CN109637845B - Method for constructing all-solid-state flexible supercapacitor based on double-solid-state redox electrolyte - Google Patents
Method for constructing all-solid-state flexible supercapacitor based on double-solid-state redox electrolyte Download PDFInfo
- Publication number
- CN109637845B CN109637845B CN201811295160.8A CN201811295160A CN109637845B CN 109637845 B CN109637845 B CN 109637845B CN 201811295160 A CN201811295160 A CN 201811295160A CN 109637845 B CN109637845 B CN 109637845B
- Authority
- CN
- China
- Prior art keywords
- electrolyte
- solid
- flexible
- oxide
- preparing
- 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.)
- Active
Links
- 239000003792 electrolyte Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 11
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 239000004744 fabric Substances 0.000 claims abstract description 28
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 24
- 239000012528 membrane Substances 0.000 claims abstract description 22
- 238000007789 sealing Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000003990 capacitor Substances 0.000 claims abstract description 15
- 238000005341 cation exchange Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000010030 laminating Methods 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000004806 packaging method and process Methods 0.000 claims abstract description 5
- 239000003566 sealing material Substances 0.000 claims abstract description 5
- 238000003491 array Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 40
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 239000002135 nanosheet Substances 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000010335 hydrothermal treatment Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 12
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 12
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyethylene terephthalate Polymers 0.000 claims description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000002070 nanowire Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229920003023 plastic Polymers 0.000 claims description 8
- 239000004033 plastic Substances 0.000 claims description 8
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 229910001887 tin oxide Inorganic materials 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000002073 nanorod Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 claims description 6
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 6
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 6
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 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 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- JYKIWJXDKPVNQZ-UHFFFAOYSA-L [O-]S([O-])(=O)=O.O.[V+5] Chemical compound [O-]S([O-])(=O)=O.O.[V+5] JYKIWJXDKPVNQZ-UHFFFAOYSA-L 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 230000009977 dual effect Effects 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims 2
- 238000005987 sulfurization reaction Methods 0.000 claims 1
- 238000007731 hot pressing Methods 0.000 abstract description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 42
- 235000010265 sodium sulphite Nutrition 0.000 description 21
- 150000001768 cations Chemical class 0.000 description 7
- 239000000565 sealant Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000005457 optimization Methods 0.000 description 6
- 239000011244 liquid electrolyte Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H01G11/54—Electrolytes
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention provides a method for constructing an all-solid-state flexible supercapacitor based on a dual-solid redox electrolyte, which comprises the following steps of: preparing an electrode: growing different metal oxide arrays on the flexible carbon cloth to be used as the positive electrode and the negative electrode of the flexible super capacitor; preparing a solid electrolyte: dissolving polyvinyl alcohol, and adding electrolyte to prepare electrolyte; assembling: respectively coating electrolytes on the surfaces of the electrodes for forming; hot-pressing and sealing: and putting a cation exchange membrane between the electrodes, laminating, standing, drying, and finally packaging with a sealing material. The redox electrolyte can additionally provide pseudocapacitance, and the redox electrolyte can generate chemical bond with the modified metal oxide, so that the redox electrolyte can exert higher capacity, thereby constructing a super capacitor with ultrahigh energy density and widening potential.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a method for preparing a solid redox electrolyte and applying a dual-solid redox electrolyte to a supercapacitor.
Background
The super capacitor is composed of a shell, an electrolyte, a diaphragm, a positive electrode and a negative electrode, wherein the electrolyte plays a key role in the super capacitor energy storage and internal current conduction, and the electrolyte with high decomposition voltage, high conductivity, high mechanical stability and better wetting of the electrode surface is a target sought by super capacitor developers. The electrolyte of the supercapacitor comprises: aqueous electrolyte, organic electrolyte, and solid electrolyte. The electrolyte used initially is generally in a liquid state, and in order to improve the voltage window of the electrolyte, the liquid electrolyte generally uses organic solvents to dissolve ionic compounds, and the solvents are mostly flammable and toxic, and the liquid substances are easy to leak, which seriously affects the safety of the super capacitor. The solid electrolyte has good reliability, no electrolyte leakage, high specific energy and wider cycle voltage. Therefore, the development trend of supercapacitors is to use safe and easily processed solid electrolytes instead of liquid electrolytes.
