such as spray coating, casting, dip coating, spin coating, roll coating, &amp; printing, gravure Printing or lithography or screen printing. Further processing can be performed in common ways, such as removing the diluent and ripening the adduct. Appropriate organic diluents are aliphatic ethers, especially tetrahydrofuran and dioxin '圜Amidines, especially hydrocarbon mixtures, such as gasoline toluene and xylene, and Group 0 alcohols, especially ethyl acetate and butyl acetate, and ketones, especially acetone 'ethyl methyl ketone and cyclohexanone. A combination of this type of diluent can be used The carrier material is often used for electrodes, preferably metal, such as aluminum and copper. Temporary carriers, such as films, especially polyester films, such as polyethylene terephthalate film ^ are advantageous The ground has a release layer 'preferably polyoxygen fired. The solid electrolyte and the separator can likewise be made thermoplastically from the mixture according to the invention, for example by injection molding, melt-washing, compression molding, kneading or extrusion, If necessary, it is followed by a calendering step. After the mixture according to the invention has been made into a film, volatile components such as solvents or plasticizers 3 can be removed. Crosslinking of the mixture according to the invention can be achieved in a manner known per se. For example, irradiation with ionic or ionizing radiation or electron beam, preferably using an acceleration voltage of 20 to 2000 kV, and a radiation dose of 5 to 50 Mrad, or w or visible light ', and it is generally advantageous here Add initiators, such as the two-sheet paper size applicable to Chinese National Standards (CNS) -27- 8.4 Worry (21〇 &gt; &lt; 297) (Please read the precautions on the back before filling in this )-Packing. Order _ Line. · Printed A7 by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, Ltd. "___B7 V. Invention Description (25) ----- Phenylethyl-ketodimethylketal or oxidation The amount of 1,3,5-trimethylphenylphosphonium triphenylphosphine is particularly 疋 at most [weight. Z., based on the polymer composition W and the polymer K individually, and the cross-linking effect can generally be Within 0.5 to 15 minutes, β is advantageously carried out in an inert gas, such as nitrogen or argon, by thermal radical polymerization. It is preferably at a temperature higher than 6 ° C, which can and advantageously is added to initiate Agents, such as azobisisobutyronitrile, generally have an amount of up to 5% by weight, preferably from 0.05 to 1% by weight. Individually based on polymer composition IV and polymer K; the polymerization reaction induced by electrochemical methods; or by ion polymerization, such as cationic polymerization catalyzed by acid, the possible catalysts are mainly acids, preferably Lewis acids, such as BF3 or in particular LiBF4a Lipi ^ Li-containing catalysts, such as LiBF4 or LiPF0, can advantageously be left in the solid electrolyte or separator with a conductive salt here. If the mixture according to the present invention is to be used as a solid electrolytic substance or separator in an electrochemical cell, a dissociable compound containing lithium cations, called a conductive salt, and other additives used if necessary, may be incorporated. For example, especially organic solvents are called electrolytes. Adding these substances to the mixture can be done to some degree or complete during the manufacture of the layer, or it can be introduced into the layer after it has been made. Conductive salts that can be used are known &apos; and are described, for example, in Ep_A 0096 629. The conductive salts used preferentially according to the present invention are LiPF6, LiBF4, LiC104, LiAsF6, LiCF3 S03, LiC (CF3 S02) 3, LiN (CF3 S02) 2,

Li (CnF2n + JOA, where n is 2 to 20, LiN (S02) 2, LiAICl4, LiSiF6, LiSbF6, or a mixture of two or more thereof 'It is preferable to use LiBF4 as the conductive salt system. Especially preferred-28 -;-Seed coat 1T. ^ (Please read the notes on the back before filling in this page) This paper size is applicable to Chinese National Standards (CNS) (2! Οχ 297,; &gt; ίί) 5. Description of the invention (26) A ? B7 Yin Fan, the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, uses a combination of formulas (Ela) to (E5a) esters and LiBF4 as conductive salts, and uses the combination of formula (E3a) esters and LiBh as conductive salts with particular preference. The usable electrolytes, in addition to the vinegars present in the mixture, are the compounds discussed in the plasticizers above, preferably using general organic electrolytes, preferably esters, such as ethyl carbonate Esters, propylene carbonate, dimethyl carbonate, and diethyl carbonate or mixtures of these types of compounds. Novel solid electrolytes, separators, and / or electrodes suitable for use in electrochemical cells should advantageously have a thickness of 5 to 500 microns 'Preferably 10 to 500 microns' more 10 to 200 microns, and especially 20 to 100 microns. If this novel mixture is to be used or used to prepare a cathode, one of the conventional conductive, electrochemically active compounds (cathode compounds) is incorporated, preferably Lithium compounds. Specific examples are: LiC〇02, LiNi02, LiNixC〇y〇2, LiNixC〇yAlz02, of which ocxyzu, Lix Μη02 (〇 &lt; χ s 1), Lix Mn2 04 (0 &lt; x ^ 2), Lix Mo02 (0 &lt; x S 2), Lix Mn03 (0 &lt; xs 1), Lix Mn02 (0 &lt; x s2), LixMn2 04 (0 &lt; x S2), Lix V2 04 (〇 &lt; x ^ 2.5), Lix V2 03 (0 &lt; xs 3.5), Lix V02 (〇 &lt; x ^ 1), Lix W02 (0 &lt; xS 1), Lix W03 (0 &lt; xs 1), Lix Ti02 (〇 &lt; xsl), Lix Ti2 04 ( 〇 &lt; χ ^ 2), Lix Ru02 (0 &lt; x S 1), Lix Fe2 03 (0 &lt; xg 2), LixFe3 04 (0 &lt; x ^ 2), Lix Cr2 03 (0 &lt; x ^ 3), Lix Cr3 04 (0 &lt; xg3.8), Lix V3 S5 (0 &lt; xg 1.8), LixTa2S2 (0 &lt; xS 1), LixFeS (0 &lt; xg 1), LixFeS2 (〇 &lt; xS υ, Li (0 &lt; x S 2.4), Lix MoS2 (0 &lt; x S 3), Lix TiS2 (0 &lt; x S 2), Lix ZrS2 (0 &lt; xg 2), LixNbSe2 (0 &lt; xS3), Lix VSe2 (0 &lt; xS 1), LixNiPS2 ( 0 &lt; xS 1.5), LixFe PS2 (0 &lt; x Sl_5). For anode use, the body material incorporated is known from the previous conductive and electrochemically active compounds (anode compounds). Please read the note below

I Binding -29- This paper * size is applicable to China National Samples (CNS) Λ4 is present (21〇 × 297 ': ΜΜ printed by the Central Standards Bureau of the Ministry of Economic Affairs f Cooperative printed A7 ------__ B7 V. Invention Explanation (27)-, which can specifically indicate the following: Fun, light metal alloy, micronized carbon black, natural and synthetic graphite, synthetic graphitized carbon powder and carbon fiber, oxides such as titanium dioxide, zinc oxide, tin oxide, barium oxide And tungsten oxide, as well as carbonates, such as titanium carbonate, molybdenum carbonate and zinc carbonate. When this novel mixture is used or used to make anodes, it contains up to 20% by weight of conductivity based on the total weight of the mixture Carbon black, and if necessary, add the usual additives indicated above. If this mixture is used or used to make the cathode, it contains 0 to 20 weight based on its total weight. The novel mixture can be used as a single solid electrolyte and / or separator and / or electrode in an electrochemical cell, or as a mixture with other solid electrolyte separators and / or electrodes. The invention further provides a Kind of composite, which can be used especially in electrochemical cells, preferably in the form of a thin film, more preferably in the form of a thin film having an overall thickness of 15 to 15 μm, especially a film having an overall thickness of 50 to 500 μm It includes at least one first layer that includes a conductive, electrochemically active substance and at least one second layer that includes a novel mixture as defined above, and does not contain a conductive, electrochemically active compound. The present invention also describes a method of manufacturing a composite of this type, comprising the following stages: (I) manufacturing at least one first layer as defined above. (Π) manufacturing at least one second layer as defined above: and -3 〇- This paper size is applicable to China National Standards (CNS) Λ4 is present (210X ^ 7 ^) ^ (Please read the precautions on the back before filling out this page)-Installation, βτ line Α7 Β7 Central Bureau of Standards, Ministry of Economic Affairs Printed by Yuegong Consumer Cooperative Co., Ltd. 5. Description of the invention (28 (m) Then use conventional methods to combine at least one first layer with at least one first layer to provide various layers. It is preferably on a temporary carrier Generate at least one second layer According to the invention, conventional temporary carriers, such as release films, made from polymers or preferably coated paper, such as siliconized polyester films, can be used here. However, they can also be produced on permanent carriers. The second layer, such as the collector, or even no carrier at all. The combination and manufacture of the layers as defined above is performed using atmospheric pressure methods to provide the layers or