CN204360933U - Super lithium-ion capacitor - Google Patents
Super lithium-ion capacitor Download PDFInfo
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- CN204360933U CN204360933U CN201420666419.6U CN201420666419U CN204360933U CN 204360933 U CN204360933 U CN 204360933U CN 201420666419 U CN201420666419 U CN 201420666419U CN 204360933 U CN204360933 U CN 204360933U
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The utility model provides a kind of super lithium-ion capacitor, comprise positive pole, negative pole, barrier film and electrolyte, positive pole comprises the first collector and is arranged at the activated carbon layer of the first collection liquid surface, negative pole comprises the second collector and is arranged at the hard carbon layer of the second collection liquid surface, barrier film is arranged between positive pole and negative pole, insulate to make positive pole and negative electricity, electrolyte and positive pole and negative pole physical contact and electrical contact, exchange between positive pole and negative pole to allow ion, super lithium-ion capacitor also comprises lithium lamella, lithium lamella is between hard carbon layer and barrier film and be arranged on the surface of hard carbon layer.The utility model has the advantage of, positive active material is active carbon, negative electrode active material is hard carbon and lithium sheet, preparation process is simple, collector does not need through special processing, easily obtains, and the operating voltage of the capacitor finally obtained can reach 4.0V, specific energy can reach 25WH/kg, and cycle life can reach 300,000 times.
Description
Technical field
The utility model relates to field of chemical power source, particularly a kind of super lithium-ion capacitor with high-energy-density and long circulation life.
Background technology
In recent years, lithium rechargeable battery obtains very large development, and this battery cathode generally uses the carbon materials such as graphite, and positive pole uses cobalt acid lithium, LiMn2O4 etc. containing lithium metal oxide.After this battery assembling, during charging, negative pole provides lithium ion to positive pole, and when discharging, the lithium ion of positive pole returns negative pole, is therefore called as " rocking chair type battery ".Compared with using the lithium battery of lithium metal, this battery has the feature of high security and high cycle life.
But due to the distortion of positive electrode easy recurring structure in the process of removal lithium embedded, therefore, the cycle life of lithium rechargeable battery is still restricted.Therefore in recent years, the architectural study that lithium rechargeable battery and double layer capacitor combine is become new focus.
The carbon materials such as lithium-ion capacitor general anode material selection graphite, hard carbon, positive electrode selects the absorbent charcoal material of electric double layer characteristic, is carried out the pre-doping of lithium ion by anticathode material, and negative pole current potential is significantly declined, thus improves energy density.
A kind of lithium-ion capacitor is disclosed in patent CN200580001492.8, the plus plate current-collecting body that this lithium-ion capacitor uses and negative current collector all have the hole running through positive and negative, electrode layer is formed respectively by positive active material and negative electrode active material, carry out electrochemical contact by anticathode, in advance lithium ion is carried in negative pole.Disclose a kind of preprocess method of electrochemical capacitor negative pole in patent CN200780024069.6, on substrate, form lithium layer by vapor phase method or liquid phase method, then this lithium layer is transferred to the electrode layer of negative pole.The technics comparing that the method for these pre-doping relates to is complicated, and needs to carry out special processing to raw material, brings certain difficulty to manufacture process.
Utility model content
Technical problem to be solved in the utility model is, provide a kind of super lithium-ion capacitor, its operating voltage can reach 4.0V, and specific energy can reach 20WH/kg, and cycle life can reach 300,000 times.
In order to solve the problem, the utility model provides a kind of super lithium-ion capacitor, comprise positive pole, negative pole, barrier film and electrolyte, described positive pole comprises the first collector and is arranged at the activated carbon layer of described first collection liquid surface, described negative pole comprises the second collector and is arranged at the hard carbon layer of described second collection liquid surface, described barrier film is arranged between described positive pole and described negative pole, insulate to make described positive pole and described negative electricity, described electrolyte and described positive pole and described negative pole physical contact and electrical contact, exchange between described positive pole and described negative pole to allow ion, described super lithium-ion capacitor also comprises lithium lamella, described lithium lamella is between described hard carbon layer and described barrier film and be arranged on the surface of described hard carbon layer.
Further, the capacity of described lithium lamella active material is 10%-80% of the capacity of hard carbon active material.
Further, described lithium sheet cover part hard carbon layer surface or cover whole hard carbon layer surface.
Further, described first collector is aluminium foil, and described second collector is Copper Foil or described first collector is Copper Foil, and described second collector is aluminium foil.
Further, between described first collector and described activated carbon layer and between the second collector and described hard carbon layer, also conductive layer is respectively arranged with.