The energy density difference is now the main reason limiting the development of supercapacitors, since redox electrolytes can additionally provide pseudocapacitance and redox electrolytes have a wider operating potential, whose energy density (E) is related to its operating potential window (V) and its capacity (C) according to the energy density formula E-1/2 CV 2. However, at present, the redox electrolyte mainly uses liquid electrolyte, has poor mechanical properties and is easy to leak, and can only be applied to a symmetrical super capacitor, and the voltage window range is narrow, so that the application of the redox electrolyte is greatly limited.
The flexible electronic device, especially the flexible substrate, has wide application prospect in the fields of information, energy, medical treatment, national defense and the like due to the characteristics of unique flexibility/ductility, light weight, easy carrying, high efficiency, low cost, manufacturing process and the like. Such as foldable smart phones, flexible electronic displays, thin film solar panels, screen displays, satellites, and the like.
Disclosure of Invention
The technical problem is as follows: in order to solve the defects of the prior art, the invention provides a method for constructing an all-solid-state flexible supercapacitor based on a dual-solid redox electrolyte.
The technical scheme is as follows: according to the invention, the cation exchange membrane is used as the diaphragm, and the non-symmetrical supercapacitor constructed based on the double redox solid electrolyte is prepared. The preparation steps are as follows: and separating the positive electrode material and the negative electrode material coated with the positive and negative solid electrolytes by using a cation exchange membrane, and then packaging by using an aluminum plastic membrane to prepare the 2.0V ultra-wide working potential window asymmetric supercapacitor. The method specifically comprises the following steps:
step 1 electrode preparation
Growing different metal oxide arrays on the flexible carbon cloth to be used as the positive electrode and the negative electrode of the flexible super capacitor, and then cutting the flexible carbon cloth to the required size; establishing a chemical bond between the modified and solid redox electrolytes;
step 2 solid electrolyte preparation
Adding polyvinyl alcohol into deionized water, heating and stirring the deionized water until the polyvinyl alcohol is dissolved, and adding electrolyte into the deionized water to prepare electrolyte;
step 3 Assembly
Respectively coating electrolytes on the surfaces of a positive electrode and a negative electrode of the flexible supercapacitor, and waiting for electrolyte molding in an air environment;
step 4 hot press sealing
And (3) putting a cation exchange membrane between the positive electrode and the negative electrode of the flexible supercapacitor, laminating, standing, drying, and finally packaging with a sealing material to obtain the flexible all-solid-state supercapacitor.
As an optimization scheme: the anode material for preparing the electrode is any one of various anode materials such as carbon materials, manganese oxide, ruthenium oxide or cobalt oxide.
As a further optimization scheme: the cathode material for preparing the electrode is any one of various cathode materials such as tin oxide, iron oxide or vanadium oxide and the like.
As a further optimization scheme: the anode of the solid redox electrolyte is one of vanadyl sulfate, m-phenylenediamine or benzenediol.
As a further optimization scheme: the electrode of the flexible supercapacitor can be modified by any one of a phosphating reaction, a vulcanization reaction and a reduction reaction.
As a further optimization scheme: the sealing material packaged in the step 4 is an aluminum plastic film or a PET film.
