JPS63239779A - Solid electrolyte and electrochemical reaction tank housing the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a battery containing a solid electrolyte (electrochemical reaction tank).
) and cathodes of capacitors and cells, solid electrolytes themselves, and methods of manufacturing the electrolytes and cathodes.

The inventors have discovered that certain types of solid electrolytes containing liquids are nevertheless advantageously dry to handle, dimensionally stable and flexible, and exhibit good elastic resilience. It has some compression customization and an unexpectedly good conductivity rate. Solid electrolytes are thus useful in the production of high energy density devices such as batteries with unexpectedly high power densities (i.e. power per unit weight) and capacitors with unexpectedly high capacitance densities approximately defined at room temperature. It is suitable for this purpose and also enables its manufacture.

This type of solid electrolyte is described in detail below and is known herein as a "solid electrolyte."

According to the invention, therefore, an electrochemical reactor contains an electrically conductive anode and a cathode separated by a solid electrolyte, and in the case of an electrochemical reaction vessel, an anode and a cathode which can undergo an electrochemical reaction with each other. An electrochemical reactor or electrolytic capacitor is provided.

According to a preferred embodiment, the anode, cathode and solid electrolyte are thin films such that the battery or capacitor itself is highly dense, yet flexible so that it conforms to any desired shape.

The invention also provides the solid electrolyte itself.

The solid electrolyte consists of: a) a matrix consisting of a sheet of atoms bonded to side-chain gold sheets containing functional groups that do not contain active hydrogen atoms; b) a polar aprotic liquid dispersed in the matrix; c)
It contains gold and ionized ammonium, alkali metal or alkaline earth metal salt dissolved in the base material and/or liquid.

The sheets of atoms in the matrix (to which the side chains are attached) can be, for example, two essentially organic sheets, for example organic sheets optionally containing sulfur, nitrogen, phosphorus or oxygen atoms. Sheets containing polymeric chains: inorganic-organic sheets, such as sheets containing silicon and oxygen atoms, such as sheets containing polymeric polysiloxane chains: or inorganic sheets, such as aluminosilicate sheets derived from clay.

When the sheets are comprised of organic or inorganic-organic polymer chains, each sheet can optionally consist of cross-linked polymer chains.

These sheets are preferably hydrocarbons, polyethers or polysiloxanes optionally having crosslinking functional groups such as oxy groups or crosslinked -C=C- groups. Preferably, the chain of such crosslinked sheets contains no or at most few free crosslinking functional groups, such as -C=C- functional groups.

Crosslinking functional groups, such as -C=C- functional groups, are preferably pendant and can be located in the side chains, for example in terminal positions.

In order to obtain good mechanical properties, e.g. tear resistance, and to ensure that the solid electrolyte remains solid when using polar liquids at selected loading rates, it is desirable to cross-link the chain of sheets. . However, excessive cross-linking tends to adversely affect other desirable physical properties of the solid electrolyte, such as its extensibility, viable liquid loading concentration, and conductivity. Optimal crosslinking is directed by a balance of physical properties and varies widely depending on the particular matrix material (among others). Within the solid electrolyte composition range given below, such optimization is primarily a matter of routine testing. However, as an example, it may be appropriate to crosslink λ to t% of the monomer units of the main chain consisting of sheet chains, often through functional groups pendant from such monomers. many. Sheet chains typically have to, per chain.
ro.

λ, soo, to, oo per chain with
.

On average, it contains 5 main chain units.

When each sheet consists essentially of cross-linked polymer chains (organic or inorganic-organic), each chain contains on average at least two, preferably at least three, e.g. and 70 to 70,000 side chains (as described above).

Polar groups in such side chains can be, for example, ester or ether linkages.

Preferably when each sheet consists essentially of cross-linked hydrocarbon, polyether or polysiloxane chains, the side chains are preferably terminal camp polyether or polyether esters such as oxy groups. or, for hydrocarbons and polyethers, oxycarbonyl or carbonate groups.

"End-capped" herein means that the terminal OH group in the chain has been replaced with a group free of active hydrogen atoms, such as an ether or ester group.

In such a suitable sheet and side chain, the equivalent ratio of the side chain polar group (excluding any bonding group) to all carbon atoms in the matrix is suitably 2:3 to 1:2. can be in the range, preferably d2:,? ~l: Hiro for example l knee 2~l:
It can be in the range of 3.

Sheet chains of suitable polyethers with side chains of the preferred polyether type mentioned above can be used, for example, with monomers containing ethylene oxide and/or propylene oxide, such as butadiene monoxide, glycicine methacrylate, glycidyl acrylate and It can be formed by copolymerization with a compound selected from vinyl glycidyl ethers and additionally with glycidol.

The free -OH groups obtained from glycidol and the terminal -OH groups of the polyether chains can be reacted with an alkylene oxide, preferably ethylene oxide, and optionally derivatives thereof, using e.g. basic or acidic catalysts to form polar groups as described above. can form side chains containing Free OH groups can be reacted, for example, by forming alkoxy groups, by reacting them with alkyl halides, such as methyl chloride, in the presence of basic catalysts, or by forming ester groups with carboxylic acids or anhydrides. Active hydrogen atoms can be removed (capped).

If any of the sheet chains mentioned above contain -C=C- groups, the sheet chains are generally subject to side chain formation and capping (
(if carried out) later, e.g.
- Can be crosslinked within the sheet using irradiation.

Crosslinking can also be achieved even in the absence of unsaturated groups, for example using free radical formers such as benzoyl, peroxides such as e-oxide, optionally with heating. However, this method results in adhesion of the matrix to the container in which it is formed, and the degree of crosslinking is very low, thus affecting the mechanical properties of the matrix (
(e.g. tear resistance) is impaired, and it is generally preferred that crosslinking is effected by reaction of crosslinking functional groups, such as -0=C- groups.