Further, the initial state-of-charge of described negative pole is 10% ~ 80%.
Further, described electrolyte comprises solute, solvent and additive, and described solute is lithium hexafluoro phosphate, and described solvent is cyclic carbonate and connects shape carbonic ester two lipoid composition, and described additive comprises film forming stabilizer, high-temperature stabiliser and the agent of high pressure over-charge protective.
Further, described barrier film adopts the one in polyethene microporous membrane, microporous polypropylene membrane, composite membrane, inorganic ceramic membrane, paper barrier film.
The utility model has the advantage of, the super lithium-ion capacitor positive active material of the utility model is active carbon, and negative electrode active material is hard carbon and lithium sheet, and preparation process is simple, and collector does not need through special processing, easily obtains.The operating voltage of the capacitor finally obtained can reach 4.0V, and specific energy can reach 25WH/kg, and cycle life can reach 300,000 times.
Accompanying drawing explanation
Fig. 1 is the structural representation of the super lithium-ion capacitor of the utility model;
Fig. 2 is the cycle-index of the super lithium-ion capacitor of the utility model and the curve chart of capability retention.
Embodiment
Elaborate below in conjunction with the embodiment of accompanying drawing to the super lithium-ion capacitor that the utility model provides.
See Fig. 1, the super lithium-ion capacitor of the utility model comprises positive pole 10, negative pole 20, barrier film 40 and electrolyte (not indicating in accompanying drawing).
Described positive pole 10 comprises the first collector 11 and is arranged at the activated carbon layer 12 on described first collector 11 surface.The active material of described activated carbon layer 12 is activated carbon, and activated carbon is coated on the first collector 11 after can mixing with binding agent, to form activated carbon layer 12 on the surface of described first collector 11.In this embodiment, described first collector 11 is Copper Foil.
Described negative pole 20 comprises the second collector 21 and is arranged at the hard carbon layer 22 on described second collector 21 surface.The active material of described hard carbon layer 22 is hard carbon.Hard carbon is coated on the second collector 21 after can mixing with binding agent, to form hard carbon layer 22 on the surface of described second collector 21.In this embodiment, described second collector 21 is aluminium foil.In other embodiments of the utility model, described first collector 11 is Copper Foil, then described second collector 21 is just aluminium foil, and described first collector 11 is aluminium foil, then described second collector 21 is just Copper Foil.
The ratio of the active material of the first carbonaceous active layer 12 of described positive pole 10 and the second carbonaceous active layer 22 of negative pole 20 is identical with the ratio of the active material of both positive and negative polarity in prior art, is not repeated herein.
Described barrier film 40 is arranged between described positive pole 10 and described negative pole 20, and described barrier film 40 is provided for described positive pole 10 and described negative pole 20 electric insulation, and described barrier film allows ion to pass through, and transmits between described positive pole 10 and described negative pole 20 to make ion.Described barrier film 40 comprises polyethene microporous membrane, microporous polypropylene membrane, composite membrane, inorganic ceramic membrane, paper barrier film, nonwoven fabrics barrier film for compact ultracapacitor, for the cellulosic separator etc. of huge super capacitor.In the utility model, the material of described barrier film 10 is not limited.
Described electrolyte and described positive pole 10 and described negative pole 20 physical contact and electrical contact.Described electrolyte is made up of solute, solvent and additive, and solute is lithium hexafluoro phosphate (LiPF
6), solvent is cyclic carbonate and linear carbonate two lipoid composition, and additive has into membrane stabilizer, low temperature and high-temperature stabiliser and the agent of high pressure over-charge protective etc.
Described cyclic carbonate comprises one or more in propylene carbonate (PC), vinyl carbonate (EC).Described chain carbonic ether comprises one or more in dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl ethyl carbonate fat (MPC).Described one-tenth membrane stabilizer is selected from vinylene carbonate fat (VC), vinyl acetate to (VA), pi-allyl ethyl carbonate ester (AEC), vinyl ethylene carbonate (VEC), carbon dioxide (CO
2), sulfur dioxide (SO
2), sulfurous acid ethene fat (ES), 1,2--trifluoroacetic acid base ethane (BTE), carbon disulfide (CS2) or lithium carbonate (LI
2cO
3) in one or more.Described high temperature protection agent is selected from one or more in di-oxalate lithium borate (LiBOB), dimethyl ethane amine (DMAC); The agent of described high pressure over-charge protective is selected from biphenyl (BP), ring ethylo benzene (CHB), coke acid esters, naphthalene, cyclohexane, cyclic ethylene, benzene, toluene, this base adamantane, adamantane, 1; one or more in 3,5--tricyano benzene, imidazole natrium, thianthrene, anthracene or butyl ferrocene.
