CN104616901A - Sodium ion super capacitor and preparation method thereof - Google Patents

Sodium ion super capacitor and preparation method thereof Download PDF

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Publication number
CN104616901A
CN104616901A CN201510042208.4A CN201510042208A CN104616901A CN 104616901 A CN104616901 A CN 104616901A CN 201510042208 A CN201510042208 A CN 201510042208A CN 104616901 A CN104616901 A CN 104616901A
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China
Prior art keywords
sodium ion
sodium
negative
ultracapacitor
positive
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CN201510042208.4A
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Chinese (zh)
Inventor
安仲勋
黄廷立
吴明霞
颜亮亮
许检红
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Shanghai Runtong Electric Vehicle Technology Co Ltd
Shanghai Aowei Technology Development Co Ltd
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Shanghai Runtong Electric Vehicle Technology Co Ltd
Shanghai Aowei Technology Development Co Ltd
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Priority to CN201510042208.4A priority Critical patent/CN104616901A/en
Publication of CN104616901A publication Critical patent/CN104616901A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a sodium ion super capacitor. The sodium ion super capacitor consists of a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode and electrolyte. The sodium ion super capacitor is characterized in that the negative electrode is made of active carbon, the negative electrode is made of a negative electrode material of a sodium ion battery; the electrolyte adopts non-aqueous organic electrolyte containing sodium ions. The sodium ion super capacitor is low in utilization cost, the rich sodium ions transfer between positive and negative electrodes to realize a charging and discharging principle of a capacitor to prepare the novel sodium ion super capacitor. The prepared novel sodium ion super capacitor has characteristics of being high in energy density and high in power density, and can be widely applied to the fields of electric vehicles, electronic tools, solar energy storage, and wind energy storage.

Description

A kind of sodium ion ultracapacitor and preparation method thereof
Technical field
The present invention relates to a kind of sodium ion ultracapacitor and preparation method thereof.
Background technology
Ultracapacitor is a kind of model electrochemical energy storage device between traditional capacitor and battery, and it compares traditional capacitor higher energy density, and static capacity can reach thousand farads to ten thousand farads levels; Comparing battery and have higher power density and the cycle life of overlength, therefore it combines the advantage of traditional capacitor and battery, is a kind of chemical power source had a extensive future.It has that specific capacity is high, power is large, the life-span is long, the warm limit for width that works, the feature such as non-maintaining.
According to the difference of energy storage principle, ultracapacitor can be divided three classes: double electric layer capacitor (EDLC), pseudo capacitance ultracapacitor and hybrid super capacitor, wherein double electric layer capacitor mainly utilize electrode/electrolyte interface separation of charge to be formed electric double layer to realize the storage of electric charge and energy; Pseudo capacitance ultracapacitor mainly realizes the storage of electric charge and energy by electrode surface faraday's " pseudo-capacitance " that redox reaction produces fast; And hybrid super capacitor is the unpolarized electrode (as nickel hydroxide) that a pole adopts battery, another pole adopts the polarizing electrode (as activated carbon) of double electric layer capacitor, and the design of this mixed type can increase substantially the energy density of ultracapacitor.
One of current hybrid super capacitor as extensively using at present, lithium-ion capacitor is used in every field widely.But lithium is as rare metal, its resource storage capacity is limited, will be restricted in final a large amount of use procedure.Be subject to the inspiration of lithium-ion capacitor, enrich storage capacity simultaneously due to sodium element, sodium ion capacitor will come into one's own.
Summary of the invention
The object of the invention is to utilize the transfer of with low cost, resourceful sodium ion between both positive and negative polarity to realize the principle of the discharge and recharge of capacitor, prepare novel sodium ion ultracapacitor, to meet the needs of association area development.