Suitable hydrocarbon sheet chains can be preformed by polymerization of 10=c-groups and optionally via cross-linking functional groups such as preferably f′i pendant 10=C-functional groups. It can be preformed by subsequently or simultaneously crosslinking the sheet chain.

Thus, for example, the sheet chain may in some cases contain at least one cross-linking -〇=C- functional group (which is often pendant and in the side chain as described above) in the final sheet chain. ) to give 2
together with a first monomer containing a single -C=C- functional group and a side chain moiety as described above; Can be formed by polymerization of monomeric volumes. The side chain moiety may be a suitable end-capped polyether or polyether ester chain.

Thus, for example, the first monomer volume may contain methoxypolyethylene oxide methacrylate or acrylate, or polyethylene oxide dimethacrylate or diacrylate, or polyethylene oxide carbonate diacrylate, optionally copolymerized with allyl methacrylate or acrylate as comonomer. It can be a methacrylate or a diacrylate, which is subsequently homopolymerized.

In the case of cross-linking, end-capping of side chains and cross-linking of sheet chains depend on the presence or absence of cross-linking -C=C- groups. As mentioned above, it can be implemented.

Suitable polymerization of the -C=C- groups in the monomers can be carried out using free radical or group transfer initiators or gamma-irradiation. The formation of the crosslinked matrix from the monomers is particularly advantageous since such conditions can be adjusted to provide essentially simultaneous or immediate crosslinking. When using difunctional comonomers, it can be operated as a one-pot method.

The organic sheet comprises polysiloxane chains.
In the case of an inorganic sheet, the polysiloxane chains (together with the side chains attached thereto) have the following formula: where R is individually alkyl or 6 alkyl or optionally cross-linked CI~
6 alkenyl, especially a methyl group or a crosslinking oxy group, each group containing a group as defined for R (with the same preferred groups as R) or a terminally capped polyether or a HOIJ ether ester Preferably, at least 2Q%, preferably at least 0% of the groups A have side chains (as described above), such as cap-shaped polyalkylene oxide or polyalkylene oxide carbonate groups. It is.

/''/' The polysiloxane chains can be crosslinked within the sheet via the group R when it is an oxy group or via the above-mentioned R and/or -C═C- functional groups. Preferably, the matrix contains no or at most only a small number of free -C-C- functional groups.

In the case of this type of sheet, the matrix is formed by preforming the individual chains, subsequently terminating the side chains if desired as described above, and then crosslinking by heating. It is appropriate to obtain it. For crosslinkable functional groups where R is an oxy group, the corresponding sheet chain (where R is H)
is preformed and sufficient water is present to provide the desired number of oxy functionalities. Cross-linking is preferably carried out in an inert atmosphere, such as an atmosphere of nitrogen; oxygen may be present if desired, but this tends to promote cross-linking, thus reducing the Produces a skin layer.

If no unsaturation is present, free radical transfer initiated crosslinking can be effected as described above for organic polymer sheets.

If the sheet is an inorganic sheet, such as an aluminosilicate sheet, it can be formed in a conventional manner and side chains as described above can be added to the sheet.

From the foregoing description, it can be summarized that the base material is, inter alia (a) added with side chains as defined above to a corresponding sheet-like base material having no side chains, or (b) VL polymer chain-bonded. It will be seen that K can be formed by crosslinking a matrix of polymeric chains having such side chains.

In the case of (b), the raw material base material or the raw material base material is preferably a base material that does not easily crystallize at 0,100°C.

Formation of the matrix by any of the above methods is generally performed during the manufacture of the solid electrolyte, which is described in detail below.

Although a suitable polar aprotic liquid dispersed in the matrix may be compatible with the remainder of the solid electrolyte, the liquid has a dielectric constant of at least 0, preferably at least 0, and/or
or a liquid having a dipole moment of at least /j Debye, preferably at least 3 Debye. The liquid may be a pure liquid or a mixture of liquids (dissolved in each other) or a solution of a solid solute other than the above-mentioned salt fraction of a solid electrolyte. Within the above definition, suitable and preferred liquids include NO2, CN or preferably -At-E-A2-fi, where and A2 are each individually a bond, -〇- or -NR- (where R is 01% 4 alkyl group), E is -co-, -5o-.

-802- or -P(0)A5- (where A3 is A and as defined in Person 2, or is 10- when Person and A2 are each a bond)] It is a liquid consisting of or having a component consisting of. mosquito\
The liquid, or a section thereof, may also contain other substituents which do not have acidic hydrogen atoms but are known to increase polarity, such as 2ndtt&amino groups, esterified carbonyl groups and the like. It can also contain substituted aminocarbonyl groups.

Suitable and preferred polar aprotic liquids or liquids containing -A, -E-A2- groups include R4-A, -P(0)(
Formula R, -AI including A 5-R5)-A 2-R2
-E-A2-R2 (wherein R1, R2 and R6 are each individually hydrogen or an optionally substituted hydrocarbyl group,
For some i, R1 and R2 together form a cyclic R1-A1
-E-A2-R2 with an optionally substituted hydrocarbasyl group forming the compound optionally substituted with oxy, but not as a terminal group, including acyl, e.g. C1, alkyl and C2,6 alkyl α,ω-dyl groups, respectively 〇、〜、。 There is a liquid or segment of the alkyl group).

Thus, the liquid or its fraction contains amide (-CO
NB-) such as dialkylformamides such as dimethylformamide and N-methylpyrrolidone, sulfoxides (-80-) such as dimethylsulfoxide and thiophene-1-oxide, sulfones (-8o2-) such as dimethylsulfone and sulfolane, carbonates (-0-C
O-0) For example, bis(bo-11 alkoxyalkyl) including optionally oxa-substituted dialkyl and alkylene carbonates such as diethyl carbonate, dipropyl carbonate and bis(methoxyethoxyethyl) and bis(methoxypropoxypropyl) carbonates. ) carbonate, and ethylene and propylene carbinates.