As a further optimization scheme: the preparation method of the metal oxide comprises the following specific steps:
preparation of manganese oxide: dissolving 0.15g of potassium permanganate in 40 g of water, then carrying out hydrothermal treatment at 100 ℃ for 10h to successfully prepare a manganese oxide nanosheet growing on a carbon cloth, then reducing the manganese oxide nanosheet by using argon or a reducing agent to improve the generation of a low valence state of manganese, and introducing an oxygen vacancy to improve the conductivity and improve the capacity;
preparing the iron oxide nano rod: dissolving 0.54g of ferric chloride and 0.284g of sodium sulfate in 40mL of aqueous solution, and then carrying out hydrothermal treatment at 120 ℃ for 6h to successfully prepare the iron oxide nanowires growing on the carbon cloth;
preparing nano-sheet cobalt oxide: dissolving 0.582g of cobalt nitrate and 0.6006g of urea in water, transferring the solution to a hydrothermal kettle, putting carbon cloth into the hydrothermal kettle, carrying out hydrothermal treatment at 120 ℃ for 6 hours, and annealing the solution at 350 ℃ for 2 hours in the air to successfully prepare a cobalt oxide nanosheet;
preparing tin oxide nano-sheets: 0.54g of stannous chloride and 0.284g of citric acid are dissolved in 40mL of aqueous solution, and then hydrothermal is carried out for 6h at 180 ℃, so as to successfully prepare the tin oxide nanowire growing on the carbon cloth.
Preparing vanadium oxide nanowires: dissolving 0.4g of vanadium sulfate oxygen and 0.284g of citric acid in 40mL of aqueous solution, and carrying out hydrothermal treatment at 170 ℃ for 6h to successfully prepare the vanadium oxide nanowires growing on the carbon cloth.
Preparation of ruthenium oxide: ruthenium oxide nanoparticles are coated on a flexible substrate in a mixture with a binder conductive agent.
Has the advantages that: 1. the redox electrolyte can additionally provide pseudocapacitance, and the redox electrolyte can generate chemical bond with the modified metal oxide, so that the redox electrolyte can exert higher capacity, thereby constructing a super capacitor with ultrahigh energy density and widening potential. 2. The invention uses a dual solid redox electrolyte, with high safety and low self-discharge.
Drawings
FIG. 1 is a cyclic voltammogram based on the different potentials of sodium sulfite and potassium ferricyanide in the solid redox electrolyte of example 1 of the present invention;
FIG. 2 is a structural schematic diagram of a supercapacitor device based on a non-facing relationship of a double solid electrolyte of an iron oxide cathode and a manganese oxide anode;
fig. 3 is a bending and folding working diagram of the supercapacitor device according to the present invention based on the non-facing orientation of the dual solid redox electrolytes of the iron oxide cathode and the manganese oxide anode.
Detailed Description
The present invention is further illustrated by the following figures and specific examples, which are to be understood as illustrative only and not as limiting the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
Example 1
Step 1
Preparation of manganese oxide: 0.15g of potassium permanganate is dissolved in 40 water, and then hydrothermal is carried out for 10 hours at 100 ℃, so as to successfully prepare the manganese oxide nano-sheet growing on the carbon cloth. Then reducing by argon or a reducing agent to improve the generation of low valence state of manganese, and introducing oxygen vacancy to improve the conductivity and capacity.
Preparing the iron oxide nano rod: dissolving 0.54g of ferric chloride and 0.284g of sodium sulfate in 40mL of aqueous solution, and then carrying out hydrothermal treatment at 120 ℃ for 6h to successfully prepare the iron oxide nanowires growing on the carbon cloth.
Step 2
Preparation of sodium sulfite solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 0.5M sodium sulfite was added with stirring until completely dissolved.
Preparing a potassium ferricyanide-sodium sulfate solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then, 0.5M sodium sulfate was added thereto with stirring until completely dissolved. Finally, 0.06M potassium ferricyanide was added until completely dissolved.
Step 3
Assembling the double-solid-state electrolyte all-solid-state flexible asymmetric supercapacitor: respectively coating the electrolyte on the surfaces of the flexible positive electrode and the flexible negative electrode, and waiting for the electrolyte to be molded in an air environment;
step 4
And (3) placing a cation diaphragm between the flexible positive electrode and the flexible negative electrode, laminating the positive electrode and the negative electrode together, standing and drying. Then, the cation exchange membrane and the positive and negative electrodes coated with the electrolyte are sealed and fixed by using a plastic-aluminum film (PET) and a sealant, and finally, the device is assembled by hot-pressing sealing.
Example 2
Step 1
Preparation of manganese oxide: 0.15g of potassium permanganate is dissolved in 40 water, and then hydrothermal is carried out for 10 hours at 100 ℃, so as to successfully prepare the manganese oxide nano-sheet growing on the carbon cloth.