Described super lithium-ion capacitor also comprises lithium lamella 30, and described lithium lamella 30 is between described hard carbon layer 22 and described barrier film 40 and be arranged on the surface of described hard carbon layer 22.Charge to super lithium-ion capacitor with certain electric current, make negative pole 20 have certain nuclear power state (SOC), the lithium now in lithium lamella is converted in Lithium-ion embeding hard carbon layer 22.Described lithium lamella 30 is arranged on the surface of hard carbon layer 22, can improve the specific energy of described super lithium-ion capacitor and improve the cyclical stability of super lithium-ion capacitor.Preferably, the capacity of the active material of described lithium lamella 30 is 10%-80% of capacity of the active material of hard carbon layer 22, so that provide sufficient lithium ion for described hard carbon layer 22.Further, described lithium lamella 30 cover part hard carbon layer 22 surface or cover whole hard carbon layer 22 surface.
Further, between described first collector 11 and described active carbon layer 12 and between the second collector 21 and described hard carbon layer 22, the first conductive layer 13 and the second conductive layer 23 is also respectively arranged with.Described first conductive layer 13 obviously reduces the contact resistance between the first collector 11 and active carbon layer 12, described second conductive layer 23 significantly reduces the contact resistance between the second collector 21 and hard carbon layer 22, strengthens the adhesive rate of described active carbon layer 12 and the first collector 11 and described hard carbon layer 22 and the second collector 21 simultaneously.
Further, the initial state-of-charge of described negative pole is 10% ~ 80%, and its advantage is, can be pre-formed electric double layer capacitance on negative pole 20.
The active material of the positive pole of the super lithium-ion capacitor of the utility model is active carbon, and the active material of negative pole is hard carbon and lithium sheet, and preparation process is simple, and collector does not need through special processing, easily obtains.The operating voltage of the capacitor finally obtained can reach 4.0V, and specific energy can reach 20WH/kg, and cycle life can reach 300,000 times.
See Fig. 2, the super lithium-ion capacitor of the utility model is after 8000 circulations, and capability retention also more than 90%, and does not have the trend of decay.Visible, super lithium-ion capacitor stable performance of the present utility model and specific capacity is high.
Enumerate several embodiments of the utility model super lithium-ion capacitor preparation method below.
Embodiment 1
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 8 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 20Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is EC and DMC; mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), the capacitor be assembled into.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 80%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 2
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 11 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 28Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte, wherein solvent is EC and DMC, and mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), is assembled into capacitor.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 80%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 3
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 13 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 32Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is EC and DMC; mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), the capacitor be assembled into.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 80%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 4
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 16 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 40Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is EC and DMC; mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), the capacitor be assembled into.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 80%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 5
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 11 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 32Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is EC and DMC; mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), the capacitor be assembled into.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 70%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 6
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 10 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 32Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is EC and DMC; mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), the capacitor be assembled into.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 60%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 7
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 8 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 32Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is EC and DMC; mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), the capacitor be assembled into.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 50%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 8
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 6 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 32Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is EC and DMC; mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), the capacitor be assembled into.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 40%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 9
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 4 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 32Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is EC and DMC; mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), the capacitor be assembled into.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 30%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 10
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 3 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 32Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is EC and DMC; mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), the capacitor be assembled into.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 20%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 11
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 2 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 32Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is EC and DMC; mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), the capacitor be assembled into.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 10%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 12
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 11 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 32Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is PC, DEC and EMC; mass fraction is 33.3 parts, additive for becoming membrane stabilizer vinyl acetate (VA), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), is assembled into capacitor monomer.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 70%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
Embodiment 13
The making of negative plate: be coated on Copper Foil by conductive layer slurry, thickness is 8 microns, and then hard carbon, conductive agent and binding agent mix according to the ratio of 90:5:5, and then furnishing slurry is coated on Copper Foil, and face amount is 4Ah/m
2, drying (80 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) are made into negative plate containing hard carbon layer.By the roll squeezer roll-in to 11 micron of lithium sheet in drying shed (dew point temperature≤-38 DEG C), be cut into the size the same with negative plate, be compressed on hard carbon layer surface.