One group of such liquids includes ethylene or propylene carbonate, dialkylformamides or -sulfoxides, preferably in which each alkyl group is a C1,4 alkyl group, or cyclic ethers such as tetrahydrofuran, or higher viscosity Liquids such as sulfolane or higher molecular weight congeners of the foregoing, such as bis(bo-11 alkoxyalkyl)carbinates such as bis(methoxyethoxyethyl) carbonate.

Suitable liquids include cyclic amides such as N-methylpyro11 and cyclic carbonates such as propylene carbonate.

The liquid is typically used per 100 parts by weight of the base material! , 23
It may be present in the matrix as 0 parts by weight, preferably 37-200 parts by weight.

The matrix is, as a practical matter, insoluble in polar aprotic liquids, or even if it is soluble, the concentration of the matrix/liquid therein is insufficient to dissolve the matrix to an appreciably large extent. It is clear that there is. Of course, if any salt is insoluble in the matrix, the liquid concentration should be sufficient to sufficiently dissolve the salt. Suitable materials and degrees within these constraints are either obvious or a matter of routine testing.

ionized ammonium dissolved in the matrix and/or liquid;
The ions in the alkali metal or alkaline earth metal salts are preferably all individually separated or can be present as ion pairs or as higher aggregates such as triplet ions. The salt is suitably NT(4-Na e K −
It may be a salt of Ll or Mg, suitably a salt of Na, K or Li, preferably a salt of Ll. Suitable examples of salt anions include -valent and divalent anions, especially I''-, 5CN-
,PF,,7”,kSE;i;fiC14-BPh4”
-, brukaryl sulfonate ion and preferably O
There are F, SO, , C lead, - and BF4 -. A preferred salt is lithium triflate CF65o3Li. Mixtures of salts can also be used.

The above-mentioned salt is, for example, to-it, ooo parts by weight of the base material,
Suitably from 200 to 18,000 parts by weight, more preferably from 200 to 7000 parts by weight and preferably from 400 to 70 parts by weight.
It may be present in the matrix in a matrix:salt equivalent ratio of 7 parts by weight of salt per 00 parts by weight of salt. If the matrix contains oxygen atoms in the side chains and/or sheets, these ratios can be expressed in terms of the number of equivalents of the matrix oxygen atoms. The salt is η~ioo
It may be present as (preferably) 0 to ttQ equivalents/Syl equivalents per equivalent host oxygen atom.

In another aspect of the invention, the solid electrolyte may be formed in any feasible order, i.e. (a) forming a matrix, and (middle) incorporating a highly ionized salt into said matrix or its precursor. (c) It can be formed by a method comprising introducing a polar apropane liquid into the base material or its precursor.

In the case of an organic or organic-inorganic electric combination matrix, the steps are preferably carried out in the order (b), (a) and (c).

In such cases, the ionized salt is incorporated into a precursor of the matrix, which precursor may be an uncrosslinked polymeric precursor of the crosslinked matrix, or an oligomer or monomer or It can be a mixture of materials that are uncrosslinked or a precursor to a crosslinked polymeric matrix. Formation of the matrix thus involves polymerization and/or crosslinking, which may be carried out with or without a solvent or vehicle.

To summarize, in such a case, the ionized salt or its solution is dissolved in the base material precursor or its solution in step (B), and the precursor is added to step (4) while removing the solvent as necessary. Polymerization and/or crosslinking in step (c) to form a solid matrix and introduction of an aprotic liquid in step (c), if necessary under vacuum and/or at elevated temperature, e.g. This can be done by exposing the raw bottom material to the vapor of a liquid.For blending large amounts of liquid,
It may be necessary to immerse the base material in a liquid.

The liquid should contain a large amount of salt, for example as a 7M or 2M solution, to prevent the salt from leaching or leaching out of the matrix. To prevent the incorporation of separate salts into the matrix, the chemistry of the salts in the matrix and in the solution prior to soaking is important, unless of course incorporating separate salts in this manner is undesirable. The potentials should be matched. However, for some base materials and some salts in the liquid, the high-strength salts will probably cause the solid state charge to release due to the formation of ionic aggregates. undesirably reduces the electrical conductivity of the material.

For example, optimization of conductivity can be carried out using the following tables (Eμ, l) to (Eμ
, 4c) are immediate and regular exam questions.

In an electrochemical reactor or a decomposition capacitor,
The solid electrolyte can have any thickness, provided it is coherent and continuous, and it is clearly advantageous and preferred that it be as thin as possible. The solid electrolyte is typically 10
00-λμ thickness e.g. 200, 10μ and ioo~t
A thickness of oμ can be used. For the electrodes described below, at lower thicknesses the solid electrolyte must be applied to the support, i.e. the anode and/or the cathode, without either the anode or the cathode being supported as described below. It may be desirable to over-coat the precursor on the support and form the matrix in situ.

The electrodes in the capacitor may be made of any suitable inert and conductive material, such as metals commonly used in such devices. Conductive current collectors additional to and in contact with the electrodes are generally not required.

The anode in the cell is generally made of a material in which oxidizing electrons can be reduced to release cation chains. The cathode is generally made of a material that can correspondingly accept the electrons to be reduced (i.e., a potential oxidant).
)Yoshi Naru. In one embodiment, these electrode reaction methods are reversible, such as cell f secondary batteries.

