GB2143228A - Electrolytes - Google Patents
Electrolytes Download PDFInfo
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- GB2143228A GB2143228A GB8318902A GB8318902A GB2143228A GB 2143228 A GB2143228 A GB 2143228A GB 8318902 A GB8318902 A GB 8318902A GB 8318902 A GB8318902 A GB 8318902A GB 2143228 A GB2143228 A GB 2143228A
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- Prior art keywords
- electrolyte
- acid
- boric acid
- dimethyl
- complex
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims description 40
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 30
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004327 boric acid Substances 0.000 claims abstract description 25
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 8
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 7
- -1 oxalic acid Chemical compound 0.000 claims abstract description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007859 condensation product Substances 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 22
- 239000003990 capacitor Substances 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011888 foil Substances 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 125000006850 spacer group Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- BGBNXIKULUCCOO-BTJKTKAUSA-N (z)-but-2-enedioic acid;n,n-diethylethanamine Chemical compound CCN(CC)CC.OC(=O)\C=C/C(O)=O BGBNXIKULUCCOO-BTJKTKAUSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GHKICRQMVSWOTM-UHFFFAOYSA-N OB(O)O.OCCO.N.N.N Chemical compound OB(O)O.OCCO.N.N.N GHKICRQMVSWOTM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 239000010407 anodic oxide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- CAPAZTWTGPAFQE-UHFFFAOYSA-N ethane-1,2-diol Chemical compound OCCO.OCCO CAPAZTWTGPAFQE-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- OCKHUPCREYAULF-UHFFFAOYSA-N n,n-dimethylformamide;n-methylmethanamine Chemical compound CNC.CN(C)C=O OCKHUPCREYAULF-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/166—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solute
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
A non-aqueous electrolyte for use in electrolytic devices comprises an organo-boron complex, consisting of a condensation product of boric acid and an aliphatic dicarboxylic acid, particularly oxalic acid, or an gamma -hydroxy carboxylic acid, in a non-aqueous solvent.
Description
SPECIFICATION
Electrolytes
This invention relates to electrolytes and in particular to substantially non-aqueous electrolytes for use in electrolytic devices.
High conductivity substantially non-aqueous electrolytes are used for electrolytic capacitors (tantalum, aluminium, etc.) to form the cathodic contact to the dielectric (oxide) film. These electrolytes must possess chemical stability over a wide temperature range, typically - 55"C to + 1 25 C, the ability to heal damaged oxide by electrochemical oxide growth and as low a resistivity as possible. For aluminium electrolytic capacitors, the electrolyte must also be chemically benign to aluminium and its anodic oxide.
According to the present invention there is provided a substantially non-aqueous electrolyte, for use in electrolytic devices, comprising an organo-boron complex in a non-aqueous solvent, the complex consisting of a condensation product of boric acid and an aliphatic dicarboxylic acid or an a-hydroxy carboxylic acid.
The solvent employed for capacitor electrolytes is partly dictated by cost and toxicity and is limited by temperature range requirements. The common solvents used include ethylene glycol (1,2 ethane diol); N, N-dimethyl-formamide; N, N-dimethyl-acetamide; y-butyrolactone; N-methyl2-pyrrolidone; glycol ethers and propylene carbonate. The requirement of chemical compatibility with aluminium, for aluminium electrolytic capacitors, rules out any chloride, bromide and iodide containing ions, as well as sulphate or its derivatives. Any ion used to form a conducting solution must itself be chemically compatible with aluminium and not give breakdown products which can react with aluminium.
It is well known to use combinations of various organic acids and boric acid in combination with ammonia or aliphatic amines to prepare suitable stable electrolytes. Some well-knownorgano-boron compounds using aromatic 1,2 substituted acids or phenols or phenol and carboxylic acid in combination with borates such as borodisalycilate have been used.
We have now found, in contradiction to chemical text-book rules for the aqeuous formation of stable complexes, that oxalic acid and a-hydroxy carboxylic acids can form stable complexes with boric acid, and that these form the basis for very high conductance solutions in substantially non-aqueous solvents.
