CN109727786A - Electrode material for lithium ion super capacitor - Google Patents
Electrode material for lithium ion super capacitor Download PDFInfo
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- CN109727786A CN109727786A CN201811535104.7A CN201811535104A CN109727786A CN 109727786 A CN109727786 A CN 109727786A CN 201811535104 A CN201811535104 A CN 201811535104A CN 109727786 A CN109727786 A CN 109727786A
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- Prior art keywords
- lithium ion
- super capacitor
- electrode material
- porous carbon
- ion super
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 239000003990 capacitor Substances 0.000 title claims abstract description 39
- 239000007772 electrode material Substances 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 64
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000002028 Biomass Substances 0.000 claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 235000018290 Musa x paradisiaca Nutrition 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 102000002322 Egg Proteins Human genes 0.000 claims description 2
- 108010000912 Egg Proteins Proteins 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 235000014103 egg white Nutrition 0.000 claims description 2
- 210000000969 egg white Anatomy 0.000 claims description 2
- 239000010903 husk Substances 0.000 claims description 2
- 240000008790 Musa x paradisiaca Species 0.000 claims 2
- 239000003610 charcoal Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 13
- 229910017604 nitric acid Inorganic materials 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 241000234295 Musa Species 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- -1 stannic oxide compound Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of electrode materials for lithium ion super capacitor, including the biomass-based active carbon as positive electrode and as porous carbon/tin dioxide composite material of negative electrode material, and positive electrode and the mass ratio of negative electrode material are 0.5~4:1 in lithium ion super capacitor.Compared with prior art, product of the invention has higher energy density and power density, longer service life, and material therefor is mainly biomass castoff etc..
Description
Technical field
The invention belongs to lithium ion super capacitor technical fields, are related to a kind of electrode for lithium ion super capacitor
Material and its preparation process.
Background technique
Increasingly sharpening for energy crisis and environmental pollution, has promoted the exploitation of new and effective energy storage device or system, lithium
Ion battery and supercapacitor cause the extensive concern of people because of the feature of its uniqueness.Lithium ion battery has energy density
Greatly, the advantages that operating voltage height, memory-less effect, however its power density is low, cycle life is short；Supercapacitor has higher
Power density and longer cycle life, however its energy density is low.By the advantage phase of lithium ion battery and supercapacitor
In conjunction with the device for producing a kind of cycle life with high-energy density, high power density and length becomes the target of people.
Lithium ion super capacitor is the combination of supercapacitor and lithium ion battery, and performance has both the spy of the two
Point.Compared with lithium ion battery, power density with higher and longer cycle life；Compared with traditional capacitor,
Energy density with higher.The energy storage principle of lithium ion super capacitor is mainly the electric double layer capacitance and method of supercapacitor
The high reversible redox chemistry of pseudo-capacitance and lithium ion battery is drawn to react.New type lithium ion super capacitor material is to work as
The hot spot of preceding research.
Porous carbon is common lithium ion super capacitor electrode material, usually has big specific surface area and Kong Rong,
Electric double layer is formed on electrode/electrolyte solution interface and generates capacitor to store charge, using porous carbon as the super capacitor of electrode
Device substantially belongs to double layer capacitor.In general, the effective ratio area of porous carbon is bigger, the electric double layer capacitance generated
It is bigger, but in addition to specific surface area, the gap structure and surface nature of porous carbon also will affect the performance of supercapacitor.
Porous carbon, which is used as electrode material for super capacitor, has many merits, but energy density is low and operating voltage range is narrow
The deficiencies of limit its large-scale application to a certain extent.Want than under, metal oxide can provide the farad of high reversible
Capacitor and higher energy density, but its to easily lead to supercapacitor circulation steady for adjoint faraday's reaction during the work time
The problems such as qualitative poor, charge and discharge time course.