Thus, for example, the anode can suitably be or contain an alkali metal such as Na, K or preferably LL. Alkali metals can be used, for example, as alloying components in lithium-aluminum alloys or, less conveniently, as dopants in potentially salinizable (conducting) polymers, especially when expanded. Polymers with delocalized electron systems such as bo'J (p-)22dine) can also be used as dopants in hapolyacetylenes. The anode material is often the same element or contains the same element as the alkali metal cation of the highly ionized salt in the solid electrolyte. In such cases, the matrix should not contain hydrogen atoms reactive with the anode metal, such as those hydrogen atoms being α-bonded to the carbonyloxy group. Conveniently, the anode is a thin foil, sheet or plate.

The anode can have any thickness provided it is coherent and continuous, and it is obviously desirable to be as thin as possible (provided that the cell does not rely on conduction in the plane of the electrode). ). The anode typically has a thickness of 2100~
! μ, for example -210~! You can get it with θμ. At very small thicknesses, the anode can be attached to supports such as cell walls and/or Fi'w.
, it will be appreciated that it must be applied to the quality. It may even be necessary to apply the cyanode onto the support, for example by vapor deposition; such support may be or contain a conductive mesh, foil or coating;
For example, it can be a metallic current collector, such as Niracle, with at least one terminal or terminal accessory.

Correspondingly, the cathode may suitably consist of a transition metal compound in a higher oxidation state, i.e. a compound in which the transition metal is in a higher oxidation state and from which it can be reduced to a lower oxidation state, i.e. a potential oxidant. It can be done. mosquito\
Compounds include transition metal chalcogenides such as oxides,
Staphyids and selenites such as TiS2. V2O5
,V6O1,,V2S5°Nb5s2 *MoO,!
*Mo55 *MnO2e FeS2 a CuO
.

Chalcogenides of C11Sa transition metal complexes, such as phosphosulfides, such as N1PS, and oxynolides, such as F.0CZ2 and Cr0Br-, nitrides of transition metal complexes, such as heronitrides, such as TiNCJ, Zr.
NCb and HfNBr and other transition metal salts such as Cu
5B20b -cu4o(po4)2- CuBi2
0a-B10(Cr04)2 and human gBi(CrOa
) There are 2. One less convenient alternative is to provide the cathode in the form of a conductive polymer doped with an anion (p-), in which the anion can be the same as that of a highly ionized salt, or in the form of an extended delocalized It may consist of a latent oxidant in the form of a neutral polymer with an electron system. The above neutral polymers are reduced to give chlorinable (conductive) polymers which are compounded and doped by diffusion of cations during use from the highly ionized salts of the solid electrolyte. Examples include reduced poly-p-phinidine n-doped with Ll+ cations.

Suitable compounds include Tl52. V2O, and MnO□
There are some compounds, especially V6O,3, where the cathodic redox process is potentially reversible.

In use, internal current conduction between the anode and cathode occurs through the movement of cations, such as LL+, through the solid electrolyte.

Preferably, the cathode comprises a solid particulate dispersion of a latent oxidant and a highly conductive material in a solid electrolyte matrix.

Typical and preferred solid electrolytes in the cathode include the solid electrolytes described above.

Any suitably highly conductive material can be used in the dispersion, for example carzen black, acetylene black or metals such as transition metals.

The proportion of said material in the cathode is typically between lO and 104
Preferably, a potential oxidant of io, to: 7 to 30,
Preferably 104 dispersed conductive materials and 10,
104, preferably 30 to 604 solid electrolyte.

All of the above are weight i% based on total weight.

The dispersed phase is generally present in particles having a particle size of less than 40 microns, such as less than 20 microns or less than 3 microns.

The cathode can have any thickness provided it is coherent and continuous, and it is clearly advantageous and preferred to be as thin as possible if one does not rely on conduction in the plane of the celga cathode; Typically, the thickness may be 1roo to 3μ, for example iozo to 30μ. It will be appreciated that at very low thicknesses the cathode must be applied to a support such as the cell wall and/or the electrolyte. It may even be necessary to form the cathode matrix in situ on such a support. The base material can be formed as described above, for example, by coating a precursor on a support. For anodes, such a support may be a current collector of a conductive mesh, foil or coated layer of metal, such as nickel, with at least one terminal or terminal fitting, or It can contain this.

According to another aspect of the invention, the cathode can be formed in substantially the same general and preferred manner as the solid electrolyte, but with additional steps.

(ii) latent oxidants (potvn) in the matrix or its precursor;
tial ozidmnt) and a conductive material are dispersed in a conventional manner.

In the case of a polymer matrix, the steps are preferably carried out in the order of (b), ii), (a) and (c).

The carrier or cell assembly described above is desirably sealed in an insulative package, preferably a moisture and air impermeable package, such as a barrier polymer. If the cell assembly is the preferred thin film embodiment, the film may be laid flat and the cell assembly may be narrowed by two thermoplastic films such as polyester such as polyethylene terephthalate or Bo II ether sulfone. The edges of the film may be melt-sealed, optionally with adhesive, to enclose the assembly. The assembly may be further enclosed in a barrier plastic, such as Vicran (ICI).The assembly may also be mounted on a conventional circuit substrate and sealed to the substrate with a thermoplastic or thermoset cover. A high surface area, high capacity embodiment of a capacitor (pRF) or a similar high current embodiment of a cell is one in which the components are in overlapping interleaved strips formed into a roll. In this case, only one layer of insulation is required and the assembly is narrowed by the radially extending inner and outer surfaces of adjacent folds of insulation. If desired, the roll surface can be coated with a similar layer of insulation to seal the assembly.

The cells can be finished by conventional layering/coating techniques. For example, if the cells are elongated strips, the nickel mesh, foil or A1 strip can be placed and held in an insulating thermoplastic sheet, for example by evaporation.

Thereafter, the cathode can be coated onto a sheet or, especially for very thin cathodes, a fluid precursor of the cathode (in a suitable vehicle such as acetonate).

