CN102651484B - A kind of energy storage device having lithium ion battery and super capacitor feature concurrently - Google Patents
A kind of energy storage device having lithium ion battery and super capacitor feature concurrently Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The present invention relates to a kind of energy storage device having lithium ion battery and super capacitor feature concurrently, be made up of positive pole, negative pole, barrier film, electrolyte and housing, both positive and negative polarity is applied respectively by active material, conductive agent and binding agent to make on a current collector, positive active material is the biomass active Carbon Materials that can carry out ion reversible absorption, and negative pole is the lithium titanyl compound that can carry out the reversible deintercalation of lithium ion; It has the absorbent charcoal material of the electric double layer energy storage characteristic of super capacitor, in conjunction with the lithium titanyl compound of doff lithium energy storage characteristic with lithium ion battery, form the energy storage device having lithium ion battery and super capacitor feature concurrently, material therefor, for the maturing material of energy storage device extensive use, environmental friendliness, wide material sources, cost is lower.
Description
Technical field
The present invention relates to a kind of energy storage device having lithium ion battery and super capacitor feature concurrently, belong to battery and super capacitor technology field.
Background technology
The development of new-energy automobile, facilitates the continuous lifting of the chemical power source technology such as lead-acid battery, Ni-MH battery, lithium ion battery, fuel cell, super capacitor, metal-air cell, Zinc ion battery.Single dynamical system is difficult to meet instructions for use.Combine the energy storage device with different-energy and power characteristic use, while meeting instructions for use, greatly can improve the efficiency of device, increase the service life.Such as, lithium ion battery and super capacitor are formed composite power source, as the power source of automobile, super capacitor can in the high-power output operating mode work such as startup, acceleration, climbing, lithium ion battery provides the continual mileage required drive of automobile, the combination of the two, improves the power performance of automobile, extends the useful life of battery.Itself and battery are formed composite power source by lot of domestic and foreign car enterprise, for the operating mode of the high-power output such as startup, climbing, acceleration of car, improve battery utilization ratio, extending battery life; On the other hand, be applied to city electric bus as main power source, utilize website to get on or off the bus the time, complete charging; Recently, car is had again to look forward to super capacitor being used for extended-range electric vehicle, successful.But the energy density of super capacitor is lower, limit its onboard scale application.
In order to improve the energy density of super capacitor, people carry out developing material from raising ratio capacitance and raising voltage two angles.Metal oxide, as electrode active material, can produce fake capacitance in the charge and discharge process of electric capacity, increases substantially the specific capacity of monomer.Application number 200910043613.2 reports a kind of for the preparation of ultracapacitor RuO
2the coating and thermal decomposition process of electrode material.By RuCl
3and SnCl
2be mixed with thick shape solution, even application, on substrate, through 200 ~ 500 DEG C of heat treatments, obtains RuO
2thin-film material, carry out electrochemical property test, ratio capacitance reaches 612 ~ 634F/g.Application number 200910133119.5 describes a kind of preparation method of the expanded graphite/metal oxide composite for electrode of super capacitor.By transition metal oxide nano-particles by the dispersed formation stable dispersions of surfactant, expanded graphite is added in dispersion liquid, places 10 ~ 24 hours, dry must expanded graphite/metal oxide composite.It is simple that the method prepares super capacitor active material technique, and cost is low, have very strong industrial application value.Application number 00819536.6 reports one and prepares 2 ~ 20nm mesoporous carbon/metal oxide precursor by gas phase process or liquid phase process, changed into mesoporous carbon/metal oxide by heat treatment, the super capacitor ratio capacitance of assembling significantly improves, and reaches 254F/g.Application number 200910012011.0 is reported
A kind of aqueous super electric capacity in road, 2.4 ~ 3.0V is brought up to by 1.2 ~ 1.6V operating voltage of routine, this capacitor by manganese oxide/absorbent charcoal composite material as positive active material, active carbon, as negative electrode active material, has good electrochemical behavior and comparatively ideal power density and energy density.
In recent years, while the outside of carrying out battery and super capacitor composite power source is optimized, the inside starting energy storage device combines, mainly by the characteristic element of a certain energy storage device and the characteristic element of other energy storage devices, by the optimal design of system, realize merging in same monomer, improve the power density, energy density etc. of energy storage device.Such as, the plumbous charcoal that lead-acid battery and super capacitor combine surpasses battery, the nickel charcoal super capacitor that Ni-MH battery is combined with super capacitor, the lithium ion super battery capacitor (lithium ion super capacitor batteries, lithium-ion capacitor) that lithium ion battery is combined with super capacitor.
