JP2008182182A - Non-porous carbon with charging curve indicative of sharp bend and electric double-layer capacitor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To increase capacitance of an electric double-layer capacitor. <P>SOLUTION: In an electric double-layer capacitor, a polarizable electrode containing non-porous carbon having a crystallite similar to graphite is impregnated with an organic electrolyte dissolving an electrolyte in an organic solvent, a capacitance onset voltage is 1.6 to 3.2 V and in a case where constant current charging is implemented for the first time, an initial capacitance determined from a charge quantity revealed within a time until an inter-electrode voltage reaches the capacitance onset voltage is 4 to 11 F/cc. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electric double layer capacitor in which a polarizable electrode is immersed in non-porous carbon having a crystallite-like microcrystal and an organic electrolyte.

  Capacitors can be repeatedly charged and discharged with a large current and are promising for power storage with high charge / discharge frequency. Therefore, the capacitor is desired to improve energy density, rapid charge / discharge characteristics, durability, and the like.

Patent Document 1 describes nonporous carbon as a polarizable electrode used in an electric double layer capacitor. This carbon material has graphite-like microcrystals and a specific surface area of 300 m ² / g or less, which is relatively small. It is considered that an electrode containing non-porous carbon forms an electric double layer by inserting an electrolyte ion between fine graphite-like microcrystal layers with a solvent when a voltage is applied.

  Patent Document 2 describes that a polarizable electrode is produced using needle coke or infusibilized pitch as a raw material. Needle coke refers to calcined coke with well-developed acicular crystals and good graphitization. Needle coke has high electrical conductivity, a very low coefficient of thermal expansion, and high anisotropy based on the graphite crystal structure. Needle coke is generally produced by a delayed coking method using a specially treated coal tar pitch or petroleum heavy oil as a raw material.

  Patent Document 3 describes an electric double layer capacitor in which an electrode containing nonporous carbon is immersed in an organic electrolyte. The organic electrolyte must exhibit ionic conductivity, and the solute is a salt in which a cation and an anion are combined. Examples of the cation include lower aliphatic quaternary ammonium such as tetraethylammonium, tetrabutylammonium, and triethylmethylammonium, lower aliphatic quaternary phosphonium such as tetraethylphosphonium, and imidazolium derivatives. As anions, tetrafluoroboric acid and hexafluorophosphoric acid are described. The solvent of the organic electrolyte is a polar aprotic organic solvent. Specifically, ethylene carbonate, propylene carbonate, γ-butyrolactone, sulfolane and the like are described.

  An electric double layer capacitor obtained by immersing an electrode containing non-porous carbon in an organic electrolyte exhibits different charge / discharge characteristics as compared with an electric double layer capacitor using activated carbon as an electrode active material. The charge / discharge characteristics are described in Non-Patent Document 1, pages 77 to 81, for example. FIG. 1 is a graph showing an example of a behavior in which the voltage changes with time when constant current charging and discharging are repeated for this type of electric double layer capacitor (Non-Patent Document 1, page 80, FIG. 3- (Quoted from 15).

  In the charge / discharge curve of FIG. 1, the voltage rises within a short time during the first constant current charge starting from 0 V, and the voltage rise suddenly slows from about 2.2 V. In other words, the slope (dV / dt) is substantially constant before about 2.2V, decreases sharply at about 2.2V, and becomes substantially constant again after about 2.2V. It has become.

  In the constant current charging curve, the capacitance corresponds to the slope of the curve. A high slope value means a low capacitance, and a low slope value means a high capacitance. Then, the first constant current charging curve in FIG. 1 shows that the electrostatic capacity is small at the initial stage of charging, and the electrostatic capacity is substantially developed from about 2.2V.

  On the other hand, in the second and subsequent charging, the voltage increases monotonously, and a certain capacitance is obtained from the beginning of charging as in the case of the conventional activated carbon electrode. In other words, once this type of electric double layer capacitor experiences a voltage, the capacitance increases and a large capacitance can be obtained.

  However, in order to be put into practical use as an auxiliary power source for electric vehicles, batteries, power generators, etc., it is desired that the electric double layer capacitor further increase the capacitance and improve the durability.