Summary of the invention
It is super for lithium ion that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind
The electrode material and its preparation process of grade capacitor.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of electrode material for lithium ion super capacitor, including as positive electrode biomass-based active carbon and
As porous carbon/tin dioxide composite material of negative electrode material, and positive electrode and negative electrode material in lithium ion super capacitor
Mass ratio be 0.5~4:1.
Further, in the negative electrode material, the ratio of porous carbon and stannic oxide is 5:1~1:5.
Further, in the positive electrode, the biomass material in biomass-based active carbon is banana skin, corn
Core, the leaf of bamboo, coconut husk, fish-bone or egg white.
Further, the biomass material is banana skin.
Further, the biomass-based active carbon is prepared by the following method to obtain:
After taking biomass material cleaning, dry, charing, crushing, charing particle is obtained, then will charing particle and potassium hydroxide
Mixing, then high-temperature activation in a nitrogen atmosphere, washing, filtering, it is dry after to get arriving biomass-based active carbon.
Further, the mass ratio for carbonizing particle and potassium hydroxide is 2-4:1.
Further, the condition of high-temperature activation are as follows: temperature is 600~900 DEG C, and activation time is 2~6 hours；
Nitrogen flow rate is 0.5~2L/min, and heating rate is 3~5 DEG C/min.
Further, the porous carbon/tin dioxide composite material is prepared by the following method to obtain:
It is compound to reheat obtained porous carbon/stannous chloride for Vacuum Package after first porous carbon is mixed with anhydrous stannous chloride
Material, then, roasting is under air atmosphere to get arriving.
Further, the process conditions heated after Vacuum Package are as follows: heated 1~20 hour at 240~600 DEG C；
The process conditions roasted under air atmosphere are as follows: roasted 1~20 hour at 100~300 DEG C.
Further, the porous carbon is carbon material (such as active carbon, carbon nanotube, graphite with Different Pore Structures
Alkene, porous, electrically conductive carbon black etc.) and its modified product, modified product is by nitric acid oxidation, hydrogen reducing, ammonia processing or stone
The product obtained after black alkene load.
Further, nitric acid oxidation specifically: take porous carbon drying to be placed in container, injection concentrated nitric acid is until completely
Porous carbon is not crossed, then, the oil bath heating 2h at 60 DEG C is completed after natural cooling, washing, filtering, drying；
Ammonia processing specifically: carbon modified porous after nitric acid oxidation is placed in atmosphere furnace, furnace chamber is vacuumized and in ammonia
Under gas atmosphere, in 700 DEG C of high temperature ammoniated treatment 4h, that is, complete；
It is graphene-supported specifically: after taking porous carbon dry, to be added in graphene oxide solution, after being stirred, 180
12h is kept the temperature at DEG C, products therefrom is cooling, washs, is dry, that is, completes.
Still more preferably, in ammonia treatment process: ammonia flow velocity is 2L/min, and heating rate is 3 DEG C/min；
During graphene-supported: the mass ratio of porous carbon and graphene oxide is 1:1.
Compared with prior art, the invention has the following advantages that
(1) present invention mainly prepares porous carbon for lithium ion super capacitor electrode by fertile material of natural biomass
Material, raw material sources are extensive, low in cost, and the preparation method can realize effective recycling to agricultural wastes.
(2) compared with existing lithium ion super capacitor, product has higher energy density and power density, longer
Service life.
Detailed description of the invention
Fig. 1 is the SEM figure of 1 gained positive electrode of embodiment.
Fig. 2 is 1 gained porous carbon of embodiment/stannic oxide cathode SEM figure.
Fig. 3 is the curve of 1 gained positive electrode capacity and cycle-index of embodiment.
Fig. 4 is the curve of 1 gained capacity of negative plates and cycle-index of embodiment.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to
Following embodiments.
In following embodiment, used material or treatment process then show to be that this field is normal unless otherwise instructed
The treatment process that material or general adjustment obtain.