Application number 200910212790.9 reports a kind of leaching colloidal charcoal super capacitor, and negative pole adopts activated carbon negative electrode, and positive pole adopts plumbous positive pole, and electrolyte adopts colloidal electrolyte, and discharge capacity and high temperature performance significantly improve.Application number 200810111891.2 describes a kind of hickelous nydroxide positive pole mixing carbon nano-tube and carbonyl nickel, and the ultracapacitor formed with the carbon fiber of electronickelling process, maximum energy storage density reaches 20Wh/kg.Application number 201010265362.5 describes a kind of nano nickel oxide composite electrode for ultracapacitor and preparation method thereof, and in Powdered nano oxidized nickel material, mix a certain amount of metallic element make composite material, electrode specific capacity is high, and cost is low.Application number is 200410093962.2 report a kind of high tension super capacitor, the negative material of the oxide of argentiferous is made pastel coating on metal foil, after drying, roll-in make negative plate, the embedding lithium more de-lithiumation of part becomes, form ultracapacitor with active carbon positive pole, there is the maximum operating voltage of about 4V.Application number 200710035205.3 reports a kind of superbattery electric capacity, positive-active electrode material adopts the mixture of Lithium-ion embeding compound and porous carbon material, negative electrode active electrode material adopts the mixture of porous carbon material and graphite type material, have the feature of electric capacity and the difunctional energy storage of battery concurrently, while keeping lithium ion battery high-voltage, high-energy-density, also there is the characteristics such as the high power density of ultracapacitor, heavy-current discharge, good cycle life.Application number 200810046091.7 reports a kind of high potential super capacitor electrode material containing C, Fe and P element, and wherein the mass content of C is not less than 10%, and operating potential is relative to Li
ten/ Li can reach 4.3V, has good cyclical stability.Application number 201010280801.X reports a kind of LiFePO4 load at active carbon as positive active material, and preparation method's cost is low, and the charge-discharge performance of superbattery electric capacity monomer is good, and under 20C multiplying power, specific capacity is greater than 60mAh/g.
Super capacitor relies on the adsorpting aggregation ion energy storage of porous material due to it, and energy density is lower, limits its scale application.For battery, due to electrode material generation chemical reaction, the power density of battery cannot reach the level of super capacitor; The composite power source of battery and super capacitor outside coupling, add the complexity of system, the advantage of the two can not give full play to.
Summary of the invention
The object of the present invention is to provide a kind of energy storage device having lithium ion battery and super capacitor feature concurrently, by having the biomass-based active carbon of the electric double layer energy storage characteristic of super capacitor, be combined in same monomer with the lithium titanyl material of the doff lithium energy storage characteristic with lithium ion battery, achieve the coupling of lithium ion battery by outside and super capacitor, the fusion having the energy storage device of lithium ion battery and super capacitor feature concurrently internally.
Technical scheme of the present invention is achieved in that a kind of energy storage device having lithium ion battery and super capacitor feature concurrently, it is characterized in that its preparation method is as follows: by positive active material, conductive agent and binding agent in mass ratio 80:15:5 be coated on aluminium foil, cut, dry, coating another side makes positive plate, is coated on aluminium foil, cuts negative electrode active material, conductive agent and binding agent 80 ~ 85:10 in mass ratio ~ 15:5, drying, coating another side makes negative plate; Separate with barrier film in the middle of positive/negative plate, inject electrolyte, encapsulating housing, obtains energy storage device monomer; Wherein positive active material is made up of activated carbon from activated sludge, and its raw material adopts the one in rice husk, apricot shell, stalk, specific area>=1200m
2/ g, (1) rice husk matrix activated carbon: the rice husk by cleaning, after removal of impurities, carbonizes 2 hours at 380 DEG C of nitrogen atmospheres, be immersed in the potassium hydroxide solution of 2M and stir 6 hours, spend deionized water, dry; Then according to alkali carbon ratio 3:1 mixing potassium hydroxide and the rice husk that carbonized, leave standstill after 12 hours, 700 DEG C of activation 2 hours, deionized water washed, dry, obtained rice husk matrix activated carbon; (2) apricot based active carbon: by the apricot shell after cleaning, pulverizing, carbonize 2 hours at 400 DEG C of nitrogen atmospheres, then according to alkali carbon ratio 3:1 mixing potassium hydroxide and the rice husk that carbonized, leave standstill after 12 hours, 750 DEG C of activation 1 hour, deionized water washed, drying, obtains apricot based active carbon; (3) straw base active carbon: by the stalk after cleaning, pulverizing, carbonize 1 hour at 300 DEG C of nitrogen atmospheres, then according to alkali carbon ratio 3:1 mixing potassium hydroxide and the stalk that carbonized, leave standstill after 12 hours, 700 DEG C of activation 1 hour, deionized water washed, drying, obtains straw base active carbon; Negative electrode active material is the compound that lithium titanyl, Graphene and expanded graphite are formed, and deviate from energy storage by the embedding of lithium ion, its quality ratio of components is 90 ~ 99:0.5 ~ 5:0.5 ~ 9.5; Barrier film is the one in polypropylene diaphragm, polyethylene diagrams, polypropylene and polyethylene composite film, cellulosic separator.