JP 2005-286178 A JP2002-25867 JP 2000-77273 A Ikuo Okamura "Electric Double Layer Capacitor and Power Storage System" 3rd Edition, Nikkan Kogyo Shimbun, 2005

  The present invention solves the above-mentioned conventional problems, and its object is to increase the capacitance of an electric double layer capacitor in which a polarizable electrode containing nonporous carbon is immersed in an organic electrolyte. There is.

The present invention comprises a polarizable electrode containing non-porous carbon having graphite-like microcrystals immersed in an organic electrolyte,
The capacitance expression voltage is 1.6 to 3.2 V,
When the constant current charging is performed for the first time, the initial capacitance obtained from the amount of charge generated within the time until the voltage between the electrodes reaches the capacitance expression voltage is 4 to 11 F / cc,
The non-porous carbon is
A pre-calcination step of calcining graphitizable carbon at 840-960 ° C. for 2-8 hours under an inert atmosphere;
An alkali activation step in which the calcined powder is mixed with 1 to 5 times the weight of the alkali hydroxide powder and the powder mixture is calcined at 600 to 900 ° C. for 2 to 8 hours in an inert atmosphere;
A step of washing the activated powder mixture to remove alkali hydroxide; and a post-baking step of baking the obtained carbon powder at 200 to 800 ° C. for 2 to 8 hours in an inert atmosphere;
An electric double layer capacitor manufactured by a method including:

  The present invention also provides non-porous carbon having graphite-like microcrystals used in such electric double layer capacitors.

  Here, the “capacitance expression voltage” refers to a voltage at which the electrostatic capacity develops during the first constant current charge, and is represented by the symbol “Ve”. The expression of the electrostatic capacity is shown as the point at which the charging curve starts to depart from the imaginary line that overlaps the initial voltage rising from 0 V in the initial constant current charging curve. However, depending on the shape of the constant current charging curve, it may be difficult to clearly read that point.

In such a case, the voltage change is recorded over time while charging the constant current constant voltage (CCCV) of the electric double layer capacitor under a predetermined charging condition, and the curvature is increased in the process of increasing the voltage of the obtained charging curve. It is good also as that the electrostatic capacitance was expressed when became maximum. That is, at the initial stage of charging when the CCCV charging curve is rising, the voltage at the point where the curvature is maximum may be regarded as the electrostatic capacity expression voltage (Ve). The predetermined charging condition is a charging current of 1 mA / cm ² as in the embodiment. The initial charging period is, for example, up to 10,000 seconds after starting charging, preferably up to 5000 seconds, more preferably up to 3000 seconds, and further preferably up to 2000 seconds. Ve may be determined by performing preliminary measurement in advance.

  According to the present invention, the capacitance of the electric double layer capacitor is increased and the durability is improved.

  In the present invention, the term “electrode including nonporous carbon” means a polarizable electrode formed using nonporous carbon as an electrode active material (active ingredient). Preferred non-porous carbon is carbon powder obtained by heat-treating a carbon raw material in an inert atmosphere and further heat-treating in the presence of an alkali hydroxide powder and / or an alkali metal. As the carbon raw material, graphitizable carbon generally called soft carbon can be used. The graphitizable carbon may be carbon that is graphitized by heating. For example, coke green powder, mesophase carbon, infusible vinyl chloride and the like correspond to graphitizable carbon.

  For example, a graphite precursor obtained by removing quinoline insolubles from a soft pitch of coal and carbonizing using a refined raw material may be used as the carbon raw material. Although the reason is not clear, such a graphite precursor contains trace elements such as nitrogen and sulfur, and is considered to have an appropriate elemental composition.

  In producing the polarizable electrode used in the present invention, for example, the graphitizable carbon is first prepared. The center particle diameter of graphitizable carbon is 10 to 5000 μm, preferably 10 to 100 μm. Further, the ash content in the polarizable electrode affects the generation of surface functional groups, and it is important to reduce it. The graphitizable carbon used in the present invention is 70 to 98% fixed carbon and 0.05 to 2% ash. Preferably, it has the characteristics that fixed carbon is 80 to 95% and ash content is 1% or less.

  The powdery graphitizable carbon is first fired in an inert atmosphere, for example, in an atmosphere of nitrogen or argon for 2 to 8 hours. This firing process is called a pre-baking process. The pre-baking temperature is adjusted so that the furnace temperature is 800 to 1000 ° C. At this time, it is considered that the crystal structure of the carbon structure peculiar to the present invention is formed by the temperature and heat applied to the graphitizable carbon. When the pre-baking temperature is less than 800 ° C., the alkali activation proceeds excessively, and when it exceeds 1000 ° C., the alkali activation proceeds insufficiently. A preferred pre-baking temperature is 840 ° C. to 960 ° C., more preferably 900 to 940 ° C., or more than 900 ° C.

  However, specific furnace temperature values (set values, measured values) and their ranges are not necessarily requirements for determining the crystal structure of the carbon structure. This is because the temperature applied to the graphitizable carbon does not match the in-furnace temperature depending on the structure, type and scale of the firing furnace and the arrangement of the sample in the furnace.

  The firing time is essentially irrelevant to the reaction, but if it is generally less than 2 hours, heat is not transferred to the entire reaction system, and uniform nonporous carbon is not formed. It doesn't make sense to exceed 8 hours.

  The pre-fired carbon powder is mixed with an alkali hydroxide having a weight ratio of 1 to 5 times, preferably 1 to 3 times, more preferably about 1.3 to 2.5 times. The powder mixture is then fired at 600 to 900 ° C. for 2 to 8 hours under an inert atmosphere. This process is called alkali activation, and it is considered that the alkali metal vapor penetrates the carbon structure and has the effect of loosening the crystal structure of carbon. A preferable alkali activation temperature is 700 to 800 ° C, more preferably 720 to 780 ° C.

  When the amount of the alkali hydroxide is less than 1 time or the firing temperature is less than 700 ° C., the activation does not proceed sufficiently and the capacity is not developed at the first charge. If the amount of alkali hydroxide exceeds 5 times or the firing temperature exceeds 800 ° C., the activation proceeds too much and the surface area tends to increase, and the surface state becomes the same as that of normal activated carbon. The specific gravity decreases and the energy density decreases. As the alkali hydroxide, KOH, CsOH, RbOH or the like may be used, but KOH is preferable because of its excellent activation effect and low cost.

  If the material is sufficiently warmed, the firing time is essentially unrelated, but if the firing time is less than 2 hours, the material does not have sufficient heat and a part that is not partially activated appears. There is no point in firing for more than 8 hours.

  The resulting powder mixture is then washed to remove the alkali hydroxide. In the washing, for example, particles are collected from the carbon after the alkali treatment, filled in a stainless steel column, 120 ° C. to 150 ° C., 10 to 100 kgf, preferably 10 to 50 kgf of pressurized water vapor is introduced into the column, This can be done by continuing to introduce pressurized steam until the pH is about 7 (usually 6 to 10 hours). After completion of the alkali removal step, an inert gas such as argon or nitrogen is passed through the column and dried to obtain the target carbon powder.

  The obtained carbon powder is fired for 2 to 8 hours under an inert atmosphere. This firing process is called a post-baking process. The post-baking temperature is adjusted so that the furnace temperature is 200 to 800 ° C. When post-baking is performed, the functional group on the carbon surface is removed, and the withstand voltage of the electric double layer capacitor is improved. A preferable post-baking temperature is 250 to 500 ° C, more preferably 300 to 400 ° C.

  The firing time is essentially irrelevant to the reaction, but if it is generally less than 2 hours, heat is not transferred to the entire reaction system, and uniform nonporous carbon is not formed. It doesn't make sense to exceed 8 hours.

The carbon powder obtained through the above steps has a specific surface area of 300 m ² / g or less, and has a small number of pores that can take in various electrolyte ions, solvents, CO ₂ gas, etc., so-called “non-porous carbon” "are categorized. The specific surface area can be determined by a BET method using CO ₂ as an adsorbent.

