CN105405679B - A kind of ternary oxide and hard carbon base hybrid super capacitor - Google Patents
A kind of ternary oxide and hard carbon base hybrid super capacitor Download PDFInfo
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- CN105405679B CN105405679B CN201510996357.4A CN201510996357A CN105405679B CN 105405679 B CN105405679 B CN 105405679B CN 201510996357 A CN201510996357 A CN 201510996357A CN 105405679 B CN105405679 B CN 105405679B
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Abstract
The invention belongs to capacitor and cell art, it is related to ultracapacitor, particularly a kind of ternary oxide and hard carbon base hybrid super capacitor, it is made up of positive pole, negative pole, the barrier film to fall between and organic electrolyte, its positive pole is using ternary metal oxide and the mixture of Large ratio surface electric double layer, negative pole is hard carbon, and electrolyte uses organic solvent and associated additives containing lithium ion.Electrochmical power source prepared by the present invention have high-energy-density (90~100Wh/Kg can be reached), high power density (>Characteristic 6500W/Kg), cycle life can be widely applied to the fields such as electric automobile, electric tool, solar energy storage, wind energy energy storage more than 30,000 times under 10C multiplying powers.
Description
[technical field]
The invention belongs to capacitor and cell art, is related to ultracapacitor, particularly organic mixed super electricity
Container.
[background technology]
Ultracapacitor is a kind of model electrochemical energy storage device between traditional capacitor and battery, and it is compared to biography
System capacitor has higher energy density, and static capacity can be up to thousand farads to ten thousand farads levels；There is higher work(compared to battery
The cycle life of rate density and overlength, therefore be that one kind has a extensive future the advantages of it combines traditional capacitor and battery
Electrochmical power source.It has the characteristics that specific capacity is high, power is big, long lifespan, the warm limit for width of work, non-maintaining.
According to the difference of energy storage principle, ultracapacitor can be divided into three classes：Double layer capacitor (EDLC), faraday are accurate
Electric capacity ultracapacitor and hybrid super capacitor, wherein double layer capacitor mainly utilize electrode/electrolyte interface electricity
Lotus separates formed electric double layer to realize the storage of electric charge and energy；Pseudo capacitance ultracapacitor is mainly by electricity
Faraday's " pseudo-capacitance " caused by the quick redox reaction in pole surface realizes the storage of electric charge and energy；And mixed type
Ultracapacitor is the unpolarized electrode (such as nickel hydroxide) that a pole uses battery, and another pole uses the polarization of double layer capacitor
Electrode (such as activated carbon), the design of this mixed type can increase substantially the energy density of ultracapacitor.
It is super that ultracapacitor by electrolyte point can be divided into inorganic electrolyte, organic bath, three kinds of polymer dielectric
Capacitor, wherein inorganic electrolyte apply more acidity (such as H for high concentration2SO4) or alkaline (such as KOH) the aqueous solution, in
Property aqueous electrolyte application it is less；Organic bath then typically uses quaternary amine or lithium salts and the organic solvent of high conductivity
(such as acetonitrile) forms mixed electrolytic solution, and nowadays polymer dielectric only rests on laboratory stage, there is no commercially produced product
Occur.
Ultracapacitor uses organic bath, the operating voltage of capacitor can be increased substantially, according to E=1/2CV2
Understand, be very helpful to improving capacitor energy density.Nowadays, ripe organic ultracapacitor is typically all using symmetrical
Type structure, i.e. both positive and negative polarity use identical Carbon Materials, and electrolyte is made up of ammonium salt and the organic solvent of high conductivity (such as acetonitrile),
The power density of this capacitor is very high, can reach 5000-6000W/Kg, but its energy density is relatively low, can only achieve 3-5Wh/
Kg, therefore, in order to further improve the energy density of organic ultracapacitor, people employ the structure design of mixed type, i.e.,
Both positive and negative polarity uses different active materials.In recent years, the research of organic mixed super capacitor is on the increase, and is occurred as just
Pole uses polythiophene using activated carbon, negative pole using lithium titanate and positive pole, and negative pole is using organic ultracapacitors such as lithium titanates.
In the patent of Application No. 200510110461.5, positive pole uses LiMn2-XMXO4, negative pole uses activated carbon, the ultracapacitor
Ratio energy reach as high as 50Wh/Kg (based on positive and negative electrode active material gross mass calculate).It is but such organic mixed
The energy density and power density of ultracapacitor are all undesirable.In the patent of Application No. 200710035205.3, positive pole
Using Lithium-ion embeding compound and the mixture and their compound of porous carbon material, negative pole uses porous carbon material and stone
The mixture and their compound of ink.The lithium ion ternary material LiNi that such ultracapacitor is used1/3Co1/3Mn1/3O2,
Theoretical capacity is 280mAh/g, but can only actually play 140~160mAh/g, exceeds 160mAh/g, can cause the material lattice
Collapse, invertibity is deteriorated, and cycle life is not high.In the patent of Application No. 201010114600.2, positive electrode using lithium from
The mixture of sub- inlaid scheme and porous carbon material, there is also same problem.In addition current high power lithium ion cell, big
Under multiplying power (more than 10C) charging, because the structure that Carbon anode comes is destroyed, Li dendrite separates out in negative terminal surface, causes negative pole reversible
Capacity reduces, and battery capacity decay is serious, and cycle life is deteriorated.