Preparing tin oxide nano-sheets: 0.54g of stannous chloride and 0.284g of citric acid are dissolved in 40mL of aqueous solution, and then hydrothermal is carried out for 6h at 180 ℃, so as to successfully prepare the tin oxide nanowire growing on the carbon cloth.
Step 2
Preparation of sodium sulfite solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 0.5M sodium sulfite was added with stirring until completely dissolved.
Preparing a potassium ferricyanide-sodium sulfate solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then, 0.5M sodium sulfate was added thereto with stirring until completely dissolved. Finally, 0.06M potassium ferricyanide was added until completely dissolved.
Step 3
Assembling the double-solid-state electrolyte all-solid-state flexible asymmetric supercapacitor: respectively coating the electrolyte on the surfaces of the flexible positive electrode and the flexible negative electrode, and waiting for the electrolyte to be molded in an air environment;
step 4
And (3) placing a cation diaphragm between the flexible positive electrode and the flexible negative electrode, laminating the positive electrode and the negative electrode together, standing and drying. And then sealing and fixing the cation exchange membrane and the positive and negative electrodes coated with the electrolyte by using an aluminum plastic membrane and a sealant, and finally assembling the device by hot-press sealing.
Example 3
Step 1
Preparation of manganese oxide: 0.15g of potassium permanganate is dissolved in 40 water, and then hydrothermal is carried out for 10 hours at 100 ℃, so as to successfully prepare the manganese oxide nano-sheet growing on the carbon cloth. Argon or a reducing agent is then reduced to enhance the production of manganese in its lower valence state and to introduce oxygen vacancies to enhance conductivity.
Preparing the iron oxide nano rod: dissolving 0.54g of ferric chloride and 0.284g of sodium sulfate in 40mL of aqueous solution, and then carrying out hydrothermal treatment at 120 ℃ for 6h to successfully prepare the iron oxide nanowires growing on the carbon cloth.
Step 2
Preparation of sodium sulfite solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 0.5M sodium sulfite was added with stirring until completely dissolved.
Preparation of sodium sulfite solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 0.5M sodium sulfite was added with stirring until completely dissolved.
Preparing a potassium ferricyanide-potassium hydroxide solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 6M potassium hydroxide was added with stirring until completely dissolved. Finally, 0.06M potassium ferricyanide was added until completely dissolved.
Step 3
Assembling the double-solid-state electrolyte all-solid-state flexible asymmetric supercapacitor: respectively coating the electrolyte on the surfaces of the flexible positive electrode and the flexible negative electrode, and waiting for the electrolyte to be molded in an air environment;
step 4
And (3) placing a cation diaphragm between the flexible positive electrode and the flexible negative electrode, laminating the positive electrode and the negative electrode together, standing and drying. And then sealing and fixing the cation exchange membrane and the positive and negative electrodes coated with the electrolyte by using an aluminum plastic membrane and a sealant, and finally assembling the device by hot-press sealing.
Example 4
Step 1
Preparing nano-sheet cobalt oxide: 0.582g of cobalt nitrate and 0.6006g of urea are dissolved in water, then the solution is transferred to a hydrothermal kettle, carbon cloth is placed in the hydrothermal kettle for hydrothermal treatment at 120 ℃ for 6 hours, and then annealing is carried out at 350 ℃ for 2 hours in the air, so that the cobalt oxide nanosheet is successfully prepared.
Preparing the iron oxide nano rod: dissolving 0.54g of ferric chloride and 0.284g of sodium sulfate in 40mL of aqueous solution, and then carrying out hydrothermal treatment at 120 ℃ for 6h to successfully prepare the iron oxide nanowires growing on the carbon cloth.
Step 2
Preparation of sodium sulfite solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 0.5M sodium sulfite was added with stirring until completely dissolved.
Preparation of sodium sulfite solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 0.5M sodium sulfite was added with stirring until completely dissolved.
Preparing a potassium ferricyanide-potassium hydroxide solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 6M potassium hydroxide was added with stirring until completely dissolved. Finally, 0.06M potassium ferricyanide was added until completely dissolved.
Step 3
Assembling the double-solid-state electrolyte all-solid-state flexible asymmetric supercapacitor: respectively coating the electrolyte on the surfaces of the flexible positive electrode and the flexible negative electrode, and waiting for the electrolyte to be molded in an air environment;
step 4
And (3) placing a cation diaphragm between the flexible positive electrode and the flexible negative electrode, laminating the positive electrode and the negative electrode together, standing and drying. And then sealing and fixing the cation exchange membrane and the positive and negative electrodes coated with the electrolyte by using an aluminum plastic membrane and a sealant, and finally assembling the device by hot-press sealing.
Example 5
Step 1
Preparing nano-sheet cobalt oxide: 0.582g of cobalt nitrate and 0.6006g of urea are dissolved in water, then the solution is transferred to a hydrothermal kettle, carbon cloth is placed in the hydrothermal kettle for hydrothermal treatment at 120 ℃ for 6 hours, and then annealing is carried out at 350 ℃ for 2 hours in the air, so that the cobalt oxide nanosheet is successfully prepared.
Preparing the iron oxide nano rod: dissolving 0.54g of ferric chloride and 0.284g of sodium sulfate in 40mL of aqueous solution, and then carrying out hydrothermal treatment at 120 ℃ for 6h to successfully prepare the iron oxide nanowires growing on the carbon cloth.
Step 2
Preparation of sodium sulfite solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 0.5M sodium sulfite was added with stirring until completely dissolved.
Preparation of sodium sulfite solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 0.5M sodium sulfite was added with stirring until completely dissolved.
Preparation of HQ-sodium sulfate solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 6M sodium sulfate was added with stirring until completely dissolved. Finally 1M HQ was added until complete dissolution.
Step 3
Assembling the double-solid-state electrolyte all-solid-state flexible asymmetric supercapacitor: respectively coating the electrolyte on the surfaces of the flexible positive electrode and the flexible negative electrode, and waiting for the electrolyte to be molded in an air environment;
step 4
And (3) placing a cation diaphragm between the flexible positive electrode and the flexible negative electrode, laminating the positive electrode and the negative electrode together, standing and drying. And then sealing and fixing the cation exchange membrane and the positive and negative electrodes coated with the electrolyte by using an aluminum plastic membrane and a sealant, and finally assembling the device by hot-press sealing.
Example 6
Step 1
Preparing nano-sheet cobalt oxide: 0.582g of cobalt nitrate and 0.6006g of urea are dissolved in water, then the solution is transferred to a hydrothermal kettle, carbon cloth is placed in the hydrothermal kettle for hydrothermal treatment at 120 ℃ for 6 hours, and then annealing is carried out at 350 ℃ for 2 hours in the air, so that the cobalt oxide nanosheet is successfully prepared.
Preparing the iron oxide nano rod: dissolving 0.54g of ferric chloride and 0.284g of sodium sulfate in 40mL of aqueous solution, and then carrying out hydrothermal treatment at 120 ℃ for 6h to successfully prepare the iron oxide nanowires growing on the carbon cloth.
Step 2
Preparation of sodium sulfite solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 0.5M sodium sulfite was added with stirring until completely dissolved.
Preparation of sodium sulfite solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 0.5M sodium sulfite was added with stirring until completely dissolved.
Preparing a vanadium sulfate oxygen-sodium sulfate solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 6M sodium sulfate was added with stirring until completely dissolved. Finally, 1M vanadyl sulfate was added until completely dissolved.
Step 3
Assembling the double-solid-state electrolyte all-solid-state flexible asymmetric supercapacitor: respectively coating the electrolyte on the surfaces of the flexible positive electrode and the flexible negative electrode, and waiting for the electrolyte to be molded in an air environment;
step 4
And (3) placing a cation diaphragm between the flexible positive electrode and the flexible negative electrode, laminating the positive electrode and the negative electrode together, standing and drying. And then sealing and fixing the cation exchange membrane and the positive and negative electrodes coated with the electrolyte by using an aluminum plastic membrane and a sealant, and finally assembling the device by hot-press sealing.
Example 7
Step 1
Preparation of ruthenium oxide: ruthenium oxide nanoparticles are coated on a flexible substrate in a mixture with a binder conductive agent.
Preparing vanadium oxide nanowires: dissolving 0.4g of vanadium sulfate oxygen and 0.284g of citric acid in 40mL of aqueous solution, and carrying out hydrothermal treatment at 170 ℃ for 6h to successfully prepare the vanadium oxide nanowires growing on the carbon cloth.
Step 2
Preparing a solid electrolyte of vanadyl sulfate, m-phenylenediamine or benzenediol: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 0.5M vanadyl sulfate, M-phenylenediamine or benzenediol is added while stirring until completely dissolved.
Preparation of m-phenylenediamine or benzenediol: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then, 0.5M M-phenylenediamine or benzenediol was added thereto with stirring until completely dissolved.
Preparing a vanadium sulfate oxygen-sodium sulfate solid electrolyte: 3g of polyvinyl alcohol (trade name 1799) was added to 20mL of deionized water, heated to 85 ℃ with stirring until dissolved, and allowed to stand until the bubbles disappeared. Then 6M sodium sulfate was added with stirring until completely dissolved. Finally, 1M vanadyl sulfate was added until completely dissolved.
Step 3
Assembling the double-solid-state electrolyte all-solid-state flexible asymmetric supercapacitor: respectively coating the electrolyte on the surfaces of the flexible positive electrode and the flexible negative electrode, and waiting for the electrolyte to be molded in an air environment;
step 4
And (3) placing a cation diaphragm between the flexible positive electrode and the flexible negative electrode, laminating the positive electrode and the negative electrode together, standing and drying. And then sealing and fixing the cation exchange membrane and the positive and negative electrodes coated with the electrolyte by using an aluminum plastic membrane and a sealant, and finally assembling the device by hot-press sealing.
The redox electrolyte can additionally provide pseudocapacitance, and the redox electrolyte can generate chemical bond with the modified metal oxide, so that the redox electrolyte can exert higher capacity, and a super capacitor with ultrahigh energy density is constructed; the redox electrolyte with high redox potential is selected, so that the hydrolysis of metal oxide can be inhibited, and the potential is widened; the current situation that the solid redox electrolyte can only be applied to the formed super capacitor is broken through, the advantage of a high-capacity high-potential window of the redox solid electrolyte is successfully utilized, the assembled asymmetric super capacitor can normally work at the maximum of 2.4V, and the method has important significance for the development of a flexible super capacitor with high energy density and high safety.
The anode and the cathode of the invention adopt the solid redox electrolyte, thus providing a new idea for the application prospect of the redox electrolyte; the positive electrode and the negative electrode adopt different solid redox electrolytes, so that the method is suitable for different conditions of various positive and negative electrolytic electrolytes, can maximize the utilization rate of positive and negative electrode materials, and has an important promotion effect on the development of the double-solid electrolyte which is not regarded as a supercapacitor.
Claims (2)
1. A method for constructing an all-solid-state flexible supercapacitor based on a dual-solid redox electrolyte is characterized by comprising the following steps of:
step 1 electrode preparation
Growing different metal oxide arrays on the flexible carbon cloth to be used as the positive electrode and the negative electrode of the flexible super capacitor, and then cutting the flexible carbon cloth to the required size; establishing a chemical bond between the modified and solid redox electrolytes; the anode material for preparing the electrode is any one of carbon materials, manganese oxide, ruthenium oxide or cobalt oxide, the cathode material for preparing the electrode is any one of tin oxide, iron oxide or vanadium oxide, and the anode of the solid redox electrolyte is one of vanadyl sulfate, m-phenylenediamine or benzenediol;
step 2 solid electrolyte preparation
Adding polyvinyl alcohol into deionized water, heating and stirring the deionized water until the polyvinyl alcohol is dissolved, and adding electrolyte into the deionized water to prepare electrolyte;
step 3 Assembly
Respectively coating electrolytes on the surfaces of a positive electrode and a negative electrode of the flexible supercapacitor, and waiting for electrolyte molding in an air environment; the electrode of the flexible super capacitor can be modified by any one of the methods of phosphorization reaction, sulfuration reaction and reduction reaction,
step 4 hot press sealing
And (3) putting a cation exchange membrane between the positive electrode and the negative electrode of the flexible supercapacitor, laminating, standing, drying, and finally packaging the cation exchange membrane by using a sealing material, wherein the packaging sealing material is an aluminum plastic membrane or a PET (polyethylene terephthalate) membrane, so that the flexible all-solid-state supercapacitor is obtained.
