CN101840787A - Method for manufacturing positive pole plate of lithium-ion capacitor and lithium-ion capacitor using same - Google Patents
Method for manufacturing positive pole plate of lithium-ion capacitor and lithium-ion capacitor using same Download PDFInfo
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- CN101840787A CN101840787A CN201010181090A CN201010181090A CN101840787A CN 101840787 A CN101840787 A CN 101840787A CN 201010181090 A CN201010181090 A CN 201010181090A CN 201010181090 A CN201010181090 A CN 201010181090A CN 101840787 A CN101840787 A CN 101840787A
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Abstract
The invention discloses a method for manufacturing a positive pole plate of a lithium-ion capacitor, comprising the following steps: 1) coating size containing super capacitor active materials on an aluminum foil current collector, and drying; 2) coating positive pole size of a lithium ion battery on the aluminum foil current collector containing super capacitor active materials; and 3) drying, cold pressing, drying again, cutting into pieces and stripping to prepare the positive pole plate of the lithium-ion capacitor. The method for manufacturing positive pole plates of lithium-ion capacitors is easily operated, overcomes the shortcomings of unstable size when the positive pole materials of the lithium ion battery and the active materials of the super capacitor active materials are mixed, and is easy for batch production. In addition, the invention also discloses the positive pole plate of a lithium-ion capacitor and the lithium-ion capacitor using the same.
Description
Technical field
The present invention relates to a kind of lithium-ion capacitor, especially a kind of manufacture method of lithium-ion capacitor positive plate, and the lithium-ion capacitor that uses this positive plate.
Background technology
Advantage such as though ultracapacitor has the power height, the life-span is long and charging rate is fast, its voltage is low, energy density is low, and application in many aspects all is restricted.
Activated carbon for super capacitors is as positive pole, and lithium-ion capacitor then is that the graphite with embedding lithium state is negative pole, and its highest working voltage can be brought up to 4.2V from 2.7V, and correspondingly capacity and energy all have greatly improved.Therefore, lithium-ion capacitor has application widely.
The key of lithium-ion capacitor is the realization of negative pole embedding lithium state, disclosed the manufacturing technology of multiple lithium-ion capacitor in the prior art, all disclosed lithium-ion capacitor as Chinese invention patent application CN 200680046167.5, Chinese invention patent application CN 200580010863.6, Chinese invention patent application CN 200410093962.2 and Chinese invention patent application CN 200780024069.6.But, above-mentioned prior art all be with lithium metal as the lithium ion supply source, the existence of lithium metal makes the assembling process inconvenience, also can bring various unsafe factors simultaneously, causes safety problem in assembling process easily.
In addition, Chinese invention patent application CN 200710098687.7 has also disclosed a kind of lithium-ion capacitor, and its method that adopts is: mix rich lithium compound in the porous carbon material of positive pole or conducting polymer, during activation, realize the pre-embedding lithium of anticathode.But when the preparation electrode slurry, the proportion of porous carbon material or conducting polymer and rich lithium compound (for example cobalt acid lithium) differs greatly, and is difficult to form the stabilized uniform slurry, makes slurry coating difficulty therefore to be unsuitable for large-scale industrial production.
In view of this, necessary provide a kind of operate simple and easy, be easy to lithium-ion capacitor of mass production and preparation method thereof.
Summary of the invention
The objective of the invention is to: a kind of manufacture method of operating simple and easy, as to be easy to mass production lithium-ion capacitor positive plate is provided, and the lithium-ion capacitor that uses this positive plate.
In order to realize the foregoing invention purpose, the invention provides a kind of manufacture method of lithium-ion capacitor positive plate, it may further comprise the steps:
1) coating contains the slurry of ultracapacitor active material and dries on the collector aluminium foil;
2) be coated with the anode sizing agent that is coated with lithium ion battery on the collector aluminium foil of ultracapacitor active material again; And
3) through the positive plate of drying, cold pressing, oven dry again, cut-parts, itemize technology making lithium-ion capacitor.
