WO2012173156A1 - 電気化学素子 - Google Patents
電気化学素子 Download PDFInfo
- Publication number
- WO2012173156A1 WO2012173156A1 PCT/JP2012/065161 JP2012065161W WO2012173156A1 WO 2012173156 A1 WO2012173156 A1 WO 2012173156A1 JP 2012065161 W JP2012065161 W JP 2012065161W WO 2012173156 A1 WO2012173156 A1 WO 2012173156A1
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- WIPO (PCT)
- Prior art keywords
- nozzle
- viscosity
- electrolyte
- electrochemical element
- electrolytic solution
- Prior art date
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- 239000003792 electrolyte Substances 0.000 claims abstract description 39
- 239000008151 electrolyte solution Substances 0.000 claims description 76
- 239000007788 liquid Substances 0.000 claims description 39
- 239000007921 spray Substances 0.000 claims description 37
- 239000003990 capacitor Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002848 electrochemical method Methods 0.000 claims 1
- 238000002347 injection Methods 0.000 description 30
- 239000007924 injection Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 18
- 238000000889 atomisation Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 239000002608 ionic liquid Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 7
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- 239000011230 binding agent Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005323 electroforming Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 230000007274 generation of a signal involved in cell-cell signaling Effects 0.000 description 2
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- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B17/00—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups
- B05B17/04—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods
- B05B17/06—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations
- B05B17/0607—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations generated by electrical means, e.g. piezoelectric transducers
- B05B17/0638—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations generated by electrical means, e.g. piezoelectric transducers spray being produced by discharging the liquid or other fluent material through a plate comprising a plurality of orifices
- B05B17/0646—Vibrating plates, i.e. plates being directly subjected to the vibrations, e.g. having a piezoelectric transducer attached thereto
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/14—Arrangements or processes for adjusting or protecting hybrid or EDL capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
- H01G13/04—Drying; Impregnating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
- H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to an ultra-small electrochemical device such as an ultra-small secondary battery, an ultra-small primary battery, an ultra-small electric double layer capacitor, and an ultra-small pseudo electric double layer capacitor.
- the present invention relates to an electrochemical element that employs a new electrolyte solution injection method that enables accurate and rapid quantitative supply and enables permeation and diffusion in the cathode and anode mixture of the electrochemical element.
- a mobile device called a smartphone is a mobile device intended to be multi-functional such as a personal computer function, an e-mail function, a game function, an e-book function, and a music function in addition to a conventional mobile phone.
- a typical example is a device called Apple's i-Phone, which has been popular in the US since 2007, in Korea in 2008, and in Japan in 2009 since it began to rapidly spread. is there.
- This new portable device initially used an ML-type battery (MnO 2 / Li primary battery) as a power back-up, but with the increase in the number of multifunctional portable devices, the price of portable devices has increased. Because the device is used for a longer period of time, the coin-type ML type battery has insufficient battery capacity, battery life, voltage and current for instantaneous software activation. It is replaced by a chip-type ultra-small electric double layer capacitor (hereinafter abbreviated as EDLC), and this small coin type is produced at about 200 million pieces / month mainly in Japan and Korea. Is continuing.
- EDLC chip-type ultra-small electric double layer capacitor
- This difficulty in mass production can be achieved by supplying a small amount of high-viscosity ionic liquid such as EMIBF4 (Ethyle, Methyle, Imidazolium tetraoroFuluoroBorate), and using a high-viscosity electrolyte as an electrode mixture for electrochemical devices in a short time.
- EMIBF4 Ethyle, Methyle, Imidazolium tetraoroFuluoroBorate
- a high-viscosity electrolyte as an electrode mixture for electrochemical devices in a short time.
- the current situation is that it has a big problem in diffusion absorption. Since recent portable devices require a relatively larger current, a low-resistance high-concentration electrolytic solution or an ionic liquid that can withstand solder reflow is used in Neat (100%).
- the viscosity of such a high-concentration electrolytic solution is 15 to 35 mPa ⁇ s (15 to 35
- Measures such as these include injection in several batches, injection with the electrolyte temperature raised, centrifugation after injection, and decompression treatment, all of which take time and effort.