[content of the invention]
It is an object of the invention to solve above-mentioned technical problem, there is provided a kind of ternary oxide and hard carbon base hybrid super electricity
Container.
To achieve the above object, design a kind of ternary oxide and hard carbon base hybrid super capacitor, by positive pole, negative pole,
Barrier film and the electrolyte composition to fall between, it is characterised in that：
A positive poles：Using ternary metal oxide, Large ratio surface electric double layer material, conductive agent, binding agent mixture, institute
State ternary metal oxide and use Ni1/3Co1/3Mn1/3O2Or Ni1/3Co1/3Al1/3O2,
B negative poles：Using hard carbon, the mixture of binding agent, by pre-doping lithium ion to negative pole hard carbon,
C electrolyte, using the non-aqueous organic solvent containing lithium ion.
The Large ratio surface electric double layer material is made up of activated carbon or graphene or CNT or other equivalent materials, real
Existing electrochemical energy storage and electric double layer physics energy storage.
Heretofore described hard carbon refers to difficult graphitized carbon, typically with specific capacity high (reaching 300-700mAh/g), again
The characteristics of rate performance is good, while insertion of the lithium ion in this kind of material will not cause structure significantly to expand, and have and fill well
Discharge cycle performance, it includes resin carbon and organic polymer pyrolytic carbon, and the resin carbon includes phenolic resin carbon, epoxy
Resin carbon, poly furfuryl alcohol resin carbon, furfural resin carbon, and the organic polymer pyrolytic carbon include benzene carbon, poly furfuryl alcohol pyrolytic carbon,
Polyvinyl chloride pyrolytic carbon, phenolic aldehyde pyrolytic carbon.
Described conductive agent includes graphite powder, carbon black, acetylene black or their mixture with high conductivity, and institute
The binding agent stated is using polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF), hydroxypropyl methyl cellulose (HPMC), carboxymethyl
Cellulose receive (CMC) and butadiene-styrene rubber (SBR) in one or more.
Lithium salts in electrolyte of the present invention includes LiClO4、LiBF4、LiPF6、LiCF3SO3、LiN(CF3SO2)、
LiBOB、LiAsF6At least one of；Non-aqueous organic solvent includes ethylene carbonate, propene carbonate, gamma-butyrolacton, carbonic acid
Dimethyl ester, diethyl carbonate, butylene, methyl ethyl carbonate, methyl propyl carbonate, ethylene sulfite, propylene sulfite,
One or more in ethyl acetate, propyl acetate, methyl propionate, methyl acetate, acetonitrile.These Organic Electricities being made up of lithium salts
Solution liquid has high ionic conductivity, can provide quick passage for the migration of lithium ion in charge and discharge process, increase reaction
Speed；Have that electrochemically stable potential range wide (being stable between 0-5V), heat endurance be good, temperature in use model simultaneously
The features such as enclosing width so that the stability of ultracapacitor discharge and recharge reaction greatly improves, and is advantageous to carrying for capacitor cycle life-span
Rise.
Described barrier film includes polyethene microporous membrane (PE), microporous polypropylene membrane (PP), composite membrane (PP+PE+PP), inorganic
Ceramic membrane, paper barrier film, for its thickness typically at 10-50 μm, aperture has good absorption electrolyte at 0.03 μm -0.05 μm
Ability and high-temperature stability；The collector of described positive plate includes aluminium foil, aluminium net, and the collector of described negative plate includes copper
Paper tinsel, copper mesh
A kind of method for preparing ternary oxide and hard carbon base hybrid super capacitor, it is characterised in that including：
(1) preparation process of positive plate：First by ternary metal oxide, Large ratio surface electric double layer material, conductive agent, ball
Mill mixes in mass ratio, dissolves binding agent, the good mixture of ball milling is poured into the binder solution dissolved, is tuned into slurry, so
After be coated on plus plate current-collecting body, drying, roll, cut, being dried in vacuo and be prepared into positive plate；
(2) preparation process of negative plate：Hard carbon, binding agent are mixed in mass ratio first, slurry is tuned into, is then coated on
On negative current collector, drying, roll, cut, being dried in vacuo and be prepared into negative plate；
(3) number of assembling steps：The positive and negative plate prepared through lamination or is wound into battery core, is put into aluminum plastic film, aluminum hull or steel
In shell；The 3rd pole with lithium source is loaded into correct position, is easy to negative pole pre-doping；Then dry, fluid injection and pre- sealing；
(4) the pre- device sealed is subjected to pre-doping, completes to remove the 3rd pole after pre-doping, then sealing eventually,
Complete device.