  A polarizable electrode can be produced by a method similar to the conventional one. For example, in order to produce a sheet-like electrode, the nonporous carbon obtained by the above method is pulverized to about 5 to 100 μm to adjust the particle size. Thereafter, for example, carbon black as a conductive auxiliary agent for imparting conductivity to the carbon powder and, for example, polytetrafluoroethylene (PTFE) as a binder are added and kneaded, and formed into a sheet by pressure drawing. Mold.

  In addition to carbon black, powdered graphite and the like can be used as the conductive auxiliary agent, and as the binder, PVDF, PE, PP and the like can be used in addition to PTFE. At this time, the blending ratio of the nonporous carbon, the conductive auxiliary agent (carbon black), and the binder (PTFE) is generally about 10 to 1: 0.5 to 10: 1 to 0.25. .

  The produced polarizable electrode for an electric double layer capacitor can be used for an electric double layer capacitor having a conventionally known structure. The structure of the electric double layer capacitor is shown, for example, in FIG. 1 of Patent Document 1, FIG. 6 of Patent Document 2, FIGS. 1 to 4 of Patent Document 3, and the like. In general, such an electric double layer capacitor can be assembled by impregnating an electrolytic solution after forming a positive electrode and a negative electrode by superposing sheet-like carbon electrodes via a separator.

  As the electrolytic solution, a so-called organic electrolytic solution obtained by dissolving an electrolyte as an solute in an organic solvent can be used. Examples of the electrolyte include salts of lower aliphatic quaternary ammonium, lower aliphatic quaternary phosphonium or imidazolinium derivatives and tetrafluoroboric acid or hexafluorophosphoric acid, as described in Patent Document 3. Those commonly used by those skilled in the art can be used.

  Among them, a preferable electrolyte is a pyrrolidinium compound salt. Preferred pyrrolidinium compound salts have the formula

[Wherein, each R is independently an alkyl group or an alkylene group linked together, and X ⁻ is a counter anion. ]
It has the structure shown by. The pyrrolidinium compound salt is known and may be synthesized by a method known to those skilled in the art.

  Preferred for the ammonium component of the pyrrolidinium compound salt is that in the above formula, each R is independently an alkyl group having 1 to 10 carbon atoms or an alkylene group having 3 to 8 carbon atoms linked together. More preferred are those wherein R is an alkylene group having 4 to 5 carbon atoms linked together. Further preferred are those in which R is a butylene group linked together. Such an ammonium component is called spirobipyrrolidinium (SBP).

  Pyrrolidinium compounds, especially spirobipyrrolidinium, have a seemingly complex molecular structure and appear to have a large ionic diameter. However, when this compound is used as the electrolyte ion of the organic electrolyte, the effect of suppressing the expansion of the electrode containing nonporous carbon on the negative electrode side is particularly great, and the energy density of the electric double layer capacitor is greatly improved. Although not intended to be limited theoretically, it is thought that the effective ion diameter of pyrrolidinium compounds and spirobipyrrolidinium is small because the spread of the electron cloud is suppressed by the spiro ring structure.

The counter anion X ⁻ may be any one that has been conventionally used as an electrolyte ion of an organic electrolyte. For example, a tetrafluoroborate anion, a fluoroborate anion, a fluorophosphate anion, a hexafluorophosphate anion, a perchlorate anion, a borodisalicylate anion, and a borodisoxalate anion. Preferred counter anions are tetrafluoroborate anion and hexafluorophosphate anion. This is because these have a low molecular weight and a simple structure, and the expansion of the electrode containing nonporous carbon on the positive electrode side is suppressed.

  By dissolving the electrolyte in an organic solvent using the electrolyte as a solute, an organic electrolyte for an electric double layer capacitor can be obtained. The concentration of the electrolyte in the organic electrolyte is adjusted to 0.8 to 2.5 mol / liter, preferably 1.0 to 1.8 mol / liter. When the concentration of the electrolyte is less than 0.8 mol / liter, the number of ions contained is insufficient and sufficient capacity cannot be obtained. Moreover, even if it exceeds 2.5 mol / liter, it does not contribute to the capacity and is meaningless.

  The electrolyte may be used alone or a plurality of types may be mixed. You may use together the electrolyte conventionally used for the organic electrolyte solution. However, the ratio of the electrolyte in the solute is 50% by weight or more, preferably 75% by weight or more of the total solute weight. Among electrolytes, for example, preferable electrolytes for use in combination with pyrrolidinium compound salts include triethylmethylammonium salts and tetraethylammonium salts.