With respect to prior art, the manufacture method of lithium-ion capacitor positive plate of the present invention has the following advantages at least: the manufacture method easy operating, the unsettled shortcoming of slurry when having overcome anode material for lithium-ion batteries and mixing with the ultracapacitor active material, can realize the accurate proportioning of ultracapacitor active material, rich lithium compound material and negative material easily, be easy to mass production.
As a kind of improvement of the manufacture method of lithium-ion capacitor positive plate of the present invention, in the step 1), the described ultracapacitor active material that uses is ultracapacitor special-purpose activated charcoal, charcoal fiber or its combination.
As a kind of improvement of the manufacture method of lithium-ion capacitor positive plate of the present invention, step 2) in, the positive electrode of the doped lithium ion that can mix/go contained in the anode sizing agent of described lithium ion battery.
As a kind of improvement of the manufacture method of lithium-ion capacitor positive plate of the present invention, described positive electrode is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, nickel LiMn2O4, partly replaces positive electrode, LiFePO 4, lithium manganese phosphate, phosphoric acid vanadium lithium, conducting polymer or its mixing of composite oxides gained with other transition metal.
In addition, the present invention also provides a kind of lithium-ion capacitor positive plate, and it comprises: the collector aluminium foil, be distributed in the ultracapacitor active material on the collector aluminium foil, and be distributed in the anode material for lithium-ion batteries on the ultracapacitor active material.
In addition, the present invention also provides a kind of lithium-ion capacitor, it comprises: positive plate, negative plate, be interval in the barrier film between positive plate and the negative plate, and electrolyte, negative plate comprises negative current collector and the negative material that is distributed on the negative current collector, wherein, positive plate comprises the collector aluminium foil, is distributed in the ultracapacitor active material on the fluid aluminium foil collection, and is distributed in the anode material for lithium-ion batteries on the ultracapacitor active material.
As a kind of improvement of lithium-ion capacitor of the present invention, described ultracapacitor active material is ultracapacitor special-purpose activated charcoal, charcoal fiber or its combination, and the mass ratio of itself and negative material is 1.35: 1～4.50: 1.
As a kind of improvement of lithium-ion capacitor of the present invention, the mass ratio of described positive electrode and negative material is 0.35: 1～2.60: 1.
As a kind of improvement of lithium-ion capacitor of the present invention, described negative material is for embedding the negative material of lithium ion.
As a kind of improvement of lithium-ion capacitor of the present invention, described negative material is graphite, hard charcoal, soft carbon, lithium titanate or its combination.
Description of drawings
Below in conjunction with the drawings and specific embodiments, invention and useful technique effect thereof are elaborated, wherein:
Fig. 1 is the partial structurtes schematic diagram of lithium-ion capacitor of the present invention.
Fig. 2 is the charging and discharging curve figure of lithium-ion capacitor embodiment 1 of the present invention.
Fig. 3 is the charging and discharging curve figure of lithium-ion capacitor embodiment 2 of the present invention.
Fig. 4 is the charging and discharging curve figure of lithium-ion capacitor embodiment 3 of the present invention.
Fig. 5 is the charging and discharging curve figure of lithium-ion capacitor embodiment 4 of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, describe the present invention in detail, but embodiments of the invention are not limited thereto.Specific embodiment embodiment 1
The preparation of lithium-ion capacitor positive plate: with ultracapacitor special-purpose activated charcoal (1800m
2/ g) make slurry at 87: 3: 10 by mass ratio with conductive agent SuperP, bonding agent Kynoar (PVDF), be coated on the collector aluminium foil and and dry down at 120 ℃, coating weight is 6.51mg/cm
2Cobalt acid lithium, conductive agent SuperP, bonding agent PVDF are mixed the lithium ion battery anode glue size of making certain viscosity by mass ratio at 95: 2.5: 2.5, be coated on the collector aluminium foil that scribbles layer of active carbon, its coating weight is 4.13mg/cm
2, cold pressing after the oven dry down at 120 ℃; To under 180 ℃ of high temperature, toast 40 minutes according to the positive plate that aforementioned technology makes, cut edge, after the cut-parts, itemize, make the lithium-ion capacitor positive plate that meets the demands.