- the atmosphere in the vacuum chamber is gradually increased to inject the solution.
- Patent Document 1 a method in which the inside of the battery tank is depressurized by a vacuum pump, and the inside of the battery tank is communicated with the electrolyte reservoir by a three-way valve, and the electrolyte is sucked and injected (see Patent Document 2) ) Etc. are known.
- a nozzle plate having a large number of fine nozzles is vibrated by a piezoelectric vibrator and the liquid supplied to the nozzle plate is sprayed from the nozzles, or a nozzle plate having a large number of fine nozzles
- the device that sprays the liquid supplied between the adjacent ultrasonic vibrators from the nozzle is a small and energy-saving feature. Widely applied to atomizers.
- Fig. 9 shows a typical conventional liquid injection method.
- a cathode mixture 2 (with a thickness of 400 to 700 ⁇ m) is stored in a 414 coin-type EDLC (3.8 mm ⁇ * 1.4 mm t) stainless steel (SUS 304) Cap 1.
- An ionic liquid has been supplied to this mixture by a droplet method such as a syringe type.
- the conventional electrolyte such as TEABF4 by this conventional method could be supplied.
- an ionic liquid such as EMIBF4 that can withstand solder reflow has a high viscosity, a large surface tension, and does not diffuse or penetrate into the mixture even when the electrolytic solution 3 is dropped.
- the current situation is that pressure is applied under reduced pressure to supply electrolyte.
- JP-A-8-273659 JP-A-8-298110 Special Table 2002-536173 Publication JP 2000-271517 A JP 2005-511275 Gazette JP 2010-142737 A JP 2003-220702 A
- ultra-compact EDLC is also required to have low resistance and large current instantaneous charge / discharge.
- MSD surface mount
- solder reflow conditions 260 ° C * 10 seconds. Therefore, EMIBF4 ionic liquid is supplied at a concentration of 100% (expressed as “Neat”), so accurate micro-quantitative supply (0.1 to 10 ⁇ L / time) is extremely difficult. The equipment will be damaged due to leakage.
- this concentrated electrolyte has a large surface tension, it is difficult to impregnate the electrode mixture of EDLC, and time is required. Therefore, when the electrolyte is supplied, the temperature is increased, pressure reduction, pressurization is repeated, and production is performed. This is the current situation.
- Viscosity of organic ionic liquids and high-concentration electrolytes is 10 to 40 mPa ⁇ s (10 to 40 cps).
- Conventional known atomizers have 10 mPa ⁇ s (10 cps). Since it is an aqueous low viscosity such as the following ink, it cannot be atomized and supplied with a high viscosity solution.
- the organic high-concentration electrolyte uses high purity with a water content of 10 ppm or less, so the viscosity and surface tension are large, and the dripping particles are an electrode mixture for electrochemical devices.
- An object of the present invention is to provide a novel electrochemical device capable of injecting a high concentration and high viscosity electrolytic solution in order to solve various conventional problems.
- the first aspect of the present invention is an electrochemical element in which an electrolytic solution is instantaneously supplied in a small amount and in a dispersed amount, and a high concentration and high viscosity electrolytic solution can be rapidly supplied to the electrochemical device. It is what I did.
- the electrochemical element is any one of a primary battery, a secondary battery, an electric double layer capacitor, and a pseudo electric double layer capacitor, and can be applied to these.
- an electrolytic solution having a high viscosity of 10 to 40 mPa ⁇ s (10 to 40 cps) at 20 ° C. is supplied to the electrochemical device.
- the vibrating element is used as a means for supplying the dispersed quantitative amount
- the electrolytic solution is intermittently supplied from a nozzle having holes with a density of 1 to 6000 / cm 2 .
- a high-concentration, high-viscosity electrolyte solution is allowed to permeate and diffuse into the electrode mixture of the electrochemical element.
- the fifth aspect of the present invention is that the nozzle metal is a nickel-based alloy and the pore diameter is in the range of 1 to 100 ⁇ m, so that the nozzle can be produced by electroforming technology and the electrolyte solution is 0.1 to 10 ⁇ L / It is possible to reliably supply a fixed amount in a small amount of time, to quickly supply a high-viscosity electrolyte such as EMIBF4, and to perform diffusion impregnation into an electrode mixture.
