JPS612278A - Battery - Google Patents

Abstract

PURPOSE:To obtain a polymer battery having no performance deterioration by utilizing hydrogen fluorine solution of tertiary amine or quaternary ammonium salt as electrolyte of a battery in which a polymer material having conjugated double bond in a principal chain is used in at least one electrode. CONSTITUTION:A polymer material having conjugated double bond in a principal chain is polyacetylene, poly(P-phenylene), poly(P-phenylene sulfide), polypyrrole, polythiophene. Tertiary amine or quaternary ammonium salt is at least one of tertiary amine, tertiary amine Lewis acid salt, tertiary amine Bronsted acid salt, and quaternary ammonium salt having such structure that hydrogen atom of tertiary amine Bronsted amine is substituted by hydrocarbon group. Electrolyte of this invention is utilized for a box type battery, a cylindrical battery, a sheet- shaped battery, a button type battery, and a rod type battery having large coulomb efficiency, energy density, energy efficiency, and power density.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a new development technology related to wet batteries or solid batteries called plastic batteries. We aim to provide batteries or secondary batteries to customers, including those for power storage, private power, automobiles, office machines, videos, televisions, radios, radios, cameras, It can be expected to be used in a wide variety of fields, including watches, medical instruments, stationery, beauty instruments, lighting, physical and chemical experiments, and biological experiments.

[Conventional technology]

In recent years, polyacetylene frost: a pond-like plastic battery that uses a solution of an alkali salt such as perchloric acid, fluorine-containing condensed acid, or trifluoromethanesulfonic acid dissolved in an organic solvent as an electrolyte, and various types of batteries that use a lithium cathode have been developed. Lithium batteries are being actively developed, but as a result of repeated research by the present inventors on the problem of performance degradation, which is the biggest drawback of these batteries, we have found that they are significantly affected by impurities, especially water, present in the electrolyte. It was found that even if this moisture existed in an amount of 100 to 100 ppm, the required battery performance was considerably reduced. The electrolyte for conventional Plasti-Nox batteries uses a highly hygroscopic aprotic polar organic solvent dissolved in a highly hygroscopic alkali salt, etc., but both the solvent and the electrolyte must be used with extreme caution. It is necessary to use products that have been dried, dehydrated, and purified, and all possible measures must be taken regarding their formulation and handling. However, in reality, it is very troublesome to ensure that this operation is perfect when manufacturing a battery, and even when it is normally carried out in a dry room, it may contain 2000 to soooo ppm of water. For this reason, the expected battery performance could not be fully satisfied.

[Problem that the invention seeks to solve]

The present inventors have been engaged in research on aprotic polar organic solvents for many years, but complete dehydration of these solvents is not economically easy, and in particular, under dehydration conditions, some impurity occurs due to decomposition of the solvent. I learned that there are times when this happens. The inventors of the present invention have carried out intensive research, and have further investigated the various conditions required for the electrolyte for the Sukure Plus 1,000 NOx battery, and have now finally invented a completely new electrolyte. We tried to solve the shortcomings of .

[Means for Solving the Problems] [Operation] The present inventors have developed a solution using a tertiary amine salt or a quaternary amine salt as an electrolyte for a battery that uses a polymeric material having a conjugated double bond in its main chain as at least one electrode. A battery was fabricated using a hydrogen chloride solution of a grade ammonium salt.

Polymer materials with conjugated double bonds in their main chains are typical low-dimensional conductive compounds and composite materials containing them.
Specific examples of low-dimensional conductive compounds include polyacetylene, polyalkyne, polyphenylene, polyphenylene oxide, polyphenylene sulfide, polythiazyl, polypyrrole, polythiophene, polyfuran, polyindole, polyaniline, polyarylene vinylene, polydiacetylene, etc. Important low-dimensional conductive compounds include polyacetylene, poly(p-phenylene), and poly(p-phenylene).
(p-phenylene sulfite), polypyrrole, and polythiophene (also referred to as polythenylene). Composite regulations that include this are low-dimensional′! n, a metal material whose surface is coated with an electrically conductive compound, carbon+gt-1, carbon fiber material, plastic, plastic material, glass material i15, or ceramic material. Furthermore, low-dimensional Jn conductive compounds can be used as metallic materials.
It is a hybrid composite material with carbon material or carbon fiber material. These shapes are plate-like, sheet-like, film-like,
It may be fabric-like, linear, net-like, etc., as long as it is shaped so that it can be used as an electrode.

Tertiary amine salts or quaternary ammonium salts are tertiary amines reacted with hydrogen fluoride, tertiary amine Lewis acid salts, tertiary amine Brønsted acid salts, and tertiary amine Brönsted salts. It is a single or a compound of two or more quaternary ammonium salts having a structure in which the hydrogen atom of the stedate salt is substituted with a hydrocarbon group. Typical tertiary amines constituting the tertiary amine salt are trimethylamine, triethylamine, tripropylamine, tributylamine, tribentylamine, methyldiethylamine, diethylmethylamine, dimethylpropylamine, pyridine, picoline, lutidine, quinoline, Isoquinoline, N-methylpyrrole, N-ethylpyrrole, isopyrrole, N-methylpyrazole, N-ethylpyrazole, N-methylimidazole, N-ethylimidazole, 2-isoimidazole, N-methyltriazole, isotriazole, N-
Methyltetrazole, N-ethyltetrazole, isotetrazole, pyridazine, pyrimidine, pyrazine, N-
Methylpiperidine, N-ethylpiperidine, N,N-dimethylpiperazine, N.

N-diethylpiperazine, tetramethylethylenecyamine, dimethylpropylenediamine, dimethylaniline, cyconitylaniline, dimethyltoluidinetriazine, diradizine, N-methylindole, N-methylisoindole, indolenine, propylene These include solid indole, N-methylisoindole, N-methylhensimidazole, N-methylindazole, indazine, N-methylbenz-1-heriazole, 11-ethylbenz-1-heriazole, and benzisodiazole. The Lewis acids constituting these Lewis acid salts are preferably fluorine-containing compounds, and their molecular formula is BF.
:l, SiFa,,GeF,,SbF4,NF,,
NF5, PF3, PF,, △SF. ,AsFs,S
bF:+ , SbF5, NbF, , Hf F4 , T
aF, , SO2 F2, SOF4, SO. F.PSF
3, NSFXNSF3, T i F:l, 'T'jF
a, ZrF2, ZrFn, TIOF2, ZrOF
It is 2nd prize. Moreover, if the acid group of the Brønsted acid that constitutes these Brønsted acid salts is represented by a chemical formula, it is BF.
4-,SIF,-,5iF6-1PFb'',
ASF6-. 5bFs-, TiF6-, Z
rF6--, NbF, -1, Nb R7--, Hf
R6-1, TaR6-, TaFt ---, CF3
COO-, CF3 SO3-, HFz-1(HF) I
, )IF2-, etc., which are fluorine-containing compounds are suitable for the present invention. The third one shown above
The class amine may be any isomer or a mixture of two or more types, and the above-mentioned fluorine-containing compounds may be used alone or in a mixture of two or more types. Further, the quaternary ammonium cation moiety of the quaternary ammonium salt is generally represented by RI+R2,R3,RsN''.

Here, Rl+ R2, Rz, and R4 are hydrocarbon groups or substituted hydrocarbon groups, and they may be the same or different, and may have a ring structure. Typical hydrocarbon groups R+, R2, R's or R
Examples of 6 include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a phenyl group, a Schiff 11 pentyl group, a cyclohexyl group, a benzyl group, and a phenylethyl group. Substituted hydrocarbon groups include atomic groups represented by the following chemical formulas, namely RIOCH2CH2,
R10CHRz CH2, RI OCR2R7C
H2R,0CHR2CHR3,R,0CH2CRz R
x, RI 0CRI R2CHR3, RI 0CR2
R1CHR4, RI R2NCH2CH2, R, lg2
NCHT? , * CHz , RI R2NCR:l
Rs CH2, R, I2 NCH2CR3Ra, etc., those in which R,, R2, R,, R, and H are replaced, and homologous atomic groups in which the carbon chain portion is further extended according to these systems. Typical cations that have a ring structure are N, N-dialkylmorpholinium, N-alkyl/N-phenylmorpholinium,
N, N-dialkylmorpholinium, N, N-dialkylpiperidinium, N-alkyl/N-phenylpiperidinium, N, N-dimethylquinolinium, N
-alkylpyridinium, N-hensylpyridinium,
N, N, N= , N'-tetraal°
Gyltriethylenediammonium, N, N' -Dialkyl N, N= -diphenyltriethylenediammonium, N, N, N= , N" -Tetrahensyltriethylenediammonium, N, N, N'
, N''tetraalkylpiperazinium, N,N-dimethylquinolinium, etc., and these may be pure or a mixture.

The hydrogen fluoride solution of a tertiary amine salt or quaternary ammonium salt referred to in the present invention is a solution in which the above-mentioned tertiary amine salt or quaternary ammonium salt is dissolved in anhydrous hydrogen fluoride (HF). , Hydrogen fluoride, which is a solvent, can be used by distillation, electrolysis, fluorine gas reaction method, halogenated fluorine reaction method,
It can be easily converted into an anhydride using a xenon fluoride reaction method or the like. In the present invention, the water content in the hydrogen fluoride used for electrolytic solution adjustment is preferably 1100 ppm or less, and more preferably 50 ppm or less. It can be quantified using Furthermore, the water content in the hydrogen fluoride solution of the tertiary amine salt or quaternary ammonium salt is preferably 200 ppm or less, preferably 1100 ppm or less, particularly preferably soppm or less, and an electrolyte containing water of 200 ppm or more is used. If this occurs, the performance of the battery will be significantly reduced.

In the present invention, anhydrous hydrogen fluoride, which is easy to purify and is inexpensive, is used as a solvent, and an expensive organic solvent which is difficult to purify is not used. In addition, the volatility of hydrogen fluoride is the third factor shown above.
Based on the discovery that when processed into a hydrogen fluoride solution of a grade amine salt or a quaternary ammonium salt, the concentration of solute in the electrolyte decreases significantly as the solute concentration increases. It was applied. Furthermore, the characteristic corrosivity of hydrogen fluoride rapidly decreases with the addition of solutes such as tertiary amine salts or quaternary ammonium salts as referred to in the present invention. It has been clarified that there is no adverse effect on battery materials such as aluminum alloys such as aluminum alloys such as aluminum alloys, larmin, stainless steel, etc., and even if there is corrosion, the corrosion is minimal.

The electrolytic solution of the present invention is a hydrogen fluoride solution containing a tertiary amine salt or a quaternary ammonium salt, and the amount of hydrogen fluoride relative to these salts should not be particularly limited. Numerous experiments have shown that it is advantageous to use hydrogen fluoride in a range of 3 to 1000 mol, particularly preferably 5 to 50 mol. Furthermore, when using this electrolytic solution, an aprotic solvent that does not react with hydrogen fluoride can be added to further suppress the volatility of hydrogen fluoride. Examples of such compounds include ethers, ketones, etc. , esters, nitriles, dihydric hydrocarbons, and acid amides. Of course, water, alcohols, aldehydes, acids, acid anhydrides, and oximes should be excluded since they cause undesirable reactions with hydrogen fluoride.

In addition, paraffin hydrocarbons, aromatic hydrocarbons, polyolefins, fluorinated hydrocarbons, fluorine-containing resins, fluorine-containing ethers, and carbon blanks can be used as electrolyte conduction regulators and viscosity imparting agents or fillers for solidification. , graphite, graphite processed products, low-dimensional conductive compounds, graphite fluoride, alkali fluorides, alkaline earth metal fluorides, silicofluorides, borofluorides, etc. are used.

Their use in appropriate amounts in the electrolyte also helps stabilize the electrolyte and even facilitates battery assembly.

Now, the battery referred to in the present invention may be either a primary battery or a secondary battery, and both electrodes thereof may be made of a polymer material having a conjugated double bond in the main chain, and the anode side may be a polymer material having a conjugated double bond in the main chain. It may be made of a polymeric material, and the cathode side may be made of metal (such as solid aluminum or aluminum alloy). In addition, when a polymeric material is used as an electrode, in order to improve its mechanical strength, electrical conductivity, and conductivity, as described above, a support of the polymeric material and a metal plate, a graphite plate, a porous metal plate, etc. are used. It is also advisable to use plates, wire mesh, metal wires, etc. Appearances of batteries to which the method of the present invention can be applied are box-shaped batteries,
These include cylindrical batteries, sheet-type batteries, button-type batteries, rod-type batteries, etc., and it is possible to manufacture batteries that are extremely superior in terms of coupling efficiency, energy density, energy efficiency, and output density.