A solution or dispersion of the cathode material in Trill or, in the case of a cathode containing an organic polymer, a polymerized precursor of said polymer, is applied to the product sheet using, for example, a doctor knife. can be applied, followed by any necessary solvent removal/insertion and/or curing. A solid electrolyte can then be applied onto the cathode, or a fluid precursor of the solid electrolyte can be wrapped around the cathode and converted into a solid electrolyte.

Finally, a strip of anode foil, for example lithium foil, optionally a nickel current collector on any insulating layer and the insulating layer itself can be wound one after the other. The order of the steps can, of course, be reversed if desired. The insulating sheet can then be sealed around the edges to provide separate encapsulation.

Capacitors can be similarly finished.

The cell of the present invention is 0. j person/- or more current density e.g. /A
/lrl and higher current densities are possible.

Typical voltages are in the range λ,j, 4Av.

/ j Owh/h can generate energy.

The use of solid electrolytes is not limited to cells and canositors, but extends to any high energy application where solid state ionic conductors are appropriate. For example, a solid electrolyte may be used in the 11thium salt embodiment in a conventional tungsten oxide composite electrode for electrically dull windows.

The invention will be illustrated by the following examples. The preparation and properties of matrix precursors for solid electrolytes are described in the following report.

Report 1 Ethylene oxide (ED)/methyl J-gol glycidyl ether (MDGE)/alglycidyl ether (DI)
) Production of methyl digol glycidyl ether was prepared using the following formula: % Formula % The catalyst was shaped as follows. A 214 solution of Et, Al (Et means ethyl group) in heptane is diluted with anhydrous diethyl ether to 0.1 mol/j a degree, cooled to 0°C and diluted with water (17,j mol 1 Seven Ru Et
5Aj) was added dropwise over 11 minutes with stirring. Acetylacetone (0.2 mol 17l Et5A#) was added dropwise at 0° C. with stirring.

Stirring at 0° C. was maintained for lj minutes: this was followed by overnight stirring at room temperature, and all steps were carried out under an inert nitrogen atmosphere.

The following materials: MDGI(/rid) AGE (French d) and toluene (Zooat') were charged into a stirred and nitrogen purged 1AOO11d stainless steel autoclave.

Catalyst (/Ir, 1) as described above and ethylene oxide (10* as liquid) were added with continued stirring to the whole and the temperature was raised to 110° C. for 2 hours. The resulting high temperature viscous polymer solution! The catalyst is deactivated by discharging it into a /A jar containing - of methanol. The autoclave was hot washed twice with a total of jOQ- of toluene. The wash solution was bulked up with the polymer solution and mixed thoroughly.

The polymer solution was rotary evaporated to a volume of JOOdl, poured into polyester shelves in a fume cabinet, and left overnight to allow the solvent to evaporate. The terpolymer was finally dried in a vacuum oven at /8,41 t to obtain a viscous rubber-like product.

The molecular weight of the product was determined by gel permeation chromatography using lithium bromide in dimethylformamide as the solvent.

Molecular weight = 3: to, oo.

/00 MHz NMR was used to measure the relative amounts of the three monomers incorporated into the final terpolymer and the following results were obtained. Example 1 A terpolymer of c>it (D/
) 2! mt of anhydrous acetonyl).

Lithium triflate (CF580.Li') was added to the solution to give a l:l ratio of oxygen and lithium atoms present in the polymer.

The solution was poured into a glass/polytetrafluoroethylene bottom mold and the solvent was slowly evaporated under a stream of nitrogen. The 200 micron thick films were dried under vacuum for 4 hours at RO<0>C to remove any standing water or solvent, and their ionic conductivity was measured by standard AC impedance techniques over a range of temperatures.

Conductivity at -0℃ = 2×/0-5rnho@txa)
/S' terpolymer (D/') while stirring λ! d
of acetonate) and added lithium triflate to obtain an oxygen:11 tium ratio of /1:/. /
, 0 weight of anhydrous penzoylno R-oxide was added to the solution, which was injected as described above into a 200 micron thick film under a stream of nitrogen.

The film was lightly crosslinked by heating in a vacuum oven for 30 minutes/10°C.

Electrical conductivity (20'(c) = 31 X/0- mh
acetonide 11 of terpolymer (1)/) (8, wt/wt 4) +1 thium triflate (13 wt/'wt) and penzoyl oxide (J wt/wt 4) The solution was injected into a film, and this film was cured as in &) above to obtain a film with a thickness of jOμ.

-) (addition of P(c) anhydrous propylene carbonate is placed at the bottom of the dehumidifier;
Molecular sieves were added to it. The dried crosslinked film from ti)a) was placed in the vapor space above the liquid for a suitable period of time at room temperature and a total pressure of -2fiHy. Generally, approximately 4 parts of propylene carbinate are absorbed per hour based on the weight of the polymer, and this rate remains substantially constant for at least 4 hours.

Solid electrolytes (El,/) to (El, J) were produced in this manner.

The following solid electrolytes were prepared by repeating the above method using the following liquids: Sulfolane (El, 4A) and (El,
j) Methyl digol carbinate (El, A) and (El, 7) N-methylpyrrolidone (B/, r) and (El
, ri) are all listed in the table below.

The dried cross-linked film from 1i)b) above was similarly treated with pc up to a weight increase of 104 to form a solid electrolyte (El
, 10) were obtained.

All of these solid electrolyte films are easy to handle and sufficiently dimensionally stable.

The film was kept dry before use in the cell.

Report 1) Methoxypolyethoxyethyl methacrylate (MP
M) Production of base material precursor (monomer) (Dλ, / ) MethoxyP EG J r O-Me (OCH2CH
2) 7.5-0H (t4A8, r?:a, dried on one molecule surface) and HPLC grade methylene chloride (lr
07) and dimethylaminopyridine (μ, λμ?) were added to the ZOOd flask without mechanical stirring.