Embodiment 1
The preparation of lithium ion super capacitor anode:
Banana skin is placed in air dry oven, dry 12h at being 90 DEG C in temperature, after pulverizing and sieving, particle size control
Particle is put into material boat in 120um by system, and material boat is placed in atmosphere furnace, carries out carbonization treatment, ammonia flow velocity in a nitrogen atmosphere
It is 500 DEG C from room temperature temperature programming to temperature for 0.5L/min, the processing time is 3 hours, and heating rate is 5 DEG C/min；Then
Carbide is dispersed in potassium hydroxide saturated solution, the mixing ratio of potassium hydroxide solution and carbide is 4:1, and mixing time is
1 hour, alkali carbon mix was obtained after dry；Alkali carbon mix is placed in atmosphere furnace, carries out high-temperature activation in a nitrogen atmosphere
Processing, nitrogen flow rate 0.5L/min are 850 DEG C from room temperature temperature programming to temperature, and activation time is 3 hours, heating rate
For 5 DEG C/min, washing, filtering, drying finally obtain positive porous carbon (i.e. banana skin matrix activated carbon).By positive porous carbon, lead
Electric agent (Super P) and binder (PVDF) ratio of 80:10:10 in mass ratio weigh, and N-Methyl pyrrolidone is added into one
Step is uniformly mixed, and is then coated on aluminium foil, positive plate is obtained after vacuum drying
The preparation of lithium ion super capacitor cathode:
It is (i.e. positive porous that porous carbon is prepared using biomass corncob as raw material (under the conditions of same process) according to the above method
Carbon), the anhydrous stannous chloride and porous carbon ground and mixed that mass ratio is 1:1 are then taken, uniformly mixed powder is transferred to glass
In glass bottle, post package is vacuumized.Vial after encapsulation is transferred in tube furnace and heats 12h at 280 DEG C, is obtained porous
Carbon/stannous chloride composite material.Finally by porous carbon/stannous chloride composite material 230 DEG C of roasting 4h in air atmosphere, much
Hole carbon/stannic oxide compound.In mass ratio by porous carbon/stannic oxide, conductive agent (Super P) and binder (PVDF)
The ratio of 70:15:15 weighs, and N-Methyl pyrrolidone is added and is further uniformly mixed, is then coated on copper foil, after vacuum drying
Obtain negative electrode tab.
The thickness for controlling coating layer, makes the active material of positive plate and the active material (i.e. two kinds of electrode materials) of negative electrode tab
Mass ratio be 1.55, buckle type lithium-ion supercapacitor is assembled into the glove box of argon atmosphere.It is simultaneously pair with lithium piece
Electrode tests the chemical property of positive and negative anodes respectively.
Fig. 1 is the SEM figure of positive porous carbon obtained by this example, as shown in Figure 1, porous carbon is mainly by not of uniform size, surface
Smooth particle composition.Fig. 2 is cathode porous carbon/tin dioxide composite material SEM figure obtained by this example, as shown in Fig. 2,
Stannic oxide is evenly distributed on porous carbon surface.Fig. 3 is the curve of positive electrode capacity and cycle-index obtained by this example, such as Fig. 3 institute
Show, which decays in 1400 circles and specific capacity is maintained at 90mAh/g or so.Fig. 4 is cathode obtained by this example
The curve of capacity and cycle-index, as shown in figure 4, the specific capacity of the electrode material drops to 700mAh/g in preceding 30 circle, then
Constantly rise and reaches maximum 900mAh/g in 650 circles.The specific capacity of lithium ion super capacitor obtained by this example is (with positive material
Subject to the active material quality of material) with the curve of cycle-index show that the lithium ion super capacitor has good cycle life.
Embodiment 2
Lithium ion super capacitor positive and negative anodes are prepared respectively by embodiment 1, by controlling the thickness of coating layer, make positive plate
Active material and the mass ratio of active material of negative electrode tab be 3, and be assembled into the glove box of argon atmosphere button lithium from
Sub- supercapacitor.
Embodiment 3
The resulting corncob base porous carbon of embodiment 1 is placed in air dry oven, is dried at least at being 100 DEG C in temperature
It is transferred to after 8 hours in dome flask, injection concentrated nitric acid did not had carbon dust up to it completely, then utilized oil bath pan by dome flask
Cooled to room temperature after 3h, washing, filtering, dry nitric acid oxidation porous carbon are heated at 55 DEG C.Nitric acid oxidation is porous
Carbon and anhydrous stannous chloride 1.5:1 ground and mixed in mass ratio, and Vacuum Package is in vial.Vial after encapsulation is turned
It moves in tube furnace and heats 8h at 280 DEG C, obtain porous carbon/stannous chloride composite material.Finally by porous carbon/dichloride
Tin composite material 230 DEG C of roasting 6h in air atmosphere, obtain porous carbon/stannic oxide compound.And using the composite material as lithium
The negative electrode active material of ion supercapacitor, by being assembled into buckle type lithium-ion supercapacitor described in example 1.
Embodiment 4
1 gained banana skin base porous carbon of embodiment is subjected to nitric acid oxidation processing by mode in embodiment 3, then by nitric acid
The porous carbon of oxidation is put into material boat, and material boat is placed in atmosphere furnace, is vacuumized to furnace chamber and carries out height under ammonia atmosphere
Nitrogenous porous carbon is obtained after warm ammoniated treatment, nitrogen flow rate 3L/min is 800 DEG C from room temperature temperature programming to temperature, processing
Time is 2 hours, and heating rate is 5 DEG C/min.And using the material as the positive active material of lithium ion super capacitor, by real
It applies and is assembled into buckle type lithium-ion supercapacitor described in example 1.
Embodiment 5
Compared with Example 1, the overwhelming majority all, in addition to porous carbon positive in the capacitor of the present embodiment and cathode are more
Hole carbon/tin dioxide composite material mass ratio is 0.5.
Embodiment 6
Compared with Example 1, the overwhelming majority all, in addition to porous carbon positive in the capacitor of the present embodiment and cathode are more
Hole carbon/tin dioxide composite material mass ratio is 4.
Embodiment 7
Compared with Example 1, the overwhelming majority all, in addition in the present embodiment: porous carbon in negative electrode material preparation process
And the ratio of stannic oxide is 5:1.
Embodiment 8
Compared with Example 1, the overwhelming majority all, in addition in the negative electrode material preparation process of the present embodiment: porous carbon
And the ratio of stannic oxide is 1:5.
Embodiment 9
Compared with Example 1, the overwhelming majority all, in addition in the positive porous carbon preparation process of the present embodiment: hydrogen-oxygen
Changing potassium and carbonizing the mixing ratio of particle is 2:1.
Embodiment 10
Compared with Example 1, the overwhelming majority all, in addition in the positive porous carbon preparation process of the present embodiment: hydrogen-oxygen
Changing potassium and carbonizing the mixing ratio of particle is 4:1.
Embodiment 11
Compared with Example 1, the overwhelming majority all, in addition in the positive porous carbon preparation process of the present embodiment: high temperature
Activation temperature is 600 DEG C, and activation time is 6 hours.
Embodiment 12
Compared with Example 1, the overwhelming majority all, in addition in the positive porous carbon preparation process of the present embodiment: high temperature
Activation temperature is 900 DEG C, and activation time is 2 hours.
Embodiment 13
Compared with Example 1, the overwhelming majority all, in addition in the positive porous carbon preparation process of the present embodiment: high temperature
Activation temperature is 900 DEG C, and activation time is 2 hours.
Embodiment 14
Compared with Example 1, the overwhelming majority all, in addition in the negative electrode material preparation process of the present embodiment:
The condition of heating in vacuum is to heat 20 hours at 240 DEG C.
Embodiment 15
Compared with Example 1, the overwhelming majority all, in addition in the negative electrode material preparation process of the present embodiment:
The condition of heating in vacuum is to heat 1 hour at 600 DEG C.
Embodiment 16
Compared with Example 1, the overwhelming majority all, in addition in the negative electrode material preparation process of the present embodiment:
The condition roasted under air atmosphere is to roast 20 hours at 100 DEG C.
Embodiment 17
Compared with Example 1, the overwhelming majority all, in addition in the negative electrode material preparation process of the present embodiment:
The condition roasted under air atmosphere is to roast 1 hour at 300 DEG C.
In the above various embodiments, in negative electrode material preparation process, porous carbon in addition to can directly adopt positive porous carbon this
Outside biomass porous carbon material, processing can also be modified to it, modification mode has nitric acid oxidation, hydrogen reducing, ammonia
Gas disposal is graphene-supported etc..Specifically, nitric acid oxidation can specifically: take porous carbon drying to be placed in container, inject dense
Nitric acid until do not had porous carbon completely, and then, the oil bath heating 2h at 60 DEG C is i.e. complete after natural cooling, washing, filtering, drying
At；Ammonia processing can specifically: carbon modified porous after nitric acid oxidation is placed in atmosphere furnace, vacuumizes to furnace chamber and is in flow velocity
Under the ammonia atmosphere of 2L/min, it is that 3 DEG C/min is warming up to 700 DEG C of high temperature ammoniated treatment 4h with heating rate, that is, completes；Graphene
Load can specifically: after taking porous carbon dry, is added in graphene oxide solution, the mass ratio of porous carbon and graphene oxide is
1:1 after being stirred, keeps the temperature 12h at 180 DEG C, and products therefrom is cooling, washs, is dry, that is, completes.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (9)
1. being used for the electrode material of lithium ion super capacitor, which is characterized in that including the biomass-based work as positive electrode
Property charcoal and porous carbon/tin dioxide composite material as negative electrode material, and positive electrode and negative in lithium ion super capacitor
The mass ratio of pole material is 0.5~4:1.
2. a kind of electrode material for lithium ion super capacitor according to claim 1, which is characterized in that described
In negative electrode material, the ratio of porous carbon and stannic oxide is 5:1~1:5.
3. a kind of electrode material for lithium ion super capacitor according to claim 1, which is characterized in that described
In positive electrode, the biomass material in biomass-based active carbon is banana skin, corncob, the leaf of bamboo, coconut husk, fish-bone or egg white.
4. a kind of electrode material for lithium ion super capacitor according to claim 3, which is characterized in that described
Biomass material is banana skin.
5. a kind of electrode material for lithium ion super capacitor according to claim 1 to 4, which is characterized in that
The biomass-based active carbon is prepared by the following method to obtain:
After taking biomass material cleaning, dry, charing, crushing, charing particle is obtained, then charing particle is mixed with potassium hydroxide
Close, then high-temperature activation in a nitrogen atmosphere, washing, filtering, it is dry after to get arriving biomass-based active carbon.
6. a kind of electrode material for lithium ion super capacitor according to claim 5, which is characterized in that charing
The mass ratio of grain and potassium hydroxide is 2-4:1.
7. a kind of electrode material for lithium ion super capacitor according to claim 5, which is characterized in that high temperature is living
The condition of change are as follows: temperature is 600~900 DEG C, and activation time is 2~6 hours；
Nitrogen flow rate is 0.5~2L/min, and heating rate is 3~5 DEG C/min.
8. a kind of electrode material for lithium ion super capacitor according to claim 1 to 4, which is characterized in that
Porous carbon/the tin dioxide composite material is prepared by the following method to obtain:
Vacuum Package after first porous carbon is mixed with anhydrous stannous chloride reheats and porous carbon/stannous chloride composite material is made,
Then, it roasts under air atmosphere to get arriving.
9. a kind of electrode material for lithium ion super capacitor according to claim 8, which is characterized in that vacuum seal
The process conditions heated after dress are as follows: heated 1~20 hour at 240~600 DEG C；
The process conditions roasted under air atmosphere are as follows: roasted 1~20 hour at 100~300 DEG C.
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