- EMIBF4 high-viscosity electrolyte
- the surface of the nozzle ejection hole is subjected to a surface treatment excellent in wear resistance, chemical resistance, and liquid resistance, thereby providing durability.
- DLC Diamondlike Carbon
- fluorine processing is applied as a surface treatment of the nozzle ejection hole to provide water repellency.
- the vibration time when the electrolyte has a viscosity of 10 mPa ⁇ s (10 cps) or more, the vibration time is 20 ms or less, and when the electrolyte has a viscosity of 30 mPa ⁇ s (30 cps) or more, the vibration time. Is set to 10 ms or less, so that it is possible to avoid atomization spraying even with a highly viscous electrolyte.
- a ninth aspect of the present invention includes a nozzle plate having the nozzle and supplied with the electrolyte solution, and a vibrator that vibrates the nozzle for dispersion and quantitative supply, and the vibrator is vibrated intermittently.
- An atomizing spray device that intermittently stops the vibration of the vibrator before the spray outlet side of the nozzle is wet-covered with the electrolytic solution.
- the atomizing spray device includes a detecting unit that detects a temperature of the electrolytic solution, and a determining unit that determines the length of the electric signal according to the detected temperature.
- the nozzle plate is set to have a distance between the adjacent nozzles of 150 ⁇ m or more, thereby preventing the nozzles on the spray outlet side from being connected by a liquid film to prevent atomization spraying. Is.
- the electrolytic solution is fine particles and is intermittently dropped, so that the surface tension is reduced.
- electrolyte solution can be osmotically diffused between mixture particles. Therefore, a high-viscosity ionic liquid that is a high-viscosity electrolyte is also easily wetted, and the adsorbed gas in the mixture is easily desorbed and continuously dissipated outside the mixture as the ionic liquid penetrates. Therefore, it permeates and diffuses at high speed in the electrode mixture.
- an excellent effect that it can be applied to a primary battery, a secondary battery, an electric double layer capacitor, and a pseudo electric double layer capacitor can be obtained.
- the electrochemical device According to the electrochemical device according to the third aspect, it is possible to reliably supply an electrolytic solution having a high viscosity of 10 to 40 mPa ⁇ s (10 to 40 cps) at 20 ° C., which could not be supplied by the prior art. Is obtained.
- the electrolyte solution is intermittently supplied from the nozzle used as the means for supplying the dispersed quantitative amount, whereby the electrolyte solution of high concentration and high viscosity is mixed with the electrode mixture of the electrochemical element.
- the excellent effect that it can permeate and diffuse inside is obtained.
- a nozzle used as a means for supplying a distributed quantitative amount can be produced by electroforming technology, and an electrolytic solution can be reliably supplied in a small amount of 0.1 to 10 ⁇ L / time.
- an electrolytic solution can be reliably supplied in a small amount of 0.1 to 10 ⁇ L / time.
- the surface of the nozzle outlet used as a means for supplying a constant amount of dispersion is excellent in wear resistance, chemical resistance, liquid resistance and durability. The excellent effect of being able to be obtained is obtained.
- the surface of the nozzle outlet used as the means for supplying the dispersed quantitative amount is given water repellency, so that the ejected liquid droplets of the electrolyte are discharged onto the surface of the nozzle outlet. It is possible to obtain an excellent effect of being able to quickly supply a fixed amount of a high concentration and high viscosity electrolyte solution to an electrochemical element.
- the vibration time as the viscosity increases it is possible to obtain an excellent effect that it is possible to prevent the high-viscosity electrolytic solution from being unable to be atomized and sprayed.
- the electrochemical element according to the ninth aspect it is possible to suppress the nozzle from being blocked even with a high-viscosity electrolyte, and to continuously atomize and spray without preventing the droplets from being generated from the nozzle. Moreover, it is possible to atomize and spray not only low-viscosity electrolytes but also particularly high-viscosity electrolytes without modification or decomposition of the electrolyte solution, with the simple structure of the liquid supply structure and the atomization spray structure. An excellent effect can be obtained.
