CN107154487A - A kind of utilization organic dyestuff discarded object makes the method and its application that novel energy stores material - Google Patents
A kind of utilization organic dyestuff discarded object makes the method and its application that novel energy stores material Download PDFInfo
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- CN107154487A CN107154487A CN201710350733.1A CN201710350733A CN107154487A CN 107154487 A CN107154487 A CN 107154487A CN 201710350733 A CN201710350733 A CN 201710350733A CN 107154487 A CN107154487 A CN 107154487A
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- organic dyestuff
- discarded object
- combination electrode
- dyestuff
- novel energy
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- 239000000975 dye Substances 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 53
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 39
- 238000004146 energy storage Methods 0.000 claims abstract description 31
- 239000001000 anthraquinone dye Substances 0.000 claims abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002699 waste material Substances 0.000 claims abstract description 9
- 239000011149 active material Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 230000002441 reversible effect Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 150000002829 nitrogen Chemical class 0.000 claims description 6
- 150000003233 pyrroles Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 230000005611 electricity Effects 0.000 claims description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000011232 storage material Substances 0.000 abstract description 21
- 239000007772 electrode material Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 229910052744 lithium Inorganic materials 0.000 description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- NZGYWTCXWOIYFB-UHFFFAOYSA-N 1,3-dioxolan-2-one trifluoromethanesulfonic acid Chemical compound O=C1OCCO1.OS(=O)(=O)C(F)(F)F NZGYWTCXWOIYFB-UHFFFAOYSA-N 0.000 description 1
- KVYRCBOUKXJXDK-UHFFFAOYSA-N 3,4-dimethylphenazine-1,2-diamine hydrochloride Chemical compound Cl.C1=CC=CC2=NC3=C(C)C(C)=C(N)C(N)=C3N=C21 KVYRCBOUKXJXDK-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- LSRGXLRLWFDKNR-UHFFFAOYSA-N FC(F)(F)[S] Chemical compound FC(F)(F)[S] LSRGXLRLWFDKNR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical compound [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- -1 anthraquinonyl Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The method and its application that novel energy stores material are made the invention discloses a kind of utilization organic dyestuff discarded object, respectively with nitrogenous dyestuff methylene blue (MB) and anthraquinone dyes alizarin red (ARS) for raw material, mesoporous carbon (CMK 3) is adsorbent, using physisorphtion, MB/CMK 3 and the combination electrode materials of ARS/CMK 3 is made, and is applied in the cell positive materials such as lithium ion and capacitor.Specific method is：(1) organic dyestuff discarded object is dissolved and waste liquid is made；(2) organic dyestuff is extracted from waste liquid；(3) organic dyestuff is combined with electric double layer capacitance active material, prepares combination electrode；(4) combination electrode is assembled into energy storage device.Not only preparation technology is simple by the present invention, reproducible；And raw materials used rich reserves, cost is low；Simultaneously by the use of common organic dyes discarded object in sewage as the active material of energy storage material, environmental pollution can be mitigated, constructing for novel energy storage material is realized；Prepared combination electrode specific capacity is high in addition, good cycle.
Description
Technical field
It is more particularly to a kind of to utilize organic dyestuff discarded object the present invention relates to energy storage field of material technology
Make the method and its application that novel energy stores material.
Background technology
The energy is the foundation stone of human social development, the new clean energy resource of development and utilization for the whole mankind existence and can hold
Supervention exhibition is particularly important.And rechargeable lithium ion, sodium-ion battery and ultracapacitor are used as new energy
Source is stored and power supply device, with having extended cycle life, memory-less effect and suitable energy density or power density etc. it is excellent
Point, is not only the main powering device of current numerous portable formula electronic product, and obtain in fields such as electric automobile, space flight and aviation
To being widely applied.Therefore, greatly developing can the novel energy memory device such as charge-discharge battery, ultracapacitor, it has also become
The important component of new energy system.Generally, the specific capacity of sodium, lithium ion battery and ultracapacitor, cycle life, work
The performance indications such as voltage are mainly determined by the performance of electrode material.Therefore, various countries' researcher grinding in electrode material
Study carefully aspect and carried out substantial amounts of work, be currently concentrated mainly in terms of new material, new preparation process, new modified approach.Tradition
Electrode material be that some have the transistion metal compound of electro-chemical activity, carbon material and part organic material.These electricity
Pole material presents preferable performance, is partly applied to commercialization secondary cell or ultracapacitor, and show
Considerable market value is gone out.But, the problem of also facing various.For example, the electrode based on transistion metal compound
Material, be faced with because of resource exhaustive exploitation and caused by the manufacturing cost that constantly rises；Organic material is faced with electrochemical stability
Problem, cycle performance is poor；Carbon material can only be used as GND.Therefore, new, cheap, efficient energy storage material is built
Material is the important directions for developing secondary power supply.