  As the organic solvent, those conventionally used for organic electric double layer capacitors may be used. For example, ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (GBL), sulfolane (SL), and the like are preferable because of their excellent electrolyte solubility and high safety. Also useful are those containing these as a main solvent and at least one of dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) as a sub-solvent. This is because the low temperature characteristics of the electric double layer capacitor are improved. Further, when acetonitrile (AC) is used as the organic solvent, the conductivity of the electrolytic solution is increased, which is preferable in terms of characteristics. However, the use may be limited.

  The electric double layer capacitor of the present invention has a voltage change curve different from the conventional one in the constant current charging process of electric field activation. “Electric field activation” refers to an initial charging process of an electric double layer capacitor formed by immersing an electrode containing non-porous carbon in an organic electrolyte, that is, a process in which a voltage is first experienced by a polarizable electrode. . It is expressed in this way on the assumption that the first charging process plays the role of activating the electrostatic capacity.

FIG. 2 is a graph showing a behavior in which the voltage changes with time when an electric double layer capacitor formed by immersing an electrode containing nonporous carbon in an organic electrolyte is subjected to constant current charging for the first time. It is. At this time, the charging current is 1 mA / cm ² and the end point of the voltage is a voltage (3.7 V) equal to or higher than the rated voltage (3.5 V in this case). Curve b shows the voltage change of the electric double layer capacitor of the present invention, and curves a and c show the voltage change of the conventional electric double layer capacitor.

  In the curve b, the electrostatic capacity expression voltage at which the voltage increase starts to become slow is lower than that in the curve c. Moreover, in the curve b, the bending which shows the expression of an electrostatic capacitance is sharper than the curve a. As shown by the curve b, when the electrostatic capacity expression voltage is relatively low and the bending indicating the expression of the electrostatic capacity is sharp, uniform pores that contribute to the capacity are formed, mainly in the depth direction. Sufficient electric field activation proceeds, and the capacitance of the electric double layer capacitor increases. Further, the durability of the electric double layer capacitor is also improved.

Specifically, for example, when constant current charging at 1 mA / cm ² is performed up to 3.7 V for the first time, the electrostatic capacity expression voltage is 3.2 V or less, less than 3.2 V, preferably 1.6 to 3 .2V, 1.5-3.1V, 2.0-3.0V, 2.4-3.0V, 2.2-2.9V, 2.4-2.9V. When the electrostatic capacity expression voltage exceeds 3.2 V, the electrolytic solution is deteriorated, and the electrostatic capacity and durability of the electric double layer capacitor are not sufficiently improved.

  The initial capacitance developed within the time until the voltage between the electrodes reaches Ve is 11F / cc or less, 10F / cc or less, 9F / cc or less, preferably 8.5F / cc or less, more preferably 8F / cc. cc or less. Preferably, the initial capacitance is 4 to 11 F / cc, preferably 4.5 to 10 F / cc, more preferably 5 to 9 F / cc, and 6 to 8 F / cc. When the initial capacitance exceeds 11 F / cc, the bend indicating the development of the capacitance becomes dull, and the improvement in the capacitance and durability of the electric double layer capacitor becomes insufficient.

  In order to adjust Ve and the initial capacitance within the appropriate ranges, it is preferable to set the furnace temperature to a relatively high temperature in the pre-baking step. For example, the pre-baking furnace temperature is appropriately set in the range of 800 to 1000 ° C., preferably 840 to 960 ° C., more preferably 900 to 940 ° C., or more than 900 ° C. or 905 to 940 ° C.

  The non-porous carbon prepared by the method of the present invention has a low Ve and can be electrolytically activated at a low voltage. This indicates that the pore diameter of the portion where the cation is adsorbed is large in the non-porous carbon. For this reason, the electric double layer capacitor of the present invention can be put to practical use even if a cation having a relatively large ion diameter is used as an electrolyte component, with a small increase in rated voltage (that is, actual use voltage).

  That is, in the electric double layer capacitor of the present invention, even when a cation having a relatively large ionic diameter is used, the capacity is expressed by electrolytic activation as in the case of using an electrolyte having a relatively small ionic diameter such as SBP. Can be made. Further, even when a cation having a relatively large ion diameter is used, the performance such as the capacity of the electric double layer capacitor is equivalent to that when using a cation having a relatively small ion diameter.

Examples of the cation having a relatively large ion diameter include tetraethylammonium (TEA ⁺ ), tetrabutylammonium (TBA ⁺ ), triethylmethylammonium (TEMA ⁺ ), tetraethylphosphonium (TEP ⁺ ), and 1-ethyl-3-methyl. Examples include imidazolium (EMI ⁺ ). As the anion which is a counter anion of the cation, the same anion as described for SBP can be used.

  The following examples further illustrate the present invention, but the present invention is not limited thereto. In the examples, “part” or “%” is based on weight unless otherwise specified.

Example 1
Production of non-porous carbon Remove quinoline insolubles from the soft pitch of coal, put graphite precursor powder (manufactured by Nippon Steel Co., Ltd.) carbonized using refined raw material into an alumina crucible, and muffle it While circulating nitrogen in a furnace, it was fired at 900 ° C. and naturally cooled. Next, the fired product was mixed with 1.5 times the potassium hydroxide powder per weight ratio. Each was put in an alumina crucible and covered with an alumina lid to shut off the outside air.

  While this mixture was circulated with nitrogen in a muffle furnace, the temperature in the furnace was adjusted to 750 ° C., and the mixture was activated for 4 hours. The fired product was taken out, washed lightly with pure water, and then washed by applying ultrasonic waves. The time is 1 minute. The water was then separated using a Buchner funnel. The same washing operation was repeated until the pH of the washing water reached around 7. Then, the washed product was dried with a vacuum dryer.

  The dried carbon powder was put in a crucible, post-fired at 300 ° C. for 10 hours, then taken out and allowed to cool to room temperature.

Production of Capacitor Cell The obtained carbon was pulverized with 10 mmφ alumina balls for 1 hour using a ball mill (AV-1 manufactured by Fujiwara Seisakusho). When the particle size was measured with a Coulter counter, all of them became powdery with a center particle diameter of about 10 microns.

  Powdered carbon (CB) was mixed at a mixing ratio of 10: 1: 1 of acetylene black (AB) and polytetrafluoroethylene powder (PTFE), and kneaded in a mortar. In about 10 minutes, PTFE was stretched and formed into flakes. This was pressed with a press machine to obtain a carbon sheet having a thickness of 300 microns.

The carbo sheet was punched into a 20 mmφ disk and assembled into a three-electrode cell as shown in FIG. This disk contains 83.3% non-porous carbon. The reference electrode used was a sheet of # 1711 activated carbon formed by the same method as above. These cells were dried in a vacuum at 220 ° C. for 24 hours and cooled. An electrolyte solution was prepared by dissolving spirobipyrrolidinium tetrafluoroborate (SBPBF ₄ ) in propylene carbonate to a concentration of 2.0 mol / liter. Then, the obtained electrolytic solution was injected into the cell to produce an electric double layer capacitor cell.

Measurement of Capacitance Expression Voltage (Ve) The triode cell was charged at a constant current of 1 mA / cm ² up to the rated voltage (3.7 V). A curve b in FIG. 4 shows a voltage change with time in the charging process. When Ve was determined from this curve, it was 2.5V.

Capacitance measurement Among the created capacitor cells, a power system charge / discharge test device “CDT-RD20” is connected to a capacitor cell different from that used for Ve measurement, and constant current charging at 1 mA / cm ² is performed. It went to 3.7V. The initial capacitance developed within the time until the voltage between the electrodes reached the capacitance development voltage was 8.0 F / cc.

Constant current constant voltage charge was performed for 25200 seconds, and constant current discharge was performed at 1 mA / cm ² . Curves b in FIGS. 5 and 6 are graphs showing a behavior in which the voltage changes with time when the obtained capacitor cell is charged and discharged for the first time. Then, 3 cycles of charging / discharging were implemented with the rated voltage of 3.5V.

  The capacitance at the third cycle was determined by a method of obtaining from the integrated discharge power called the energy conversion method, and the value divided by the sum of the volumes of the polarizable electrodes of both electrodes was adopted as the volume density (F / cc). The results are shown in Table 2.

Measurement of Durability As described in Japan Electronic Machinery Industry Standard EIAJ RC-2377, 3.13, 4.23 (durability) a) (DC test) of JIS C 5101-1 was performed under the following conditions.

[Table 1]

  Thereafter, the volume density of the capacitor cell was obtained again, and the rate of change was adopted as durability. The results are shown in Table 2.

Example 2
The capacitor cell and triethylmethylammonium tetrafluoroborate (TEMABF ₄₎ in the same manner as in Example 1 except for the use in an amount of 1.4 mol / l in place of spirobipyrrolidinium tetrafluoroborate (SBPBF ₄₎ Prepared and tested for properties and performance. The results are shown in Table 2. A curve g in FIG. 6 is a graph showing a behavior in which the voltage changes with time when the obtained capacitor cell is charged and discharged for the first time.

Example 3
A capacitor cell was prepared in the same manner as in Example 1 except that the furnace temperature in the pre-baking step was 940 ° C., and the characteristics and performance were tested. The results are shown in Table 2.

  A curve d in FIG. 4 shows a voltage change with time in the charging process. A curve d in FIG. 5 is a graph showing a behavior in which the voltage changes with time when the obtained capacitor cell is charged and discharged for the first time.

Example 4
The capacitor cells in the same manner in Example 1 except using triethylmethylammonium tetrafluoroborate (TEMABF ₄₎ in an amount of 1.8 mol / l in place of spirobipyrrolidinium tetrafluoroborate (SBPBF ₄₎ Prepared and tested for properties and performance. The results are shown in Table 2. A curve h in FIG. 6 is a graph showing a behavior in which the voltage changes with time when the obtained capacitor cell is charged and discharged for the first time.

Examples 5-12
A capacitor cell was prepared in the same manner as in Example 1 except that the conditions shown in Table 2 were used, and the characteristics and performance were tested. The results are shown in Table 2.

Comparative Example 1
A capacitor cell was prepared in the same manner as in Example 1 except that the furnace temperature in the pre-baking step was adjusted to 650 ° C., and the characteristics and performance were tested. The results are shown in Table 2.

  A curve a in FIG. 4 shows a change in voltage over time during the charging process. A curve a in FIG. 5 is a graph showing a behavior in which the voltage changes with time when the obtained capacitor cell is charged and discharged for the first time.

Comparative Example 2
The capacitor cells in the same manner as in Comparative Example 1 except that instead of triethyl methyl ammonium tetrafluoroborate (TEMABF ₄₎ used in an amount of 1.4 mole / liter of spirobipyrrolidinium tetrafluoroborate (SBPBF ₄₎ Prepared and tested for properties and performance. The results are shown in Table 2.

Comparative Example 3
A capacitor cell was prepared in the same manner as in Example 1 except that the furnace temperature in the pre-baking process was adjusted to 970 ° C. and the furnace temperature in the alkali activation process was adjusted to 770 ° C., and the characteristics and performance were tested. did. The results are shown in Table 2.

  A curve e in FIG. 4 shows a voltage change with time in the charging process. A curve e in FIG. 5 is a graph showing a behavior in which the voltage changes with time when the obtained capacitor cell is charged and discharged for the first time.

Comparative Example 4
The capacitor cells in the same manner as in Comparative Example 3 except for using an amount of triethyl methyl ammonium tetrafluoroborate (TEMABF ₄₎ a 1.8 mole / l instead of spirobipyrrolidinium tetrafluoroborate (SBPBF ₄₎ Prepared and tested for properties and performance. The results are shown in Table 2.

Comparative Example 5
A capacitor cell was prepared in the same manner as in Example 1 except that the furnace temperature in the pre-baking step was adjusted to 980 ° C., and the characteristics and performance were tested. The results are shown in Table 2.

  A curve f in FIG. 4 shows a voltage change with time in the charging process. A curve f in FIG. 5 is a graph showing a behavior in which the voltage changes with time when the obtained capacitor cell is charged and discharged for the first time.

Comparative Example 6
The capacitor cells in the same manner as in Comparative Example 5 except that instead of triethyl methyl ammonium tetrafluoroborate (TEMABF ₄₎ used in an amount of 1.8 mole / liter spirobipyrrolidinium tetrafluoroborate (SBPBF ₄₎ Prepared and tested for properties and performance. The results are shown in Table 2.

Comparative Examples 7-12
A capacitor cell was prepared in the same manner as in Example 1 except that the conditions shown in Table 2 were used, and the characteristics and performance were tested. The results are shown in Table 2.

  A curve i in FIG. 7 shows a change in voltage over time in the process of charging the capacitor cell of Comparative Example 8.

It is the graph which showed the example of the behavior which a voltage changes with time when constant current charge and discharge are repeated to an electric double layer capacitor formed by immersing an electrode containing nonporous carbon in an organic electrolyte. It is the graph which showed the behavior which a voltage changed with time when constant current charge was performed for the first time with respect to the electric double layer capacitor formed by immersing the electrode containing non-porous carbon in organic electrolyte. It is an assembly drawing which shows the structure of the electric double layer capacitor of an Example. It is the graph which showed the behavior in which a voltage changes with time, when charging the capacitor cell of an example for the first time. It is the graph which showed the behavior in which a voltage changes with time when charging / discharging was performed for the capacitor cell of an example for the first time. It is the graph which showed the behavior in which a voltage changes with time when charging / discharging was performed for the capacitor cell of an example for the first time. It is the graph which showed the behavior in which a voltage changes with time, when charging the capacitor cell of comparative example 8 for the first time.

Explanation of symbols

1, 11 ... Insulating washer,
2 ... Top cover,
3 ... Spring,
4, 8 ... collector electrode,
5, 7 ... Polarizable electrodes,
6 ... separator,
9 ... Guide,
10, 13 ... O-ring,
12 ... the body,
14 ... Presser plate,
15 ... Reference electrode,
16 ... Bottom cover.

Claims (7)

A polarizable electrode containing non-porous carbon having graphite-like microcrystals is immersed in an organic electrolytic solution in which an electrolyte is dissolved in an organic solvent,
The capacitance expression voltage is 1.6 to 3.2 V,
When the constant current charging is performed for the first time, the initial capacitance obtained from the amount of charge generated within the time until the voltage between the electrodes reaches the capacitance expression voltage is 4 to 11 F / cc,
The non-porous carbon is
A pre-calcination step of calcining graphitizable carbon at 840-960 ° C. for 2-8 hours under an inert atmosphere;
An alkali activation step in which the calcined powder is mixed with 1 to 5 times the weight of the alkali hydroxide powder and the powder mixture is calcined at 600 to 900 ° C. for 2 to 8 hours in an inert atmosphere;
A step of washing the activated powder mixture to remove alkali hydroxide; and a post-baking step of baking the obtained carbon powder at 200 to 800 ° C. for 2 to 8 hours in an inert atmosphere;
An electric double layer capacitor produced by a method comprising:   The electric double layer capacitor according to claim 1, wherein the initial capacitance is 6 to 10 F / cc.   The electric double layer capacitor according to claim 1 or 2, wherein the electrostatic capacity expression voltage is 2.0 to 3.1V.   The organic electrolyte is a compound selected from the group consisting of spirobipyrrolidinium, tetraethylammonium, tetrabutylammonium, triethylmethylammonium, tetraethylphosphonium and 1-ethyl-3-methylimidazolium as the cation component of the electrolyte The electric double layer capacitor according to claim 1, comprising:   The electric double layer capacitor according to any one of claims 1 to 3, wherein the organic electrolytic solution contains spirobipyrrolidinium or triethylmethylammonium as a cation component of the electrolyte.   The electric double layer capacitor according to any one of claims 1 to 5, wherein the graphitizable carbon is a graphite precursor obtained by removing quinoline insolubles from a soft pitch of coal and carbonizing using a refined raw material.   The non-porous carbon which has the graphite-like microcrystal used for the electric double layer capacitor in any one of Claims 1-6.

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