The flask was immersed in a cold water bath and methacrylic anhydride (tz, o y of scratch purity) was added through the addition funnel over 30 minutes. The reaction mixture was stirred at room temperature for 77 hours. Transfer the solution to a separation funnel and add 2 x 200d dilute HCJ
(j 40-μOd concentration f(C#') in water followed by λ
×λooowozSodium carbonateSodium carbonate solution was washed with 10 ml of water.

The solution was dried over MgSO4/H20 and filtered. Irganox 1010 antioxidant (Oif) is added, the solution is rotary evaporated and then transferred to the vacuum line with stirring! Time was pumped.

-6, Finally, the MPM was distilled in a short path at 130° C. under vacuum (txlO-linol). The mixture was collected and stored in the freezer until needed.

Before use, synthetic AM (obtained from Aldrich) was distilled under vacuum and passed through a column of human molecular sieves to remove any remaining condensate water. l-methoxy-/-methylsiloxy-2-methylprof-/-ene (MTS)
(obtained from ALdrich) was distilled before use and stored in a PTFI container in the freezer. Tetrabutylammonium fluoride (T
B AF 1 (AldrLch) was added to CaH for λ days.
2 and filtered before use.

All operations were carried out under nitrogen in a flame-dried glass apparatus.

MTS (fjXio-
(DJ, /) (j, (7r), AM (
(7, //mj) and TBAF (/μl of /M THF solution) were added. The mixture was warmed and stirred at room temperature overnight. , r o I) 1) m Irganox/01
0 antioxidant was added to a very viscous bright solution and the solution was poured into a polyester shelf under a stream of nitrogen. The THF in the final condensation image was removed by heating with AGE in a vacuum furnace for μ hours.

The molecular weight of the raw bottom material was determined by gel permeation chromatography using lithium bromide in dimethylformamide as the solvent.

Molecular weight = /13,000 NMR was recorded at /00 MHz in CDC#.

There is virtually no free monomer in the copolymer, yip3z.

The ratio of M units to AM units was 2 liters.

Example λ Copolymer (DJ, λ) (/l) was dissolved in d of acetonitrile with stirring and lithium triflate was added to obtain an oxygen:11 tium ratio of lt:l. 1. Q
Heavy tqb of anhydrous benzoyl peroxide was added to the solution, and this was injected as described in Report 211) for 2 hours under a nitrogen stream.
This film was made into a 00μ film for 3Q minutes/1
Crosslinking was carried out by heating in a vacuum oven at 0°C.

Conductivity = j, 2 j X / 0-6mha@♂1
(Measured in Example 7).

Solid layer by operating as in Example/(iii) using similar absorption rates! S quality (E J,/ ) to (E:Jj) were obtained, all listed in the table below.

Report 3 EO/MDGK matrix precursor (uncrosslinked copolymer) (DJ)
The procedure was as in Report 1, except that AGE was omitted and MDG E of 2d was used.

Collection jt''Iff: Molecule J/, 000: Mole MDG
E j /, J.

Example 3 Stylized copolymer (D i ) (/, (1) A-1) and anhydrous penzoylnog-oxide (0.0 to 4 cμ?) were mixed while stirring at λ! d was dissolved in acetonitrile and lithium triflate was added to obtain an oxygen:11 tium ratio of /A:/. The solution was poured into a 200μ film under nitrogen flow as in Example λ. This film was crosslinked by heating in a vacuum oven at 110° C. for μ hours. Manufactured in this way. The crosslinked film was extremely difficult to remove from the wide mold.

If the bottom mold is immersed in liquid nitrogen, then the film usually separates cleanly. This film is 3 hours 10
It was redried by heating in a vacuum oven at °C.

Conductivity of cross-linked copolymer film -2Q 4x at °C
10 mha@m (measured as in Example 7).

11) Introduction of solution into base material: PC addition example/ (I
Operate as in iD to prepare solid electrolyte (E(7,/) ~ (g
J, J), all listed in the table below.

Report μ Methacrylate-terminated poly(ethylene(ethoxyoxyethoxy)ethyl methacrylate)
Preparation of matrix precursor (monomer) (D4t) Diethylene 11col (27,7t) and dibutyl carbonate (μμ,!?) were weighed in a test tube equipped with a side arm and kept under nitrogen. 1] Rum ethoxide solution (/y of 02 molar solution) was added via syringe. The scheelite mixture was magnetically stirred.

The test tube was immersed in an oil bath at iso°C. The temperature was raised to 200° C. over 1 hour at atmospheric pressure. The pressure in the device is 3
It gradually decreased over time to virtually completely distill off the butanol.

After cooling, the highly viscous 5Z resin was dissolved in chloroform (/00d) and diluted with dilute HC/O in a separatory funnel.
(io7 sickle HCA in water at 4' Orat) and then water (J×I, 04). The solution was rotary evaporated and the resin was dried under vacuum at 110° C. for 2 hours.

The molecule t was determined by vpo in methylbenzoate at 134°C and was found to be 1110 and 104.

Dimethylamide pyridine (o, it) was added to the hydroxyl-terminated 11th comer (!t) of the sacrificial material followed by anhydrous meme in a nitrogen-lined flask.
Lid/acrylic acid (2,/7 f: Aldrie
h! ! ! , high I purity) added to 100 greystone mixture
Magnetically stirred at ℃ for 3 hours. Excess methacrylic anhydride
Distilled under vacuum at 0°C. The resin was dissolved in methylene chloride, transferred to a separatory funnel, and washed once with dilute HCA and three times with water. The solution was dried with MgSO4/H2O, filtered, 200 ppm of 4-methoxyphenol antioxidant was added, and the solution was rotary evaporated until most of the methylene chloride was removed.