The present invention discloses a kind of sodium ion ultracapacitor, is made up of positive pole, negative pole, marginal barrier film and electrolyte; It is characterized in that: described positive pole adopts active carbon, negative pole adopts the negative material of sodium-ion battery, and electrolyte adopts the non-water organic electrolyte containing sodium ion.
Further, described active carbon is the high specific surface area porous charcoal of double electric layer capacitor.
Further, the negative material of described sodium-ion battery comprises: amorphous hard charcoal, sodium titanate (Na 2ti 3o 7), lithium titanate (Li 4ti 5o 12) etc. the one in sodium ion secondary battery negative material.
Further, described negative material is 30% ~ 80% by the initial state-of-charge of pre-doping sodium ion.
Further, it is characterized in that solute in described electrolyte is by sodium perchlorate (NaClO 4), sodium tetrafluoroborate (NaBF 4), sodium hexafluoro phosphate (NaPF 6), trifluoromethyl sulfonate (NaCF 3sO 3), two (trimethyl fluoride sulfonyl) imines sodium (NaN (CF 3sO 2) 2), two oxalic acid Boratex (NaBOB), hexafluoroarsenate sodium (NaAsF 6) at least one produce; Solvent in described electrolyte comprises one or more in ethylene carbonate, propene carbonate, gamma-butyrolacton, dimethyl carbonate, diethyl carbonate, butylene, methyl ethyl carbonate, methyl propyl carbonate, ethylene sulfite, propylene sulfite, ethyl acetate, acetonitrile.
Further, it is characterized in that described barrier film comprises polyethene microporous membrane, microporous polypropylene membrane, composite membrane, inorganic ceramic membrane, paper barrier film.
The present invention discloses a kind of preparation method of sodium ion ultracapacitor, it is characterized in that the battery core preparation of described sodium ion capacitor mainly comprises the following steps:
(1) preparation process of positive plate: first by the ball milling mixing by a certain percentage of active carbon, conductive agent, dissolve binding agent, pour mixture good for ball milling into dissolved binder solution in proportion, furnishing slurry, then be coated on plus plate current-collecting body, drying, roll, cut, vacuumize is prepared into positive plate;
(2) preparation process of negative plate: first by negative material, binding agent mixing, furnishing slurry, is then coated on negative current collector, drying, roll, cut, vacuumize is prepared into negative plate;
(3) number of assembling steps: the positive and negative plate prepared is made battery core through lamination.
Further, described conductive agent comprises carbon black, acetylene black or their mixture, and described binding agent comprises one or more in polytetrafluoroethylene, Kynoar, hydroxypropyl methylcellulose, CMC and butadiene-styrene rubber.
Further, the collector of described positive plate comprises aluminium foil, aluminium net, and the collector of described negative plate comprises aluminium foil, aluminium net, Copper Foil, copper mesh, titanium foil, titanium net.
Further, also comprise step (4) pre-doping, make negative material be 30% ~ 80% by the initial state-of-charge of sodium ion after pre-doping.
The present invention utilizes the transfer of with low cost, resourceful sodium ion between both positive and negative polarity to realize the principle of the discharge and recharge of capacitor, prepare novel sodium ion ultracapacitor, the sodium ion ultracapacitor prepared has the characteristic of high-energy-density, high power density, can be widely used in electric automobile, electric tool, solar energy storage, wind energy energy storage field.
Accompanying drawing explanation
Sodium ion ultracapacitor charging and discharging curve figure in the corresponding specific embodiment of the invention 1-10 of Fig. 1-10 difference.
Embodiment
Below by specific embodiment, the present invention is further illustrated, but the scope that these embodiments do not limit the present invention in any way.
Embodiment 1
The making of positive plate: be that the active carbon of 300g, conductive black, sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) are in mass ratio for mix at 90:5: 2: 3 by total amount, with deionized water furnishing slurry, be then coated on aluminium foil (the coated face capacity: 120g/m of 20 μm 2) on, drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 52*90mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
The making of negative plate: be the hard carbon of 1000g, Kynoar (PVDF) by total amount be 90:10 mixing in mass ratio, with 1-METHYLPYRROLIDONE (NMP) furnishing slurry, is then coated with (coated face capacity: 12 Ah/m on the Copper Foil of 30 μm 2), drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 53*95mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into negative plate.
