CN108630450A - A kind of negative plate and ultracapacitor for ultracapacitor - Google Patents

A kind of negative plate and ultracapacitor for ultracapacitor Download PDF

Info

Publication number
CN108630450A
CN108630450A CN201710166637.1A CN201710166637A CN108630450A CN 108630450 A CN108630450 A CN 108630450A CN 201710166637 A CN201710166637 A CN 201710166637A CN 108630450 A CN108630450 A CN 108630450A
Authority
CN
China
Prior art keywords
ultracapacitor
negative plate
titanium phosphate
phosphate sodium
electrode active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710166637.1A
Other languages
Chinese (zh)
Inventor
邓文君
李锐
潘锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Peking University Shenzhen Graduate School
Original Assignee
Peking University Shenzhen Graduate School
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Peking University Shenzhen Graduate School filed Critical Peking University Shenzhen Graduate School
Priority to CN201710166637.1A priority Critical patent/CN108630450A/en
Publication of CN108630450A publication Critical patent/CN108630450A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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

This application discloses a kind of negative plates and ultracapacitor for ultracapacitor.The negative plate of the application includes negative electrode active material, conductive agent and the binder of collector and attachment on a current collector；Negative electrode active material is the mixture of titanium phosphate sodium or titanium phosphate sodium and electric double layer energy storage material.The negative plate and ultracapacitor of the application, negative electrode active material is made with electric double layer energy storage material mixture using titanium phosphate sodium or titanium phosphate sodium, positive electrode active materials are made using electric double layer energy storage material, not only can fast charging and discharging, have extended cycle life, energy density is high, safety and environmental protection, but also material price is cheap, resourceful.The ultracapacitor of the application, capacitance section is in 0~2.0V, and cathode titanium phosphate sodium, which is not required to advance embedding sodium or lithium processing, can be directly used as cathode, and super capacitor energy density is up to 50Wh/kg, power density is more than 6000W/kg, especially suitable for fields such as electric vehicle, electric tool, energy storage.

Description

A kind of negative plate and ultracapacitor for ultracapacitor
Technical field
This application involves ultracapacitor fields, more particularly to a kind of negative plate for ultracapacitor and super electricity Container.
Background technology
Ultracapacitor is a kind of electrochemical energy storing device between traditional capacitor and battery, it is compared to traditional Capacitor has higher energy density, and compared to the cycle life that battery has higher power density and overlength, therefore it is tied The advantages of having closed traditional capacitor and battery is a kind of electrochmical power source having a extensive future.
Ultracapacitor can be divided into three classes according to energy storage principle：Double layer capacitor, pseudo capacitance super capacitor Device and hybrid super capacitor.In electrochmical power source, hybrid super capacitor be it is a kind of between symmetrical ultracapacitor and Energy storage device between battery can discharge under high current, and can provide higher energy.Ultracapacitor is according to use Electrolyte type is divided into organic and water solution system two types, that is, the electrolyte used is organic electrolyte and aqueous solution electrolysis Liquid.Nowadays commercialized organic ultracapacitor generally has a C-C structure ultracapacitors of symmetric form, electrolyte using ammonium salt and The organic solvent of high conductivity, such as acetonitrile；The power density of this capacitor is very high, can reach 6000W/kg, but its energy is close It spends relatively low, can only achieve 3-5Wh/kg；Another asymmetric hybrid super capacitor, a pole uses can be with deintercalate lithium ions Battery material, such as LiMn2O4, lithium titanate, graphite, another pole uses activated carbon, electrolyte to use the Organic Electricity containing lithium ion Liquid is solved, general can reach C-C type symmetric capacitors 2~3 times or so of ratio energy of the hybrid super capacitor are kept simultaneously Higher power density, practical application meaning bigger.
In recent years, the research of organic mixed super capacitor is on the increase, and is largely all based on the mixed of type lithium ion Close ultracapacitor.Anode uses LiMn in the patent application No. is 200510110461.52-XMxO4, cathode is using activity Charcoal, the ratio energy of the ultracapacitor reach as high as 50Wh/kg based on the calculating of positive and negative anodes active material gross mass.In application number Electric double layer energy storage material, cathode is used to use lithium titanate, energy density that can reach for anode in 201511008955.2 patent 15-25Wh/kg, power density can reach 12000W/kg.One kind is proposed in the patent application No. is 200710035205.3 Super capacitance cell, using lithium ion inlaid scheme and porous carbon mix as anode, porous carbon and graphite mixture conduct A kind of cathode, it is proposed that super capacitance cell.
Although many development of type lithium ion energy storage device research are also rapid, lithium resource is limited, lithium containing in the earth's crust Amount about 0.0065%, according to US Geological Survey latest data in 2015, the identified lithium resource amount in the world is about 3950 Ten thousand tons, about 13,500,000 tons of reserves.With the fast development and application of the energy storage device of type lithium ion, the following demand to lithium will more Greatly, facing challenges are also bigger.
Invention content
The purpose of the application is to provide a kind of new negative plate and ultracapacitor for ultracapacitor.
The application uses following technical scheme：
On the one hand the application discloses a kind of negative plate for ultracapacitor, which includes collector and attachment Negative electrode active material, conductive agent and binder on a current collector；Negative electrode active material be titanium phosphate sodium or titanium phosphate sodium with it is double The mixture of electric layer energy storage material.
The negative plate of the application is used as activity using titanium phosphate sodium or titanium phosphate sodium and the mixture of electric double layer energy storage material Material, not only specific capacity is high, power characteristic is good but also resourceful, cheap and Environmental Safety.To prepare cycle life Long, energy density height, and the ultracapacitor of safety and environmental protection is laid a good foundation.It is appreciated that the key of the application is to use The mixture of titanium phosphate sodium or titanium phosphate sodium and electric double layer energy storage material as collector, conductive agent and is glued as active material The conventional use of material of negative plate may be used in knot agent, is not specifically limited herein.But in the preferred embodiment of the application, it is Reach ideal effect, collector, conductive agent and binder etc. be defined respectively.
Preferably, electric double layer energy storage material be activated carbon, carbon nanotube, graphene, carbon fiber and charcoal-aero gel in extremely Few one kind.
Preferably, titanium phosphate sodium is the titanium phosphate sodium by modification, wherein modification includes element doping or table Face carbon coating, element doping are the doping of metallic element or nonmetalloid.
Preferably, the collector of negative plate is aluminium foil, aluminium net, copper foil or copper mesh.
The another side of the application discloses a kind of ultracapacitor, including positive plate, negative plate, between positive/negative plate Diaphragm, electrolyte and package shell, package shell is for accommodating positive plate, negative plate, diaphragm and electrolyte；Wherein, it bears Pole piece includes negative electrode active material, conductive agent and the binder of collector and attachment on a current collector, and negative electrode active material is phosphorus The mixture of sour titanium sodium or titanium phosphate sodium and electric double layer energy storage material；Positive plate includes collector and adheres on a current collector just Pole active material, conductive agent and binder, positive electrode active materials are electric double layer energy storage material；Electric double layer energy storage material is activity At least one of charcoal, carbon nanotube, graphene, carbon fiber and charcoal-aero gel.
It should be noted that the ultracapacitor of the application is using titanium phosphate sodium or titanium phosphate sodium and electric double layer energy storage material Mixture as negative electrode active material, using electric double layer energy storage material as positive electrode active materials, not only specific capacity is high, power Characteristic is good, and used is all resourceful, cheap, safety and environmental protection material, both can be using sodium salt as electrolysis Matter can also use lithium salts as electrolyte, alleviate the poor crisis of lithium resource.
Preferably, in the ultracapacitor of the application, titanium phosphate sodium is the titanium phosphate sodium of modification, and modification includes Element doping or material with carbon-coated surface；Element doping is the doping of metallic element or nonmetalloid.
Preferably, electrolyte is the organic solution of sodium ion or lithium-ion electrolyte salt, and sodium ion is by NaClO4、NaPF6、 NaBF4, dioxalic acid Boratex (abbreviation NaBOB), NaAsF6And NaCF3SO3At least one of generate, it is organic in organic solution Solvent is ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, butylene, γ-fourth At least one of lactone, methyl propyl carbonate, ethylene sulfite, ethylene sulfite and acetonitrile.Wherein, lithium ion is by routine For organic lithium ion battery lithium salts electrolyte generate.
Preferably, diaphragm is nonwoven cloth diaphragm, fibreglass diaphragm, Nafion membrane, polyethene microporous membrane, polypropylene microporous Film, polyethylene and polyacrylic composite membrane, inorganic ceramic membrane or paper diaphragm.
Preferably, what the conductive agent of positive plate and negative plate was repeatable is selected from electrically conductive graphite and/or conductive black；Anode What the binder of piece and negative plate repeated is selected from Kynoar, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, butadiene-styrene rubber At least one of with LA series of binders.
Preferably, the collector of positive plate is aluminium foil or aluminium net, and the collector of the negative plate is aluminium foil, aluminium net, copper foil Or copper mesh.
The advantageous effect of the application is：
The negative plate and ultracapacitor of the application, using the mixed of titanium phosphate sodium or titanium phosphate sodium and electric double layer energy storage material Conjunction object is as negative electrode active material, not only can fast charging and discharging, cycle using electric double layer energy storage material as positive electrode active materials Long lifespan, energy density height, safety and environmental protection, and used material price is cheap, resourceful, before there is wide application Scape.The ultracapacitor of the application, capacitance section in 0~2.0V, and cathode titanium phosphate sodium need not carry out advance embedding sodium or Lithium processing can be directly used as cathode, and the super capacitor energy density of the application is up to 50Wh/kg, be lived based on positive and negative anodes Property substance gross mass calculate power density be more than 6000W/kg, especially suitable for necks such as electric vehicle, electric tool, energy storage Domain.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of negative electrode active material in the embodiment of the present application 1；
Fig. 2 is the high rate performance test chart of carbon coating titanium phosphate sodium in the embodiment of the present application 1；
Fig. 3 is the charging and discharging curve figure of ultracapacitor in the embodiment of the present application 1.
Specific implementation mode
Novel sodium ion negative material is introduced into the hybrid architecture design of ultracapacitor by the application, fully profit With the advantages that specific capacity of such negative material is high, power characteristic is good, resourceful, cheap, safe, having developed one kind can be quick Charge and discharge, have extended cycle life, energy density is high, the sodium ion of safety and environmental protection or lithium ion hybrid super capacitor.The application Ultracapacitor, negative plate is using the mixture of titanium phosphate sodium or titanium phosphate sodium and electric double layer energy storage material as active material Material, positive plate using electric double layer energy storage material be used as active material, and use sodium ion or lithium-ion electrolyte salt it is organic Solution is electrolyte, can substitute existing type lithium ion energy storage device, and it is possible to be widely used in the large sizes such as electric vehicle Power-equipment is with a wide range of applications.
The application is described in further detail below by specific embodiment.Following embodiment is only to the application into traveling One step illustrates, should not be construed as the limitation to the application.
Embodiment one
The ultracapacitor of this example coats titanium phosphate sodium as negative electrode active material, activated carbon conduct using nano-scale carbon Positive electrode active materials, also, with 1mol/L NaClO4Organic solution as electrolyte, wherein solvent is ethylene carbonate (contracting Write EC) and dimethyl carbonate (abbreviation DMC) mixed solvent, the preparation method of ultracapacitor is as follows：
The making of positive plate：By gross mass be the activated carbon of 300g, electrically conductive graphite, conductive black, Kynoar (are abridged PVDF) in mass ratio 85:4:6:5 mixing, be tuned into slurry with NMP, be then coated on aluminium foil, after drying by roll-in, cut-parts, Vacuum drying is fabricated to positive plate.
The making of negative plate：Carbon coating titanium phosphate sodium, electrically conductive graphite, conductive black, PVDF that gross mass is 300g are pressed Mass ratio 86:5:5:4 mixing are tuned into slurry with N-Methyl pyrrolidone (abbreviation NMP), are then coated on aluminium foil, after drying It is fabricated to negative plate by roll-in, cut-parts, vacuum drying.
The nanoscale titanium phosphate sodium of this example is observed using electron-microscope scanning, the results are shown in Figure 1, it is seen then that titanium phosphate Sodium is hollow nanocube, particle size about 200nm.It is excellent that the special construction of hollow nano so that the negative material has Power characteristic.
Ultracapacitor makes：By positive plate, negative plate soldering polar ear, polyethylene purchased in market and polyacrylic compound is selected Film is diaphragm, and positive/negative plate is wound into battery core, is put into cylindrical aluminum hull, and inject after electrolyte sealing to capacitor into The electrolyte of row aging, this example is 1mol/L NaClO4Organic solution, solvent be EC/DMC mixed solvents.
The condition of performance test is：Charging and discharging currents 1A, charge cutoff voltage 2.0V, discharge cut-off voltage 0.5V. Test ratio energy, specific power and the capacity retention ratio of the ultracapacitor of this example.
Test result shows that the ultracapacitor of this example is 38Wh/kg than energy, and specific power 4000kW/kg fills It puts after recycling 20000 times, capacity retention ratio 88.3%.Charge-discharge test curve is as shown in Figure 3, it is seen then that between charge and discharge pressure area 0.5~2.0V, charging or discharging current density 1A/g, charging and discharging curve approximation isosceles triangle show that the ultracapacitor of this example has Typical capacitance characteristic.
High rate performance test is carried out to the negative plate of the ultracapacitor of this example, test condition is：Metallic sodium piece is born Pole, carbon coating titanium phosphate sodium pole piece make anode, and electrolyte is 1mol/L NaClO4Organic solution, be assembled into button cell, Charge-discharge test is carried out on new prestige battery testing cabinet, charging/discharging voltage section is 1.0-3.0V, tests its capacity with charge and discharge electricity Flow the variation of (0.5C-100C) size.Test results are shown in figure 2, it is seen then that capacity still can be kept most under the multiplying power of 100C The 75% of large capacity.
Embodiment two
The ultracapacitor of this example, negative electrode active material and positive electrode active materials are identical as embodiment one, different It is to use different binder and solvent in positive plate, uses another diaphragm, and the condition of performance test is Change, it is specific as follows：
The making of positive plate：It is the carbon nanotube of 300g, electrically conductive graphite, conductive black, carboxymethyl cellulose by gross mass Sodium (abbreviation CMC), butadiene-styrene rubber (abbreviation SBR) are 85 in mass ratio:4:6:2:3 mixing, are tuned into slurry, then with water and ethyl alcohol It is coated on aluminium foil, positive plate is fabricated to by roll-in, cut-parts, vacuum drying after drying.
The making of negative plate：By the carbon coating titanium phosphate sodium (nanoscale), electrically conductive graphite, conductive charcoal that gross mass is 300g Black, PVDF is 86 in mass ratio:5:5:4 mixing, be tuned into slurry with NMP, be then coated on copper mesh, after drying by roll-in, Cut-parts, vacuum drying are fabricated to negative plate.
Ultracapacitor makes：By positive/negative plate soldering polar ear, fibreglass diaphragm is selected, positive/negative plate is wound into electricity Core is then placed in cylindrical aluminum hull, and is injected after electrolyte sealing and carried out aging to capacitor, and the electrolyte of this example is 1mol/L NaBF4Organic solution, solvent be diethyl carbonate, methyl ethyl carbonate mixed solvent.
The condition of performance test is：Charging and discharging currents 2A, charge cutoff voltage 2.0V, discharge cut-off voltage 0.5V. Test ratio energy, specific power and the capacity retention ratio of the ultracapacitor of this example.
Test result shows that the ultracapacitor of this example is 35Wh/kg than energy, and specific power 4500kW/kg fills It puts after recycling 20000 times, capacity retention ratio 91%.
Embodiment three
The ultracapacitor of this example, positive plate is identical as embodiment two, the difference is that using nanoscale in negative plate The mixture of carbon coating Sn doping phosphoric acid titanium sodium and graphene is as negative electrode active material, wherein nanoscale titanium phosphate sodium and stone The mass ratio of black alkene is 5:1.It is specific as follows：
The making of positive plate：It is that the carbon aerogels of 300g, electrically conductive graphite, conductive black, CMC, SBR press quality by gross mass Than being 85:4:6:2:3 mixing, are tuned into slurry with water and ethyl alcohol, are then coated on aluminium foil, by roll-in, cut-parts, true after drying Sky drying is fabricated to positive plate.
The making of negative plate：The nano-scale carbon that gross mass is 300g is coated into Sn doping phosphoric acid titanium sodium and graphene mixes Object, electrically conductive graphite, conductive black, PVDF are 90 in mass ratio:2:3:5 mixing, are tuned into slurry with NMP, are then coated on copper foil On, after drying negative plate is fabricated to by roll-in, cut-parts, vacuum drying.
Ultracapacitor makes：By positive/negative plate soldering polar ear, selection Nafion membrane is diaphragm, and positive/negative plate is wound into Battery core is then placed in cylindrical aluminum hull, and is injected after electrolyte sealing and carried out aging to capacitor, and the electrolyte of this example is 1mol/L NaAsF6Organic solution, solvent be butylene and gamma-butyrolacton mixed solvent.
The condition of performance test is：Charging and discharging currents 3A, charge cutoff voltage 2.0V, discharge cut-off voltage 0.5V. Test ratio energy, specific power and the capacity retention ratio of the ultracapacitor of this example.
Test result shows that the ultracapacitor of this example is 30Wh/kg than energy, and specific power 6000kW/kg fills It puts after recycling 20000 times, capacity retention ratio 92.8%.
Example IV
The ultracapacitor of this example, using carbon coating Cu doping phosphoric acid titanium sodium as negative electrode active material, activated carbon conduct Positive electrode active materials, also, using the EC/DMC organic solutions of 1mol/L NaBOB as electrolyte, the preparation side of ultracapacitor Method is as follows：
The making of positive plate：It is in mass ratio by carbon fiber that gross mass is 300g, electrically conductive graphite, conductive black, LA132 85:4:6:2:3 mixing, are tuned into slurry with water and ethyl alcohol, are then coated on aluminium foil, dry by roll-in, cut-parts, vacuum after drying It is dry to be fabricated to positive plate.
The making of negative plate：By gross mass be the carbon coating Cu doping phosphoric acid titaniums sodium of 300g, electrically conductive graphite, conductive black, PVDF is 87 in mass ratio:3:5:5 mixing, are tuned into slurry with NMP, are then coated on aluminium foil, by roll-in, sanction after drying Piece, vacuum drying are fabricated to negative plate.
Ultracapacitor makes：By positive/negative plate soldering polar ear, diaphragm selects the nonwoven cloth diaphragm to use for nickel-hydrogen battery, will just Negative plate is wound into battery core, is then placed in cylindrical aluminum hull, and injects after electrolyte sealing and carry out aging to capacitor, this The electrolyte of example is the organic solution of 1mol/L NaBOB, and solvent is EC/DMC mixed solvents.
The condition of performance test is：Charging and discharging currents 3A, charge cutoff voltage 2.0V, discharge cut-off voltage 0.5V. Test ratio energy, specific power and the capacity retention ratio of the ultracapacitor of this example.
Test result shows that the ultracapacitor of this example is 38Wh/kg than energy, and specific power 5000kW/kg fills It puts after recycling 20000 times, capacity retention ratio 90.8%.
Embodiment five
The ultracapacitor of this example coats F doping phosphoric acid titanium sodium as negative electrode active material, graphene using nano-scale carbon Mixture with activated carbon is as positive electrode active materials, wherein the mass ratio of graphene and activated carbon is 1:5；Also, with 1mol/L NaCF3SO3Propene carbonate organic solution as electrolyte, the preparation method of ultracapacitor is as follows：
The making of positive plate：By gross mass be 300g graphene and Mixture of Activated Carbon, electrically conductive graphite, conductive black, LA132 is 90 in mass ratio:2:3:2:3 mixing, be tuned into slurry with water and ethyl alcohol, be then coated on aluminium foil, after drying by Roll-in, cut-parts, vacuum drying are fabricated to positive plate.
The making of negative plate：By gross mass be the carbon coating F doping phosphoric acid titaniums sodium of 300g, electrically conductive graphite, conductive black, PVDF is 87 in mass ratio:3:5:5 mixing, are tuned into slurry with NMP, are then coated on aluminium foil, by roll-in, sanction after drying Piece, vacuum drying are fabricated to negative plate.
Ultracapacitor makes：Diaphragm selects the nonwoven cloth diaphragm to use for nickel-hydrogen battery, positive/negative plate is built up battery core, then Lug is welded in the battery core positive and negative anodes folded, is put into molded aluminum plastic film, and is injected after electrolyte sealing to capacitor Aging is carried out, the electrolyte of this example is 1mol/L NaCF3SO3Organic solution, solvent be propene carbonate.
The condition of performance test is：Charging and discharging currents 3A, charge cutoff voltage 2.0V, discharge cut-off voltage 0.5V. Test ratio energy, specific power and the capacity retention ratio of the ultracapacitor of this example.
Test result shows that the ultracapacitor of this example is 28Wh/kg than energy, and specific power 5000kW/kg fills It puts after recycling 20000 times, capacity retention ratio 91.6%.
Embodiment six
The ultracapacitor of this example coats titanium phosphate sodium as negative electrode active material, graphene conduct using nano-scale carbon Positive electrode active materials, also, with 1mol/L NaPF6For organic solution as electrolyte, the preparation method of ultracapacitor is as follows：
The making of positive plate：It is in mass ratio by graphene that gross mass is 300g, electrically conductive graphite, conductive black, PTFE 90:2:3:5 mixing, are tuned into slurry with water and ethyl alcohol, are then pressed in aluminium net, are made by roll-in, cut-parts, vacuum drying after drying It is made positive plate.
The making of negative plate：By titanium phosphate sodium (nanoscale), electrically conductive graphite, conductive black, the PTFE that gross mass is 300g It is 87 in mass ratio:3:5:5 mixing, be tuned into slurry with water and ethyl alcohol, be then pressed in aluminium net, after drying by roll-in, cut-parts, Vacuum drying is fabricated to negative plate.
Ultracapacitor makes：Diaphragm selects the inorganic ceramic diaphragm to use for nickel-hydrogen battery, positive/negative plate is built up battery core, so Lug is welded in the battery core positive and negative anodes folded afterwards, is put into molded aluminum plastic film, and is injected after electrolyte sealing to capacitance Device carries out aging, and the electrolyte of this example is 1mol/L NaPF6Organic solution, solvent ethylene sulfite and sulfurous acid second Enester.
The condition of performance test is：Charging and discharging currents 3A, charge cutoff voltage 2.0V, discharge cut-off voltage 0.5V. Test ratio energy, specific power and the capacity retention ratio of the ultracapacitor of this example.
Test result shows that the ultracapacitor of this example is 35Wh/kg than energy, and specific power 5000kW/kg fills It puts after recycling 20000 times, capacity retention ratio 87.9%.
Embodiment seven
The ultracapacitor of this example coats the mixture of titanium phosphate sodium and graphene as negative electrode active using nano-scale carbon Material, wherein the mass ratio of nanoscale titanium phosphate sodium and graphene is 5:1；Using graphene as positive electrode active materials, and And with 1mol/L NaPF6With 1mol/L LiPF6Methyl propyl carbonate and ethylene carbonate organic solution as electrolyte, it is super The preparation method of capacitor is as follows：
The making of positive plate：By gross mass be the graphene of 300g, electrically conductive graphite, conductive black, polytetrafluoroethylene (PTFE) (are abridged PTFE it is) 90 in mass ratio:2:3:5 mixing, be tuned into slurry with water and ethyl alcohol, be then pressed in aluminium net, after drying by roll-in, Cut-parts, vacuum drying are fabricated to positive plate.
The making of negative plate：By nanoscale titanium phosphate sodium that gross mass is 300g and graphene mixture, electrically conductive graphite, lead Electric carbon black, PTFE are 87 in mass ratio:3:5:5 mixing, are tuned into slurry with water and ethyl alcohol, are then pressed in aluminium net, are passed through after drying Cross roll-in, cut-parts, vacuum drying are fabricated to negative plate.
Ultracapacitor makes：Diaphragm selects the polyethene microporous membrane to use for nickel-hydrogen battery, positive/negative plate is built up battery core, so Lug is welded in the battery core positive and negative anodes folded afterwards, is put into molded aluminum plastic film, and is injected after electrolyte sealing to capacitance Device carries out aging, and the electrolyte of this example is 1mol/L NaPF6With 1mol/L LiPF6Organic solution, solvent be carbonic acid first third Ester and ethylene carbonate.
The condition of performance test is：Charging and discharging currents 2A, charge cutoff voltage 2.0V, discharge cut-off voltage 0.5V. Test ratio energy, specific power and the capacity retention ratio of the ultracapacitor of this example.
Test result shows that the ultracapacitor of this example is 26Wh/kg than energy, and specific power 5000kW/kg fills It puts after recycling 20000 times, capacity retention ratio 89.2%.
Embodiment eight
The ultracapacitor of this example coats the mixture of titanium phosphate sodium and activated carbon as negative electrode active using nano-scale carbon Material, wherein the mass ratio of nanoscale titanium phosphate sodium and activated carbon is 3:1；Using activated carbon as positive electrode active materials, and And with 1mol/L LiBF4Acetonitrile organic solution as electrolyte, the preparation method of ultracapacitor is as follows：
The making of positive plate：It is in mass ratio by activated carbon that gross mass is 300g, electrically conductive graphite, conductive black, PTFE 85:4:6:5 mixing, are tuned into slurry with water and ethyl alcohol, are then pressed in aluminium net, are made by roll-in, cut-parts, vacuum drying after drying It is made positive plate.
The making of negative plate：The nano-scale carbon that gross mass is 300g is coated into titanium phosphate sodium and Mixture of Activated Carbon, conduction Graphite, conductive black, PTFE are 87 in mass ratio:3:5:5 mixing, are tuned into slurry with water and ethyl alcohol, are then pressed on copper foil, dry After dry negative plate is fabricated to by roll-in, cut-parts, vacuum drying.
Ultracapacitor makes：Diaphragm selects microporous polypropylene membrane, positive/negative plate is built up battery core, the electricity that then will be folded Lug is welded in core positive and negative anodes, is put into molded aluminum plastic film, and injects after electrolyte sealing and carry out aging to capacitor, this The electrolyte of example is 1mol/L LiBF4Organic solution, solvent be acetonitrile (chemical formula CH3CN)。
The condition of performance test is：Charging and discharging currents 3A, charge cutoff voltage 2.0V, discharge cut-off voltage 0.5V. Test ratio energy, specific power and the capacity retention ratio of the ultracapacitor of this example.
Test result shows that the ultracapacitor of this example is 29Wh/kg than energy, and specific power 6000kW/kg fills It puts after recycling 20000 times, capacity retention ratio 96.3%.
Embodiment nine
The ultracapacitor of this example coats titanium phosphate sodium as negative electrode active material, activated carbon conduct using nano-scale carbon Positive electrode active materials, also, with 1mol/L NaPF6CH3CN organic solutions are as electrolyte, the preparation method of ultracapacitor It is as follows：
The making of positive plate：It is in mass ratio by activated carbon that gross mass is 300g, electrically conductive graphite, conductive black, LA132 85:4:6:5 mixing, are tuned into slurry with water and ethyl alcohol, are then coated on aluminium foil, are made by roll-in, cut-parts, vacuum drying after drying It is made positive plate.
The making of negative plate：By the carbon coating titanium phosphate sodium (nanoscale), electrically conductive graphite, conductive charcoal that gross mass is 300g Black, LA132 is 87 in mass ratio:3:5:5 mixing, are tuned into slurry with water and ethyl alcohol, are then coated on copper foil, by roller after drying Pressure, cut-parts, vacuum drying are fabricated to negative plate.
Ultracapacitor makes：Diaphragm selects the nonwoven cloth diaphragm to use for nickel-hydrogen battery, after lug is welded in positive/negative plate It is wound into battery core, is then just being put into battery core in the box hat of cylinder, and injects after electrolyte sealing and aging is carried out to capacitor, this The electrolyte of example is 1mol/L NaPF6Organic solution, solvent CH3CN。
The condition of performance test is：Charging and discharging currents 3A, charge cutoff voltage 2.0V, discharge cut-off voltage 0.5V. Test ratio energy, specific power and the capacity retention ratio of the ultracapacitor of this example.
Test result shows that the ultracapacitor of this example is 33Wh/kg than energy, and specific power 6000kW/kg fills It puts after recycling 10000 times, capacity retention ratio 94.5%.
Embodiment ten
The ultracapacitor of this example, using nanoscale titanium phosphate sodium as negative electrode active material, activated carbon is living as anode Property material, also, with 1mol/L LiPF6CH3For CN organic solutions as electrolyte, the preparation method of ultracapacitor is as follows：
The making of positive plate：It is in mass ratio by activated carbon that gross mass is 300g, electrically conductive graphite, conductive black, LA132 85:4:6:5 mixing, are tuned into slurry with water and ethyl alcohol, are then coated on aluminium foil, are made by roll-in, cut-parts, vacuum drying after drying It is made positive plate.
The making of negative plate：By titanium phosphate sodium (nanoscale), electrically conductive graphite, conductive black, the PVDF that gross mass is 300g It is 87 in mass ratio:3:5:5 mixing, are tuned into slurry with NMP, are then coated on copper foil, by roll-in, cut-parts, vacuum after drying Drying is fabricated to negative plate.
Ultracapacitor makes：Diaphragm selects Japan's NKK diaphragm papers, and electricity is wound into after lug is welded in positive/negative plate Then battery core is just being put into the box hat of cylindrical type by core, and inject after electrolyte sealing and carry out aging, the electricity of this example to capacitor Solution liquid is 1mol/L LiPF6Organic solution, solvent CH3CN。
The condition of performance test is：Charging and discharging currents 3A, charge cutoff voltage 2.0V, discharge cut-off voltage 0.5V. Test ratio energy, specific power and the capacity retention ratio of the ultracapacitor of this example.
Test result shows that the ultracapacitor of this example is 33Wh/kg than energy, and specific power 5800kW/kg fills It puts after recycling 10000 times, capacity retention ratio 93.8%.
The foregoing is a further detailed description of the present application in conjunction with specific implementation manners, and it cannot be said that this Shen Specific implementation please is confined to these explanations.For those of ordinary skill in the art to which this application belongs, it is not taking off Under the premise of conceiving from the application, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the protection of the application Range.

Claims (10)

1. a kind of negative plate for ultracapacitor, it is characterised in that：The negative plate includes collector and is attached to afflux Negative electrode active material, conductive agent on body and binder；The negative electrode active material is titanium phosphate sodium or titanium phosphate sodium and double electricity The mixture of layer energy storage material.
2. negative plate according to claim 1, it is characterised in that：The electric double layer energy storage material is activated carbon, carbon nanometer At least one of pipe, graphene, carbon fiber and charcoal-aero gel.
3. negative plate according to claim 1, it is characterised in that：The titanium phosphate sodium is the titanium phosphate sodium of modification, The modification includes element doping or material with carbon-coated surface；The element doping is mixing for metallic element or nonmetalloid It is miscellaneous.
4. according to claim 1-3 any one of them negative plates, it is characterised in that：The collector is aluminium foil, aluminium net, copper foil Or copper mesh.
5. a kind of ultracapacitor, including positive plate, negative plate, the diaphragm between positive/negative plate, electrolyte, and assembling Shell, the package shell is for accommodating the positive plate, negative plate, diaphragm and electrolyte, it is characterised in that：The negative plate Include negative electrode active material, conductive agent and the binder of collector and attachment on a current collector, the negative electrode active material is phosphorus The mixture of sour titanium sodium or titanium phosphate sodium and electric double layer energy storage material；
The positive plate includes collector and attachment positive electrode active materials, conductive agent and binder on a current collector, it is described just Pole active material is electric double layer energy storage material；
The electric double layer energy storage material is at least one of activated carbon, carbon nanotube, graphene, carbon fiber and charcoal-aero gel.
6. ultracapacitor according to claim 5, it is characterised in that：The titanium phosphate sodium is the titanium phosphate of modification Sodium, the modification include element doping or material with carbon-coated surface；The element doping is metallic element or nonmetalloid Doping.
7. ultracapacitor according to claim 5, it is characterised in that：The electrolyte is that sodium ion or lithium ion are electrolysed The organic solution of matter salt, the sodium ion is by NaClO4、NaPF6、NaBF4, dioxalic acid Boratex, NaAsF6And NaCF3SO3In At least one generates, and organic solvent is ethylene carbonate, propene carbonate, dimethyl carbonate, carbonic acid two in the organic solution Ethyl ester, methyl ethyl carbonate, butylene, gamma-butyrolacton, methyl propyl carbonate, ethylene sulfite, ethylene sulfite and second At least one of nitrile.
8. ultracapacitor according to claim 5, it is characterised in that：The diaphragm is nonwoven cloth diaphragm, glass fibre Diaphragm, Nafion membrane, polyethene microporous membrane, microporous polypropylene membrane, polyethylene and polyacrylic composite membrane, inorganic ceramic membrane or paper Diaphragm.
9. according to claim 5-8 any one of them ultracapacitors, it is characterised in that：The conductive agent of positive plate and negative plate Repeatable is selected from electrically conductive graphite and/or conductive black；Repeatable being selected from of the binder of positive plate and negative plate gathers inclined At least one of vinyl fluoride, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, butadiene-styrene rubber and LA series of binders.
10. according to claim 5-8 any one of them ultracapacitors, it is characterised in that：The collector of the positive plate is The collector of aluminium foil or aluminium net, the negative plate is aluminium foil, aluminium net, copper foil or copper mesh.
CN201710166637.1A 2017-03-20 2017-03-20 A kind of negative plate and ultracapacitor for ultracapacitor Pending CN108630450A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710166637.1A CN108630450A (en) 2017-03-20 2017-03-20 A kind of negative plate and ultracapacitor for ultracapacitor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710166637.1A CN108630450A (en) 2017-03-20 2017-03-20 A kind of negative plate and ultracapacitor for ultracapacitor