With developing rapidly for China's modern age industrial or agricultural, water pollution is increasingly serious.Organic dyestuff pollution is that water body is main
One of pollution sources, and most of organic dyestuff are all with bio-toxicity and teratogenesis carcinogenicity, the extremely difficult degraded in natural environment,
Cause Polluted water area ecological balance subject to severe risks of damage, the health to the mankind and other biological constitutes greatly threat.With
Various dyestuffs are widely used, and the dyestuff for having 10%~15% is discharged into environment in the production and use process, not only broken up
The ecological balance of water body, also wastes a large amount of valuable industrial chemicals.By the way that to the most widely used dyestuff of three major types, (nitrogenous class contaminates
Material, anthraquinone dyes and triphenylmethane dye) molecular structure analyzed, it is found that the nitrogenous class dyestuff in part, anthraquinone contaminate
Material all contains reversible oxidation-reduction pair.Such as, typical nitrogenous class dye molecule such as dimethyl diaminophenazine chloride, with the oxidation of azophenlyene class also
Former functional group；Methylene blue, with phenothiazines redox functional group；Anthraquinone dyes, such as alizarin red, in certain condition
Under, it is easier to realize the interconversion reaction of anthraquinonyl and quinhydrones base, therefore with reversible redox activity.Certainly, some have
The dye molecule of redox active contains more invalid functional group simultaneously, and its specific discharge capacity may be little, but with other
After Material cladding, its length, area or volume and capacity ratio may comparative superiorities.Therefore, some dyes molecule in theory
Possesses certain charge storage.In other words, organic dyestuff discarded object in part is expected to turn into energy storage material by recycling.
Face the ecological hazard that waste water from dyestuff is brought, and the storage material that taps a new source of energy active demand, will have engine dyeing
Expect that discarded object carries out recycling, novel energy storage material efficient, based on discarded dye molecule can not only be constructed, and
And the pollution that part waste water from dyestuff is brought to ecological environment can be alleviated to a certain extent, with far-reaching theory and reality meaning
Justice.
Therefore, how a kind of utilization organic dyestuff discarded object is provided and makes the method that novel energy stores material, is ability
The problem of domain personnel's urgent need to resolve.
The content of the invention
In view of this, the method that novel energy stores material is made the invention provides a kind of utilization organic dyestuff discarded object
And its application, using the active material that the common organic dyes discarded object in sewage is energy storage material, it can not only mitigate
Environmental pollution, realizes constructing for novel energy storage material；It is reproducible and preparation technology is simple；Raw materials used storage simultaneously
Amount is abundant, and cost is low；Prepared combination electrode material specific capacity is high in addition, good cycle.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of utilization organic dyestuff discarded object makes the method that novel energy stores material, comprises the following steps：
(1) organic dyestuff discarded object is dissolved, and waste liquid is made；
(2) organic dyestuff is extracted from waste liquid made from step (1)；
(3) organic dyestuff for extracting step (2) is combined with electric double layer capacitance active material, prepares combination electrode；
(4) combination electrode prepared by step (3) is assembled into energy storage device.
It is preferred that, in the method that a kind of above-mentioned utilization organic dyestuff discarded object makes novel energy storage material, step
(1) organic dyestuff described in include with reversible redox electricity to nitrogenous class dyestuff, anthraquinone dyes.
It is preferred that, in the method that a kind of above-mentioned utilization organic dyestuff discarded object makes novel energy storage material, step
(1) solution of the dissolving organic dyestuff discarded object includes deionized water in.
It is preferred that, in the method that a kind of above-mentioned utilization organic dyestuff discarded object makes novel energy storage material, step
(3) molecule and mesoporous carbon (CMK-3) one step absorption of the method for combination electrode including the organic dyestuff are prepared in compound, described
The molecule of organic dyestuff and the step electropolymerization of polypyrrole (ppy) one.
It is preferred that, in the method that a kind of above-mentioned utilization organic dyestuff discarded object makes novel energy storage material, step
(3) method that combination electrode is prepared in comprises the following steps：
A. organic dyestuff is dissolved in deionized water and organic dye solution is made；
B. mesoporous carbon (CMK-3) is added in the organic dye solution obtained by step a and stirs 1h with up to absorption
Balance, obtains mixture；
C. mixture step b obtained is centrifuged, and centrifuges gained solid in 60 DEG C of dry 24h, then in 100 DEG C of dry 8h,
Obtain combination electrode.
It is preferred that, make the method that novel energy stores material, step (3) in a kind of above-mentioned utilization organic dyestuff discarded object
The middle method for preparing combination electrode comprises the following steps：
A. organic dyestuff is dissolved in deionized water and organic dye solution is made；
B. pyrroles (pyrrole) and p-methyl benzenesulfonic acid are added and passed through in organic dye solution made from step a, mixed
Close liquid；
C. precooling on ice bath will be placed on by mixed liquor made from step b, while leading to nitrogen to exclude the oxygen in solution
Gas, and by pyrroles, the voltolisation together with organic dye molecule is bonded in carbon cloth substrate with constant current, so that combination electrode is made.
It is preferred that, in the method that a kind of above-mentioned utilization organic dyestuff discarded object makes novel energy storage material, step a
In organic dyestuff include nitrogen class dyestuff, anthraquinone dyes；And wherein described nitrogen class dyestuff includes methylene blue (MB)；It is described
Anthraquinone dyes include alizarin red (ARS).
It is preferred that, in the method that a kind of above-mentioned utilization organic dyestuff discarded object makes novel energy storage material, methylene
Combination electrode prepared by base indigo plant (MB) is MB/CMK-3；Combination electrode prepared by alizarin red (ARS) is ARS/CMK-3.
A kind of utilization organic dyestuff discarded object makes the application that novel energy stores material, should by the energy storage material
For lithium ion, sodium ion, magnesium ion, aluminium ion battery and ultracapacitor, and it is assembled into energy storage device.
Understood via above-mentioned technical scheme, compared with prior art, being utilized the present disclosure provides one kind has engine dyeing
Expect discarded object make novel energy store material method and its application, with reversible redox electricity to nitrogenous dyestuff such as
Methylene blue (MB) and anthraquinone dyes such as alizarin red (ARS) are raw material, using mesoporous carbon (CMK-3) as adsorbent, pass through thing
Reason absorption method is prepared for out combination electrode material MB/CMK-3 and ARS/CMK-3, and as batteries such as lithium ion batteries
Positive electrode；The main active substances of the combination electrode are the common organic dyes discarded object in sewage, can mitigate environment dirty
Dye, can realize constructing for novel energy storage material again, and material preparation process is simple, safe operation, takes short, cost
It is low, it is adapted to large-scale industrial production, while prepared combination electrode material specific capacity is high, good cycle.
By the present invention using the MB/CMK-3 and ARS/CMK-3 of preparation as anode material for lithium-ion batteries activearm
Point, conductive agent is acetylene black, and binding agent is Kynoar, and mass ratio is 8：1：1；Electrolyte is 1 mole of bis trifluoromethyl sulphur
(volume ratio is 1 to the ethylene carbonate (EC) and dimethyl carbonate (DMC) of sour Asia acid amides lithium (LiTFSI):1) solution；Battery shell mould
Number be 2032, collector uses aluminium flake, and barrier film is glass fibre；Lithium metal piece is used to electrode, the following group is protected in argon atmosphere
Packed battery.Using MB/CMK-3 and ARS/CMK-3 as the positive electrode of lithium ion battery, charge and discharge platform is respectively 2.6V
And 1.8V, second of discharge and recharge reversible specific capacity can reach 174.3mAh/g and 156.8mAh/g, after discharge and recharge 20 times, specific capacity
It is maintained at 107mAh/g and 103.1mAh/g.
The raw material that the present invention is used is the common organic dyes discarded object in sewage, and rich reserves, cost is low, can not only
Mitigate environmental pollution, and constructing for novel energy storage material can be realized, while there being no use in material preparation process
Machine solvent, in addition the present invention provide method yield height, favorable reproducibility, be easy to mass produce, have broad application prospects
And market.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
The embodiment of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
The accompanying drawing of offer obtains other accompanying drawings.
Fig. 1 accompanying drawings are CMK-3 of the present invention to the change curve of the MB of example 1 adsorption capacity Qe with adsorption time Time
Figure；
Fig. 2 accompanying drawings are CMK-3 of the present invention to the change curve of the ARS of example 2 adsorption capacity Qe with adsorption time Time
Figure；
Fig. 3 accompanying drawings are cyclic voltammetry curve figures of the MB/CMK-3 of present example 1 under 0.3mV/s；
Fig. 4 accompanying drawings are cyclic voltammetry curve figures of the ARS/CMK-3 of present example 2 under 0.3mV/s；
Fig. 5 accompanying drawings are charging and discharging curve, charge-discharge performances of the MB/CMK-3 of present example 1 under 100 μ A/mg
With coulombic efficiency figure；
ARS/CMK-3 charging and discharging curve under 100 μ A/mgs of Fig. 6 accompanying drawings for present example 2, charge-discharge cycle
Can be with coulombic efficiency figure.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
The embodiment of the invention discloses a kind of utilization organic dyestuff discarded object make novel energy storage material method and
It is applied, and can not only mitigate environmental pollution, and can realize constructing for novel energy storage material, while prepared by material
Organic solvent is not used in journey, in addition the present invention provide method yield height, favorable reproducibility, be easy to mass produce.
A kind of utilization organic dyestuff discarded object makes the method that novel energy stores material, comprises the following steps：
(1) organic dyestuff discarded object is dissolved, and waste liquid is made；
(2) organic dyestuff is extracted from waste liquid made from step (1)；
(3) organic dyestuff that (3) extract step (2) is combined with electric double layer capacitance active material, prepares combination electrode；
(4) combination electrode prepared by step (3) is assembled into energy storage device.
Include having reversible redox electricity right to further optimize organic dyestuff in above-mentioned technical proposal, step (1)
Nitrogenous class dyestuff, anthraquinone dyes.
In order to further optimize above-mentioned technical proposal, in step (1) solution of dissolving organic dyestuff discarded object include going from
Sub- water.
The method of combination electrode is prepared in above-mentioned technical proposal, step (3) include organic dyestuff in order to further optimize
Molecule adsorbs the compound, molecule of organic dyestuff and the step electropolymerization of polypyrrole (ppy) one with the step of mesoporous carbon (CMK-3) one.
The method of combination electrode is prepared in above-mentioned technical proposal, step (3) comprise the following steps to further optimize：
A. organic dyestuff is dissolved in deionized water and organic dye solution is made；
B. mesoporous carbon (CMK-3) is added in the organic dye solution obtained by step a and stirs 1h with up to absorption
Balance, obtains mixture；
C. mixture step b obtained is centrifuged, and centrifuges gained solid in 60 DEG C of dry 24h, then in 100 DEG C of dry 8h,
Obtain combination electrode.
The method of combination electrode is prepared in above-mentioned technical proposal, step (3) comprise the following steps to further optimize：
A. organic dyestuff is dissolved in deionized water and organic dye solution is made；
B. pyrroles (pyrrole) and p-methyl benzenesulfonic acid are added and passed through in organic dye solution made from step a, mixed
Close liquid；
C. precooling on ice bath will be placed on by mixed liquor made from step b, while leading to nitrogen to exclude the oxygen in solution
Gas, and by pyrroles, the voltolisation together with organic dye molecule is bonded in carbon cloth substrate with constant current, so that combination electrode is made.
Include nitrogen class dyestuff, anthraquinone dyes to further optimize the organic dyestuff in above-mentioned technical proposal, step a；
And wherein nitrogen class dyestuff includes methylene blue (MB)；Anthraquinone dyes include alizarin red (ARS).
In order to further optimize above-mentioned technical proposal, combination electrode prepared by methylene blue (MB) is MB/CMK-3；Alizarin
Combination electrode prepared by red (ARS) is ARS/CMK-3.
A kind of utilization organic dyestuff discarded object makes the application that novel energy stores material, by combination electrode be applied to lithium from
Son, sodium ion, magnesium ion, aluminium ion battery and ultracapacitor, and be assembled into energy storage device.
Such as, respectively with nitrogenous dyestuff methylene blue (MB), anthraquinone dyes alizarin red (ARS) for raw material, mesoporous carbon
(CMK-3) it is adsorbent, MB/CMK-3 and ARS/CMK-3 nano composite materials is obtained by simple physical adsorption process and are used as
Combination electrode is used for energy storage material, and preparation process comprises the following steps：MB and ARS are dissolved in deionized water → added respectively
Enter mesoporous carbon (CMK-3), be stirred continuously make its be uniformly dispersed → after 1h physical adsorption process, mixed solution is in 6000rpm
Lower centrifugation 3min → gained solid dries 24h at 60 DEG C, then dries 8h at 100 DEG C, obtains MB/CMK-3 and ARS/CMK-3
Combination electrode material.
Therefore, mesoporous carbon CMK-3 can be adsorbed the MB and ARS in the aqueous solution, and provided by the present invention
Method is respectively using MB/CMK-3 and ARS/CMK-3 as the active component of anode material for lithium-ion batteries, and conductive agent is acetylene black,
Binding agent is Kynoar, and mass ratio is 8：1：1；Electrolyte is the sub- acid amides lithium (LiTFSI) of 1 mole of bis trifluoromethyl sulfonic acid
Ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio is 1:1) solution；Battery case model 2032, collector is adopted
With aluminium flake, barrier film is glass fibre；Lithium metal piece is used to electrode, the assembled battery under argon atmosphere protection, and will assemble
Battery applications in energy storage device.
Embodiment 1：
Description of the invention accompanying drawing 1, accompanying drawing 3 and accompanying drawing 5 are referred to, organic dyestuff is utilized the invention provides one kind
Discarded object makes the method and its application that novel energy stores material：
(1) 15mg MB are dissolved in 50ml deionized waters, obtain initial concentration for 300mg/L MB solution；
(2) 30mg mesoporous carbon CMK-3s are added in above-mentioned MB solution, being stirred continuously makes it be uniformly dispersed；
(3) after 1h physical adsorption process, mixed solution centrifuges 3min under 6000rpm, and gained solid is at 60 DEG C
24h is dried, then 8h is dried at 100 DEG C, MB/CMK-3 combination electrodes are obtained, material is stored for new energy, and as positive pole
Material.
In the method that provides of the present invention CMK-3 to MB adsorption capacity up to 251mg/g；The MB/ most obtained at last
CMK-3 is as the active component of anode material for lithium-ion batteries, and conductive agent is acetylene black, and binding agent is Kynoar, quality
Than for 8：1：1；Electrolyte is the ethylene carbonate (EC) and carbonic acid two of the sub- acid amides lithium (LiTFSI) of 1 mole of bis trifluoromethyl sulfonic acid
(volume ratio is 1 to methyl esters (DMC):1) solution；Battery case model 2032, collector uses aluminium flake, and barrier film is glass fibre；It is right
Electrode uses lithium metal piece, the assembled battery under argon atmosphere protection, and by the battery applications assembled in energy storage device
In.
Embodiment 2：
Refer to description of the invention accompanying drawing 2, Figure of description 4 and Figure of description 6:, the invention provides one kind
The method and its application that novel energy stores material are made using organic dyestuff discarded object：
(1) 20mgARS is dissolved in 50ml deionized waters, obtains initial concentration for 400mg/LARS solution；
(2) 30mg mesoporous carbon CMK-3s are added in ARS solution, being stirred continuously makes it be uniformly dispersed；
(3) after 1h physical adsorption process, mixed solution centrifuges 3min under 6000rpm, and gained solid is at 60 DEG C
24h is dried, then 8h is dried at 100 DEG C, ARS/CMK-3 combination electrodes are obtained, material is stored for new energy, and as positive pole
Material.
In the method that provides of the present invention CMK-3 to ARS adsorption capacity up to 330mg/g；And this method will be passed through
Obtained ARS/CMK-3 is as the active component of anode material for lithium-ion batteries, and conductive agent is acetylene black, and binding agent is to gather inclined fluorine
Ethene, mass ratio is 8：1：1；Electrolyte is the ethylene carbonate of the sub- acid amides lithium (LiTFSI) of 1 mole of bis trifluoromethyl sulfonic acid
(EC) and dimethyl carbonate (DMC) (volume ratio is 1:1) solution；Battery case model 2032, collector uses aluminium flake, and barrier film is
Glass fibre；Lithium metal piece is used to electrode, the assembled battery under argon atmosphere protection, or further by the battery assembled
Applied in energy storage device.
The embodiment of each in this specification is described by the way of progressive, and what each embodiment was stressed is and other
Between the difference of embodiment, each embodiment identical similar portion mutually referring to.For device disclosed in embodiment
For, because it is corresponded to the method disclosed in Example, so description is fairly simple, related part is said referring to method part
It is bright.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.
A variety of modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it is of the invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The most wide scope caused.
Claims (9)
1. a kind of utilization organic dyestuff discarded object makes the method that novel energy stores material, it is characterised in that including following step
Suddenly：
(1) organic dyestuff discarded object is dissolved, and waste liquid is made；
(2) organic dyestuff is extracted from waste liquid made from step (1)；
(3) organic dyestuff for extracting step (2) is combined with electric double layer capacitance active material, prepares combination electrode；
(4) combination electrode prepared by step (3) is assembled into energy storage device.
2. a kind of utilization organic dyestuff discarded object according to claim 1 makes the method that novel energy stores material, its
Be characterised by, organic dyestuff described in step (1) include with reversible redox electricity to nitrogenous class dyestuff, Anthraquinones contaminate
Material.
3. a kind of utilization organic dyestuff discarded object according to claim 2 makes the method that novel energy stores material, its
It is characterised by, the solution of the dissolving organic dyestuff discarded object includes deionized water in step (1).
4. a kind of utilization organic dyestuff discarded object according to claim 3 makes the method that novel energy stores material, its
It is characterised by, the method for combination electrode is prepared in step (3) includes the molecule and the step of mesoporous carbon (CMK-3) one of the organic dyestuff
Adsorb the compound, molecule of the organic dyestuff and the step electropolymerization of polypyrrole (ppy) one.
5. a kind of utilization organic dyestuff discarded object according to claim 4 makes the method that novel energy stores material, its
It is characterised by, the method that combination electrode is prepared in step (3) comprises the following steps：
A. organic dyestuff is dissolved in deionized water and organic dye solution is made；
B. mesoporous carbon (CMK-3) is added in the organic dye solution obtained by step a and stirs 1h with up to adsorption equilibrium,
Obtain mixture；
C. mixture step b obtained is centrifuged, and centrifugation gained solid is obtained in 60 DEG C of dry 24h, then in 100 DEG C of dry 8h
Combination electrode.
6. the side that novel energy stores material is made according to a kind of utilization organic dyestuff discarded object according to claim 4
Method, it is characterised in that the method that combination electrode is prepared in step (3) comprises the following steps：
A. organic dyestuff is dissolved in deionized water and organic dye solution is made；
B. pyrroles (pyrrole) and p-methyl benzenesulfonic acid are added and passed through in organic dye solution made from step a, mixed
Liquid；
C. precooling on ice bath will be placed on by mixed liquor made from step b, while logical nitrogen is to exclude the oxygen in solution, and
With constant current, by pyrroles, the voltolisation together with organic dye molecule is bonded in carbon cloth substrate, and combination electrode is made.
7. a kind of utilization organic dyestuff discarded object according to claim 5 or 6 makes the method that novel energy stores material,
Characterized in that, the organic dyestuff in step a includes nitrogen class dyestuff, anthraquinone dyes；And wherein described nitrogen class dyestuff includes
Methylene blue (MB)；The anthraquinone dyes include alizarin red (ARS).
8. a kind of utilization organic dyestuff discarded object according to claim 7 makes the method that novel energy stores material, its
It is characterised by, combination electrode prepared by methylene blue (MB) is MB/CMK-3；Combination electrode prepared by alizarin red (ARS) is ARS/
CMK-3。
9. a kind of utilization organic dyestuff discarded object makes the application that novel energy stores material, it is characterised in that by claim
Combination electrode described in 1-8 any one is applied to lithium ion, sodium ion, magnesium ion, aluminium ion battery and ultracapacitor,
And be assembled into energy storage device.
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| CN113036124A (en) * | 2021-02-03 | 2021-06-25 | 新乡学院 | Alizarin MOF/graphene composite electrode material, and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110060877A (en) * | 2019-04-26 | 2019-07-26 | 北京化工大学 | A kind of supercapacitor polyatom doped carbon/polyaniline composite material preparation method |
| CN110474051A (en) * | 2019-07-11 | 2019-11-19 | 北京工业大学 | A kind of application of common dyes rhodamine B as the organic positive electrode of lithium ion battery |
| CN110474051B (en) * | 2019-07-11 | 2021-01-15 | 北京工业大学 | Application of common dye rhodamine B as organic anode material of lithium ion battery |
| CN113036124A (en) * | 2021-02-03 | 2021-06-25 | 新乡学院 | Alizarin MOF/graphene composite electrode material, and preparation method and application thereof |
| CN116826030A (en) * | 2023-08-30 | 2023-09-29 | 江苏智纬电子科技有限公司 | Composite positive electrode material based on small molecular organic matters and manufacturing method thereof |
| CN116826030B (en) * | 2023-08-30 | 2023-11-21 | 江苏智纬电子科技有限公司 | Composite positive electrode material based on small molecular organic matters and manufacturing method thereof |
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