In conventional polyacetylene batteries using propylene carbonate or tetrahydrofuran as electrolyte solvents, complications such as decomposition and polymerization occur during charging and discharging.
i 1'-UJI reaction occurs, resulting in insufficient energy density, charge/discharge efficiency, charge/discharge cycles, or flatness of voltage during discharge, and self-discharge property is also quite large, making it economically advantageous. However, it has been revealed that the battery of the present invention significantly improves these points.

Furthermore, what should be noted in the present invention is that even though the battery is constructed using an electrolyte containing hydrogen fluoride, the electrolytic fluorination of each organic compound used as battery material will not occur unless extreme charging is performed. If this does not occur and the operating temperature is below 70°C even though a tertiary amine salt or quaternary ammonium salt is used as an electrolyte, fluorination decomposition etc. may occur or perfluorinated compounds may be formed. These difficult discoveries led to the present invention. However, if the regulations shown in the present invention are not met, fluorination of the organic compounds used as materials will occur even under relatively mild conditions, and this will cause the performance of the battery to deteriorate significantly. In addition, undesirable substances are generated and handling becomes troublesome, so it is natural that this point should be taken with great care.

〔Example〕

As a result of numerous experiments, the present inventors completed the present invention and confirmed the 4Ei property of the present invention.In order to further explain the technical content of the present invention, we selected representative examples from among the many experimental examples. A few examples will be selected and shown below as examples. Therefore, the present invention should not be construed as being limited to the embodiments shown below, and it is of course possible to modify the embodiments as desired without departing from the spirit and spirit of the present invention. be.

Example 1゜Aromatic hydrocarbon oil 301Tlβ, triethylaluminum 4rnl and tetrabutoxytitanium 2.5mj2
The catalyst was mixed and kept for about 30 minutes, then applied to the vapor deposition surface of a surface-treated Teflon plate (about 200 cJ) on which platinum was vapor-deposited, kept under reduced pressure, cooled to -80°C, and then mixed with acetylene gas (
It is brought into contact with about 700+sHf for 1 hour. The residual pressure of the acetylene gas was about 500 + 1 m11 g, and a dark brown polyacetylene film with a metallic luster was formed on one side of the Teflon plate, which was continuously washed with aromatic hydrocarbon oil for 5 hours and then vacuum dried. Cut two Teflon plates with polyacetylene film attached to a size of 5 cm x 5 cm. Mechanically peel off the polyacetylene film around each of these two plates to a width of 1.5 cm.
Afterwards, a fluororesin-based low melting point resin is applied, and
A 1-fin thick Teflon net is sandwiched between the polyacetylene film left in the center of the Teflon plate (2 cm x zσ), and the two Teflon plates are stacked in a Zandwisochi shape and the periphery of the Teflon plate is heated and bonded in a vacuum. Seal. At this time, a part of the thin platinum coating is made available for use as an external terminal. Insert two syringe needles into the Teflon mesh part in the middle of the sealed Teflon plate, remove the internal gas from one needle, and pour out 20m7 of hydrogen fluoride from the other needle! pyridine 5
An electrolytic solution (H2070 ppm) in which mtl is dissolved is injected, and the injection needle is removed and sealed with fluororesin. Next, connect the platinum-deposited part to the power supply and apply 0.5mA/cf.
A secondary battery is obtained by performing constant current charging of fl for 1 hour. The open circuit voltage of this battery is 3. The initial closed circuit current was 25 years old at Ov. This secondary battery could be charged and discharged several dozen times at an average voltage of 2.5 Å, was easy to manufacture, and was lightweight.

Example 2 After attaching a poly(p-phenylene sulfide) film to the vapor-deposited surface of the Teflon plate on which platinum was deposited in Example 1, a secondary battery was produced in the same manner. However, the electrolyte is hydrogen fluoride 20mj! 2.5mβ of N,N-dimethylpiperazine and 2mβ of quinoline were dissolved in (H20, 10100pp, open circuit voltage after charging was 2.5mβ).
At 0 ■, the closed circuit current was 20 years old.

Example 3 When a battery was made in the same manner as in Example 2 using polypropylene film and polypropylene net instead of the Teflon plate and Teflon net, almost the same results as in Example 2 were obtained. In this method, polyethylene, polyvinylidene fluoride or polymethylpentene can also be used in place of the polypropylene material, but SB rubber,
Acrylic resin and furanol resin were unsuitable.

Example 4: Practical side When a battery was made in the same manner as in Example 1 using a paste in which 1 g of fine polytetrafluoroethylene powder was dispersed in an electrolytic solution, the open circuit voltage was 2.5 μ and the closed circuit current was He was 22 years old and eight years old.