The making of positive plate: conductive layer is starched equal refining and be coated on aluminium foil, thickness is 8 microns, then active carbon, conductive agent and adhesive are according to the ratio mixing furnishing slurry of 90:4:6, and be then coated on Copper Foil, face amount is 32Ah/m
2, drying (120 DEG C), roll, cut-parts, 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
Select polyethene microporous membrane to be barrier film, then inject 1mol/L LiPF
6electrolyte; wherein solvent is EC and DMC; mass fraction is 50 parts, additive for becoming membrane stabilizer vinylene carbonate (VC), high-temperature stabiliser is di-oxalate lithium borate (LiBOB), the agent of high pressure over-charge protective is biphenyl (BP), the capacitor be assembled into.
Charge to monomer with the electric current of 20mA, the state-of-charge (SOC) making negative pole is 70%, then is changed in Lithium-ion embeding negative pole hard carbon layer by the lithium sheet in negative pole, then carries out performance test to this capacitor.
As follows according to the performance test system of the ultracapacitor of the utility model making:
The work system of discharge capacity and energy density is (20 ~ 30 DEG C) under normal temperature, and 1A charges to 3.8V, constant voltage 1 minute, and 1A is discharged to 2.5V, and circulation 3 circle, calculates discharging electrostatic capacity and the energy density of each circle, average.The work system that cycle life adopts is (25 ~ 30 DEG C) under normal temperature, 2.5V-3.8V, 5A charge and discharge, and circulate 100000 end, calculates the discharge capacity retention of last lap.The chemical property that the capacitor obtained produced according to the present invention records is as shown in table 1.
The performance test of the organic electrolyte capacitor that table 1 the present invention makes
| Positive electrode capacity/capacity of negative plates | State-of-charge after the embedding lithium of negative pole | Static capacity | Energy density (Wh/kg) | 100000 capability retentions (%) | |
| Embodiment 1 | 1:5 | 80% | 206 | 25.5 | 82 |
| Embodiment 2 | 1:7 | 80% | 218 | 25 | 86 |
| Embodiment 3 | 1:8 | 80% | 238 | 25.2 | 89 |
| Embodiment 4 | 1:10 | 80% | 239 | 25.1 | 90 |
| Embodiment 5 | 1:8 | 70% | 235 | 24.8 | 89.9 |
| Embodiment 6 | 1:8 | 60% | 216 | 25.9 | 87 |
| Embodiment 7 | 1:8 | 50% | 209 | 26 | 87 |
| Embodiment 8 | 1:8 | 40% | 196 | 25.2 | 85 |
| Embodiment 9 | 1:8 | 30% | 184 | 25.4 | 82 |
| Embodiment 10 | 1:8 | 20% | 169 | 25.3 | 78 |
| Embodiment 11 | 1:8 | 10% | 152 | 25.9 | 73 |
| Embodiment 12 | 1:8 | 70% | 229 | 25.7 | 84 |
| Embodiment 13 | 1:8 | 70% | 232 | 25.1 | 85 |
The above is only preferred implementation of the present utility model; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the utility model principle; can also make some improvements and modifications, these improvements and modifications also should be considered as protection range of the present utility model.
Claims (6)
1. a super lithium-ion capacitor, comprise positive pole, negative pole, barrier film and electrolyte, it is characterized in that, described positive pole comprises the first collector and is arranged at the activated carbon layer of described first collection liquid surface, described negative pole comprises the second collector and is arranged at the hard carbon layer of described second collection liquid surface, described barrier film is arranged between described positive pole and described negative pole, insulate to make described positive pole and described negative electricity, described electrolyte and described positive pole and described negative pole physical contact and electrical contact, exchange between described positive pole and described negative pole to allow ion, described super lithium-ion capacitor also comprises lithium lamella, described lithium lamella is between described hard carbon layer and described barrier film and be arranged on the surface of described hard carbon layer.
2. super lithium-ion capacitor according to claim 1, is characterized in that, the capacity of described lithium lamella active material is 10%-80% of the capacity of hard carbon layer active material.
3. super lithium-ion capacitor according to claim 1, is characterized in that, described lithium lamella cover part hard carbon layer is surperficial or cover whole hard carbon layer surface.
4. super lithium-ion capacitor according to claim 1, is characterized in that, described first collector is aluminium foil, and described second collector is Copper Foil or described first collector is Copper Foil, and described second collector is aluminium foil.
5. super lithium-ion capacitor according to claim 1, is characterized in that, between described first collector and described activated carbon layer and between the second collector and described hard carbon layer, be also respectively arranged with conductive layer.
6. super lithium-ion capacitor according to claim 1, is characterized in that, described barrier film adopts the one in polyethene microporous membrane, microporous polypropylene membrane, composite membrane, inorganic ceramic membrane, paper barrier film.
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