The general reaction for formation is
O R1 R1 OH HO C )Bo'O .HO MkR2 2 C OH + B-OH 1Be +H@ +3H20 (1) R2 C HO O' + II kRl 0 0 R2 -HYDROXY ACID BORIC ACID or O 0 OH HO 2 | | ,B-OH :Be +H@+3H20 (2) C HO 0' 0'HO OXALIC ACID BORIC ACID It is believed that the tetrahedral boron atom bearing a negative charge is protected from ionic association by the surrounding organic grouping and that high conductance solutions are hence possible.
A range of organic acids were investigated and the usefulness of a given organo-boron complex was judged initially by the increase in conductivity obtained in the cold when boric acid was added to a solution of the organic acid in dimethylformamide. Experience has shown that whilst the conductivity in dilute solution does not guarantee a high achievable conductivity at high concentration, since a number of other considerations apply, it is possible to rule out a number of possible systems using such an initial test. Table I indicates results for a range of complexes.
TABLE I
Solvent: N,N-dimethyl-formamide
Organic Conductivity at Conductivity with Ratio of
Acid concentration 0.05 m boric acid conductivities
of 0.1 m (mS) added (ms) Oxalic 0.020 0.390 19.5
Malonic 0.018 0.048 2.7
Succinic 0.013 0.013 1.0
Adipic 0.008 0.008 1.0
Maleic 0.050 0.059 1.2
Glycolic 0.013 0.538 41
Lactic 0.026 0.770 30
Malic 0.016 0.907 57
Tartaric 0.011 1.060 96
Citric 0.012 0.806 67
Salicylic 0.014 1.500 107
As can be seen from the first five acids quoted, only oxalic acid of the aliphatic dicarboxylic acids tested reacts strongly with boric acid and thus appears to be useful as an electrolyte. The last six acids indicate that in general all of the a-hydroxy acids react strongly, with salicylic acid appearing to form the most acidic complex, as is known from aqueous chemistry.
The following examples illustrate specific preparation techniques and conductivities achievable.
A Dean and Stark appartus was used for the preparation of anhydrous solutions of a range of complexes. It was found that boric acid and oxalic acid could be reacted in N,N-dimethylformamide, or N-methyl-2-pyrrolidone, to give strongly acidic highly conducting solutions. The addition of bases such as triethylamine, or reaction at 1 20 C with N,N-dimethyl-formamide to form dimethyl ammonium salts, can give highly conducting solutions in pH ranges suitable for capacitors.
Example I
50 ml N,N-dimethyl-formamide, 12.6 g oxalic acid and 3.06 g boric acid were heated together to 1 48on. This resulted in 60 ml of a yellow solution with a conductivity of 32 mS (10 - 3S, millisiemen) at room temperature. The addition of 2% by weight of water enabled anodising (anodic oxidation) to 1 00V to be carried out.
Example li 40 ml N-methyl-2-pyrrolidone, 1.0 g boric acid and 2.9 g oxalic acid were heated together to 1 50C cooled, and triethylamine added to give a maximum conductivity at room temperature of 9.5 mS. Anodic oxidation was enabled by this electrolyte at voltages up to 183V before visible scintillation accurred.
From Examples I and II it can be seen that it is possible to achieve room temperature conductivities of approximately 30 mS in N,N-dimethyl-formamide, or 10 mS in N-methyl-2pyrrolidone, using the boro-dioxalate complex of reaction (2).
The boric acid/lactic acid complex of reaction (1) was found to give high conductivity in ethylene glycol, as evidenced from the following Example Ill, N, N-dimethyl-formamide. as
evidenced from Table I, and N-methyl-2-pyrrolidone.
Example 111
40 ml ethylene glycol, 1.6 g boric acid and 8 ml lactic acid were mixed to give a basic
solution. Ammonia was added as an 0.88% solution to the basic solution, to give an electrolyte
with a maximum conductivity of 8 mS at room temperature. Heating was then employed to
remove water and check for high temperature stability. This electrolyte after heating to 1 30 C and cooling has a conductivity of 5.9 mS at room temperature, whereas after heating to 1 50 C and cooling the conductivity at room temperature is reduced to 3.8 mS. Whereas a simple boric
acid and ammonia electrolyte can achieve similar initial conductivities, on heating, however, it
loses water and ammonia to revert to a much lower conductivity than that obtained with the
electrolyte of Example Ill.The solutions of Example Ill were capable of anodising only to 60
volts.