Example 5 Anhydrous tetrabutylammonium difluoroacetate was added to hydrogen fluoride to form a saturated solution (I (2082p)
pm) in advance. Polyacetylene (thickness 100μ)
The anode (2 cm x 2 cm) was made by vacuum evaporating platinum on the aluminum foil, and the cathode (2 cm
x2cm). Both poles are placed in a polyethylene container with the metal surfaces facing outward and a polypropylene sponge (0.5 m11) facing each other as a spacer. This battery container is placed in a vacuum, and the saturated solution described in Section 2 is injected as an electrolyte into the container so that the electrodes are completely immersed. This secondary battery could be charged through a constant current of 0.2 mA for 90 minutes, its open circuit voltage was 3.1 V, and its initial closed circuit current was 30 mA.

It was found that this battery operated conveniently at temperatures between -30°C and +40°C, and could be repeatedly charged and discharged in the same manner as in Example 1.

Example 6 A secondary battery was obtained in the same manner as in Example 5, except that tributylammonium/boron trifluoride complex salt was used in place of tetrabutylammonium difluoroacetate-1-. In this case, the paste was made to be more than a saturated solution of the complex salt. The performance as a battery seemed to be slightly lower than that of Example 5. In this case, the temperature is -5°C to +4°C.
It is best to use it mainly between 5°C.

Example 7゜The 1-butylammonium trifluoro t' of Example 5
A secondary battery was obtained in the same manner as in Example 5, except that ethyldiisopropylammonium--xafluorophosphate was used in place of J-acetate-1. The performance as a battery was almost the same as in Example 5. Also, tetraprobylammonium trifluoromethanesulfone-1~
Similar results were obtained using .

Example 8 A gel of Ruchinger polyacetylene synthesized by a solution method was adhered to the surface of a platinum wire mesh, vacuum dried, and then pressed to solidify. This electrode was immersed in hot toluene and extracted continuously for 5 hours to remove the catalyst 1-7, and then dried under reduced pressure. Connect a platinum wire to this electrode and use it as an anode (1cm x 1cm)
) and cover the lithium plate with carbon fiber cloth as the cathode (1
A porous polypropylene film was placed in a polyethylene bottle as a separator to face each other. This battery was placed in an inert gas chamber and an electrolytic solution (Hz O' 10
Inject 100pp so that the electrode is immersed. When this secondary battery was charged in the same manner as in Example 1, -35 ~
It is a low-temperature battery (2.8V) that works well at -5°C, and the coulomb efficiency is 60% at 0°C, 70% at -5°C, and -15"C.
It was found that it was 82% at -25°C, 94% at -35°C, and 98% at -35°C.

Example 9゜By applying the production method of Example 4 to the batteries shown in Examples 1 to 3 and Examples 5 to 8, sheet-like batteries and bottom-shaped batteries could also be made. Number of terminals (=
One part required some modification depending on the shape of the battery, and it was necessary to package it after confirming that the connection part was complete.

〔Effect of the invention〕

The present invention relates to a battery characterized in that a hydrogen fluoride solution of a tertiary amine salt or a quaternary ammonium salt is used as an electrolyte in a battery using a polymeric material having a conjugated double bond as at least one electrode. With the completion of the present invention, it is possible to create new innovations in wet batteries or solid-state batteries of various shapes, and it can be applied to both secondary batteries and secondary batteries, and can be used by consumers to use various batteries. However, it is possible to achieve a full 50% reduction both economically and in terms of performance. In addition, the battery of the present invention (1) is lightweight and has a large output, and by carefully selecting the type of electrolyte and battery shape, it can be used within the temperature range of the earth's climate, that is, from -40℃ to 40℃.
Age between +50℃? It has now become clear that an excellent battery that can be used in a variety of situations can be provided. The technical content of the present invention provides a great advance over the configuration of conventional plastic batteries, and the idea of the present invention is also useful for developers of various batteries using conventional non-aqueous electrolytes. It also provides food for further advanced thinking.

As described above, it has been revealed that the present invention is extremely superior academically, technically, and commercially, and the effects of the invention are tremendous.

Claims (1)

[Claims] 1. A battery that uses a polymeric material having a conjugated double bond in its main chain as at least one electrode, and uses a hydrogen fluoride solution of a tertiary amine salt or a quaternary ammonium salt as an electrolyte.