The capacity of negative pole is 3.5~4 times of positive pole.
The present invention can be fabricated to the square ultracapacitor and cylinder of lamination or winding-structure according to practical situations
Type ultracapacitor, and the characteristic of high power, high-energy can be kept, its shell can use aluminum plastic film, box hat, aluminum hull.
By the present invention in that use Ni1/3Co1/3Mn1/3O2Or Ni1/3Co1/3Al1/3O2A part for positive electrode, realizes device
More than 4.5V operating voltage, and can reach unlimited number of Large ratio surface electric double layer material using cycle life on positive pole and make
For a part for blended anode material, the hard carbon material that specific capacity is high, power-performance is good is used on negative pole, so that super electricity
Container has high-energy-density, (energy density and power density are all according to actual ultracapacitor to the characteristic of high power density
Weight calculate), can be widely applied to the fields such as electric automobile, electric tool, solar energy storage, wind energy energy storage.
The present invention has a two big cores, and first, Ni is used on positive pole1/3Co1/3Mn1/3O2Or Ni1/3Co1/3Al1/3O2, can make
Hybrid capacitors maximum operating voltage is equal in 4.5V greatly, avoids LiNi1/3Co1/3Mn1/3O2And LiNi1/3Co1/3Al1/3O2Hair
Wave and collapsed close to lattice during theoretical capacity, cause the phenomenon of life-span deep fades, while positive pole of the present invention adds Large ratio surface
Electric double layer energy storage material, greatly improve big the multiplying power charge and discharge characteristic and cycle life of device.
Second, it is that the hard carbon material that specific capacity is high, power-performance is good is used on negative pole, and make the capacity of negative pole larger
Excessive, the Capacity Ratio of negative pole and positive pole makes hybrid capacitors in 100%DOD (depth of discharge) negative electrode active at 3.5~4 times
Material is in relatively low DOD (28.6%~25%), greatly prolongs the life-span of negative pole；
Above two core technology makes device keep ultracapacitor high power, have extended cycle life, pollution-free, high safety
Property, on the premise of the characteristic such as non-maintaining, increase substantially the energy density of ultracapacitor, further shorten ultracapacitor with
The gap of lithium ion battery.
[embodiment]
Below by embodiment, the present invention is further illustrated：
The main raw material(s) used in embodiment is as follows：
Ni1/3Co1/3Mn1/3O2
Ni1/3Co1/3Al1/3O2
Activated carbon
Graphene
CNT
Hard carbon
PVDF (Kynoar)
NMP (1-Methyl-2-Pyrrolidone)
Conductive black Super-P
Three layers of composite diaphragm
Embodiment 1：
The making of positive plate：By the Ni that total amount is 1000g1/3Co1/3Mn1/3O2, activated carbon, conductive black, PVDF press quality
Than for 45：45:5:5 mixing, are tuned into slurry with NMP, are then coated on 20 μm of aluminium foil with holes (coated face capacity：15Ah/m2)
On, drying (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C)
It is fabricated to positive plate.
The making of negative plate：It is 90 in mass ratio by hard carbon that total amount is 1000g, PVDF：10 mixing, are slurred with NMP
Material, then it is coated with (coated face capacity on 16 μm of copper foil with holes：52.5Ah/m2, capacity of negative plates is 3.5 times of positive pole), through drying
Dry (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C) be fabricated to it is negative
Pole piece.It is barrier film from three layers of composite diaphragm, positive plate (8), barrier film, negative plate (9) is laminated into battery core, then will be folded
The positive pole pole group of good battery core is welded on aluminum lug, negative pole pole group is welded on nickel lug, and the battery core after welding is put into
In the good aluminum plastic film of type, the lithium piece for welding nickel lug is added as the 3rd pole, for pre-doping, and injects 1mol/L LiPF6—
EC (ethylene carbonate)/DEC (diethyl carbonate) (1：1) 6g, sealing, is assembled into square hybrid capacitors.Mixed type electric capacity
By pre-doping, (i.e. negative pole and the electric discharge of lithium piece the two poles of the earth, discharge capacity are the design capacity 15Ah/m of positive pole to device2, specific how many
Converted according to the real area of positive pole), remove the 3rd unnecessary pole, eventually sealing, open-circuit voltage 4.5V, performance survey is carried out to device
Examination, work system are that 10C charges to 4.5V, stand 1min, 10C is discharged to 2.5V, and the ratio energy of device is 92Wh/Kg, compares work(
Rate is 7500W/Kg, and after 10C charge and discharges circulate 10000 times, capability retention is 95%.
Embodiment 2：
By the Ni that total amount is 1000g1/3Co1/3Al1/3O2, activated carbon, conductive black, PVDF in mass ratio be 45：45:5:5
Mixing, is tuned into slurry with NMP, is then coated on 20 μm of aluminium foil with holes (coated face capacity：15Ah/m2) on, drying (110
~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C) be fabricated to positive plate.