Example IV
Crystals of (possibly) dimethylammonium boro-dioxalate were prepared by reacting boric acid
and oxalic acid in N,N-dimethyl-formamide and removing the solvent by distillation. A solution
of 0.3 g of this crystalline product in 6 ml of y-butyrolactone gave a room temperature
conductivity of 8.0 mS.
The results of other solutions are quoted in Table II.
TABLE II
Solvent Conductivity (mS) of solution
containing 1.6% by weight of
crystalline product
N,N-dimethyl-formamide 4.8 t-butyrolactone 2.3
propylene carbonate 1.3
ethylene glycol 0.36
The results in Table II indicate that the dimethylammonium boro-dioxalate complex is soluble in a range of solvents, and at low concentrations gave fairly conducting solutions.
For the purpose of comparison Table Ill illustrates typical conductivities with conventional electrolyte systems.
TABLE III
Solvent System Electrolyte Conductivity(mS) N,N-dimethyl-formamide dimethylammonium 11 -butyrolactone/ N-inethyl-2-pyrrolidone dimethylammonium 6 ethylene glycol ammonium borate 4
Particularly from the room temperature conductivity measurements obtained from the electrolytes of Examples I to IV it will be seen that the organo-boron complexes can offer considerable conductivity increases over conventional electrolytes. The boric oxalic (borodioxalate) complexes, in particular, offer very high conductivities at room temperature in solvents containing amide functional groups, such as N,N-dimethyl4ormamide, N,N-dimethyl acetamide and N-methyl-2pyrrolidone, for example 32 mS in N,N-dimethyl-formamide, and 10 mS in N-methyl-2pyrrolidone.The boric acid/lactic acid complex also gives high conductivities, for example 30 mS in N,N-dimethyl-formamide, and 8 mS in ethylene glycol. As is apparent from the examples quoted in Table I complexes can be formed at room temperature, which have conductivities suitable for use in electrolytes, using many a-hydroxy carboxylic acids and the aliphatic dicarboxylic acids oxalic acid and malonic acid, however from the results presently obtained the most useful complexes are obtained from the a-hydroxy acids or oxalic acid.
The main advantage provided by the use of such high conductivity electrolytes comprises the reduction in series resistance in an electrolytic capacitor. At high frequency the major contribution to impedance is the electrolyte resistance, thus lower resistance means that higher operational frequencies are possible, or shorter capacitor windings can be used, or low impedance for the same size is possible.
A capacitor containing an electrolyte comprising the electrolyte of Example II with 30% by weight of y-butyrolactone was fabricated and put on test at 85 C, 1 or. After 3500 hours, the capacitor was still operating with a low leakage current.
Samples of various electrolytes were measured for conductivity, sealed in cells and heated for 2000 hours at 85"C. The conductivity before and after heating of the boro-dioxalate based electrolyte is shown in Table IV compared with a conventional glycol-borate electrolyte and a simple organic acid in the same solvent mix as the boro-dioxalate based electrolyte. This table indicates the superior performance of the boro-dioxalate based electrolytes.
TABLE IV
Electrolyte Conductivity (ms) Initial 2000hrs Ratio
Ethylene glycol/ammonia borate 2.60 1.58 0.6
Boro-dioxalate in
N-methyl-2-pyrrolidone/ t-butrolactone 6.38 4.37 0.7
Triethylammonium maleate in
N-methyl-2-pyrrolidone/ t-butyrolactone 6.64 3.36 0.5
The ability of the organo-boron complexes to yield highly conducting solutions is further evidenced from the electrolyte conductivities in Table V. For each of the eleven acids listed an 0.5M solution in N,N-dimethyl-formamide was made to which was added 0.25M boric acid.