- the electrochemical device of the tenth aspect it is possible to accurately control the vibration and stop time of the vibrator according to the temperature of the liquid, and to obtain an excellent effect of being able to atomize and spray even a high viscosity electrolyte. be able to.
- the distance between the nozzles is too short to prevent the nozzles on the spray outlet side from being connected to each other by a liquid film and cannot be atomized and sprayed. be able to.
- FIG. 1 shows a first embodiment.
- a cap 1 made of stainless steel (SUS304) contains a cathode mixture 2 and a high-concentration electrolytic solution becomes a finely divided electrolytic solution 4 and is dispersed and dropped. It has become.
- FIG. 2 shows a second embodiment, in which a coin-shaped Case (+ electrode) 5 contains an anode mixture 6, a separator 7 is laminated, and a high-concentration ionic liquid 4 is dispersed on the top. It is designed to be dripped intermittently.
- the atomizing spray device 10 shown in FIG. 3 is used as means for dispersing and dropping.
- This atomizing spray device 10 uses BaTiOx, and a piezoelectric vibrator (piezo element) 13 that vibrates a high-viscosity electrolytic solution by a piezo effect, and 1 to 6000 / cm 2 at an injection port for dispersion dripping.
- a method is adopted in which the electrolyte solution 21 of fine particles is discontinuously and intermittently removed from the nozzle 12 having ultrafine holes.
- the nozzle plate 11 is formed by electroplating (deposit) from an electroforming solution in which Pd, Co, Mo, etc. is added to a nickel base alloy.
- a nozzle 12 having a hole density of 1 piece / cm 2 is processed.
- the liquid contact surfaces of the nozzle 12 and the piezoelectric vibrator 13 are subjected to DLC processing or fluorine processing in order to improve wear resistance, chemical resistance, and liquid breakage.
- the first embodiment of the atomizing spray device 10 will be described in detail with reference to FIG.
- the nozzle plate 11 has a large number of nozzles 12 with a diameter of 12 ⁇ m at an arrangement pitch of 200 ⁇ m manufactured by electroforming technology, and is bonded to the piezoelectric vibrator 13.
- a container 20 provided on one side of the nozzle plate 11 is filled with a high-viscosity electrolyte solution 21 having a viscosity of about 10 to 40 mPa ⁇ s (10 to 40 cps) to be atomized and sprayed in contact with the nozzle 12. Yes.
- the piezoelectric vibrator 13 in this state has an impedance characteristic of a resonance frequency of about 98 kHz and is connected to a pulse generation drive circuit 14 which is an electric signal generation means.
- the electrolytic solution 21 is ejected from the nozzle 12 by ultrasonic vibration and becomes a droplet. This droplet is generated every time the piezoelectric vibrator 13 vibrates, and becomes a nebulized spray by continuously ejecting a large number of droplets.
- the viscosity of the electrolytic solution 21 is increased, the vibrational energy is not increased and the liquid crystal 21 does not leave the nozzle plate 11 as droplets.
- the inventors of the present invention have a high-viscosity electrolytic solution 21 exceeding 10 mPa ⁇ s (10 cps), and even if the vibration energy is increased, it is easily pulled back to the nozzle plate 11 before being separated as droplets, and adheres to the nozzle plate 11.
- the inventors absorb and integrate the electrolytic solution adhering to the nozzle 12 into the electrolytic solution 21 in the nozzle 12 due to surface tension when the nozzle 12 is stationary. The phenomenon was also confirmed. It was found that the generation of droplets due to the next vibration can be resumed by this absorption integration during the stop after the vibration. This phenomenon of absorption integration requires more time as the attached electrolyte solution 21 has the same amount as it has a higher viscosity. Therefore, the atomization spray can be continued without shortening the pause time as the viscosity increases. I found it.
- the nozzle 12 is prevented from being clogged with the high-viscosity electrolytic solution 21, and the high-viscosity electrolytic solution 21 is prevented from being prevented from generating droplets of the high-viscosity electrolytic solution 21 from the nozzle 12.
- Continuous atomization spraying is possible.