The preparation of lithium-ion capacitor negative plate: graphite and conductive agent SuperP, bonding agent PVDF are made slurry by mass ratio at 92: 4: 4, be coated on the copper foil of affluxion body and at 85 ℃ and dry down, coating weight is 3.58mg/cm
2Cut edge, after the cut-parts, itemize, make the lithium-ion capacitor negative plate that meets the demands.
The preparation of lithium-ion capacitor: will be made into thickness through lamination technology according to lithium-ion capacitor positive plate, negative plate and the barrier film of aforementioned prepared is 3.5mm, width is 23mm, length is the lithium-ion capacitor of 44mm, fluid injection, leave standstill 10 hours after, 3.80V change into, through exhaust, trimming for forming, test capacity is 38F.
Figure 1 shows that the partial structurtes schematic diagram of lithium-ion capacitor of the present invention, wherein, 10 is the collector aluminium foil of positive plate; 20 is the ultracapacitor active material; 30 is the positive electrode of lithium-ion capacitor; 40 is barrier film; 50 is the negative material of lithium-ion capacitor; 60 is the copper foil of affluxion body of negative plate.
Figure 2 shows that the charging and discharging curve figure of lithium-ion capacitor embodiment 1 of the present invention, as can be seen from Figure 2: its working voltage can reach 4.2V, much larger than the working voltage (2.7V) of general ultracapacitor.In addition, discharging and recharging of lithium-ion capacitor embodiment 1 of the present invention is linear for oblique line, shows that it has good capacitive property.Embodiment 2
The preparation of lithium-ion capacitor positive plate: with the special-purpose charcoal fiber of ultracapacitor (2100m
2/ g) make slurry at 87: 3: 10 by mass ratio with conductive agent SuperP, bonding agent PVDF, be coated on the collector aluminium foil and and dry down at 120 ℃, coating weight is 12.53mg/cm
2LiMn2O4, conductive agent SuperP, bonding agent PVDF are mixed the lithium ion battery anode glue size of making certain viscosity by mass ratio at 95: 2.5: 2.5, be coated on the collector aluminium foil that scribbles one deck charcoal fiber, coating weight is 6.68mg/cm
2, cold pressing after the oven dry down at 120 ℃; The positive plate that will make according to aforementioned technology is 180 ℃ of following high-temperature bakings 40 minutes, cuts edge, after the cut-parts, itemize, makes the lithium-ion capacitor positive plate that meets the demands.
The preparation of lithium-ion capacitor negative plate: soft carbon and conductive agent SuperP, bonding agent PVDF are made slurry by mass ratio at 92: 4: 4, be coated on the copper foil of affluxion body and at 85 ℃ and dry down, coating weight is 3.10mg/cm
2Cut edge, after the cut-parts, itemize, make the lithium-ion capacitor negative plate that meets the demands.
The preparation of lithium-ion capacitor: will be made into thickness through lamination technology according to lithium-ion capacitor positive plate, negative plate and the barrier film of aforementioned prepared is 5.2mm, width is 23mm, length is the lithium-ion capacitor of 44mm, fluid injection, leave standstill 10 hours after, 3.80V change into, through exhaust, trimming for forming, test capacity is 81F.