The expansion multiplying power of described expanded graphite is 250 ~ 380ml/g, particle diameter≤15um; Graphene is sandwich construction, and thickness is 5 ~ 20nm, purity >=99.5%;
Described negative electrode active material is composited by mechanical means, comprises ball milling mixing, mechanical agitation, ultrasonic disperse; Also the method for fabricated in situ can be adopted to obtain, and in-situ synthesis is that lithium titanyl, Graphene, the expanded graphite that titanium dioxide generates with lithium salts mixes according to product metering proportion 90 ~ 99:0.5 ~ 5:0.5 ~ 9.5, fires for 600 ~ 800 DEG C and forms;
Described electrolyte is by lithium salts and solvent composition, and lithium salts comprises the one in hexafluoro phosphorus lithium, trifluoromethyl sulfonic acid lithium, lithium perchlorate, LiBF4, and solvent comprises the one in dimethyl carbonate, diethyl carbonate, propene carbonate, acetonitrile solution.
Described conductive agent is the one in acetylene black, carbon nano-tube, Graphene, carbon nano-fiber.
Described binding agent is Kynoar.
Good effect of the present invention is that it will have the material of the electric double layer of super capacitor, the doff lithium energy storage characteristic of lithium ion battery, merge in same monomer, achieve the coupling of battery by outside and super capacitor, battery internally and the combination of super capacitor, material used, for the maturing material of energy storage device extensive use, environmental friendliness, raw material sources are extensive, be conducive to reducing costs, have higher than super capacitor energy density, larger than cell power density, the feature had extended cycle life.
Accompanying drawing explanation
Fig. 1 is negative pole lithium titanyl compound XRD curve of the present invention.
Fig. 2 is the N of positive pole rice husk matrix activated carbon of the present invention
2adsorption-desorption isothermal.
Fig. 3 is the charging and discharging curve of energy storage device of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the invention will be further described: as shown in Figure 1, 2, 3, a kind of energy storage device having lithium ion battery and super capacitor feature concurrently, it is characterized in that its preparation method is as follows: by positive active material, conductive agent and binding agent in mass ratio 80:15:5 be coated on aluminium foil, cut, dry, coating another side makes positive plate, negative electrode active material, conductive agent and binding agent 80 ~ 85:10 in mass ratio ~ 15:5 is coated on aluminium foil, cut, drying, coating another side makes negative plate; Separate with barrier film in the middle of positive/negative plate, inject electrolyte, encapsulating housing, obtains energy storage device monomer; Positive active material is made up of activated carbon from activated sludge, and its raw material adopts the one in rice husk, apricot shell, stalk, specific area>=1200m
2/ g, (1) rice husk matrix activated carbon: the rice husk by cleaning, after removal of impurities, carbonizes 2 hours at 380 DEG C of nitrogen atmospheres, be immersed in the potassium hydroxide solution of 2M and stir 6 hours, spend deionized water, dry; Then according to alkali carbon ratio 3:1 mixing potassium hydroxide and the rice husk that carbonized, leave standstill after 12 hours, 700 DEG C of activation 2 hours, deionized water washed, dry, obtained rice husk matrix activated carbon; (2) apricot based active carbon: by the apricot shell after cleaning, pulverizing, carbonize 2 hours at 400 DEG C of nitrogen atmospheres, then according to alkali carbon ratio 3:1 mixing potassium hydroxide and the rice husk that carbonized, leave standstill after 12 hours, 750 DEG C of activation 1 hour, deionized water washed, drying, obtains apricot based active carbon; (3) straw base active carbon: by the stalk after cleaning, pulverizing, carbonize 1 hour at 300 DEG C of nitrogen atmospheres, then according to alkali carbon ratio 3:1 mixing potassium hydroxide and the stalk that carbonized, leave standstill after 12 hours, 700 DEG C of activation 1 hour, deionized water washed, drying, obtains straw base active carbon; Negative electrode active material is the compound that lithium titanyl, Graphene and expanded graphite are formed, and deviate from energy storage by the embedding of lithium ion, its quality ratio of components is 90 ~ 99:0.5 ~ 5:0.5 ~ 9.5; Barrier film is the one in polypropylene diaphragm, polyethylene diagrams, polypropylene and polyethylene composite film, cellulosic separator.