The solutions were heated to 11 0 C, to drive off the water of condensation, cooled and their conductivities measured before and after adding triethylamine, the results being as indicated in the two left hand columns of Table V. With the first six acids 2.5M solutions in N-methyl-2pyrrolidone were also made and to which 1 25M boric acid was added. These solutions were also heated to 11 0'C, cooled and their conductivities measured before and after adding briethylamine, the results being as indicated in the two right hand columns of Table V. The high conductivity of the boro-di-glycollate in N-methyl-2-pyrrolidone with triethylamine is of particular interest.
TABLE V
Conductivity in mS
0.5M 2.5M
Acid Boric+DMF Boric+DMF Boric+NMP Boric+NMP
+TEA +TEA
Maleic 0.79 10.4 0.17 1.2
Glycollic 2.69 8.23 1.65 7.81
Salicylic 7.06 7.64 3.02 4.37 Lactic 3.4 7.6 2.52 4.87
Oxalic 5.2 7.06 2.02 4.37 Malic 3.8 5.12 1.01 1.38
Citric 2.6 4.54 Malonic 0.5 4.28
Succinic 0.1 4.2
Tartaric 2.86 4.11
Adipic 0.1 2.22
A typical method of manufacturing an electrolytic capacitor comprises arranging two electrode foils so that they alternate with two absorbent spacer sheets of a larger size than the foils and winding the resultant arrangement to form a coil structure. A respective lead wire is affixed to each foil. The coil structure is encapsulated and the spacer sheets are impregnated or saturated with an operating electrolyte, comprising one of the non-aqueous electrolyte compositions described above. The electrode foil which comprises the anode of the finished capacitor is provided with an oxide film, which comprises the device dielectric and which is applied to the foil during the formation thereof by an anodic oxidation process. Thus for aluminium electrolytic capacitors the dielectric comprises aluminium oxide. The surface of the anode may be roughened (etched) in order to increase the surface area and thus the capacitance. In dependence on the use of the capacitor the cathode foil may also be etched and/or provided with a dielectric oxide layer. The spacer sheets are of an absorbent material, such as paper, which is readily saturated with the electrolyte.
Claims (14)
1. A substantially non-aqueous electrolyte, for use in electrolytic devices, comprising an organo-boron complex in a non-aqueous solvent, the complex consisting of a condensation product of boric acid and an aliphatic dicarboxylic acid or an y-hydroxy carboxylic acid.
2. An electrolyte as claimed in claim 1, wherein the complex is a condensation product of boric acid and oxalic acid.
3. An electrolyte as claimed in claim 1, wherein the complex is a condensation product of boric acid and lactic acid.
4. An electrolyte as claimed in claim 1, wherein the complex is a condensation product of boric acid and glycollic acid.
5. An electrolyte as claimed in any one of the preceding claims wherein the organo-boron complex was formed by heating a mixture in the proportion of two moles of the organic acid to one more of boric acid in the solvent whereby to drive off the water of condensation.
6. An electrolyte as claimed in any one of the preceding claims, wherein the non-aqueous solvent comprises, N, N-dimethyl-formamide, N, N-dimethyl-acetamide, N-methyl-2-pyrrolidone, ethylene glycol, y-butyrolactone, or propylene carbonate, or mixtures thereof.
7. An electrolyte as claimed in any one of claims 1 to 6 further including triethylamine or ammonia.
8. An electrolyte as claimed in any one of claims 1 to 6, wherein the organo-boron complex comprises a dimethyl ammonium salt.
9. An electrolyte substantially as herein described with reference to the Examples or Table V.
10. An electrolytic capacitor including a substantially non-aqueous electrolyte as claimed in any one of the preceding claims.
11. A method of manufacturing an electrolytic capacitor including the steps of arranging a first absorbent spacer sheet between an anode and a cathode foil, arranging a second absorbent spacer sheet adjacent one foil, winding the resultant arrangement to form a coil and impregnating the spacer sheets with an electrolyte as claimed in any one of claims 1 to 9.
1 2. A method of manufacturing a substantially non-aqueous electrolyte, for use in electrolytic devices, comprising forming an organo-boron complex by mixing an aliphatic dicarboxylic acid, or an a-hydroxy acid, and boric acid in a non-aqueous solvent and heating the mixture to drive off the water of condensation.