The remaining methylene chloride was removed in a stream of dry air over a period of 4 hours.

Example μ Formation HPI, tree U1 (D4') (u, J, t7t) in C grade acetonitrile (20Bl), lithium triflate (0,374A5'?) and anhydrous benzoyl peroxide (0,04A A An injection solution was prepared from r 1 with stirring under nitrogen.

This solution 21d was placed in a glass mold coated with m intervals. The mold was placed in the furnace while blowing nitrogen into the furnace.

The temperature was increased to 110°C at 2°C/min and incubated for 2 hours at io°C.
and gradually cooled to room temperature overnight.

The wrinkled, rubbery film could be easily pulled out of the mold.

Electrical conductivity at 20°C = 1. J x/ OmhQ'1cm
(Measured as in Example 7).

The solid electrolyte (Eμ, / ) listed in the table below was obtained by operating as in Example t (iii).

It has been found difficult to incorporate separate propylene carbinate into the film by this method.

An alternative method is to suspend the film in propylene carina (1 mole) or in an anhydrous solution of thium triflate. The resulting film was dried by pressing between door papers.

This process was carried out in a dry box to obtain the solid electrolytes (Eμ, ko) listed in the table below.

Example! 1) One-pot production of MPM/polyethylene glycol dimethacrylate (PDM) matrix (crosslinked polymer) containing salt polyethylene glycol μ00 dimethacrylate (0
,1? : Palyaaie, manufactured by Naas), MPM (D8, t) (2, of ”) and anhydrous penzoylno ξ-oxide (0, θ21) for 20 d.
It was simultaneously dissolved in 11 liters of HPLC grade acetonide. I
+Thium triflate is added to the solution to combine the oxygen atoms present in the oligomer with 1) lithium atoms /l, :/
given in the ratio of

This solution 2I11/ was injected and cured as in Example μ, but for 24 A hours at iro°C.

Working as in Example t (Ill), solid electrolytes (E, /) to (E!, ≠) were obtained, all listed in the table below.

Report 6 The following formula: Silicon compound (4'?) and the following formula: CH3CH2:NCHCH20(C2H40)9.5C
Compound (61) of H6 was added to anhydrous toluene (/(c)1)
Dissolved in trans-PtC#2((C2H5)2S]
#2 liquid (dissolved in l- toluene/my)/,
07 was added.

This mixture was centrifuged for a few hours under N2 to obtain a fairly viscous solution. Toluene was removed under vacuum to obtain a very viscous copolymer (DA).

Examples are formulations 1, . Copolymer of 2111 (D6) and 0.11132
Lithium triflate (0:Ll ratio = 20:l) was simultaneously dissolved in jld acetonitrile without stirring.

jd of dioxane is added to reduce the evaporation of acetonide 11l. The solution was injected onto the rust-free electrode of a conductive cell and the solvent was allowed to evaporate in air for 1 hour.

Cured in air and argon.

Rapidly heat the air electrode to /4LO℃ and leave in the oven for 20 minutes in the dark/l.
It was maintained at tO 0 C and immediately removed from the oven.

The conductivity was t4t, tXio-mhos (measured as in Example 7). The thickness of the film is 17
It was 0μ.

The film was poured and placed under argon into a furnace flushed with argon. The furnace was heated to 60° C. for uj-min and allowed to cool gradually to room temperature over-night.

Example / (u
Solid electrolytes (EA,/'') to (EA,j) were incorporated into the above-mentioned "air" film as s+, all of which are listed in the table below.

Example 7 Measurement of Conductivity of Solid Electrolytes The ionic conductivity of the solid electrolyte films was measured by standard AC impedance techniques using a Solartron/210 frequency response analyzer.

The results are shown in the table below, where "liquid %" is the weight percent of the liquid in the solid electrolyte, and "increase rate %" is the weight of the liquid absorbed by the second to last film in the final processing step, taken as 100 parts. The conductivity is expressed in parts by weight of the liquid used, and the conductivity is in degrees Celsius unless otherwise indicated in parentheses.

Solid electrolyte liquid increase rate conductivity'
(X) N (mho
, tM-'X/♂) (g/, /) I17. 2
0 /, 4 (, 2j) (g /, 2) 2
1. A I40 3.0 (23) (F, /
, j) 37.3 1. O8, ≠ (2yo) 10
(Ej, 11) I3.2 Ko 7 0
．． ! ko1g/, j)! ri, J 5
'6 0.26 (B/, iG) I3.
0 /, t O, I7 (E/', 7)
4L≠, 41 10 0. Jri(
B/, ♂) Gu/, 2 7/ /,! ! /!
(Ej, Ri) to iso
Hiro! (F, 2./) I6.7 2
0 /, /+ EJ, 2) JJ'j
uo 2. /J-(EJ, J) 37
．． 3 60 3.6 (Fig, /) /j
/r /, 3ko0 (EJ, 2)
20 2! ; /, ♂ (B3.3)
3j, 3 jo 3.6 (Fi4Z
, /) 33.3 I0 0. ko3(
'E1. /) 21.1 440 2.3
(Ej,,2) j! , 3 30 j
,,2(EJ,J) I7. j O≠,
0 (Ej, Hiroshi) Hiroshi/, 2 70 3.2
The city growth rate (goods) was measured as in Example 2, which can contain added salt.

The examples were prepared in place of rz w/w % terpolymer (DA), J
0Xil/! icX is a terpolymer (DA) and the remainder! Powder with O weight t/weight% of 514 m02 (≠j weight t/
Nt%) and carzen black powder (j7It/N amount%)
A solution as in Example/1Nb) above except that it contains a mixture ♂j which is a dispersion of
A film cathode (0/) with a thickness of 60μ was obtained by pouring and curing as above.