make films, such as casting or doctor blade coating, or It can also be processed under superatmospheric pressure, such as extrusion, lamination, calendering or compression molding-if necessary, it can be expensive, electrochemical: thermal, so that the composite thus produced can be crosslinked and / or Hardening ... In addition to the second layer defined above, of course, the first layer defined above can of course also contain this new particle? Kun compound. As can be understood from the above, this method makes it possible to easily provide a composite having a release film / separator (second layer) / electrode (first layer) composition. It is also possible to provide a composite having an anode / separator and cathode composition by surface coating '. An example of this procedure is: First of all, the anode materials 'such as tin oxide, conductive carbon black, the novel mixture of conductive salts and plasticizers' such as propylene carbonate, are mutually combined, and the resulting mixture is mixed to On the collector, and then irradiate () V with UV light, and then apply the cathode material, such as UMn204, to the coated .11 binding _ order -------- line ---- Ί. (锖Read the precautions for the back teeth first and fill in the book.) The paper rule is printed in the paper 'Printed by A7 _B7 of the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (29) On the collector of conductive carbon black, and A mixture of a novel mixture, a conductive salt and a plasticizer is cast thereon. This composite was then also subjected to UV-irradiation (iris 2). By bringing the two components together, a composite is obtained which is combined with any desired solid and / or liquid electrolyte and can be used as an electrochemical cell. The anode / separator / cathode composite can be manufactured as described above even without using a carrier and / or a collector, because as defined above, the composite formed by the first and second layers is inherently mechanically stable For use in electrochemical cells. Filling this type of composite with an electrolyte and a conductive salt may occur before the layers are brought together, or preferably, after they are brought together, if necessary, after an established and appropriate collector has been established, such as After contact with the metal film, and even after the composite has been introduced into the battery can; when using the mixture according to the invention, the special microporous structure of the layers, especially due to the solids defined above Caused by the presence in the separator, and if present in the electrode, allows the electrolyte and conductive salt to be absorbed and the air in the pores to be replaced. Filling can be performed at 0 to about 100 ° C, depending on the electrolyte used. This novel electrochemical battery can be used as a car battery pack, equipment battery pack, flat battery pack or all plastic battery pack. As is clear from the above, the present invention also provides the use of the novel mixtures or composites described above to make solid electrolytes, separators, or electrodes, or for use in sensors, electrochromic windows, displays, capacitors, or ion-conducting films. Medium; it also provides solid electrolytes, separators, electrodes, sensors, electricity _-32 -_: _ This paper size is applicable to Chinese National Standards (CNS) (210X297 公 凌) I ----.--.- -Install ------- order ------ line (please read the precautions on the back of 'ijl before filling this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs® C Industrial Consumer Cooperative A7 _B7 V. Description of the invention (30) A color-changing window, a display, a capacitor, or an ion-conducting film, each of which contains the above-mentioned novel mixture or composite. The present invention further provides an electrochemical cell comprising a solid electrolyte, a separator or an electrode as defined above, or two or more types thereof, and an electrochemical cell as defined above as a car battery pack, equipped battery pack or flat The purpose of the battery pack. Example An example of preparing an ester is the preparation of a phosphate of formula 0 = P (-〇-CH2-CH2-OCH3) 3. 274 grams (3.6 moles) of methyl glycol are placed in a 1000 ml round bottom flask with 2 grams of ZnCl2t. And cool to 5 ° C. Then, over a period of 50 minutes, 153.33 grams (1 mole) of POC13 was added dropwise to keep the temperature at about 5 to 10 ° C. After the addition has been completed, the solution is clear and allowed to warm to room temperature. The resulting product mixture is then distilled at about 50 to 55 ° C under reduced pressure (80 to 90 mbar) to remove unreacted starting materials and by-products. Then, at a very low pressure (about 0.02 mbar) and about 170 ° C, further steaming is performed to obtain the desired product. Continued above: Water content of sour vinegar is 20 ppm 3 Example 1 An average particle size of 3 microns, which has been hydrophobized with epoxy silane, and its aqueous suspension has 75 grams of wollastonite (pH 8.5) (Tremin ® 800 £ 8 D, (^ 11312 from Shen 1 (£ to 6 £: 11611), by high-speed expansion; the mixer is dispersed in 300 grams of methylben and 5 grams of phosphate ester of the preparation example. Then, add the following To the mixture: 12.5 grams of polyethylene oxide (Polyox®, Union Carbide) with an average molecular weight (average number) of 2,000,000, 12.5 grams of propylene oxide-ethylene oxide _-33 -____ This paper size applies to China National Standard (CNS> Λ4 is now (21〇 × 2πΓ &gt; (Please read the notes on the back before filling in this page). Installation. The Central Bureau of Standards of the Ministry of Economic Affairs only prints and prints the cooperatives A 7 ___B7 V. Description of the invention (31 ) Dimethacrylate of alkane block polymer (Pluriol® PE600, BASF Aktiengesellschaft) and 0.02 g of UV photoinitiator (Lucirin® BDK, BASF Aktiengesellschaft) ° Then, using a spatula with a coating gap of 300 microns, at 60 Apply mixture to silicified at ° C Within 5 minutes, remove the thinner and peel off the dried coating to obtain a film of about 40 mm thick, which is placed in the field of ultra-light-emitting fluorescent tubes (TL 09, Philips). 5 cm distance, photo-crosslinking by irradiating under argon atmosphere for 10 minutes. This flexible film has superior flexural strength, and allows the bending radius to be reduced to well below 1 mm without cracking. This film is at room temperature After two weeks of storage, no spherulite-type polyethylene oxide crystals were shown, and among the organic electrolytes already mentioned and containing conductive salts, they had good swelling resistance. Organic electrolytes containing conductive salts, within minutes After a sufficient amount has passed through the spontaneous diffusion process, it is absorbed into the material and swells. From the viewpoint of weight, it is less than 50 weights. The swollen film has good strength. Comparative Example 1 12.5 grams have an average molecular weight (number average) 2,000,000 Polyox® (Polyox®, Union Carbide), 12.5 g of propylene oxide-ethylene oxide block polymer dimethacrylate (Pluriol® I &gt; E600, BASF Aktiengesellschaft) and 0.02 g of UVThe initiator (Lucirin® BDK, BASF Aktiengesellschaft) was dissolved in 200 g of THF. Then, using a spatula with a coating gap of 750 microns, the mixture was mixed at 60eC _-34 -__. -----; --.- -Install ----- Γ Order ------ line (please read the precautions on the back before filling in this page) A7 B7 Central Standard of Ministry of Economic Affairs 4 * -Printed by Bureau Staff Consumer Cooperative ^ Epoxy Silica Hydrophobic克 珍 灰石 _ (Tremin® Yinsan in 300 grams of toluene V. Description of the invention (32 compounds are coated on siliconized release paper, within 5 minutes, remove the thinner and peel off the dried coating to obtain about A 40-micron-thick film was photocrosslinked in a field of super-optical fluorescent tubes (TL 09, Philips) at a distance of 5 cm under argon atmosphere for 10 minutes. This flexible film has superior flexural strength and allows the bending radius to be reduced to well below 1 mm without cracking. After storage of this film at room temperature for two weeks, it did not show spherulite-type polyethylene oxide crystals, and it had satisfactory swelling resistance in the organic electrolytes already mentioned and containing conductive salts. The organic electrolyte containing a conductive salt is absorbed into the material in a sufficient amount through a spontaneous diffusion process within a few minutes, and swells. From the perspective of weight, it is less than 150% by weight, which is considerable in film size and thickness. change. Its strength is significantly lower than in the case of Example 1. In lithium-ion batteries, this film always causes battery failure due to excessive auto-discharge rates or micro short circuits. The results are shown in the table. Comparative Example 2

It will have an average particle size of 3 micrometers and have been used for hydration, and its aqueous suspension has a pH value of 8.5 (75 800 EST, Quarzwerke Frechen), using a high speed stirrer. Then, the following were added to the mixture ... 12.5 g of polyethylene oxide (Polyox®, Union Carbide) having an average molecular weight (number average) of 2,000,000, 12.5 g of propylene oxide-ethylene oxide burner polymer Dimethacrylate (Pluriol® PE600, BASF Aktiengesellschaft) and 0.02 g of UV 35 -------; ------------------------------ (Read the notes on the back before filling out this page)

This paper size applies to China National Standards Corporation (CNS) (210 X 297 ,: MM Β7 Β7 printed by the Central Bureau of Standards of the Ministry of Economic Affairs and printed by another consumer cooperative) ^ Five 'invention description (33) Photoinitiator (Ludiin® BDK, BASF Aktiengesellschaft). Then, using a spatula with a coating gap of 300 microns, the mixture was applied to siliconized release paper at / 60 ° C. Within 5 minutes, the diluent was removed and the dried coating was peeled off to obtain about 40 Micron-thick film. This flexible film has superior flexural strength, and allows the bending radius to be reduced to well below 1 meter without breaking. This film does not show spherulite after storage at room temperature for two weeks. Polyethylene oxide crystals, and in the already mentioned organic electrolytes containing conductive salts, have insufficient swelling resistance. Even after a few minutes of swelling, cracks appear or the film adheres to itself, so the swollen film It can no longer be processed. The results are shown in the table. Comparative Example 3

As in the case of US-A 5429891 Example 1 (F), at 30 grams of difluoroethylene hexafluoropropane copolymer (Kynarflex® 2822, Elf Atochem), 20 grams of Shixiyu • Chemically Decomposed Pyrolytic Dioxide (Aerosil R974, Degussa), whose aqueous suspension has a pH 値 of 7, 50 g of dibutyl phthalate (Palatinol C, BASF

Aktiengesellschaft) and 200 g of propylene mesh were added with 5% by weight of trimethylolpropane trimethylacrylate based on dibutyl phthalate. Then, using a spatula having a coating gap of 750 m, the mixture was applied to a glass plate, dried in an air stream for 15 minutes, and embedded in a Mylar layer having a thickness of 0.075 mm. Then, a thin film layer with a thickness of 1010 μm was crosslinked by irradiation with electrons at the energy level of 4.5 MeV, and a 5 Mrad dose and a 2.5 Mrad dose were used for each pass. This flexible film has good flexural strength. _-36-_ This paper size is applicable to China National Standard (CNS) 叱 4 叱 nuclear (210X297) 荩 (Please read the precautions on the back before filling this page).

* 1T line A7 A7 Yin Fan, Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs, V. Inventive Note (34) I. — Before using thin films in lithium-ion battery packs, complicated measures must be taken. Chemical agent, the purpose of which is "Insufficient cycling safety achieved by No. This is caused by electrode poisoning. To remove this plasticizer, extract the film five times, each time using its own weight of 50 (Diethyl ether is carried out at room temperature. After the plasticizer has been removed, the film is unstable and easily cracks when bent. The plasticizer-free film is shown in organic electrolytes that have been pointed out and contain conductive salts, Good swelling resistance. Organic electrolytes containing conductive salts are absorbed into the material by spontaneous diffusion in a sufficient amount within minutes. Λ The swelling film has good strength. The results are shown in the table below. Example 1 Comparison Example 1 Example 2 Jade ^ Example 3 2 ------- Strength when plasticizer is not applied No application is not applied Extraction is not applied No application is not applied --- Duduxi Strength when no plasticizer is used 2 2 5 ----- X 5-Swell resistance 2 3 5 2 --- Strength after swelling 2 4 6-Conductivity 2 2 4 Short-circuit protection 1 4 6 Current capacity 1 5 6 4 Cyclic stability 1 5; 1_-6 τ- — Grade: 1 Very good 2 Good one -37-_ This paper size applies the Chinese National Standard (CNS) Λ4 Grid (210 &gt; &lt; 297 ':, &gt; vs) 靖 Jing first read the notes on the back and then fill in 15 'Writing ears'-'11 .1-A7 B7 V. Description of the invention (35) 3 Satisfactory 4 Unsatisfactory 5 Bad 6 Bad enough to make the test impossible (Please read the precautions on the back before filling this page ),-° Printed by the Consumers' Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs -38- The standard of this paper is in accordance with the Chinese National Standard (CNS) to the standard (210X297)

Claims (1)