Figure 3 shows that the charging and discharging curve figure of lithium-ion capacitor embodiment 2 of the present invention, as can be seen from Figure 3: its working voltage can reach 4.2V, much larger than the working voltage (2.7V) of general ultracapacitor.In addition, discharging and recharging of lithium-ion capacitor embodiment 2 of the present invention is linear for oblique line, shows that it has good capacitive property.Embodiment 3
The preparation of lithium-ion capacitor positive plate: with ultracapacitor special-purpose activated charcoal (2300m
2/ g) make slurry at 87: 3: 10 by mass ratio with conductive agent SuperP, bonding agent PVDF, be coated on the collector aluminium foil and and dry down at 120 ℃, coating weight is 8.75mg/cm
2LiFePO 4, conductive agent SuperP, bonding agent PVDF are mixed the lithium ion battery anode glue size of making certain viscosity by mass ratio at 95: 2.5: 2.5, be coated on the collector aluminium foil that scribbles layer of active carbon, coating weight is 5.16mg/cm
2, cold pressing after the oven dry down at 120 ℃; The positive plate that will make according to aforementioned technology is 180 ℃ of following high-temperature bakings 40 minutes, cuts edge, after the cut-parts, itemize, makes the lithium-ion capacitor positive plate that meets the demands.
The preparation of lithium-ion capacitor negative plate: hard carbon and conductive agent SuperP, bonding agent PVDF are made slurry by mass ratio at 92: 4: 4, be coated on the copper foil of affluxion body and at 85 ℃ and dry down, coating weight is 3.42mg/cm
2Cut edge, after the cut-parts, itemize, make the lithium-ion capacitor negative plate that meets the demands.
The preparation of lithium-ion capacitor: will be made into thickness through lamination technology according to lithium-ion capacitor positive plate, negative plate and the barrier film of aforementioned prepared is 4.2mm, width is 23mm, length is the lithium-ion capacitor of 44mm, fluid injection, leave standstill 10 hours after, 3.1V change into, through exhaust, trimming for forming, test capacity is 60F.
Figure 4 shows that the charging and discharging curve figure of lithium-ion capacitor embodiment 3 of the present invention, as can be seen from Figure 4: its working voltage can reach 4.2V, much larger than the working voltage (2.7V) of general ultracapacitor.In addition, discharging and recharging of lithium-ion capacitor embodiment 3 of the present invention is linear for oblique line, shows that it has good capacitive property.Embodiment 4
The preparation of lithium-ion capacitor positive plate: with ultracapacitor special-purpose activated charcoal (1800m
2/ g) with charcoal fiber (2100m
2/ g), conductive agent SuperP, bonding agent PVDF be by mass ratio 43.5: 43.5: 3: 10 make slurry, are coated on the collector aluminium foil and 120 ℃ of oven dry down, coating weight is 10.16mg/cm
2With LiMn2O4 and nickle cobalt lithium manganate, conductive agent SuperP, bonding agent PVDF by mass ratio 67: 28: 2.5: 2.5 mix the lithium ion battery anode glue size of making certain viscosity, be coated on the collector aluminium foil that scribbles layer of active carbon and charcoal fiber, coating weight is 5.52mg/cm
2, cold pressing after the oven dry down at 120 ℃; The positive plate that will make according to aforementioned technology is 180 ℃ of following high-temperature bakings 40 minutes, cuts edge, after the cut-parts, itemize, makes the lithium-ion capacitor positive plate that meets the demands.
The preparation of lithium-ion capacitor negative plate: with soft carbon and graphite, conductive agent SuperP, bonding agent PVDF by mass ratio 55: 37: 4: 4 make slurry, are coated on the copper foil of affluxion body and 85 ℃ of oven dry down, coating weight is 3.51mg/cm
2Cut edge, after the cut-parts, itemize, make the lithium-ion capacitor negative plate that meets the demands.
The preparation of lithium-ion capacitor: will be made into thickness through lamination technology according to lithium-ion capacitor positive plate, negative plate and the barrier film of aforementioned prepared is 4.5mm, width is 23mm, length is the lithium-ion capacitor of 44mm, fluid injection, leave standstill 10 hours after, 3.7V change into, through exhaust, trimming for forming, test capacity is 63F.