The expansion multiplying power of described expanded graphite is 250 ~ 380ml/g, particle diameter≤15um; Graphene is sandwich construction, and thickness is 5 ~ 20nm, purity >=99.5%.
Described negative electrode active material is composited by mechanical means, comprises ball milling mixing, mechanical agitation, ultrasonic disperse; Also the method for fabricated in situ can be adopted to obtain, in-situ synthesis is titanium dioxide, lithium salts, Graphene, expanded graphite mix according to product metering proportion (90 ~ 99:0.5 ~ 5:0.5 ~ 9.5), 600 ~ 800 DEG C of sintering are made.
Described electrolyte is by lithium salts and solvent composition, and lithium salts comprises the one in hexafluoro phosphorus lithium, trifluoromethyl sulfonic acid lithium, lithium perchlorate, LiBF4, and solvent comprises the one in dimethyl carbonate, diethyl carbonate, propene carbonate, acetonitrile solution.
Described conductive agent is the one in acetylene black, carbon nano-tube, Graphene, carbon nano-fiber.
Described binding agent is Kynoar.
Embodiment 1:
Lithium titanyl, Graphene and expanded graphite is taken according to quality ratio of components 99:0.5:0.5, expanded graphite is mixed 2 hours with lithium titanyl in NMP, add the nmp solution of Graphene, mix 4 hours, except desolventizing, make negative electrode active material, be coated on aluminium foil according to negative electrode active material, acetylene black, Kynoar mass ratio 80:15:5, cut, as cathode pole piece after drying.
Rice husk by cleaning, after removal of impurities, carbonizes 2 hours at 380 DEG C of nitrogen atmospheres, is immersed in the potassium hydroxide solution of 2M and stirs 6 hours, spend deionized water, dry; Then according to alkali carbon ratio 3:1 mixing potassium hydroxide and the rice husk that carbonized, leave standstill after 12 hours, 700 DEG C of activation 2 hours, deionized water washed, dry, obtained rice husk matrix activated carbon; Be coated on aluminium foil according to active carbon, acetylene black, Kynoar mass ratio 80:15:5, cut, as positive plate after drying, both positive and negative polarity pole piece carrying active substance mass ratio is 2:1.
Positive plate, polypropylene diaphragm, negative plate are superposed successively, be put in button shell, vacuum environment, add the ethyl carbonate electrolyte of 1M hexafluoro phosphorus lithium, sealing, makes energy storage device.
Embodiment 2:
Lithium titanyl, Graphene and expanded graphite are mixed according to quality ratio of components 98:1:1 ball milling, make negative electrode active material, be coated on aluminium foil according to negative electrode active material, Graphene, Kynoar mass ratio 85:10:5, cut, dry, coating another side, as cathode pole piece, connecting tab.
By the apricot shell after cleaning, pulverizing, carbonize 2 hours at 400 DEG C of nitrogen atmospheres, then according to alkali carbon ratio 3:1 mixing potassium hydroxide and the rice husk that carbonized, leave standstill after 12 hours, 750 DEG C of activation 1 hour, deionized water washing, drying, obtained apricot based active carbon.
Be coated on aluminium foil according to active carbon, conductive carbon black, Kynoar mass ratio 80:15:5, cut, dry, coating another side, as anode pole piece, connecting tab, both positive and negative polarity pole piece carrying active substance mass ratio is 1.8:1.
Positive plate, polyethylene diagrams, negative plate are superposed successively, be put in made aluminum plastic membrane shell, vacuum environment, add the ethyl carbonate electrolyte of 1M hexafluoro phosphorus lithium, sealing, makes energy storage device.
Embodiment 3:
Take lithium carbonate, titanium dioxide, Graphene and expanded graphite (in product lithium carbonate and titanium dioxide product lithium titanyl: Graphene: expanded graphite quality ratio of components 90:5:5), ball milling mixes, nitrogen atmosphere 750 DEG C calcining 4h, makes negative electrode active material; Be coated on aluminium foil according to negative electrode active material, carbon nano-fiber, Kynoar mass ratio 85:10:5, cut, as cathode pole piece after drying.
By the stalk after cleaning, pulverizing, carbonize 1 hour at 300 DEG C of nitrogen atmospheres, then according to alkali carbon ratio 3:1 mixing potassium hydroxide and the stalk that carbonized, leave standstill after 12 hours, 700 DEG C of activation 1 hour, deionized water washing, drying, obtained straw base active carbon.
Be coated on aluminium foil according to active carbon, conductive carbon black, Kynoar mass ratio 80:15:5, cut, as anode pole piece after drying, both positive and negative polarity pole piece carrying active substance mass ratio is 1.5:1.
Positive plate, polyethylene polypropylene composite diaphragm, negative plate are superposed successively, winding, is put in box hat, vacuum environment, adds the propene carbonate electrolyte of 1M hexafluoro phosphorus lithium, and sealing, makes energy storage device.
Its material used is the maturing material of energy storage device extensive use, environmental friendliness, and raw material sources are extensive, are conducive to reducing costs, have higher than super capacitor energy density, larger than cell power density, the feature had extended cycle life.
Claims (3)
1. one kind has the energy storage device of lithium ion battery and super capacitor feature concurrently, by positive active material, conductive agent and binding agent in mass ratio 80:15:5 be coated on aluminium foil, cut, dry, coating another side makes positive plate, is coated on aluminium foil, cuts negative electrode active material, conductive agent and binding agent 80 ~ 85:10 in mass ratio ~ 15:5, drying, coating another side makes negative plate; Separate with barrier film in the middle of positive/negative plate, inject electrolyte, encapsulating housing, obtains energy storage device monomer; It is characterized in that: positive active material is made up of activated carbon from activated sludge, its raw material adopts the one in apricot shell or stalk, specific area>=1200m
2/ g, negative electrode active material is the compound that lithium titanyl, Graphene and expanded graphite are formed, and deviate from energy storage by the embedding of lithium ion, its quality ratio of components is 90 ~ 99:0.5 ~ 5:0.5 ~ 9.5; Barrier film is the one in polypropylene diaphragm, polyethylene diagrams, polypropylene and polyethylene composite film, cellulosic separator; Electrolyte is by lithium salts and solvent composition, and lithium salts comprises the one in lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, lithium perchlorate, LiBF4, and solvent comprises the one in dimethyl carbonate, diethyl carbonate, propene carbonate, acetonitrile solution; Conductive agent is the one in acetylene black, carbon nano-tube, Graphene, carbon nano-fiber; Binding agent is Kynoar; Wherein apricot shell or straw base method for preparation of active carbon as follows: by clean, pulverize after apricot shell, 2 hours are carbonized at 400 DEG C of nitrogen atmospheres, then according to alkali carbon ratio 3:1 mixing potassium hydroxide and the apricot shell that carbonized, leave standstill after 12 hours, 750 DEG C of activation 1 hour, deionized water washs, dry, obtains apricot based active carbon; Straw base active carbon: by the stalk after cleaning, pulverizing, carbonize 1 hour at 300 DEG C of nitrogen atmospheres, then according to alkali carbon ratio 3:1 mixing potassium hydroxide and the stalk that carbonized, leave standstill after 12 hours, 700 DEG C of activation 1 hour, deionized water washed, drying, obtains straw base active carbon.
2., according to a kind of energy storage device having lithium ion battery and super capacitor feature concurrently described in claim 1, it is characterized in that the expansion multiplying power of described expanded graphite is 250 ~ 380ml/g, particle diameter≤15um; Graphene is sandwich construction, and thickness is 5 ~ 20nm, purity >=99.5%.
3. according to a kind of energy storage device having lithium ion battery and super capacitor feature concurrently described in claim 1, it is characterized in that described negative electrode active material is composited by mechanical means, comprise ball milling mixing, mechanical agitation, ultrasonic disperse; Or employing fabricated in situ, namely titanium dioxide, lithium salts, Graphene, expanded graphite mix by product metering proportion 90-99:0.5-5:0.5-9.5, and 600-800 DEG C of sintering is made.
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| CN108417408A (en) * | 2018-01-17 | 2018-08-17 | 莆田市超维二维科技发展有限公司 | A kind of ultracapacitor and preparation method thereof |
| CN109706553B (en) * | 2018-12-29 | 2021-07-27 | 中喜（宁夏）新材料有限公司 | Preparation method of graphene nano silicon-magnesium flame-retardant carbon fiber |
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| CN1632893A (en) * | 2004-11-18 | 2005-06-29 | 复旦大学 | Electrochemical ultra-capacitor taking lithium ion battery electrode material as cathode |
| CN101320821A (en) * | 2007-06-04 | 2008-12-10 | 中南大学 | Energy storage device with both capacitor and lithium ion battery characteristics and manufacturing method thereof |
| CN102275911A (en) * | 2011-06-03 | 2011-12-14 | 中国林业科学研究院林产化学工业研究所 | Microporous active carbon and preparation method by chemical agent aperture regulation and control |
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