A8 B8 C8 D8 Patent application scope Gas species mixture la 'It contains a mixture Ha' consisting of the following 4 丨 substances, a) 1 to 95% by weight solid m, preferably alkaline solid rhenium, with nascent ~ particles too small 5 nanometers to 20 micrometers, and b) 5 to 99% by weight of the polymer composition XV, which can be obtained by polymerizing the following substance 4 b1) 5 to 100% by weight of the following substances based on composition IV Condensation product V.or) at least one compound V! Capable of reacting with a carboxylic acid or with a sulfonic acid or a derivative thereof or a mixture of two or more thereof with A) per mole of compound VI, at least 1 mole of carboxylic acid Or sulfonic acid w, which has at least one functional group capable of free-radical polymerization, or a derivative thereof, or a mixture of two or more kinds thereof, and 'b2) based on Composition IV, 0 to 95 weight. /. Another compound_ 'has an average molecular weight (number average) of at least 50,000, a polyether segment on its main bond or side chain, and at least one ester of formula (E1) to (E5) ----- .--: --------------- 1T ------ 0 (Please read the notes on the back before filling out this page) Central Office of Standards, Ministry of Economic Affairs, Consumer Cooperatives, Seal B ORl 0R2 0R3- 39- This paper size applies to Chinese National Standards (CNS) A4 specifications (210X 297 mm) A8 Βδ C8 D8 VI. Patent application scope 〇C ^ OR1 \ 〇R2 (E2) 〇 / OR1 P——OR2 \ 〇R3 ( E3) O / OR1, s / O ^ \ OR2 (E4) R4〇. JOR1 R3CT ^^ ^^ R2 (E5). 1111 * 'n installed 111 nn, order nnn-~~ line (please read the first Please fill out this page again) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economics 2. Each of R1, R2, R3, and R4 is the same or different from the other, and has nothing to do with each other, each of which is linear or Zhu_Chain q-CV pit group, (-CH2-CH2-〇) n_CH3, where η is 1 to 3, C3-C6-cycloalkyl or aromatic fluorenyl group, which can be substituted in turn 'and its accompanying strips .. Group R1, R2, R3 or R4 to - is a (-CH2-CH2-0) n-CH3, where η is 1-3. Two kinds of mixture, ... which contains the mixture nb, which is composed of the following substances @ 1 to 95% by weight of solid m, preferably alkaline solid m, with a nascent -40 This paper size is applicable to China National Kneading Standard (CNS) A4 specifications (210X297 mm) 388998 A8 B8 C8 D8 Patent application range Particle size 5nm to 20 microns, and b) 5 to 99% by weight of polymer composition IX, which can be obtained by polymerizing the following substance r.: .I bl) 5 to 75 weight based on polymer IX. /. Qin En radically polymerizes compound X, which is different from carboxylic acid or sulfonic acid VII or its derivative, or a mixture of two or more thereof, and b2) based on polymer IX, 25 to 95% by weight of another Compound Vm / which has an average molecular weight (number average) of at least 5000, a polyether segment on its main or side chain, and at least one ester of formula (E1) to (E5) B ORl OR2 OR3 (E1) --- -* --..-- ¾ ------- ITl _ ^ -----. 41 (Please read the note on the back before filling this page) ORl 0 = c (E2) Central Standard of the Ministry of Economic Affairs Printed by the Consumer Cooperatives of the Bureau o P OR2 ORl -OR2 OR3 (E3) -41-This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 38899B A8 B8 C8 D8 Six 'patent application scope 0 OR1 S 0 OR2 (E4) R4〇x ^ ^^ OR1 r3〇 ^^ or2 m Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs irR :: R2, R3 and R4 are the same as or other Different from the others, or branched chain ...-where n is 1 to 3 'c〆6' cycloalkyl or aromatic hydrocarbon group, which can be substituted one by one, with the proviso that at least one of the groups 囷 W㈣R4 Is (-CH2-CH2-〇) n-CH3, where ^ is 1 to 3. 3. The mixture according to the item in the scope of the patent application, wherein in at least one of the formulae Tian) to Tian 5) g, R1, R2 and R3 and / or R4 if present are the same, and are- CH2-CH2-0-CH3 or (-CHi-Ci ^ -Oh-Ci ^., 4. A mixture according to item 2 of the scope of patent application, wherein in at least one of the formulae (pi) to (E5). Cool, Rl 'R2 and R3 and / or R4 if present are the same and are _CH2-CH2-0-CH3 or (-CH2-CH2-0) 2-CH3. 5. According to item 1 of the scope of patent application A mixture of at least one of the esters is selected from the group consisting of compounds (Hla) to (£ 5): B (——00¾ — (Ela) -----— J— 装 ———— Order:- ----- Line (Please read the note on the back before writing this page) 0 C ((? 