Publications (1)

Publication Number Publication Date
CN108630450A true CN108630450A (en) 2018-10-09

Family

ID=63687884

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710166637.1A Pending CN108630450A (en) 2017-03-20 2017-03-20 A kind of negative plate and ultracapacitor for ultracapacitor

Country Status (1)

Country Link
CN (1) CN108630450A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112978714A (en) * 2021-02-07 2021-06-18 东华大学 Nitrogen-doped carbon nanotube aerogel material and preparation method thereof
CN115064665A (en) * 2022-04-29 2022-09-16 江苏理工学院 Doped modified carbon-coated sodium titanium phosphate composite material and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140159668A1 (en) * 2012-12-12 2014-06-12 Aquion Energy Inc. Composite Anode Structure for Aqueous Electrolyte Energy Storage and Device Containing Same
CN104319424A (en) * 2014-11-06 2015-01-28 中国科学技术大学 Water-system sodium ion battery as well as manufacturing method and application thereof
CN104779394A (en) * 2015-04-17 2015-07-15 复旦大学 Aqueous lithium (sodium) ion battery mixed negative material
CN105355453A (en) * 2015-10-14 2016-02-24 上海赛特康新能源科技股份有限公司 Positive electrode material and supercapacitor
CN105810912A (en) * 2016-05-10 2016-07-27 武汉理工大学 Three-dimensional graded carbon-clad NaTi<2>(PO<4>)<3>/C micrometer flower electrode material and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140159668A1 (en) * 2012-12-12 2014-06-12 Aquion Energy Inc. Composite Anode Structure for Aqueous Electrolyte Energy Storage and Device Containing Same
CN104319424A (en) * 2014-11-06 2015-01-28 中国科学技术大学 Water-system sodium ion battery as well as manufacturing method and application thereof
CN104779394A (en) * 2015-04-17 2015-07-15 复旦大学 Aqueous lithium (sodium) ion battery mixed negative material
CN105355453A (en) * 2015-10-14 2016-02-24 上海赛特康新能源科技股份有限公司 Positive electrode material and supercapacitor
CN105810912A (en) * 2016-05-10 2016-07-27 武汉理工大学 Three-dimensional graded carbon-clad NaTi<2>(PO<4>)<3>/C micrometer flower electrode material and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112978714A (en) * 2021-02-07 2021-06-18 东华大学 Nitrogen-doped carbon nanotube aerogel material and preparation method thereof
CN115064665A (en) * 2022-04-29 2022-09-16 江苏理工学院 Doped modified carbon-coated sodium titanium phosphate composite material and preparation method and application thereof

Similar Documents

Publication Publication Date Title
Zhang et al. Different types of pre-lithiated hard carbon as negative electrode material for lithium-ion capacitors
Xu et al. High performance lithium–sulfur batteries: Advances and challenges
CN105449186B (en) A kind of secondary cell and preparation method thereof
Zhang et al. Effect of pre-lithiation degrees of mesocarbon microbeads anode on the electrochemical performance of lithium-ion capacitors
CN101847513B (en) Preparation process of long-lived negative pole piece and capacitor battery using negative pole piece
CN100481609C (en) A super capacitance cell
CN104008893B (en) The preparation method of lithium ion hybrid capacitors and lithium ion hybrid capacitors thereof
CN109994322B (en) Battery type super capacitor and application thereof
CN201682023U (en) Lithium ion battery
CN101847516A (en) Capacitor battery of high-specific-energy organic system
CN101847764A (en) High-specific-energy/high-specific-power type super battery
KR20140004773A (en) Polyimide capacitance battery and manufacturing method thereof
CN105869898B (en) It is a kind of can low temperature charging lithium-ion capacitor and preparation method thereof
CN103367791B (en) A kind of new type lithium ion battery
CN110010373B (en) Electrode zinc embedding treatment method and application thereof in preparation of battery type super capacitor
CN108922788A (en) A kind of PEDOT@Na3(VOPO4)2F composite material, preparation method and its application
CN106373788A (en) Lithium ion super capacitor pre-embedded lithium pole sheet manufacture method
CN101409154B (en) Organic mixed super capacitor
CN109841425A (en) A kind of capacitor batteries and preparation method thereof
CN109859951A (en) A kind of carbon-based composite negative pole material and preparation method thereof and a kind of electrochmical power source and preparation method thereof
CN104616901A (en) Sodium ion super capacitor and preparation method thereof
Liu et al. Free-standing graphene/polyetherimide/ZrO2 porous interlayer to enhance lithium-ion transport and polysulfide interception for lithium-sulfur batteries
CN106298270B (en) A kind of positive plate of Asymmetric Supercapacitor and its preparation method and application
CN109003823A (en) The manufacturing method of lithium-ion capacitor with the high power charging-discharging ability long-life
CN108630450A (en) A kind of negative plate and ultracapacitor for ultracapacitor

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20181009