1 3. A method as claimed in claim 12 wherein the mixture is in the proportion of two moles of the organic acid to one mole of the boric acid.
14. A method as claimed in claim 1 2 or claim 1 3 wherein the non-aqueous solvent comprises N,N-dimethyl-formamide, N, N-dimethyl-acetamide, N-methyl-2-pyrrolidone, ethylene glycol, y-butyrolactone, or propylene carbonate, or mixtures thereof.
1 5. A method as claimed in any one of claims 1 2 to 14, further including the step of adding triethylamine or ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8318902A GB2143228A (en) | 1983-07-13 | 1983-07-13 | Electrolytes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8318902A GB2143228A (en) | 1983-07-13 | 1983-07-13 | Electrolytes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8318902D0 GB8318902D0 (en) | 1983-08-17 |
| GB2143228A true GB2143228A (en) | 1985-02-06 |
Family
ID=10545640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8318902A Withdrawn GB2143228A (en) | 1983-07-13 | 1983-07-13 | Electrolytes |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2143228A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0381936A1 (en) * | 1989-01-11 | 1990-08-16 | Matsushita Electric Industrial Co., Ltd. | An electrolyte for use in electrolytic capacitors |
| WO1994027335A1 (en) * | 1993-05-13 | 1994-11-24 | Wuehr Manfred | Electrolyte for use in a galvanic cell |
| EP0631340A2 (en) * | 1993-06-18 | 1994-12-28 | Hitachi Maxell Ltd. | Organic electrolytic solution cell |
| EP1074555A2 (en) * | 1999-08-02 | 2001-02-07 | Central Glass Company, Limited | Ionic metal complex and process for synthesizing same |
| EP1075036A2 (en) * | 1999-08-02 | 2001-02-07 | Central Glass Company, Limited | Electrolyte for electrochemical device |
| EP1154450A2 (en) * | 2000-05-08 | 2001-11-14 | Central Glass Company, Limited | Electrolyte for electrochemical device |
-
1983
- 1983-07-13 GB GB8318902A patent/GB2143228A/en not_active Withdrawn
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0381936A1 (en) * | 1989-01-11 | 1990-08-16 | Matsushita Electric Industrial Co., Ltd. | An electrolyte for use in electrolytic capacitors |
| US5055974A (en) * | 1989-01-11 | 1991-10-08 | Matsushita Electric Industrial Co., Ltd. | Electrolyte for use in electrolytic capacitors |
| WO1994027335A1 (en) * | 1993-05-13 | 1994-11-24 | Wuehr Manfred | Electrolyte for use in a galvanic cell |
| US5660947A (en) * | 1993-05-13 | 1997-08-26 | Wuhr; Manfred | Electrolyte for use in a galvanic cell |
| EP0631340A2 (en) * | 1993-06-18 | 1994-12-28 | Hitachi Maxell Ltd. | Organic electrolytic solution cell |
| EP0631340A3 (en) * | 1993-06-18 | 1997-02-05 | Hitachi Maxell | Organic electrolytic solution cell. |
| EP1074555A2 (en) * | 1999-08-02 | 2001-02-07 | Central Glass Company, Limited | Ionic metal complex and process for synthesizing same |
| EP1075036A2 (en) * | 1999-08-02 | 2001-02-07 | Central Glass Company, Limited | Electrolyte for electrochemical device |
| EP1075036A3 (en) * | 1999-08-02 | 2005-08-24 | Central Glass Company, Limited | Electrolyte for electrochemical device |
| EP1074555A3 (en) * | 1999-08-02 | 2005-09-07 | Central Glass Company, Limited | Ionic metal complex and process for synthesizing same |
| EP1154450A2 (en) * | 2000-05-08 | 2001-11-14 | Central Glass Company, Limited | Electrolyte for electrochemical device |
| EP1154450A3 (en) * | 2000-05-08 | 2005-10-05 | Central Glass Company, Limited | Electrolyte for electrochemical device |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8318902D0 (en) | 1983-08-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |