LITHIUM ION CAPACITOR

Abstract

A lithium ion capacitor has an electrolytic solution that contains: an electrolyte which is a mixture of LiFSI and LiBF.sub.4, where the mol ratio of LiFSI to LiBF.sub.4 is in a range of 90/10 to 30/70; a solvent that contains at least one type of cyclic or chained carbonate compound; and a film-forming agent; wherein the concentration of electrolyte in the electrolytic solution is in a range of 1.2 to 1.8 mol/L. The lithium ion capacitor can maintain its initial high capacitance and low internal resistance, while also undergoing minimal characteristics changes after exposure to a high-temperature, high-voltage environment.

Claims

1. A lithium ion capacitor having an electrolytic solution that contains: an electrolyte which is a mixture of LiFSI and LiBF.sub.4, where the mol ratio of LiFSI to LiBF.sub.4 is in a range of 90/10 to 30/70; a solvent that contains at least one cyclic or chained carbonate compound; and a film-forming agent which suppresses reductive decomposition of the solvent by reductively decomposing itself at a potential higher than that of the solvent, thereby forming a film on a negative electrode; wherein a concentration of electrolyte in the electrolytic solution is in a range of 1.2 to 1.8 mol/L.

2. A lithium ion capacitor according to claim 1, wherein the film-forming agent contains at least one of vinylene carbonate and fluoroethylene carbonate.

3. A lithium ion capacitor according to claim 1, wherein a concentration of the film-forming agent in the electrolytic solution is in a range of 0.5 to 2.0 percent by weight.

4. A lithium ion capacitor according to claim 2, wherein a concentration of the film-forming agent in the electrolytic solution is in a range of 0.5 to 2.0 percent by weight.

5. A lithium ion capacitor according to claim 1, wherein the electrolyte contains neither LiPF.sub.6 nor LiBETI.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] These and other features of this invention will now be described with reference to the drawings of preferred embodiments which are intended to illustrate and not to limit the invention. The drawings are greatly simplified for illustrative purposes and are not necessarily to scale.

[0017] FIGS. 1A, 1B, and 1C are schematic views of a lithium ion capacitor in an embodiment of the present invention wherein FIG. 1A is a perspective plan view, FIG. 1B is an exploded view, and FIG. 1C is a section view.

[0018]

TABLE-US-00001 Description of the Symbols 10 Positive electrode, 11 Positive-electrode collector, 12 Positive-electrode layer, 20 Negative electrode, 21 Negative-electrode collector, 22 Negative-electrode layer, 30 Separator, 41 Positive-electrode terminal, 42 Negative-electrode terminal, 50 Element, 60 Rubber seal, 70 Outer housing.

DETAILED DESCRIPTION OF EMBODIMENTS

[0019] The present invention is described in detail below by referring to the drawings as deemed appropriate. It should be noted, however, that the present invention is not limited to the embodiment illustrated in any way, and that, because characteristic parts of the invention may be emphasized in the drawings, the scale of each part in a given drawing may not be accurate.

[0020] FIGS. 1A, 1B, and 1C provide schematic views of a lithium ion capacitor representing an example of electro-chemical capacitor. FIG. 1A is a perspective plan view, FIG. 1B is an exploded view, and FIG. 1C is a section view. The lithium ion capacitor has, for example, an electric storage element 50 that in turn has a positive electrode 10, a negative electrode 20, and separators 30 separating the positive electrode 10 and negative electrode 20, as well as an outer housing 70 that houses this electric storage element 50. Here, a pair of terminals 41, 42 are connected to the positive electrode 10 and the negative electrode 20, respectively. The terminals 41, 42 are extended to the outside via a rubber seal 60. An electrolytic solution which will be described later is sealed in the container 70, and impregnated into active materials 12, 22 of the positive electrode 10 and negative electrode 20, or into the separators 30. By caulking the rubber seal 60 at the outer housing 70, the air-tightness of the lithium ion capacitor is maintained.

[0021] FIG. 1C illustrates a structure where a positive-electrode layer 12 and a negative-electrode layer 22 are placed on one face of a positive-electrode collector 11 and on one face of a negative-electrode collector 21, respectively. Under the present invention, the electrode structure and the like are not limited in any way, and electrode layers may be placed on both faces of each current collector, for example. It should be noted that the lithium ion capacitor is not limited to the cylindrical type as illustrated, and it may be a multilayer type or coin type or have other forms. The shape of the element 50 is not limited in any way, either, and besides having the wound structure as illustrated, the element 50 may have a multilayer structure; while the outer housing 70 may be a square housing.

[0022] The separators 30 need only be constituted in a manner preventing multiple electrodes (typically a positive electrode and a negative electrode) from physically contacting each other, and how this contact prevention is embodied is not limited in any way.

[0023] Also, preferably the separators 30 are porous so that when the electrolytic solution is held in their pores, conductive paths between the electrodes are formed in a favorable manner. The separator 30 material is not limited in any way, and examples include, but are not limited to, cellulose, polypropylene, polyethylene, fluororesin and other porous materials.

[0024] With the lithium ion capacitor of the mode shown in FIGS. 1A, 1B, and 1C, the positive-electrode layer 12 and negative-electrode layer 22 may be respectively formed on the surfaces of the positive-electrode collector 11 and negative-electrode collector 21, each made of a metal foil, via a conductive adhesive or conductive coat layer (not illustrated), if necessary.

[0025] For the metal foil used for obtaining each current collector, any sheet-shaped metal exhibiting conductivity can be used without limitation, but it is preferably made of aluminum, copper, or the like. The size, thickness, and other dimensions of the metal foil are not limited in any way, and prior art relating to electro-chemical capacitors can be referenced as deemed appropriate for these dimensions.

[0026] For the electrode layers 12, 22, any known structure used in the polarizing electrode layers of lithium ion capacitors may be used. Normally the electrode layers 12, 22 each contain an active material selected from polyaniline (PAN), polyacene semiconductor substance (PAS), active carbon, carbon black, graphite, carbon nanotube, etc., for example. The electrode layers 12, 22 may also each contain any conductive agent, binder, or other component used in the polarizing electrode layers of lithium ion capacitors, as necessary.

[0027] The present invention is characterized by the composition of its electrolytic solution.

[0028] Preferably the electrolytic solution in the lithium ion capacitor is a non-aqueous electrolytic solution and the electrolytic solution contains an organic solvent and an electrolyte.

[0029] Under the present invention, both LiBF.sub.4 and LiFSI are used at a certain ratio in the electrolyte. From the viewpoint of demonstrating the effects of the present invention, the total concentration of LiBF.sub.4 and LiFSI in the electrolytic solution is in a range of 1.2 to 1.8 mol/L. The mol ratio (X/Y) of LiFSI to LiBF.sub.4 is in a range of 90/10 to 30/70. Here, X represents the mol quantity of LiFSI contained in the electrolytic solution, while Y represents the mol quantity of LiBF.sub.4 contained in the electrolytic solution. In some embodiments, the electrolyte contains neither LiPF.sub.6 nor LiBETI. Depending on the embodiment, the electrolyte may comprise, consist essentially of, or consist of LiBF.sub.4 and LiFSI at the above ratio.

[0030] As the solvent for electrolytic solution, at least one type of cyclic or chained carbonate compound is contained. Cyclic carbonate compounds include propylene carbonate (PC), ethylene carbonate (EC), and the like, while chained carbonate compounds include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and the like.

[0031] Under the present invention, the electrolytic solution further contains a film-forming agent. A film-forming agent can suppress reductive decomposition of the solvent by reductively decomposing itself at a higher potential than that of the solvent, and thereby forming a film, and while examples of film-forming agents include vinylene carbonate (VC) and fluoroethylene carbonate (FEC), for example, the choice is not limited to the foregoing and any material may be used so long as it can act upon the negative electrode and form a stable film. The film-forming agent is contained by 0.5 to 2.0 percent by weight relative to the total quantity of electrolytic solution.

[0032] The present invention is not limited in any way, except for the constitution of the electrolytic solution, and prior art may be referenced as deemed appropriate for the shape, manufacturing method, etc., of the lithium ion capacitor. The constitution in the example below can also be referenced.

Example

[0033] The present invention is explained in greater detail below using an example. It should be noted, however, that the present invention is not limited to the embodiment of the example.

[0034] [Manufacturing Method]

[0035] A slurry containing polyacene semiconductor substance (PAS) as an electrode active material, as well as carboxy methyl cellulose and styrene butadiene rubber as a binder, was prepared and this slurry was applied on an aluminum foil to obtain a positive electrode. A negative electrode was produced in sheet shape by preparing a slurry containing non-graphitizing carbon made of phenol resin material, as an active material, as well as carboxy methyl cellulose and styrene butadiene rubber as a binder, and then applying the slurry on a perforated copper foil. Cellulose separators were sandwiched between these electrodes, after which lead terminals were attached to current collectors by means of ultrasonic welding, and they were wound together into an element which was then secured with polyimide-based adhesive tape. A rubber seal was attached to the element thus produced, after which the element was vacuum-dried at approx. 180° C. and then a lithium foil was attached to the negative electrode, and the element was placed in a container. Thereafter, an electrolytic solution which will be described later was poured into the container, and then the rubber seal was caulked, to produce a lithium ion capacitor cell.

[0036] [Evaluation Method]

[0037] Each lithium capacitor thus obtained was measured for initial characteristics, or specifically the capacitance and internal resistance at room temperature. The capacitance was calculated from the slope of the discharge curve obtained by charging the lithium ion capacitor for 30 minutes at room temperature to 3.8 V at 500 mA using a charge/discharge tester (TOSCAT-3200 manufactured by Toyo System Co., Ltd.), and then discharging it to 2.2 V at 50 mA. The internal resistance was calculated from the voltage drop obtained by charging the lithium ion capacitor for 30 minutes at room temperature to 3.8 V at 140 mA using a charge/discharge tester (TOSCAT-3200 manufactured by Toyo System Co., Ltd.), and then discharging it to 2.2 V at 140 mA.

[0038] Thereafter, a float test, involving continuous charging for 1000 hours at a voltage of 3.8 V in a thermostatic chamber adjusted to 85° C., was conducted. After the float test, the cell was let cool to room temperature, and then measured for capacitance and internal resistance. The capacitances and internal resistances after the float test were calculated as percentage values relative to the measured values of initial characteristics (100%).

[0039] The constitution of the electrolytic solution for the lithium ion capacitor associated with each manufacturing number is described below.

[0040] The manufacturing numbers with an asterisk (*) represent comparative examples.

[0041] The following acronyms are used to describe the solvents and electrolytes:

[0042] PC—Propylene carbonate

[0043] DEC—Diethyl carbonate

[0044] DMC—Dimethyl carbonate

[0045] EC—Ethylene carbonate

[0046] VC—Vinylene carbonate

[0047] FEC—Fluoroethylene carbonate

[0048] The electrolyte concentrations are expressed in units of mol/L, while the additive concentrations are expressed in units of percent by weight.

TABLE-US-00002 Manufacturing [Mol Additive, No. Electrolyte ratios] Concentration Concentration Solvent  *1 LiFSI/LiBF.sub.4 [10/0] 1.50 VC, 1.0 PC   2 LiFSI/LiBF.sub.4 [9/1] 1.50 VC, 1.0 PC   3 LiFSI/LiBF.sub.4 [8/2] 1.50 VC, 1.0 PC   4 LiFSI/LiBF.sub.4 [7/3] 1.50 VC, 1.0 PC   5 LiFSI/LiBF.sub.4 [6/4] 1.50 VC, 1.0 PC   6 LiFSI/LiBF.sub.4 [5/5] 1.50 VC, 1.0 PC   7 LiFSI/LiBF.sub.4 [4/6] 1.50 VC, 1.0 PC   8 LiFSI/LiBF.sub.4 [3/7] 1.50 VC, 1.0 PC  *9 LiFSI/LiBF.sub.4 [2/8] 1.50 VC, 1.0 PC *10 LiFSI/LiBF.sub.4 [6/4] 1.00 VC, 1.0 PC  11 LiFSI/LiBF.sub.4 [6/4] 1.20 VC, 1.0 PC  12 LiFSI/LiBF.sub.4 [6/4] 1.80 VC, 1.0 PC *13 LiFSI/LiBF.sub.4 [6/4] 2.00 VC, 1.0 PC  14 LiFSI/LiBF.sub.4 [6/4] 1.50 VC, 0.5 PC  15 LiFSI/LiBF.sub.4 [6/4] 1.50 VC, 2.0 PC  16 LiFSI/LiBF.sub.4 [6/4] 1.50 VC, 3.0 PC  17 LiFSI/LiBF.sub.4 [6/4] 1.50 FEC, 1.0 PC  18 LiFSI/LiBF.sub.4 [6/4] 1.50 VC, 1.0 PC/DEC [1/1] *19 LiFSI/LiBF.sub.4 [2/8] 1.50 VC, 1.0 EC/DMC [2/3] *20 LiBF.sub.4/LiBETI [5/5] 1.00 — PC/DMC [1/1] *21 LiPF.sub.6/LiBF.sub.4 [24/1] 1.25 — EC/PC/DMC [1/2/7]

[0049] The evaluation result of the lithium ion capacitor associated with each manufacturing number is described below.

[0050] The manufacturing numbers with an asterisk (*) represent comparative examples.

[0051] The capacitances and internal resistances in the “Initial” columns represent the measured values of initial characteristics, while the capacitances and internal resistances in the “After float test” columns represent the relative values (%) of the respective characteristics after the float test, with reference to the aforementioned measured values of initial characteristics (100%).

[0052] Capacitance [F]

[0053] Internal Resistance [Ms)]

TABLE-US-00003 Initial After float test Manufac- Internal Internal turing Capacitance resistance Capacitance resistance No. [F] [mΩ] [F] [mΩ]  *1 40 88 77 228   2 41 78 81 196   3 41 73 83 190   4 42 67 85 183   5 43 63 86 176   6 42 71 84 168   7 41 78 82 161   8 40 86 80 153  *9 36 102 78 146 *10 21 60 78 180  11 38 61 82 176  12 41 84 86 174 *13 42 100 86 172  14 41 64 82 182  15 40 76 86 172  16 39 94 86 170  17 40 62 85 177  18 39 53 86 178 *19 32 82 78 184 *20 20 76 82 162 *21 40 68 78 294

[0054] The above results are considered. The samples in manufacturing examples 1 to 8, 11, 12, 14 to 18, and 21, showed good values for the initial characteristics of capacitance and internal resistance. As shown in manufacturing example 8, increasing the quantity of LiBF4 in the electrolyte caused the capacitance to decrease and the internal resistance to increase, although the increase and decrease were within an allowable range. On the other hand, manufacturing examples 10 and 13 show that a low concentration of electrolytic solution results in a significant drop in capacitance, while the higher the concentration of electrolytic solution, the higher the viscosity of the solution becomes and the internal resistance increases, as a result.

[0055] As for the rate of maintenance of capacitance and rate of change in internal resistance after the float test, adding LiBF.sub.4 to the electrolyte tended to improve these rates, as shown in manufacturing examples 2 to 9. Also, additive quantities of 0.5 percent by weight and higher resulted in clear improvements of properties after the float test. When the additive quantity reached around 2 percent, however, the improvement in float reliability plateaued and further increasing the additive only caused the initial internal resistance to increase.

[0056] In the present disclosure where conditions and/or structures are not specified, a skilled artisan in the art can readily provide such conditions and/or structures, in view of the present disclosure, as a matter of routine experimentation. Also, in the present disclosure including the examples described above, any ranges applied in some embodiments may include or exclude the lower and/or upper endpoints, and any values of variables indicated may refer to precise values or approximate values and include equivalents, and may refer to average, median, representative, majority, etc. in some embodiments. Further, in this disclosure, “a” may refer to a species or a genus including multiple species, and “the invention” or “the present invention” may refer to at least one of the embodiments or aspects explicitly, necessarily, or inherently disclosed herein. The terms “constituted by” and “having” refer independently to “typically or broadly comprising”, “comprising”, “consisting essentially of”, or “consisting of” in some embodiments. In this disclosure, any defined meanings do not necessarily exclude ordinary and customary meanings in some embodiments.

[0057] The present application claims priority to Japanese Patent Application No. 2016-107992, filed May 30, 2016, the disclosure of which is incorporated herein by reference in its entirety including any and all particular combinations of the features disclosed therein.

[0058] It will be understood by those of skill in the art that numerous and various modifications can be made without departing from the spirit of the present invention. Therefore, it should be clearly understood that the forms of the present invention are illustrative only and are not intended to limit the scope of the present invention.