2a) $ Zhang National Standard (CNS) A4 specification (210X297 mm) 383998 Λ 8 BS C8 D8 Scope of patent application ο = Η — ο — 0¾ — —ο —〇 ^) 3 (E3a) 0 \ s (— OCHj— CHjOCH ^ (E4a) 〇 and Si (-OCH2-CH2 OCH3) 4 6. According to the scope of patent application The mixture of item 2 is selected from the group consisting of compounds (Ela) to (E5a) B (—- OCHj ——0 ^ 00 ^) 3 (E5a &gt; 〇l its f ▲ ♦ a vinegar 1 clear (E1a) (Ε2β) 〇 Ρ (-Ο — CH ^ -CK ^ -Ο -CHj). Ι3 (E3a) ^ ------ —ir ------- ^ k, '(Please read the notes on the back before filling in this page) 〇 Printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs f Cooperatives 0 \ S 0 ^ 00¾ (E4a) and Si (-OCH2-CH2 OCH3) 4 7. According to the mixture of substances listed in the scope of application for patent No. 1 (E5a) 4 0-, where the compound tla is composed of the following fer -43- Applicable to China National Standard (CNS) A4 specification (210X297 mm) A8 B8 38S998 _ ^ __ of the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 6. The scope of patent application a) 1 to 95 weight. / 0 solid m, preferably alkali The solid solid m has a primary particle size of 5 nm to 20 microns, and b) 5 to 99 wt.% Of the polymer composition IV, obtained by polymerizing the following substances from the box, to obtain M) based on the composition IV, Condensation product V α) of polyhydric alcohol VI- containing 5 to 100% by weight of the following substances, containing carbon and oxygen and Θ in its main chain) at least 1 mole a W-unsaturated carboxylic acid per mole of polyol V 1 Μ and b2) 0 to 95 weight based on composition IV. /. Another compound, Vm, has an average molecular weight (number average) of at least 5000, and has a polyether segment on its main or side chain. 8. The mixture according to item 1 of the scope of patent application, which further contains at least one conductive salt, the type of which is selected from the group consisting of LiPF6, LiBF4, LiC104, LiAsF6, LiCF3 S03, LiC (CF3 S02) 3, LiN (CF3 S02) 2, LiN (S02) 2, LiN (C F3 CF2 S02) 2, LiAlCl4, LiSiF6 and LiSbF6 »9. The mixture according to item 2 of the scope of patent application, which further contains at least one conductive salt, the type of which is- From UPF6, Li6F4, Lia04, LiAsF6, LiCF3 S03, LiC (CF3 S02) 3, LiN (CF3 S02) 2, LiN (S02) 2, LiN (C F3 CF2 S02) 2, LiAlCl4, LiSiF6 and LiSbF6. 10. A mixture according to item 8 of the patent application, which contains at least one compound (Ela) to (E5a) according to item 3 of the patent application, and LiBF4. 11. The mixture according to item 9 of the scope of patent application, which contains at least one kind of root _- 44 -_ This paper size is applicable to China National Standard (CNS) A4 specification (21 × 297 mm) (Please read «Note on the back side first» (Please fill in this page again for matters)-Assembled and printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, printed A8383998 〇 Do 6, the scope of patent application According to (Ela) to (E5a) compounds in the scope of patent application No. 3, and LiBF4. 12. A composite comprising at least one first layer comprising a conductive, electrochemically active compound, and at least one second layer comprising a mixture according to any one of claims 1 to 11 of the scope of patent application , And does not contain conductive, electrochemically active compounds. 13. A solid electrolyte, a separator's electrode, a tear sensor, an electrochromic window, a display, a capacitor, or an ion-conducting film, which in each case includes a basis for applying any one of items 1 to 11 of the scope of patent applications Of a mixture. 14. A solid electrolyte, a separator, an electrode, a sensor, an electrochromic window, a display, a capacitor, or an ion conductive film, which in each case contains a composite according to item 12 of the scope of the patent application. 15. An electrochemical cell comprising a solid electrolyte or separator or electrode according to item 13 of the scope of the patent application, or a combination of two or more thereof. 10. An electrochemical cell comprising The solid electrolyte or separator or electrode of the scope of item 14, or a combination of two or more of them. 17. A kind of automobile battery pack, equipment battery pack or flat battery pack, each of which is packaged in accordance with the scope of the patent application for item 15 Electrochemical cell. 18. An automobile battery pack, equipped battery pack or flat battery pack, each containing an electrochemical cell according to item 16 of the scope of the patent application. (Please read the notes on the back before filling this page). Binding Line -45- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)