Figure 5 shows that the charging and discharging curve figure of lithium-ion capacitor embodiment 4 of the present invention, as can be seen from Figure 5: its working voltage can reach 4.2V, much larger than the working voltage (2.7V) of general ultracapacitor.In addition, discharging and recharging of lithium-ion capacitor embodiment 4 of the present invention is linear for oblique line, shows that it has good capacitive property.
It is to be noted, though being example with cobalt acid lithium, LiMn2O4, LiFePO 4, LiMn2O4 and nickle cobalt lithium manganate only among the embodiment of this specification is illustrated the positive electrode of lithium-ion capacitor of the present invention, but, other execution modes of lithium-ion capacitor according to the present invention, positive electrode also can be lithium nickelate, nickel cobalt lithium aluminate, nickel LiMn2O4, partly replace positive electrode, lithium manganese phosphate, phosphoric acid vanadium lithium, conducting polymer or its combination of composite oxides gained with other transition metal.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the embodiment that discloses and describe above the present invention is not limited to also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms do not constitute any restriction to the present invention just for convenience of description.
Claims (10)
1. the manufacture method of a lithium-ion capacitor positive plate, it may further comprise the steps:
1) coating contains the slurry of ultracapacitor active material and dries on the collector aluminium foil;
2) be coated with the anode sizing agent that is coated with lithium ion battery on the collector aluminium foil of ultracapacitor active material again; And
3) through the positive plate of drying, cold pressing, oven dry again, cut-parts, itemize technology making lithium-ion capacitor.
2. the manufacture method of lithium-ion capacitor positive plate according to claim 1 is characterized in that: in the step 1), the described ultracapacitor active material that uses is ultracapacitor special-purpose activated charcoal, charcoal fiber or its combination.
3. the manufacture method of lithium-ion capacitor positive plate according to claim 1 is characterized in that: step 2) in, the positive electrode of the doped lithium ion that can mix/go contained in the anode sizing agent of described lithium ion battery.
4. the manufacture method of lithium-ion capacitor positive plate according to claim 3 is characterized in that: described positive electrode is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, nickel LiMn2O4, partly replaces positive electrode, LiFePO 4, lithium manganese phosphate, phosphoric acid vanadium lithium, conducting polymer or its mixing of composite oxides gained with other transition metal.
5. lithium-ion capacitor positive plate, it comprises: the collector aluminium foil, be distributed in the ultracapacitor active material on the collector aluminium foil, and be distributed in the anode material for lithium-ion batteries on the ultracapacitor active material.
6. lithium-ion capacitor, it comprises: positive plate, negative plate, be interval in the barrier film between positive plate and the negative plate, and electrolyte, negative plate comprises negative current collector and the negative material that is distributed on the negative current collector, it is characterized in that: described positive plate comprises the collector aluminium foil, is distributed in the ultracapacitor active material on the fluid aluminium foil collection, and is distributed in the anode material for lithium-ion batteries on the ultracapacitor active material.
7. lithium-ion capacitor according to claim 6 is characterized in that: described ultracapacitor active material is ultracapacitor special-purpose activated charcoal, charcoal fiber or its combination, and the mass ratio of itself and negative material is 1.35: 1～4.50: 1.
8. lithium-ion capacitor according to claim 6 is characterized in that: the mass ratio of described positive electrode and negative material is 0.35: 1～2.60: 1.
9. lithium-ion capacitor according to claim 6 is characterized in that: described negative material is for embedding the negative material of lithium ion.
10. lithium-ion capacitor according to claim 9 is characterized in that: described negative material is graphite, hard charcoal, soft carbon, lithium titanate or its combination.
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| CN102891299A (en) * | 2012-09-12 | 2013-01-23 | 黎军 | High-rate lithium ion battery cathode material and preparation method and application thereof |
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