- the liquid supply structure and the atomization spray structure can be atomized and sprayed not only with a low viscosity but also with a particularly high viscosity, without any modification or decomposition of the electrolyte solution 21 with the simple structure. It was.
- the electrolytic solution 21 has a higher viscosity, it is more difficult to form droplets, and thus it tends to adhere to the nozzle plate 11.
- the attached electrolyte 21 gradually increases with each vibration. If the vibration time is increased as the viscosity increases, the highly viscous electrolyte solution 21 cannot be atomized. In order to avoid this, when the viscosity of the electrolytic solution 21 is 10 mPa ⁇ s (10 cps) or more, the vibration time is set to 20 ms or less, and when the viscosity of the electrolytic solution 21 is 30 mPa ⁇ s (30 cps) or more, the vibration is generated. Is set to 10 ms or less.
- FIG. 6 shows a second embodiment of the atomizing spray device 10.
- a nozzle plate 12 having nozzles 11 is arranged so as to face a separate body from the piezoelectric vibrator 14, and the nozzle plate 12 and the piezoelectric vibrator are arranged.
- 14 is a device in which a high-viscosity electrolyte solution 21 is supplied to a gap of several tens to several hundreds of ⁇ m between the end face 14 and the end face of the piezoelectric vibrator 14 is vibrated to vibrate the high-viscosity electrolyte solution 21.
- the mechanism in which the high-viscosity electrolytic solution 21 and the nozzle plate 11 relatively vibrate is the same as that in the first embodiment described above, and the operation is the same.
- the same experiment as in the first example was performed in an apparatus in which the surface of the spray outlet 15 of the nozzle plate 11 in the second example described above was subjected to a fluorine-based water repellent (oil repellent) treatment.
- the contact angle of the cosmetic liquid 21 when the water repellent treatment was not performed in the first embodiment was about 80 degrees, whereas the high viscosity on the surface 15 of the spray outlet of the nozzle plate 11 in the second embodiment was high.
- the contact angle of the electrolytic solution 21 is about 100 degrees.
- FIG. 7 shows a third embodiment of the atomizing spray device.
- This device is an injection device for a high-viscosity electrolytic solution.
- the liquid 41 to be atomized and sprayed based on the atomizing spray device of the first embodiment is a high-concentration electrolytic solution, and the nozzle plate 42 has one nozzle plate at the center. It has a nozzle 44 and is bonded to the vibrator 43.
- This vibrator is repeatedly vibrated and stopped intermittently as in the first embodiment by a drive circuit 52 which is an electric signal generating means.
- a pharmaceutical capsule 50 is disposed below the nozzle 44, and a droplet 46 of the electrolyte discharged from the nozzle 44 is injected into the capsule 50 having a capacity of 5 microliters ( ⁇ L).
- the liquid droplets 46 are ejected as if they were liquid columns while the nozzle plate 42 vibrates, and the liquid droplets are interrupted while the vibration is stopped.
- FIG. 7 shows an example where one nozzle is used, but it is possible to change the number of the nozzles to one or more depending on the concentration, viscosity, and shape and size of the electrochemical element.
- a resistance temperature sensor 45 which is a temperature detecting means for viscous liquid is disposed in the vicinity of the nozzle plate 42, and this temperature sensor resistance is read from the AD conversion input terminal of the microcomputer 51, and the ROM 53 which the microcomputer 51 refers to It is composed of a determining means that performs calculation with reference to the conversion table of the discharge rate corresponding to the chemical temperature stored in the table, and sequentially determines the discharge time. The determined discharge time is set as the length of the electric signal.
- the vibrator 43 is vibrated by the drive circuit 52 (electric signal generating means), and as a result, the amount of atomized spray of the viscous liquid is controlled.
- the 414 type EDLC coin type was used to evaluate the various characteristics of the conventional example (No 1 to 6) and the example of the present invention (No 7 to 12). Detailed description.
- an activated carbon sheet having a thickness of 450 ⁇ m was prepared by a known method using activated carbon CEP-21 manufactured by JX Nippon Oil & Energy and a binder, and used as a cathode anode.
- the binder used F type for heat resistance, and No5, 6, 11 and 12 used acrylate type.
- the electrolyte used was ionic liquid EMIBF4 manufactured by Guangei Chemical Industry Co., Ltd. at Neat.
- a mixed solution (30:70) with TEABF4 (Tetra, Ethyle, Anmonium Tetra-Fuloro-Borate) was used.
- 3) Separator A heat-resistant separator made of glass fiber and pulp was used.
- Electrolyte supply method The method according to the present invention uses the atomizing spray device shown in FIG. 7, and the nozzle has an aperture diameter of 10 ⁇ m, the number of nozzles is five, and an injection volume of 0.8 ⁇ L is intermittently injected. . In the conventional method, a micro syringe pump was used and continuous injection was performed with one nozzle. 5) Injection temperature: The injection environment temperature was 20 ° C. and 40 ° C. because of high viscosity. 6) Depressurization and pressurization conditions at the time of liquid injection: Conventional depressurization and pressurization conditions of equipment conditions were used.
- EDLC characterization conditions and characterization 1) Injection status and absorption status: EDLC's activated carbon polarizable electrode requires heat-resistant conditions for the binder, so the liquid injection situation of the conventional example that used a mixed binder of fluorine-based binder and acrylate-based is continuous injection with one nozzle Relatively poor liquid absorption. However, in this invention, since the 5 nozzles were used and intermittent injection was carried out, the liquid absorption condition was excellent.
- the EDLC coin type has been described above, but as other applications of the present invention, other electrochemical elements such as a primary battery, a secondary battery, a pseudo capacitor, a coin type, a chip type, a wound type, The same effect has been confirmed for the cylindrical type.
- High-performance electrochemical devices use an organic electrolyte solution having a high viscosity and a high concentration, so that the problem of liquid injection for mass production is the biggest issue.
- the present invention by intermittently injecting liquid from a plurality of microporous nozzles, the surface tension of the high-viscosity electrolytic solution is reduced and does not re-aggregate when dropped.
- the gas-liquid exchange is performed smoothly, the injection speed is improved, the line speed is improved from 50 to 60 ppm to 110 to 120 ppm, and the high temperature is increased. It is possible to provide an electrochemical element that has been confirmed to be free from blistering and leakage in an accelerated test, and has extremely high utility value in the industry.
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Abstract
Description
しかし、上記の従来例の種々の霧化装置は、何れもプリンター用のインキのような希薄水溶液相当の低粘度のものが殆どで、イオン液体、ワクチン、油のような10mPa・s(10cps)以上の高粘度の液体の霧化装置には、実用化されなかった。
最近、二次電池も携帯電話のような小型応用機器から自動車、クレーン、建機のように大型応用機器の用途が増加し、携帯パソコンや携帯機器でもスマートフォンに代表されるように多機能化が進行し、超小型EDLCも低抵抗、大電流の瞬時充放電が求められ、特に、超小型EDLCは、MSD(面実装)機能を要求され、ハンダリフロー条件(260℃*10秒)が要求されるためEMIBF4のイオン液体を100%(Neatと表現する)濃度で、供給するので、正確な微量定量供給(0.1~10μL/回)が極めて困難で、供給量がばらつくとEDLCの膨れや漏液を伴い、機器を破損することになる。さらに、この濃厚電解液は、表面張力が大で、EDLCの電極合剤に含浸が難しく、時間を要するので、電解液供給時に、昇温させたり、減圧、加圧を繰り返し、生産を行ったりしている現状である。
1)二次電池やEDLCで、低抵抗、大電流放電用途が急増し、電解液がより高濃度となり、生産中に結晶の晶出がある。
2)ラインスピードが50PPMから100~120PPMの高速度生産が要請されている。
3)超小型EDLCが当初90~110円/個であったが、市場拡大に伴い、10~12円/個にコストダウンが要請されている。
4)生産環境がクリーンルームから-65℃のドライルーム環境での生産が要請されている。
1)霧化技術の課題:有機系のイオン液体や高濃度電解液の粘度が10~40mPa・s(10~40cps)であり、これまでの公知の霧化装置は、10mPa・s(10cps)以下のインクのような水系の低粘度であるため高粘度溶液では、霧化供給できない。
2)高粘度霧化微粒子の拡散の課題:有機系高濃度電解液は、含有水分が10ppm以下の高純度を用いるので、粘度や表面張力が大で、滴下粒子が電気化学素子の電極合剤やセパレータに瞬時に拡散吸収が困難で、合剤中の吸着空気や吸着ガスとの気液置換反応が困難であった。
このように大量生産の急速なスケールアップと高性能化とコストダウンを要請され、革新的な高濃度電解液の迅速、正確な定量供給方式の確立が急務である。
また高濃度の大きな液滴の粒子について、表面張力が大であるため電解液を滴下後も合剤に浸透させることができなかったという従来例の課題を解決することができる。
図1は第一実施形態を示したもので、ステンレス(SUS304)製のCap1には、陰極合剤2が収納され、高濃度電解液は微粒子化電解液4となって、分散滴下されるようになっている。
図2は第二実施形態を示したもので、コイン型のCase(+極)5には、陽極合剤6が収納され、セパレータ7が積層され、この上部に、高濃度イオン液体4が分散間欠に滴下されるようになっている。
発明者らは、10mPa・s(10cps)を超える高粘度の電解液21では振動エネルギーを大きくしても液滴として分離する前にノズル板11に引き戻されやすくなってノズル板11に付着し、ノズル板11に付着した電解液21は徐々に凝集し、ノズル12を塞ぎ、液滴の発生を阻害するという現象を確認した。この現象は、プリンターやネブライザーのような低粘度溶液では、生じない現象である。
圧電振動子13の電圧パルスによる振動により、図5に示すようにノズル12から液滴31が発生し、高粘度の電解液21は霧化32を始める。
図7は、ノズルが1個の例であるが、電解液の濃度、粘度、電気化学素子の形状やサイズに応じて、1~複数個に変化させることが可能である。
図8に示すように、従来例(No1~6)と、本発明の例(No7~12)とを比較した諸得性の評価を414型EDLCコイン型において、行ったので、これに基づいて詳述する。
1)EDLC用分極性電極はJX日鉱日石エネルギー製活性炭CEP-21及びバインダーを用いて、公知の方法で、450μm厚の活性炭シートを作成し、陰極陽極に用いた。
バインダーは、耐熱性は、F系を使用し、No5、6、11、12は、アクリレート系を使用した。
2)電解液は、広栄化学工業(株)製イオン液体EMIBF4をNeatで用いた。比較のためTEABF4(Tetra ,Ethyle, Anmonium Tetra-Fuloro-Borate)との混合溶液(30:70)を使用した。
3)セパレータ:ガラス繊維とパルプからなる耐熱性のセパレータを使用した。
4)電解液の供給方法:本発明による方法は、図7に示す霧化噴霧装置を用い、ノズルは、開孔径が10μmでノズル数が5個で、注液量0.8μLを間欠注入した。従来方法は、マイクロシリンジポンプを用い、1ノズルで、連続注入した。
5)注液温度:注液環境温度を高粘度のため20℃と40℃で、行った。
6)注液時の減圧加圧条件:従来からの設備条件の減圧、加圧条件を用いた。
1)注液状況と吸液状況:
EDLCの活性炭分極性電極は、バインダーに耐熱条件が求められるためフッ素系のバインダーとアクリレート系との混合バインダーを用いていた従来例の注液状況は、1個のノズルで、連続注液のため相対的に、吸液性が悪い。しかし、本発明では、5個のノズルを用い、間欠注液するため吸液状況は、優れていた。
EDLCの電圧は、注液量に関係無く、2.7V、3.3Vを示すが、その他の諸特性は、電解液の注液吸収量に比例することが、容易に認められる。
即ち、本発明の例のように、微多孔系の多孔ノズルで、分散注液される場合は、図1~図2に示したように、注液量が電極合剤2中に分散拡散され、液の内部への浸透拡散と合剤中に吸着されていたガスの逸散がスムースに行われるため60℃の加速漏液試験や膨れに良い結果を示すことが容易に認められる。
本発明の応用例として、EDLCコイン型について上述したが、本発明のその他の応用として、一次電池、二次電池、擬似キャパシタなどのその他の電気化学素子のコイン型、チップ型、捲回型、円筒型にも同様の効果を確認している。
高性能電気化学素子は、高粘度、高濃度の有機電解液を使用するため大量生産のための注液問題が最大の課題である現状である。
本発明によれば、微多孔性の複数個ノズルから間欠注液することで、高粘度の電解液の表面張力が低下し、また、滴下時に再凝集することもない。このため、電極合剤中に分散拡散して、気液交換がスムースに行われ、注液速度が改善され、ラインスピードが50~60ppmから110~120ppmに約2倍に改善され、しかも、高温加速試験で、膨れや漏液がないことも確認した電気化学素子を提供でき、産業上極めて利用価値の大なるものである。
10 霧化噴霧装置
11、42 ノズル板
12、44 ノズル
13 圧電振動子
14 パルス発生駆動回路(電気信号発生手段)
15 噴霧出口側
21、41 電解液
43 振動子
45 抵抗温度センサー(温度検出手段)
51 マイコン(決定手段)
52 駆動回路(電気信号発生手段)
Claims (11)
- 電解液が瞬時に、微量、分散定量供給される電気化学素子。
- 前記電気化学素子が、一次電池、二次電池、電気二重層キャパシタ、擬似電気二重層キャパシタの何れかである請求項1に記載の電気化学素子。
- 前記電解液が、20℃で10~40mPa・sの高粘度を有する請求項1又は請求項2に記載の電気化学素子。
- 前記分散定量供給の手段として、振動素子を用い、密度が1~6000個/cm2の噴出孔を有するノズルから前記電解液を間欠的に供給する請求項1又は請求項2に記載の電気化学素子。
- 前記ノズルの金属がニッケル基合金で、前記噴出孔の孔径が1~100μmの範囲である請求項4に記載の電気化学素子。
- 前記噴出孔の表面に耐摩耗性、耐薬品性、耐液切れ性に優れた表面処理を施す請求項4に記載の電気化学素子。
- 前記表面処理として、DLC(Diamondlike Carbon)加工またはフッ素加工を施す請求項6に記載の電気化学素子。
- 前記電解液の粘度が10mPa・s以上の場合は前記振動の時間を20ms以下とし、前記電解液の粘度が30mPa・s以上の場合は前記振動の時間を10ms以下とする請求項4に記載の電気化学素子。
- 前記ノズルを有し前記電解液が供給されるノズル板を備えると共に、
前記分散定量供給のために、前記ノズルを振動させる振動子と、前記振動子を間欠的に振動するための電気信号を発生する手段とを有し、前記ノズルの噴霧出口側が前記電解液で濡れ覆われる前に前記振動子の振動を間欠的に停止する霧化噴霧装置とを備え、
間欠的に、前記電解液を定量供給する請求項4に記載の電気化学素子。 - 前記霧化噴霧装置は、前記電解液の温度を検出する検出手段と、この検出した温度に応じて前記電気信号の長さを決定する決定手段とを有し、該電気信号の長さによって前記ノズルから霧化噴霧される電解液量を制御する請求項9に記載の電気化学素子。
- 前記ノズル板は、隣接する前記ノズル同士の間の距離が150μm以上である請求項9に記載の電気化学素子。
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CN104726918A (zh) * | 2015-03-09 | 2015-06-24 | 张小可 | 喷雾式有色金属表面处理工艺及设备 |
CN106784520B (zh) * | 2017-01-16 | 2023-08-11 | 河南创力新能源科技股份有限公司 | 一种用于蓄电池的杠杆式自动限位防短路补加液装置 |
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Also Published As
Publication number | Publication date |
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KR101665208B1 (ko) | 2016-10-11 |
KR20140056216A (ko) | 2014-05-09 |
US20140162094A1 (en) | 2014-06-12 |
CN103748647A (zh) | 2014-04-23 |
JP5795200B2 (ja) | 2015-10-14 |
CN103748647B (zh) | 2017-05-31 |
TW201301637A (zh) | 2013-01-01 |
TWI595697B (zh) | 2017-08-11 |
JP2013004383A (ja) | 2013-01-07 |
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