The TF4535 cellulose esters barrier film selecting NKK company is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into battery core, then the positive pole pole group of the battery core folded is welded on aluminum lug, negative pole pole group is welded on copper lug, battery core after welding is put into the aluminum plastic film of forming, and with sodium sheet as third electrode, inject 1mol/L NaPF 6-EC(ethylene carbonate)/DEC(diethyl carbonate) (1:1) 15g, be assembled into square chemical power source.
Before changing into, it is first a very positive pole of hard carbon material with active material, sodium sheet metal is negative pole, the constant current of 22mA is adopted to discharge 3 hours, carry out sodium ion pre-doping (now pre-doping amount is 30% of initial carrying capacity), capacitor after pre-doping, and after being clipped by third electrode, is finally packaged into square structure.Carry out performance test normal temperature 25 DEG C, work system is 0.6A(5C) charge to 3.8V, leave standstill 5min, 0.6A(5C) and being discharged to 2.2V, the capacity of device is 276F.Charging and discharging curve as shown in Figure 1.
Embodiment 2
The making of positive plate: by total amount be the active carbon of 300g, conductive black, CMC, SBR in mass ratio for 90:7: 2: 3 mixing, with deionized water furnishing slurry, be then coated on aluminium foil (the coated face capacity: 120g/m of 20 μm 2) on, drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 52*90mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
The making of negative plate: be the hard carbon of 1000g, PVDF by total amount be 90:10 mixing in mass ratio, with NMP furnishing slurry, is then coated with (coated face capacity: 12 Ah/m on the Copper Foil of 30 μm 2), drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 53*95mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into negative plate.
The TF4535 cellulose esters barrier film selecting NKK company is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into battery core, then the positive pole pole group of the battery core folded is welded on aluminum lug, negative pole pole group is welded on copper lug, battery core after welding is put into the aluminum plastic film of forming, and with sodium sheet as third electrode, inject 1mol/L NaPF 6-EC(ethylene carbonate)/DEC(diethyl carbonate) (1:1) 15g, be assembled into square chemical power source.
Before changing into, it is first a very positive pole of hard carbon material with active material, sodium sheet metal is negative pole, the constant current of 22mA is adopted to discharge 5 hours, carry out sodium ion pre-doping (now pre-doping amount is 50% of initial carrying capacity), capacitor after pre-doping, and after being clipped by third electrode, is finally packaged into square structure.Carry out performance test normal temperature 25 DEG C, work system is 0.6A(5C) charge to 3.8V, leave standstill 5min, 0.6A(5C) and being discharged to 2.2V, the capacity of device is 283F.Charging and discharging curve as shown in Figure 2.
Embodiment 3
The making of positive plate: by total amount be the active carbon of 300g, conductive black, CMC, SBR in mass ratio for 90:7: 2: 3 mixing, with deionized water furnishing slurry, be then coated on aluminium foil (the coated face capacity: 120g/m of 20 μm 2) on, drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 52*90mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
The making of negative plate: be the Li of 1000g by total amount 4ti 5o 12, PVDF is 90:10 mixing in mass ratio, with NMP furnishing slurry, is then coated with (coated face capacity: 10 Ah/m on the aluminium foil of 30 μm 2), drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 53*95mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into negative plate.
The TF4535 cellulose esters barrier film selecting NKK company is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into battery core, then the positive pole pole group of the battery core folded is welded on aluminum lug, negative pole pole group is welded on copper lug, battery core after welding is put into the aluminum plastic film of forming, and with sodium sheet as third electrode, inject 1mol/L NaPF 6-AN(acetonitrile) 15g, be assembled into square chemical power source.
Before changing into, first is Li with active material 4ti 5o 12one very positive pole of material, sodium sheet metal is negative pole, adopts the constant current of 15mA to discharge 3 hours, carry out sodium ion pre-doping (now pre-doping amount is 30% of initial carrying capacity), capacitor after pre-doping, and after being clipped by third electrode, is finally packaged into square structure.Carry out performance test normal temperature 25 DEG C, work system is 0.75A(5C) charge to 2.7V, leave standstill 5min, 0.75A(5C) and being discharged to 1.5V, the capacity of device is 389F.Charging and discharging curve as shown in Figure 3.
Embodiment 4
The making of positive plate: by total amount be the active carbon of 300g, conductive black, CMC, SBR in mass ratio for 90:7: 2: 3 mixing, with deionized water furnishing slurry, be then coated on aluminium foil (the coated face capacity: 120g/m of 20 μm 2) on, drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 52*90mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
The making of negative plate: be the Li of 1000g by total amount 4ti 5o 12, PVDF is 90:10 mixing in mass ratio, with NMP furnishing slurry, is then coated with (coated face capacity: 10 Ah/m on the Copper Foil of 30 μm 2), drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 53*95mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into negative plate.
The TF4535 cellulose esters barrier film selecting NKK company is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into battery core, then the positive pole pole group of the battery core folded is welded on aluminum lug, negative pole pole group is welded on copper lug, battery core after welding is put into the aluminum plastic film of forming, and with sodium sheet as third electrode, inject 1mol/L NaPF 6-AN(acetonitrile) 15g, be assembled into square chemical power source.
Before changing into, first is Li with active material 4ti 5o 12one very positive pole of material, sodium sheet metal is negative pole, adopts the constant current of 15mA to discharge 5 hours, carry out sodium ion pre-doping (now pre-doping amount is 50% of initial carrying capacity), capacitor after pre-doping, and after being clipped by third electrode, is finally packaged into square structure.Carry out performance test normal temperature 25 DEG C, work system is 0.75A(5C) charge to 2.7V, leave standstill 5min, 0.75A(5C) and being discharged to 1.5V, the capacity of device is 380F.Charging and discharging curve as shown in Figure 4.
Comparative example 5
The making of positive plate: by total amount be the active carbon of 300g, conductive black, CMC, SBR in mass ratio for 90:7: 2: 3 mixing, with deionized water furnishing slurry, be then coated on aluminium foil (the coated face capacity: 120g/m of 20 μm 2) on, drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 52*90mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
The making of negative plate: be the hard carbon of 1000g, PVDF by total amount be 90:10 mixing in mass ratio, with NMP furnishing slurry, is then coated with (coated face capacity: 12 Ah/m on the Copper Foil of 30 μm 2), drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 53*95mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into negative plate.
The TF4535 cellulose esters barrier film selecting NKK company is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into battery core, then the positive pole pole group of the battery core folded is welded on aluminum lug, negative pole pole group is welded on copper lug, battery core after welding is put into the aluminum plastic film of forming, inject 1mol/L NaPF 6-AN(acetonitrile) 15g, be assembled into square chemical power source.Pre-doping process (now pre-doping amount is 0% of initial carrying capacity) is not carried out to this monomer, be finally packaged into square structure.Carry out performance test normal temperature 25 DEG C, work system is 0.6A(5C) charge to 4.0V, leave standstill 5min, 0.6A(5C) and being discharged to 3.3V, the capacity of device is 230F.Charging and discharging curve as shown in Figure 5.
Comparative example 6
The making of positive plate: by total amount be the active carbon of 300g, conductive black, CMC, SBR in mass ratio for 90:7: 2: 3 mixing, with deionized water furnishing slurry, be then coated on aluminium foil (the coated face capacity: 120g/m of 20 μm 2) on, drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 52*90mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
The making of negative plate: be the hard carbon of 1000g, PVDF by total amount be 90:10 mixing in mass ratio, with NMP furnishing slurry, is then coated with (coated face capacity: 12 Ah/m on the Copper Foil of 30 μm 2), drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 53*95mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into negative plate.
The TF4535 cellulose esters barrier film selecting NKK company is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into battery core, then the positive pole pole group of the battery core folded is welded on aluminum lug, negative pole pole group is welded on copper lug, battery core after welding is put into the aluminum plastic film of forming, and with sodium sheet as third electrode, inject 1mol/L NaPF 6-EC(ethylene carbonate)/DEC(diethyl carbonate) (1:1) 15g, be assembled into square chemical power source.
Before changing into, it is first a very positive pole of hard carbon material with active material, sodium sheet metal is negative pole, the constant current of 22mA is adopted to discharge 2 hours, carry out sodium ion pre-doping (now pre-doping amount is 20% of initial carrying capacity), capacitor after pre-doping, and after being clipped by third electrode, is finally packaged into square structure.Carry out performance test normal temperature 25 DEG C, work system is 0.6A(5C) charge to 3.8V, leave standstill 5min, 0.6A(5C) and being discharged to 2.2V, the capacity of device is 240F.Charging and discharging curve as shown in Figure 6.
Comparative example 7
The making of positive plate: by total amount be the active carbon of 300g, conductive black, CMC, SBR in mass ratio for 90:7: 2: 3 mixing, with deionized water furnishing slurry, be then coated on aluminium foil (the coated face capacity: 120g/m of 20 μm 2) on, drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 52*90mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
The making of negative plate: be the hard carbon of 1000g, PVDF by total amount be 90:10 mixing in mass ratio, with NMP furnishing slurry, is then coated with (coated face capacity: 12 Ah/m on the Copper Foil of 30 μm 2), drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 53*95mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into negative plate.
The TF4535 cellulose esters barrier film selecting NKK company is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into battery core, then the positive pole pole group of the battery core folded is welded on aluminum lug, negative pole pole group is welded on copper lug, battery core after welding is put into the aluminum plastic film of forming, and with sodium sheet as third electrode, inject 1mol/L NaPF 6-EC(ethylene carbonate)/DEC(diethyl carbonate) (1:1) 15g, be assembled into square chemical power source.
Before changing into, it is first a very positive pole of hard carbon material with active material, sodium sheet metal is negative pole, the constant current of 22mA is adopted to discharge 8.5 hours, carry out sodium ion pre-doping (now pre-doping amount is 85% of initial carrying capacity), capacitor after pre-doping, and after being clipped by third electrode, is finally packaged into square structure.Carry out performance test normal temperature 25 DEG C, work system is 0.6A(5C) charge to 3.8V, leave standstill 5min, 0.6A(5C) and being discharged to 2.2V, the capacity of device is 293F.Charging and discharging curve as shown in Figure 7.
Comparative example 8
The making of positive plate: by total amount be the active carbon of 300g, conductive black, CMC, SBR in mass ratio for 90:7: 2: 3 mixing, with deionized water furnishing slurry, be then coated on aluminium foil (the coated face capacity: 120g/m of 20 μm 2) on, drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 52*90mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
The making of negative plate: be the Li of 1000g by total amount 4ti 5o 12, PVDF is 90:10 mixing in mass ratio, with NMP furnishing slurry, is then coated with (coated face capacity: 10 Ah/m on the Copper Foil of 30 μm 2), drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 53*95mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into negative plate.
The TF4535 cellulose esters barrier film selecting NKK company is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into battery core, then the positive pole pole group of the battery core folded is welded on aluminum lug, negative pole pole group is welded on copper lug, battery core after welding is put into the aluminum plastic film of forming, inject 1mol/L NaPF 6-AN(acetonitrile) 15g, be assembled into square chemical power source.Pre-doping process (now pre-doping amount is 0% of initial carrying capacity) is not carried out to this monomer, be finally packaged into square structure.Carry out performance test normal temperature 25 DEG C, work system is 0.75A(5C) charge to 2.7V, leave standstill 5min, 0.75A(5C) and being discharged to 2.2V, the capacity of device is 306F.Charging and discharging curve as shown in Figure 8.
Comparative example 9
The making of positive plate: by total amount be the active carbon of 300g, conductive black, CMC, SBR in mass ratio for 90:7: 2: 3 mixing, with deionized water furnishing slurry, be then coated on aluminium foil (the coated face capacity: 120g/m of 20 μm 2) on, drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 52*90mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
The making of negative plate: be the Li of 1000g by total amount 4ti 5o 12, PVDF is 90:10 mixing in mass ratio, with NMP furnishing slurry, is then coated with (coated face capacity: 10 Ah/m on the Copper Foil of 30 μm 2), drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 53*95mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into negative plate.
The TF4535 cellulose esters barrier film selecting NKK company is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into battery core, then the positive pole pole group of the battery core folded is welded on aluminum lug, negative pole pole group is welded on copper lug, battery core after welding is put into the aluminum plastic film of forming, and with sodium sheet as third electrode, inject 1mol/L NaPF 6-AN(acetonitrile) 15g, be assembled into square chemical power source.
Before changing into, first is Li with active material 4ti 5o 12one very positive pole of material, sodium sheet metal is negative pole, adopts the constant current of 15mA to discharge 2 hours, carry out sodium ion pre-doping (now pre-doping amount is 20% of initial carrying capacity), capacitor after pre-doping, and after being clipped by third electrode, is finally packaged into square structure.Carry out performance test normal temperature 25 DEG C, work system is 0.75A(5C) charge to 2.7V, leave standstill 5min, 0.75A(5C) and being discharged to 1.5V, the capacity of device is 383F.Charging and discharging curve as shown in Figure 9.
Comparative example 10
The making of positive plate: by total amount be the active carbon of 300g, conductive black, CMC, SBR in mass ratio for 90:7: 2: 3 mixing, with deionized water furnishing slurry, be then coated on aluminium foil (the coated face capacity: 120g/m of 20 μm 2) on, drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 52*90mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into positive plate.
The making of negative plate: be the Li of 1000g by total amount 4ti 5o 12, PVDF is 90:10 mixing in mass ratio, with NMP furnishing slurry, is then coated with (coated face capacity: 10 Ah/m on the Copper Foil of 30 μm 2), drying (110 ~ 120 DEG C), roll, cut-parts (are of a size of: 53*95mm 2), 24h vacuumize (120 ~ 130 DEG C) is made into negative plate.
The TF4535 cellulose esters barrier film selecting NKK company is barrier film, positive plate (8), barrier film, negative plate (9) are laminated into battery core, then the positive pole pole group of the battery core folded is welded on aluminum lug, negative pole pole group is welded on copper lug, battery core after welding is put into the aluminum plastic film of forming, and with sodium sheet as third electrode, inject 1mol/L NaPF 6-AN(acetonitrile) 15g, be assembled into square chemical power source.
Before changing into, first is Li with active material 4ti 5o 12one very positive pole of material, sodium sheet metal is negative pole, adopts the constant current of 15mA to discharge 8.5 hours, carry out sodium ion pre-doping (now pre-doping amount is 85% of initial carrying capacity), capacitor after pre-doping, and after being clipped by third electrode, is finally packaged into square structure.Carry out performance test normal temperature 25 DEG C, work system is 0.75A(5C) charge to 2.7V, leave standstill 5min, 0.75A(5C) and being discharged to 1.5V, the capacity of device is 393F.Charging and discharging curve as shown in Figure 10.
Embodiment is prepared monomer performance data and is seen attached list 1
Operating voltage/V Internal resistance/m Ω Capacity/F Storage power/wh Peak power output/w Cycle life/time
Embodiment 1 2.2~3.8 11.99 276 0.368 301.13 100000
Embodiment 2 2.2~3.8 12.13 283 0.377 297.60 100000
Embodiment 3 1.5~2.7 13.48 389 0.272 135.21 100000
Embodiment 4 1.5~2.7 13.46 380 0.266 135.41 100000
Embodiment 5 3.3~4.0 11.3 230 0.163 353.98 800
Embodiment 6 2.2~3.8 12.36 240 0.32 292.07 6000
Embodiment 7 2.2~3.8 11.80 293 0.390 305.93 5000
Embodiment 8 2.2~2.7 13.65 306 0.104 133.51 10000
Embodiment 9 1.5~2.7 13.81 383 0.268 131.96 12000
Embodiment 10 1.5~2.7 13.91 393 0.275 131.02 9000
Can find out according to the charging and discharging curve of above-described embodiment and monomer performance data, the pre-doping of sodium ion capacitor amount initial charge amount be less than 30% or be greater than 80% time, sodium ion electric capacity does not have complete charging and discharging curve; When the amount of the pre-doping of sodium ion capacitor is between 30% to 80% of initial charge amount, sodium ion capacitor has complete charging and discharging curve and long circulation life.
Just several preferred embodiment of the present invention described in this specification, above embodiment is only in order to illustrate technical scheme of the present invention but not limitation of the present invention.All those skilled in the art, all should be within the scope of the present invention under this invention's idea by the available technical scheme of logical analysis, reasoning, or a limited experiment.

Claims (10)

1. a sodium ion ultracapacitor, is made up of positive pole, negative pole, marginal barrier film and electrolyte; It is characterized in that: described positive pole adopts active carbon, negative pole adopts the negative material of sodium-ion battery, and electrolyte adopts the non-water organic electrolyte containing sodium ion.
2. sodium ion ultracapacitor as claimed in claim 1, is characterized in that: described active carbon is the high specific surface area porous charcoal of double electric layer capacitor.
3. sodium ion ultracapacitor as claimed in claim 1, is characterized in that: the negative material of described sodium-ion battery comprises: amorphous hard charcoal, sodium titanate (Na 2ti 3o 7), lithium titanate (Li 4ti 5o 12) etc. the one in sodium ion secondary battery negative material.
4. sodium ion ultracapacitor as claimed in claim 3, it is characterized in that, described negative material is 30% ~ 80% by the initial state-of-charge of sodium ion after pre-doping.
5. sodium ion ultracapacitor as claimed in claim 1, is characterized in that solute in described electrolyte is by sodium perchlorate (NaClO 4), sodium tetrafluoroborate (NaBF 4), sodium hexafluoro phosphate (NaPF 6), trifluoromethyl sulfonate (NaCF 3sO 3), two (trimethyl fluoride sulfonyl) imines sodium (NaN (CF 3sO 2) 2), two oxalic acid Boratex (NaBOB), hexafluoroarsenate sodium (NaAsF 6) at least one produce; Solvent in described electrolyte comprises one or more in ethylene carbonate, propene carbonate, gamma-butyrolacton, dimethyl carbonate, diethyl carbonate, butylene, methyl ethyl carbonate, methyl propyl carbonate, ethylene sulfite, propylene sulfite, ethyl acetate, acetonitrile.
6. sodium ion ultracapacitor as claimed in claim 1, is characterized in that described barrier film comprises polyethene microporous membrane, microporous polypropylene membrane, composite membrane, inorganic ceramic membrane, paper barrier film.
7. a preparation method for sodium ion ultracapacitor, is characterized in that the battery core preparation of described sodium ion capacitor mainly comprises the following steps:
(1) preparation process of positive plate: first by the ball milling mixing by a certain percentage of active carbon, conductive agent, dissolve binding agent, pour mixture good for ball milling into dissolved binder solution in proportion, furnishing slurry, then be coated on plus plate current-collecting body, drying, roll, cut, vacuumize is prepared into positive plate;
(2) preparation process of negative plate: first by negative material, binding agent mixing, furnishing slurry, is then coated on negative current collector, drying, roll, cut, vacuumize is prepared into negative plate;
(3) number of assembling steps: the positive and negative plate prepared is made battery core through lamination.
8. the preparation method of sodium ion ultracapacitor as claimed in claim 7, it is characterized in that described conductive agent comprises carbon black, acetylene black or their mixture, described binding agent comprises one or more in polytetrafluoroethylene, Kynoar, hydroxypropyl methylcellulose, CMC and butadiene-styrene rubber.
9. the preparation method of sodium ion ultracapacitor as claimed in claim 7, it is characterized in that the collector of described positive plate comprises aluminium foil, aluminium net, the collector of described negative plate comprises aluminium foil, aluminium net, Copper Foil, copper mesh, titanium foil, titanium net.
10. the preparation method of sodium ion capacitor as claimed in claim 7, is characterized in that, also comprise step (4) pre-doping, make negative material be 30% ~ 80% by the initial state-of-charge of sodium ion after pre-doping.
CN201510042208.4A 2015-01-27 2015-01-27 Sodium ion super capacitor and preparation method thereof Pending CN104616901A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104966621A (en) * 2015-05-14 2015-10-07 中国科学院青岛生物能源与过程研究所 Solvent co-intercalated sodium ion capacitor
CN107369560A (en) * 2017-08-04 2017-11-21 哈尔滨工业大学 A kind of flexible sodium ion capacitor and preparation method thereof
CN107993855A (en) * 2017-11-16 2018-05-04 三峡大学 A kind of preparation method of high voltage sodium ion ultracapacitor
CN110546727A (en) * 2017-03-17 2019-12-06 宽广位元电池公司 Electrolyte for supercapacitor and high power battery applications
CN111223670A (en) * 2019-12-11 2020-06-02 中国科学院大连化学物理研究所 Planar sodium ion capacitor and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102903540A (en) * 2012-10-18 2013-01-30 中国科学院长春应用化学研究所 Electrochemical capacitor
CN103050290A (en) * 2012-12-20 2013-04-17 上海奥威科技开发有限公司 Internally combined super capacitor
EP2704248A1 (en) * 2011-04-29 2014-03-05 Shenzhen Hifuture Electric Co., Ltd. Polyimide capacitance battery and manufacturing method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2704248A1 (en) * 2011-04-29 2014-03-05 Shenzhen Hifuture Electric Co., Ltd. Polyimide capacitance battery and manufacturing method thereof
CN102903540A (en) * 2012-10-18 2013-01-30 中国科学院长春应用化学研究所 Electrochemical capacitor
CN103050290A (en) * 2012-12-20 2013-04-17 上海奥威科技开发有限公司 Internally combined super capacitor

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104966621A (en) * 2015-05-14 2015-10-07 中国科学院青岛生物能源与过程研究所 Solvent co-intercalated sodium ion capacitor
CN104966621B (en) * 2015-05-14 2018-10-02 中国科学院青岛生物能源与过程研究所 A kind of solvent is total to embedded type sodium ion capacitor
CN110546727A (en) * 2017-03-17 2019-12-06 宽广位元电池公司 Electrolyte for supercapacitor and high power battery applications
CN107369560A (en) * 2017-08-04 2017-11-21 哈尔滨工业大学 A kind of flexible sodium ion capacitor and preparation method thereof
CN107993855A (en) * 2017-11-16 2018-05-04 三峡大学 A kind of preparation method of high voltage sodium ion ultracapacitor
CN111223670A (en) * 2019-12-11 2020-06-02 中国科学院大连化学物理研究所 Planar sodium ion capacitor and preparation method and application thereof

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