CN105244174A - Convoluted electrolytic-electrochemical hybrid capacitor and fabrication method thereof - Google Patents
Convoluted electrolytic-electrochemical hybrid capacitor and fabrication method thereof Download PDFInfo
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- CN105244174A CN105244174A CN201510670328.9A CN201510670328A CN105244174A CN 105244174 A CN105244174 A CN 105244174A CN 201510670328 A CN201510670328 A CN 201510670328A CN 105244174 A CN105244174 A CN 105244174A
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Abstract
The invention discloses a convoluted electrolytic-electrochemical hybrid capacitor and a fabrication method thereof. The convoluted electrolysis-electrochemical hybrid capacitor comprises a winding core and an electrolyte, wherein the winding core comprises a positive electrode plate, a negative electrode plate and electrolytic papers; the positive electrode plate is a positive electrode foil for an aluminum electrolytic capacitor, and a positive electrode guide foil bar is arranged on the positive electrode plate; the negative electrode plate is obtained by loading an electrode material for an electrochemical capacitor on a negative electrode conductive substrate to serve as a negative electrode paste of a negative electrode active substance, and a negative electrode guide foil bar is arranged on the negative electrode plate; and the positive electrode plate, the negative electrode plate and the electrolytic papers are sequentially stacked in an order of the negative electrode plate, the electrolytic papers and the positive electrode plate from bottom to top, the positive electrode plate is arranged at the tail, the electrolytic papers are placed under the negative electrode plate at the lowest layer, and the winding core is formed by winding. In the hybrid capacitor, a winding mode is adopted to improve effective contact area of the electrode plates of a monomer capacitor, and thus, the capacitance of the hybrid capacitor monomer is improved. The hybrid capacitor is compatible with characteristics of high voltage and large capacity and is low in cost.
Description
Technical field
The present invention relates to mixed capacitor, be specifically related to a kind of convoluted electrolysis-electrochemical mixed capacitor and preparation method thereof.
Background technology
Electrochemical capacitor, because taking into account the feature of traditional capacitor and battery, enjoys people to pay close attention in recent years.But due to the restriction by electrolyte decomposition voltage, monomer operating voltage is generally no more than 3V.From the density energy formula E=1/2CU of capacitor
2be not difficult to find out, low-work voltage means low energy densities.Increasing substantially monomer voltage is the task of top priority that electrochemical capacitor plays a role in energy storage and dynamic field.Compared with electrochemical capacitor, operating voltage and the power density of electrolytic capacitor are high, and its lower monomer capacity can not meet fast-developing electronic industry to the demand of Large Copacity energy storage device.
Evans devises one " mixing " capacitor: its anode is Ta/Ta
2o
5, be tantalum electrolytic capacitor, negative electrode is Ta/RuO
2, be electrochemical capacitor.The anode voltage U of capacitor
a, cathode voltage U
cwith anode capacitance C
a, cathode capacitance C
cpass be: U
a/ U
c=C
c/ C
a, work as C
c>>C
a, U
a>>U
c.If namely the electric capacity of negative electrode is much larger than anode capacitance, the voltage that negative electrode is shared is then very little.During charging, most of voltage is added in anodic oxide dielectric instead of electrolyte, avoiding problems electrolyte decomposition under high voltages.Therefore, " mixing " type capacitor need not can meet high voltage requirement by cascaded structure, ensures higher capacity simultaneously.But, because ruthenium and tantalum are all rare metals, also there is the shortcoming of cost height and environmental pollution as capacitor material, and in most cases, RuO
2for pressed powder, its technology for preparing electrode is loaded down with trivial details, therefore is not suitable as the extensive energy storage material used.Therefore, adopt cheap and eco-friendly capacitor electrode material to replace the Rare Metals Materials such as ruthenium and tantalum, the mixed capacitor preparing high voltage large capcity with simple process accelerates its quick approach applied in energy storage field.
Summary of the invention
It is low and have convoluted electrolysis-electrochemical mixed capacitor of high voltage and Large Copacity feature and preparation method thereof concurrently that the technical problem to be solved in the present invention is to provide a kind of cost.