The making of negative plate：It is 90 in mass ratio by hard carbon that total amount is 1000g, PVDF：10 mixing, are slurred with NMP
Material, then it is coated with (coated face capacity on 16 μm of copper foil with holes：52.5Ah/m2, capacity of negative plates is 3.5 times of positive pole), through drying
Dry (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C) be fabricated to it is negative
Pole piece.It is barrier film from three layers of composite diaphragm, positive plate (8), barrier film, negative plate (9) is laminated into battery core, then will be folded
The positive pole pole group of good battery core is welded on aluminum lug, negative pole pole group is welded on nickel lug, and the battery core after welding is put into
In the good aluminum plastic film of type, the lithium piece for welding nickel lug is added as the 3rd pole, for pre-doping, and injects 1mol/L LiPF6—
EC (ethylene carbonate)/DEC (diethyl carbonate) (1：1) 6g, sealing, is assembled into square hybrid capacitors.Mixed type electric capacity
By pre-doping, (i.e. negative pole and the electric discharge of lithium piece the two poles of the earth, discharge capacity are the design capacity 15Ah/m of positive pole to device2, specific how many
Converted according to the real area of positive pole), remove the 3rd unnecessary pole, eventually sealing, open-circuit voltage 4.7V, performance survey is carried out to device
Examination, work system are that 10C charges to 4.7V, stand 1min, 10C is discharged to 2.5V, and the ratio energy of device is 99Wh/Kg, compares work(
Rate is 8500W/Kg, and after 10C charge and discharges circulate 10000 times, capability retention is 87%.
Embodiment 3：
The making of positive plate：By the Ni that total amount is 1000g1/3Co1/3Mn1/3O2, activated carbon, conductive black, PVDF press quality
Than for 45：45:5:5 mixing, are tuned into slurry with NMP, are then coated on 20 μm of aluminium foil with holes (coated face capacity：15Ah/m2)
On, drying (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C)
It is fabricated to positive plate.
The making of negative plate：It is 90 in mass ratio by hard carbon that total amount is 1000g, PVDF：10 mixing, are slurred with NMP
Material, then it is coated with (coated face capacity on 16 μm of copper foil with holes：60Ah/m2, capacity of negative plates is 3.5 times of positive pole), drying
(110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h is dried in vacuo (120~130 DEG C) and is fabricated to negative pole
Piece.It is barrier film from three layers of composite diaphragm, positive plate (8), barrier film, negative plate (9) is laminated into battery core, then will be folded
Battery core positive pole pole group be welded on aluminum lug, negative pole pole group is welded on nickel lug, the battery core after welding is put into shaping
In good aluminum plastic film, the lithium piece for welding nickel lug is added as the 3rd pole, for pre-doping, and injects 1mol/L LiPF6—EC
(ethylene carbonate)/DEC (diethyl carbonate) (1：1) 6g, sealing, is assembled into square hybrid capacitors.Hybrid capacitors
By pre-doping, (i.e. negative pole and the electric discharge of lithium piece the two poles of the earth, discharge capacity are the design capacity 15Ah/m of positive pole2, specific how many basis
The real area conversion of positive pole), remove the 3rd unnecessary pole, eventually sealing, open-circuit voltage 4.5V, performance survey is carried out to device
Examination, work system are that 10C charges to 4.5V, stand 1min, 10C is discharged to 2.5V, and the ratio energy of device is 90Wh/Kg, compares work(
Rate is 7000W/Kg, and after 10C charge and discharges circulate 10000 times, capability retention is 98%.
Embodiment 4：
By the Ni that total amount is 1000g1/3Co1/3Al1/3O2, activated carbon, conductive black, PVDF in mass ratio be 45：45:5:5
Mixing, is tuned into slurry with NMP, is then coated on 20 μm of aluminium foil with holes (coated face capacity：15Ah/m2) on, drying (110
~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C) be fabricated to positive plate.
The making of negative plate：It is 90 in mass ratio by hard carbon that total amount is 1000g, PVDF：10 mixing, are slurred with NMP
Material, then it is coated with (coated face capacity on 16 μm of copper foil with holes：60Ah/m2, capacity of negative plates is 3.5 times of positive pole), drying
(110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C) be fabricated to negative pole
Piece.It is barrier film from three layers of composite diaphragm, positive plate (8), barrier film, negative plate (9) is laminated into battery core, then will be folded
Battery core positive pole pole group be welded on aluminum lug, negative pole pole group is welded on nickel lug, the battery core after welding is put into shaping
In good aluminum plastic film, the lithium piece for welding nickel lug is added as the 3rd pole, for pre-doping, and injects 1mol/L LiPF6—EC
(ethylene carbonate)/DEC (diethyl carbonate) (1：1) 6g, sealing, is assembled into square hybrid capacitors.Hybrid capacitors
By pre-doping, (i.e. negative pole and the electric discharge of lithium piece the two poles of the earth, discharge capacity are the design capacity 15Ah/m of positive pole2, specific how many basis
The real area conversion of positive pole), remove the 3rd unnecessary pole, eventually sealing, open-circuit voltage 4.7V, performance survey is carried out to device
Examination, work system are that 10C charges to 4.7V, stand 1min, 10C is discharged to 2.5V, and the ratio energy of device is 94Wh/Kg, compares work(
Rate is 8000W/Kg, and after 10C charge and discharges circulate 10000 times, capability retention is 90%.
Comparative example 5：
The making of positive plate：By the LiNi that total amount is 1000g1/3Co1/3Mn1/3O, activated carbon, conductive black, PVDF press matter
Amount is than being 45：45:5:5 mixing, are tuned into slurry with NMP, are then coated on 20 μm of aluminium foil with holes (coated face capacity：15Ah/
m2) on, drying (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130
DEG C) it is fabricated to positive plate.
The making of negative plate：It is 90 in mass ratio by hard carbon that total amount is 1000g, PVDF：10 mixing, are slurred with NMP
Material, then it is coated with (coated face capacity on 16 μm of copper foil with holes：60Ah/m2, capacity of negative plates is 3.5 times of positive pole), drying
(110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C) be fabricated to negative pole
Piece.It is barrier film from three layers of composite diaphragm, positive plate (8), barrier film, negative plate (9) is laminated into battery core, then will be folded
Battery core positive pole pole group be welded on aluminum lug, negative pole pole group is welded on nickel lug, the battery core after welding is put into shaping
In good aluminum plastic film, the lithium piece for welding nickel lug is added as the 3rd pole, for pre-doping, and injects 1mol/L LiPF6—EC
(ethylene carbonate)/DEC (diethyl carbonate) (1：1) 6g, sealing, is assembled into square electrochmical power source.Open-circuit voltage is 0V, device
After being melted into (i.e. the activation of capacitor performance), performance test is carried out, work system is that 10C charges to 4.2V, stands 5min,
10C is discharged to 2.5V, and the ratio energy of capacitor is 73Wh/Kg, specific power 5288W/Kg, is circulated 10000 times by 10C charge and discharges
Afterwards, capability retention is 78%；Work system is that 10C charges to 4.5V, stands 5min, 10C is discharged to 2.5V, the ratio of capacitor
Energy is 91Wh/Kg, specific power 6288W/Kg, and after 10C charge and discharges circulate 10000 times, capability retention is 38%；
Comparative example 6：
The making of positive plate：By the LiNi that total amount is 1000g1/3Co1/3Mn1/3O, activated carbon, conductive black, PVDF press matter
Amount is than being 45：45:5:5 mixing, are tuned into slurry with NMP, are then coated on 20 μm of aluminium foil with holes (coated face capacity：15Ah/
m2) on, drying (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130
DEG C) it is fabricated to positive plate.
The making of negative plate：It is 90 in mass ratio by hard carbon that total amount is 1000g, PVDF：10 mixing, are slurred with NMP
Material, then it is coated with (coated face capacity on 16 μm of copper foil with holes：60Ah/m2, capacity of negative plates is 3.5 times of positive pole), drying
(110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C) be fabricated to negative pole
Piece.It is barrier film from three layers of composite diaphragm, positive plate (8), barrier film, negative plate (9) is laminated into battery core, then will be folded
Battery core positive pole pole group be welded on aluminum lug, negative pole pole group is welded on nickel lug, the battery core after welding is put into shaping
In good aluminum plastic film, the lithium piece for welding nickel lug is added as the 3rd pole, for pre-doping, and injects 1mol/L LiPF6—EC
(ethylene carbonate)/DEC (diethyl carbonate) (1：1) 6g, sealing, hybrid capacitors pass through pre-doping (i.e. negative pole and lithium piece
The two poles of the earth are discharged, and discharge capacity is the design capacity 15Ah/m of positive pole2, specifically how much converted according to the real area of positive pole), remove
The 3rd unnecessary pole, sealing, is assembled into square electrochmical power source eventually.Open-circuit voltage is 2.8V, and device is through being melted into (i.e. capacitor performance
Activation) after, carry out performance test, work system is that 10C charges to 4.2V, stands 5min, 10C is discharged to 2.5V, capacitor
Ratio energy be 70Wh/Kg, specific power 5378W/Kg, after 10C charge and discharges circulate 10000 times, capability retention is 80%；
Work system is that 10C charges to 4.5V, stands 5min, and 10C is discharged to 2.5V, and the ratio energy of capacitor is 90Wh/Kg, specific power
For 6476W/Kg, after 10C charge and discharges circulate 10000 times, capability retention is 42%；
Comparative example 7：
The making of positive plate：By the Ni that total amount is 1000g1/3Co1/3Mn1/3O2, activated carbon, conductive black, PVDF press quality
Than for 45：45:5:5 mixing, are tuned into slurry with NMP, are then coated on 20 μm of aluminium foil with holes (coated face capacity：15Ah/m2)
On, drying (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C)
It is fabricated to positive plate.
The making of negative plate：It is 90 in mass ratio by hard carbon that total amount is 1000g, PVDF：10 mixing, are slurred with NMP
Material, then it is coated with (coated face capacity on 16 μm of copper foil with holes：45Ah/m2, capacity of negative plates is 3 times of positive pole), drying
(110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C) be fabricated to negative pole
Piece.It is barrier film from three layers of composite diaphragm, positive plate (8), barrier film, negative plate (9) is laminated into battery core, then will be folded
Battery core positive pole pole group be welded on aluminum lug, negative pole pole group is welded on nickel lug, the battery core after welding is put into shaping
In good aluminum plastic film, the lithium piece for welding nickel lug is added as the 3rd pole, for pre-doping, and injects 1mol/L LiPF6—EC
(ethylene carbonate)/DEC (diethyl carbonate) (1：1) 6g, sealing, is assembled into square hybrid capacitors.Hybrid capacitors
By pre-doping, (i.e. negative pole and the electric discharge of lithium piece the two poles of the earth, discharge capacity are the design capacity 15Ah/m of positive pole2, specific how many basis
The real area conversion of positive pole), remove the 3rd unnecessary pole, eventually sealing, open-circuit voltage 4.5V, performance survey is carried out to device
Examination, work system are that 10C charges to 4.5V, stand 1min, 10C is discharged to 2.5V, and the ratio energy of device is 95Wh/Kg, compares work(
Rate is 7600W/Kg, and after 10C charge and discharges circulate 10000 times, capability retention is 65%.
Embodiment 8：
The making of positive plate：By the Ni that total amount is 1000g1/3Co1/3Mn1/3O2, activated carbon, conductive black, PVDF press quality
Than for 45：45:5:5 mixing, are tuned into slurry with NMP, are then coated on 20 μm of aluminium foil with holes (coated face capacity：15Ah/m2)
On, drying (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C)
It is fabricated to positive plate.
The making of negative plate：It is 90 in mass ratio by hard carbon that total amount is 1000g, PVDF：10 mixing, are slurred with NMP
Material, then it is coated with (coated face capacity on 16 μm of copper foil with holes：75Ah/m2, capacity of negative plates is 3 times of positive pole), drying
(110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C) be fabricated to negative pole
Piece.It is barrier film from three layers of composite diaphragm, positive plate (8), barrier film, negative plate (9) is laminated into battery core, then will be folded
Battery core positive pole pole group be welded on aluminum lug, negative pole pole group is welded on nickel lug, the battery core after welding is put into shaping
In good aluminum plastic film, the lithium piece for welding nickel lug is added as the 3rd pole, for pre-doping, and injects 1mol/L LiPF6—EC
(ethylene carbonate)/DEC (diethyl carbonate) (1：1) 6g, sealing, is assembled into square hybrid capacitors.Hybrid capacitors
By pre-doping, (i.e. negative pole and the electric discharge of lithium piece the two poles of the earth, discharge capacity are the design capacity 15Ah/m of positive pole2, specific how many basis
The real area conversion of positive pole), remove the 3rd unnecessary pole, eventually sealing, open-circuit voltage 4.5V, performance survey is carried out to device
Examination, work system are that 10C charges to 4.5V, stand 1min, 10C is discharged to 2.5V, and the ratio energy of device is 87Wh/Kg, compares work(
Rate is 6800W/Kg, and after 10C charge and discharges circulate 10000 times, capability retention is 67%.
Embodiment 9：
The making of positive plate：By the Ni that total amount is 1000g1/3Co1/3Mn1/3O2, activated carbon, conductive black, PVDF press quality
Than for 80：10:5:5 mixing, are tuned into slurry with NMP, are then coated on 20 μm of aluminium foil with holes (coated face capacity：15Ah/m2)
On, drying (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C)
It is fabricated to positive plate.
The making of negative plate：It is 92 in mass ratio by hard carbon that total amount is 1000g, PVDF：8 mixing, are slurred with NMP
Material, then it is coated with (coated face capacity on 16 μm of copper foil with holes：52.5Ah/m2, capacity of negative plates is 3.5 times of positive pole), through drying
Dry (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C) be fabricated to it is negative
Pole piece.It is barrier film from three layers of composite diaphragm, positive plate (8), barrier film, negative plate (9) is laminated into battery core, then will be folded
The positive pole pole group of good battery core is welded on aluminum lug, negative pole pole group is welded on nickel lug, and the battery core after welding is put into
In the good aluminum plastic film of type, the lithium piece for welding nickel lug is added as the 3rd pole, for pre-doping, and injects 1mol/L LiPF6—
EC (ethylene carbonate)/DEC (diethyl carbonate) (1：1) 6g, sealing, is assembled into square hybrid capacitors.Mixed type electric capacity
By pre-doping, (i.e. negative pole and the electric discharge of lithium piece the two poles of the earth, discharge capacity are the design capacity 15Ah/m of positive pole to device2, specific how many
Converted according to the real area of positive pole), remove the 3rd unnecessary pole, eventually sealing, open-circuit voltage 4.5V, performance survey is carried out to device
Examination, work system are that 10C charges to 4.5V, stand 1min, 10C is discharged to 2.5V, and the ratio energy of device is 98Wh/Kg, compares work(
Rate is 7400W/Kg, and after 10C charge and discharges circulate 10000 times, capability retention is 89%.