An exemplary embodiment of a reaction vessel assembly according to the invention will now be described with reference to the accompanying drawings (not to scale).

FIG. 1 is a side view of the seed string solid body, FIG. It is an illustrative cross-sectional view of the seed string solid seen along the BB line.

Example tii) Solid electrolyte (E) produced in b)
l , the film l of 10) is used as the cathode film O/ (
% Adjacent layer λ and thickness of flow side t)! A lithium foil 3 of Oμ is sandwiched between and elastically held against the adjacent anodes (the said layers, films and foils being in good agreement with each other), with a planar area of 100 μ. Manufactured.

The cell is melt-sealed between two sheets of polyester (Melinex, manufactured by rOI), each sheet having one side biased to make electrical contact with the anode or cathode of the cell. , a nickel plate (thickness 120 mm) acts as a current collector from the anode or cathode, respectively.
It is coated with 100μ thick nickel on a μ plastic film.

Polyester sheet! The comrades have the same surface 5tl, but in plan view they have a larger area than the cell≠, and are sealed around the cell, keeping only their long ends well aligned, and the metal surface is attached to the terminal lug 7. form. Sealing is then done around the edges of the cell tie using a layer of adhesive. The sealed cell (including most of the lugs 7) was coated with one layer 10 of an air and water impermeable barrier polymer (Vicran, manufactured by I01 Company).

The protruding lugs 7 serve as external connections to the cell and can be fitted with suitable terminals if desired.

The thickness of the resulting seed string solid is smaller than the thickness.

3. Has an open circuit voltage of 10V, about /20μAty at room temperature
A steady current density of tr-'' was produced.

Example i.

Preparation of Composite Cathode (02) Comprising Solid Electrolyte A film cathode (C2) was obtained by treating the solution and dispersion as in Example R in the same manner, except that polyphenylene powder was used instead of MnO2 powder.

Polyphenylene F used! , , supplied by IOI and/or European Patent Publication No. 74.60! r issue and 1st Q7. It can be produced by the method described in No. 5 Publication.

Example // A cell assembly was manufactured in the same manner as in Example except that a cathode (0/) was used instead of a cathode (0/).

This assembly! Charged with a constant current of θμ, polyphenylene t=p-do7'L,7'C: (O6H4
) n tx , n0F3803--+1: (04Ha
)x(OF3803)x]nt'''' - The resulting cell had an open circuit voltage of about 3.7v and a good steady state operating current.

Precursors of all solid electrolytes in the coating were prepared in Example 1 and IO.
can be used with latent oxidants and similarly processed to form corresponding composite cathodes.

Example 13 Another assembly comprising solid electrolytes A cell was prepared as in Example 1 using all the solid electrolytes/i in the table above (optionally with the corresponding composite cathode of Example 1). Can form an assembly.

[Brief explanation of the drawing]

FIG. 1 is a side view of a tank assembly according to the present invention. FIG. 2 is a plan sectional view of the tank assembly seen from line AA,
FIG. 3 is an illustrative cross-sectional view of the tank assembly seen from line BB. In the figure, / is a solid electrolyte film, λ is a cathode, %3 is an anode lithium foil, and ≠ is a cell. j is polyester sheet, 6 is Ni coat, 7 is terminal lug, ♂ is metal surface, ? 10 represents the adhesive and 10 represents the impermeable polymer layer.

Claims (1)

[Claims] 1. A solid electrolyte for an electrochemical reaction tank, comprising: a) a base material consisting of a sheet of atoms in which side chains containing polar groups that do not contain active hydrogen atoms are bonded to the sheet; b) A solid electrolyte comprising: a) a polar aprotic liquid dispersed in the matrix, and c) highly ionized ammonium or an alkali metal or alkaline earth metal salt dissolved in the matrix and/or the liquid. 2. The solid electrolyte according to claim 1, wherein the aprotic polar liquid is a liquid having a dielectric constant of at least 50 and/or a dipole moment of at least 3 Debye. 3. The solid electrolyte according to claim 2, wherein the aprotic polar liquid is ethylene or propylene carbonate, dialkylformamide or -sulfoxide, cyclic ether, sulfolane, bis(polyalkoxyalkyl) carbonate or cyclic amide. The solid electrolyte according to claim 1, wherein the liquid is present in the matrix in an amount of 35 to 200 parts by weight per 100 parts by weight of the matrix. (a) forming a matrix, (b) incorporating a highly ionized salt into said matrix or its precursor, and (c) forming said matrix or its precursor in any practicable order; (a) a matrix consisting of a sheet of atoms having attached to the sheets side chains containing polar groups that do not contain active hydrogen atoms; (b) said matrix; (c) highly ionized ammonium or an alkali metal or alkaline earth metal salt dissolved in the base material and/or the liquid. 6. Consisting of a solid dispersion of a potential oxidizer and a highly conductive material contained in a solid electrolyte matrix according to claim 1,
Cathode for electrochemical reactors. 7.30 to 40 as particles with a particle size of less than 40 microns
60% MnO_2 and 2-10% carbon black,
7. A cathode according to claim 6 containing (w/w % based on total cathode) acetylene black or a transition metal. 8. In any practicable order, namely (a) forming a matrix, (b) blending a highly ionized salt in the matrix or its precursor, and (c) forming the matrix or its precursor. Claim 6 comprising introducing a polar aprotic liquid into a precursor; (d) dispersing a potential oxidizer and a highly conductive material in the matrix or its precursor in a conventional manner. Method of manufacturing the described cathode. 9. An electrochemical reaction tank comprising a conductive anode and a cathode that can electrochemically react with each other and are separated by a solid electrolyte according to claim 1.