Convoluted electrolysis-electrochemical mixed capacitor of the present invention, comprise core and electrolyte, described core comprises anode strip, cathode sheets and electrolytic paper, wherein:
Described anode strip is anode foil for aluminum electrolytic capacitor, anode strip is provided with anode and leads chaff;
Described cathode sheets be by load on negative electrode conducting base by the cathode slurry gained of electrode for electrochemical capacitor material as cathode active material, cathode sheets is provided with cathode guide chaff; Described electrode for electrochemical capacitor material is one or more the combination be selected from porous carbon materials, metal oxide and conducting polymer;
Described anode strip, cathode sheets and electrolytic paper are stacked successively by the order from the bottom to top in cathode sheets, electrolytic paper and anode strip, finish up and place electrolytic paper with anode strip under undermost cathode sheets, carry out winding afterwards and form core.
In technique scheme, described negative electrode conducting base can be aluminium foil or cathode foil of aluminum electrolytic capacitor.Described electrolyte can be the one being selected from aqueous electrolyte, organic system electrolyte and ionic liquid, preferably adopts electrolyte for aluminum electrolytic capacitor in the application.
Further, the present invention proposes to adopt aluminum plastic film to carry out soft encapsulation to core, effectively can control the production cost of mixed capacitor.
The present invention also comprises the manufacture method of above-mentioned convoluted electrolysis-electrochemical mixed capacitor, and this manufacture method comprises the making of core, and the manufacture method of described core comprises the following steps:
1) anode strip and negative electrode conducting base are provided;
2) cathode slurry is provided, get cathode active material, binding agent and conductive agent and prepare cathode slurry by the proportioning of 80 ~ 98wt%:10 ~ 1wt%:10 ~ 1wt%, wherein, described cathode active material is electrode for electrochemical capacitor material, is specially one or more the combination be selected from porous carbon materials, metal oxide and conducting polymer;
3) load cathode slurry on negative electrode conducting base, obtains cathode sheets;
4) cathode sheets and anode strip are carried out cutting into corresponding size on demand, dry;
5) respectively after the drying on cathode sheets and anode strip welded cathode lead chaff and anode leads chaff;
6) be that the order of cathode sheets, electrolytic paper and anode strip is stacked successively by order from the bottom to top, finish up with anode strip, and place electrolytic paper under undermost cathode sheets, reel afterwards, obtain core.
The step 1 of above-mentioned manufacture method) in, described anode strip is anode foil for aluminum electrolytic capacitor, and described negative electrode conducting base can be aluminium foil or cathode foil of aluminum electrolytic capacitor.
The step 2 of above-mentioned manufacture method) in, described binding agent and conductive agent are that routine of the prior art is selected, particularly, binding agent can be polymethylacrylic acid powder, polymethyl methacrylate powder, polytetrafluoroethylpowder powder or emulsion equimolecular quantity 100 ten thousand to 1,000 ten thousand the combination of one or more arbitrary proportion of high molecular polymer; Conductive agent can be specifically one or both the combination in the conductive carbon materials such as electrically conductive graphite, conductive black and conductive acetylene be black, when conductive agent be chosen as above-mentioned two or more combination time, the proportioning between them is any proportioning.In this step, described porous carbon materials, metal oxide and conducting polymer can be that routine of the prior art is selected, and particularly, porous carbon materials can be active carbon, Graphene or carbon aerogels etc.; Metal oxide can be ruthenium-oxide, manganese oxide or cobalt oxide etc.; Conducting polymer can be polyaniline, polythiophene or polypyrrole etc.When preparing cathode slurry, solvent used is that routine of the prior art is selected, and can be specifically the inorganic or organic solvent such as water, NMP or DMAc.
The step 3 of above-mentioned manufacture method) in, by existing conventional method, cathode slurry is loaded on negative electrode conducting base, carry out load as the method for coating or deposition can be adopted; When carrying out applying or depositing, should carry out the two-sided of negative electrode conducting base, the density of coating or deposition preferably controls at 5-10mg/cm simultaneously
2.After load completes, carry out drying, namely obtain cathode sheets.
The step 5 of above-mentioned manufacture method) in, described cathode guide chaff and anode are led chaff and are strip aluminium; Specifically can adopt the mode of Cold welding or ultra-sonic welded that cathode guide chaff and anode are led chaff to be welded on respectively on cathode sheets and anode strip.
The step 6 of above-mentioned manufacture method) in, generally, usually stacked what complete from the bottom to top in cathode sheets, electrolytic paper and anode strip, and can reel place electrolytic paper under cathode sheets after; Also can up carry out stacked, until the number of plies of cathode sheets reaches necessary requirement by above-mentioned stacking order continuation as required.In this step, stacked good cathode sheets, electrolytic paper and anode strip are placed on up-coiler as required and are wound into required shape, as square or cylindrical etc., the application is preferably wound into square, adopt aluminum plastic film to encapsulate to facilitate, thus reduce production cost further.
Said method is only obtain core, and the manufacture method of convoluted electrolysis-electrochemical mixed capacitor of the present invention also comprises technology routinely and encapsulates core, injects electrolyte, changes into and secondary encapsulation operation after acquisition core.From the angle consideration of saving cost, Simplified flowsheet further, preferably with aluminum plastic film, core is encapsulated after acquisition core, carry out conventional injection electrolyte afterwards again, change into and secondary encapsulation operation.Particularly, gained core aluminum plastic film is encapsulated and stays an opening, then be placed in 60-80 DEG C of drying box and toast 1-3h, transfer to rapidly afterwards in impregnation cylinder, sealing vacuumizes 20-60min, injects electrolyte, again vacuumize 30-40min, then pressurize 1.2-1.5MPa, pressurize 20-30min, and circulation vacuumizes-pressure process 3-5 time; Finally take out core, get rid of excess electrolyte, carry out secondary encapsulation immediately, after guaranteeing liquid injection port sealing, carry out undetected testing entirely and namely obtain convoluted electrolysis-electrochemical mixed capacitor.Wherein, described electrolyte can be the one being selected from aqueous electrolyte, organic system electrolyte and ionic liquid, preferably adopts electrolyte for aluminum electrolytic capacitor in the application.
Compared with prior art, feature of the present invention is:
1, a kind of design of high voltage large capcity electrolysis-electrochemical mixed capacitor of novel structure is provided, specifically using anode foil for aluminum electrolytic capacitor as anode, using electrode for electrochemical capacitor material load on negative electrode conducting base as negative electrode, prepare and have electrolytic capacitor high voltage and the jumbo mixed capacitor of electrochemical capacitor concurrently.The present invention breaches the energy storage mode of original electrochemical capacitor, is brand-new research direction.
2, the mixed capacitor of convoluted flexible package is provided, utilize the pliability of foil matrix, the mode of proposition winding improves effective contact area of monolithic capacitor pole piece, thus improves the capacity of mixed capacitor monomer, can be applied to new forms of energy energy storage and dynamic field.
3, proposition aluminum plastic film carries out soft encapsulation, can effectively control its production cost, have certain development prospect.
Accompanying drawing explanation
Fig. 1 is the structural representation of a kind of stacked structure of core in convoluted electrolysis-electrochemical mixed capacitor of the present invention;
Fig. 2 is the structural representation of core in convoluted electrolysis-electrochemical mixed capacitor of the present invention;
Fig. 3 is the structural representation of the embodiment of the present invention 1 when preparing core in winding process;
Fig. 4 is the pictorial diagram of convoluted electrolysis-electrochemical mixed capacitor that embodiment 1 obtains.
Number in the figure is:
1 electrolytic paper; 2 cathode sheets; 3 anode strips; 4 cathode guide chafves; 5 anodes lead chaff.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and to understand content of the present invention better, but the present invention is not limited to following examples.
Embodiment 1: the structure of core in convoluted electrolysis-electrochemical mixed capacitor
Convoluted electrolysis-electrochemical mixed capacitor of the present invention, comprise core and electrolyte, described core comprises anode strip 3, cathode sheets 2 and electrolytic paper 1, wherein anode strip 3, cathode sheets 2 and electrolytic paper 1 stacked structure as shown in Figure 1, are respectively electrolytic paper 1, cathode sheets 2, electrolytic paper 1 and anode strip 3 from the bottom to top.Wherein said anode strip 3 is anode foil for aluminum electrolytic capacitor, anode strip 3 is provided with anode and leads chaff 5; Described cathode sheets 2 be by load on negative electrode conducting base by the cathode slurry gained of electrode for electrochemical capacitor material as cathode active material, cathode sheets 2 is provided with cathode guide chaff 4; Porous carbon materials can be active carbon, Graphene or carbon aerogels etc.; Metal oxide can be ruthenium-oxide, manganese oxide or cobalt oxide etc.; Conducting polymer can be polyaniline, polythiophene or polypyrrole etc.When preparing cathode slurry, solvent used is that routine of the prior art is selected, and can be specifically the inorganic or organic solvent such as water, NMP or DMAc.Described negative electrode conducting base can be aluminium foil or cathode foil of aluminum electrolytic capacitor, usually adopts aluminium foil.Described anode strip 3, cathode sheets 2 and electrolytic paper 1 is stacked successively by the order from the bottom to top in cathode sheets 2, electrolytic paper 1 and anode strip 3, to finish up with anode strip 3 and at undermost cathode sheets 2 times placement electrolytic papers 1, carry out afterwards reeling (can be wound into square or cylindrical, be wound into square in present embodiment) form core, as shown in Figure 2.
By existing conventional method, the core of said structure is carried out aluminum plastic film encapsulation, injects electrolyte, changed into and secondary encapsulation, convoluted electrolysis-electrochemical mixed capacitor of the present invention can be obtained.
Embodiment 2: the manufacture method of convoluted electrolysis-electrochemical mixed capacitor
1) using anode foil for aluminum electrolytic capacitor as anode strip 3, take aluminium foil as negative electrode conducting base;
2) cathode slurry is provided, get cathode active material (activated carbon, AC), binding agent CMC and conductive agent SP is uniformly mixed in aqueous solvent by the weight ratio of 82:8:10, forms the slurry (i.e. cathode slurry) with certain viscosity;
3) coated cathode slurry on the two sides of negative electrode conducting base, controlling two-sided surface density during coating is 8mg/cm
2, dry at 80 DEG C after having applied, obtain cathode sheets 2;
4) by gained cathode sheets 2 and anode strip 3 according to design need cut into corresponding size, dry;
5) chaff 4 is led according to welded cathode on the relevant position in design respectively cathode sheets 2 after the drying and anode strip 3 and anode leads chaff 5;
6) by stacked successively in the order of electrolytic paper 1, cathode sheets 2, electrolytic paper 1 and anode strip 3 from the bottom to top, stacked complete be placed on up-coiler and carry out reel (as shown in Figure 3), obtain core;
7) obtained core aluminum plastic film encapsulated and stay an opening to inject electrolyte, and toast 1h in 65 DEG C of drying boxes; Then, transfer to rapidly in impregnation cylinder, sealing vacuumizes 20min, and inject electrolyte for aluminum electrolytic capacitor, again vacuumize 30min, then pressurize 1.2MPa, pressurize 25min, and circulation vacuumizes-pressure process 3 times; Finally take out core, get rid of excess electrolyte, carry out secondary encapsulation immediately, after guaranteeing liquid injection port sealing, carry out entirely undetected testing, namely obtain convoluted electrolysis-electrochemical mixed capacitor, as shown in Figure 4.
Al/Al is prepared by method described in embodiment 2
2o
3convoluted electrolysis-the electrochemical mixed capacitor of ‖ AC/Al type, wherein electrolytic paper 1/ barrier film, cathode sheets 2 and anode strip 3 are respectively: anode strip 3:303mm*24mm, cathode sheets 2:338mm*24mm, electrolytic paper 1/ barrier film: 375mm*28mm, 2.Meanwhile prepare Al/Al by the existing customary preparation methods of capacitor
2o
3‖ Al type conventional aluminium electrolytic capacitor, Al/AC ‖ AC/Al type electrochemical capacitor, and their index such as voltage, capacity, energy density is detected, result as described in Table 1:
Table 1:
Claims (7)
1. convoluted electrolysis-electrochemical mixed capacitor, comprises core and electrolyte, it is characterized in that: described core comprises anode strip (3), cathode sheets (2) and electrolytic paper (1), wherein:
Described anode strip (3) is anode foil for aluminum electrolytic capacitor, anode strip (3) is provided with anode and leads chaff (5);
Described cathode sheets (2) be by load on negative electrode conducting base by the cathode slurry gained of electrode for electrochemical capacitor material as cathode active material, cathode sheets (2) is provided with cathode guide chaff (4); Described electrode for electrochemical capacitor material is one or more the combination be selected from porous carbon materials, metal oxide and conducting polymer;
Described anode strip (3), cathode sheets (2) and electrolytic paper (1) are stacked successively by the order from the bottom to top in cathode sheets (2), electrolytic paper (1) and anode strip (3), finish up with anode strip (3) and place electrolytic paper (1) under undermost cathode sheets (2), carrying out winding afterwards and form core.
2. convoluted electrolysis-electrochemical mixed capacitor according to claim 1, is characterized in that: described negative electrode conducting base is aluminium foil or cathode foil of aluminum electrolytic capacitor.
3. convoluted electrolysis-electrochemical mixed capacitor according to claim 1, is characterized in that: described electrolyte is the one being selected from aqueous electrolyte, organic system electrolyte and ionic liquid.
4. convoluted electrolysis-electrochemical mixed capacitor according to claim 1, is characterized in that: described electrolyte is electrolyte for aluminum electrolytic capacitor.
5. the manufacture method of convoluted electrolysis-electrochemical mixed capacitor described in claim 1, comprise the making of core, the manufacture method of described core comprises the following steps:
1) anode strip (3) and negative electrode conducting base are provided;
2) cathode slurry is provided, get cathode active material, binding agent and conductive agent and prepare cathode slurry by the proportioning of 80 ~ 98wt%:10 ~ 1wt%:10 ~ 1wt%, wherein, described cathode active material is electrode for electrochemical capacitor material, is specially one or more the combination be selected from porous carbon materials, metal oxide and conducting polymer;
3) load cathode slurry on negative electrode conducting base, obtains cathode sheets (2);
4) cathode sheets (2) and anode strip (3) are carried out cutting into corresponding size on demand, dry;
5) respectively cathode sheets (2) and anode strip (3) are gone up welded cathode and are led chaff (4) and anode leads chaff (5) after the drying;
6) be that the order of cathode sheets (2), electrolytic paper (1) and anode strip (3) is stacked successively by order from the bottom to top, finish up with anode strip (3), and electrolytic paper (1) is placed under undermost cathode sheets (2), reel afterwards, obtain core.
6. the manufacture method of convoluted electrolysis-electrochemical mixed capacitor according to claim 5, is characterized in that: after acquisition core, also comprise technology routinely encapsulate core, inject electrolyte, change into and secondary encapsulation operation.
7. the manufacture method of convoluted electrolysis-electrochemical mixed capacitor according to claim 5, it is characterized in that: also comprise after acquisition core and with aluminum plastic film, core being encapsulated, carry out conventional injection electrolyte afterwards again, change into and secondary encapsulation operation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786861A (en) * | 2019-01-17 | 2019-05-21 | 中国科学院上海硅酸盐研究所 | A kind of hybrid electrochemical energy storage device |
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| JP2014056953A (en) * | 2012-09-13 | 2014-03-27 | Mitsubishi Paper Mills Ltd | Separator for capacitor and capacitor |
| CN104283456A (en) * | 2013-07-04 | 2015-01-14 | 纳米新能源（唐山）有限责任公司 | Self-charging energy storage device |
| CN104617335A (en) * | 2015-01-27 | 2015-05-13 | 上海奥威科技开发有限公司 | Low-temperature chemical power supply and production method thereof |
| CN104851594A (en) * | 2015-04-13 | 2015-08-19 | 湖南艾华集团股份有限公司 | Aluminum-electrolytic-electrochemical hybrid capacitor and preparation method |
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- 2015-10-16 CN CN201510670328.9A patent/CN105244174A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014056953A (en) * | 2012-09-13 | 2014-03-27 | Mitsubishi Paper Mills Ltd | Separator for capacitor and capacitor |
| CN104283456A (en) * | 2013-07-04 | 2015-01-14 | 纳米新能源（唐山）有限责任公司 | Self-charging energy storage device |
| CN104617335A (en) * | 2015-01-27 | 2015-05-13 | 上海奥威科技开发有限公司 | Low-temperature chemical power supply and production method thereof |
| CN104851594A (en) * | 2015-04-13 | 2015-08-19 | 湖南艾华集团股份有限公司 | Aluminum-electrolytic-electrochemical hybrid capacitor and preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109786861A (en) * | 2019-01-17 | 2019-05-21 | 中国科学院上海硅酸盐研究所 | A kind of hybrid electrochemical energy storage device |
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