Embodiment 10
The making of positive plate：By the Ni that total amount is 1000g1/3Co1/3Mn1/3O2, activated carbon, conductive black, PVDF press quality
Than for 20：70:5:5 mixing, are tuned into slurry with NMP, are then coated on 20 μm of aluminium foil with holes (coated face capacity：15Ah/m2)
On, drying (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C)
It is fabricated to positive plate.
The making of negative plate：It is 95 in mass ratio by hard carbon that total amount is 1000g, PVDF：5 mixing, are slurred with NMP
Material, then it is coated with (coated face capacity on 16 μm of copper foil with holes：52.5Ah/m2, capacity of negative plates is 3.5 times of positive pole), through drying
Dry (110~120 DEG C), roll, (size is for cut-parts：37.5*59.5mm2), 24h vacuum drying (120~130 DEG C) be fabricated to it is negative
Pole piece.It is barrier film from three layers of composite diaphragm, positive plate (8), barrier film, negative plate (9) is laminated into battery core, then will be folded
The positive pole pole group of good battery core is welded on aluminum lug, negative pole pole group is welded on nickel lug, and the battery core after welding is put into
In the good aluminum plastic film of type, the lithium piece for welding nickel lug is added as the 3rd pole, for pre-doping, and injects 1mol/L LiPF6—
EC (ethylene carbonate)/DEC (diethyl carbonate) (1：1) 6g, sealing, is assembled into square hybrid capacitors.Mixed type electric capacity
By pre-doping, (i.e. negative pole and the electric discharge of lithium piece the two poles of the earth, discharge capacity are the design capacity 15Ah/m of positive pole to device2, specific how many
Converted according to the real area of positive pole), remove the 3rd unnecessary pole, eventually sealing, open-circuit voltage 4.5V, performance survey is carried out to device
Examination, work system are that 10C charges to 4.5V, stand 1min, 10C is discharged to 2.5V, and the ratio energy of device is 90Wh/Kg, compares work(
Rate is 9000W/Kg, and after 10C charge and discharges circulate 10000 times, capability retention is 96%.
Ni as can be seen from the above embodiments1/3Co1/3Mn1/3O2Or Ni1/3Co1/3Al1/3O2For positive pole, it is subject to Large ratio surface
Electric double layer material is compound, and negative pole is hard carbon, and after negative pole pre-doping lithium ion, lithium ion reversible both positive and negative polarity reaction or absorption are real
Now it is more than or equal to 4.5V operating voltage energy storage.
Comparative example shows Ni1/3Co1/3Mn1/3O2With LiNi1/3Co1/3Mn1/3Compared to the negative pole as mixed capacitor
With higher operating voltage.Comparative example shows that both positive and negative polarity is larger with the aging effects for comparing the series capacitors, for
Between suitable both positive and negative polarity proportioning of the invention is 3.5~4.
Above said content is only the basic explanation under present inventive concept, and is appointed according to what technical scheme was made
What equivalent transformation, all should belong to protection scope of the present invention.
Claims (10)
1. a kind of ternary oxide and hard carbon base hybrid super capacitor, by positive pole, negative pole, the barrier film and electricity to fall between
Solve liquid composition, it is characterised in that：
A positive poles：Using ternary metal oxide, Large ratio surface electric double layer material, conductive agent, binding agent mixture, described three
First metal oxide uses Ni1/3Co1/3Mn1/3O2Or Ni1/3Co1/3Al1/3O2,
B negative poles：Using hard carbon, the mixture of binding agent, by pre-doping lithium ion to negative pole hard carbon,
C electrolyte, using the non-aqueous organic solvent containing lithium ion.
A kind of 2. ternary oxide and hard carbon base hybrid super capacitor as claimed in claim 1, it is characterised in that：Quality
Than ternary metal oxide：Large ratio surface electric double layer material：Conductive agent：Binding agent=(20-80)：(70-10):5:5.
A kind of 3. ternary oxide and hard carbon base hybrid super capacitor as claimed in claim 2, it is characterised in that：It is described big
It is made up than surface electric double layer material of activated carbon or graphene or CNT.
A kind of 4. ternary oxide and hard carbon base hybrid super capacitor as claimed in claim 1, it is characterised in that：Quality
Than hard carbon：Binding agent=(90-95)：(10-5).
A kind of 5. ternary oxide and hard carbon base hybrid super capacitor as claimed in claim 4, it is characterised in that：
The hard carbon uses difficult graphitized carbon, including resin carbon and organic polymer pyrolytic carbon, and the resin carbon includes phenolic aldehyde tree
Fat carbon, epoxy resin carbon, poly furfuryl alcohol resin carbon, furfural resin carbon, and the organic polymer pyrolytic carbon includes benzene carbon, poly- chaff
Alcohol pyrolytic carbon, polyvinyl chloride pyrolytic carbon, phenolic aldehyde pyrolytic carbon.
A kind of 6. ternary oxide and hard carbon base hybrid super capacitor as claimed in claim 1, it is characterised in that：
Described conductive agent includes graphite powder, carbon black, acetylene black or their mixture, and described binding agent includes poly- four
One or more in PVF, Kynoar, hydroxypropyl methyl cellulose, CMC and butadiene-styrene rubber.
A kind of 7. ternary oxide and hard carbon base hybrid super capacitor as claimed in claim 1, it is characterised in that：
Lithium ion in described electrolyte is by LiClO4、LiBF4、LiPF6、LiCF3SO3、LiN(CF3SO2)、LiBOB、LiAsF6
At least one of produce, and the non-aqueous organic solvent in described electrolyte include ethylene carbonate, propene carbonate,
Gamma-butyrolacton, dimethyl carbonate, diethyl carbonate, butylene, methyl ethyl carbonate, methyl propyl carbonate, sulfurous acid ethene
One or more in ester, propylene sulfite, ethyl acetate, propyl acetate, methyl propionate, methyl acetate, acetonitrile.
A kind of 8. ternary oxide and hard carbon base hybrid super capacitor as claimed in claim 1, it is characterised in that：
Described barrier film includes polyethene microporous membrane, microporous polypropylene membrane, polypropylene+polyethylene+polyacrylic composite membrane, inorganic
Ceramic membrane, paper barrier film, its thickness is typically at 10-50 μm, and aperture is at 0.03 μm -0.05 μm；The collector bag of described positive plate
Aluminium foil, aluminium net are included, the collector of described negative plate includes copper foil, copper mesh.
9. a kind of method for preparing ternary oxide according to claim 1 and hard carbon base hybrid super capacitor, its feature
It is, including：
(1) preparation process of positive plate：Ternary metal oxide, Large ratio surface electric double layer material, conductive agent, ball milling are pressed first
Mass ratio mixes, and dissolves binding agent, the good mixture of ball milling is poured into the binder solution dissolved, slurry is tuned into, then applies
Cloth drying, is rolled, cut, being dried in vacuo and be prepared into positive plate on plus plate current-collecting body；
(2) preparation process of negative plate：Hard carbon, binding agent are mixed in mass ratio first, slurry is tuned into, is then coated on negative pole
On collector, drying, roll, cut, being dried in vacuo and be prepared into negative plate；
(3) number of assembling steps：The positive and negative plate prepared through lamination or is wound into battery core, is put into aluminum plastic film, aluminum hull or box hat
In；The 3rd pole with lithium source is loaded into correct position, is easy to negative pole pre-doping；Then dry, fluid injection and pre- sealing；
(4) the pre- device sealed is subjected to pre-doping, completes to remove the 3rd pole after pre-doping, then sealing eventually, is completed
Device.
10. method as claimed in claim 9, it is characterised in that：The capacity of negative pole is 3.5~4 times of positive pole.
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| CN1773639A (en) * | 2005-11-17 | 2006-05-17 | 复旦大学 | Non-water body electrochemical mixed capacitor with lithium ion battery material as positive pole |
| CN101079510A (en) * | 2007-06-25 | 2007-11-28 | 中南大学 | A super capacitance cell |
| CN101281822A (en) * | 2008-05-15 | 2008-10-08 | 上海奥威科技开发有限公司 | Inorganic mixed type lithium ion super capacitor |
| CN101409154A (en) * | 2008-09-24 | 2009-04-15 | 上海奥威科技开发有限公司 | Organic mixed super capacitor |
| CN101847516A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Capacitor battery of high-specific-energy organic system |
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|---|---|---|---|---|
| CN1773639A (en) * | 2005-11-17 | 2006-05-17 | 复旦大学 | Non-water body electrochemical mixed capacitor with lithium ion battery material as positive pole |
| CN101079510A (en) * | 2007-06-25 | 2007-11-28 | 中南大学 | A super capacitance cell |
| CN101281822A (en) * | 2008-05-15 | 2008-10-08 | 上海奥威科技开发有限公司 | Inorganic mixed type lithium ion super capacitor |
| CN101409154A (en) * | 2008-09-24 | 2009-04-15 | 上海奥威科技开发有限公司 | Organic mixed super capacitor |
| CN101847516A (en) * | 2010-02-26 | 2010-09-29 | 上海奥威科技开发有限公司 | Capacitor battery of high-specific-energy organic system |
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