2. The method of claim 1 for constructing an all-solid-state flexible supercapacitor based on dual solid redox electrolytes, wherein: the preparation method of the metal oxide comprises the following specific steps:
preparation of manganese oxide: dissolving 0.15g of potassium permanganate in 40 g of water, then carrying out hydrothermal treatment at 100 ℃ for 10h to successfully prepare a manganese oxide nanosheet growing on a carbon cloth, then reducing the manganese oxide nanosheet by using argon or a reducing agent to improve the generation of a low valence state of manganese, and introducing an oxygen vacancy to improve the conductivity and improve the capacity;
preparing the iron oxide nano rod: dissolving 0.54g of ferric chloride and 0.284g of sodium sulfate in 40mL of aqueous solution, and then carrying out hydrothermal treatment at 120 ℃ for 6h to successfully prepare the iron oxide nanowires growing on the carbon cloth;
preparing nano-sheet cobalt oxide: dissolving 0.582g of cobalt nitrate and 0.6006g of urea in water, transferring the solution to a hydrothermal kettle, putting carbon cloth into the hydrothermal kettle, carrying out hydrothermal treatment at 120 ℃ for 6 hours, and annealing the solution at 350 ℃ for 2 hours in the air to successfully prepare a cobalt oxide nanosheet;
preparing tin oxide nano-sheets: dissolving 0.54g of stannous chloride and 0.284g of citric acid in 40mL of aqueous solution, and then carrying out hydrothermal treatment at 180 ℃ for 6h to successfully prepare the tin oxide nanowire growing on the carbon cloth;
preparing vanadium oxide nanowires: dissolving 0.4g of vanadium sulfate oxygen and 0.284g of citric acid in 40mL of aqueous solution, and then carrying out hydrothermal treatment at 170 ℃ for 6h to successfully prepare vanadium oxide nanowires growing on carbon cloth;
preparation of ruthenium oxide: ruthenium oxide nanoparticles are coated on a flexible substrate in a mixture with a binder conductive agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811295160.8A CN109637845B (en) | 2019-01-09 | 2019-01-09 | Method for constructing all-solid-state flexible supercapacitor based on double-solid-state redox electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811295160.8A CN109637845B (en) | 2019-01-09 | 2019-01-09 | Method for constructing all-solid-state flexible supercapacitor based on double-solid-state redox electrolyte |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109637845A CN109637845A (en) | 2019-04-16 |
| CN109637845B true CN109637845B (en) | 2021-06-22 |
Family
ID=66067062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811295160.8A Active CN109637845B (en) | 2019-01-09 | 2019-01-09 | Method for constructing all-solid-state flexible supercapacitor based on double-solid-state redox electrolyte |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109637845B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110676073A (en) * | 2019-10-18 | 2020-01-10 | 长沙理工大学 | Electrolyte, enhanced all-solid-state flexible supercapacitor based on electrolyte and preparation method of enhanced all-solid-state flexible supercapacitor |
| CN111146013A (en) * | 2020-01-10 | 2020-05-12 | 厦门理工学院 | Hollow micro-tube electrode material based on ramie, and synthesis method and application thereof |
| CN111524716B (en) * | 2020-01-10 | 2022-04-29 | 厦门理工学院 | Preparation and application of composite electrode material with manila herb as carbon source |
| CN111261417A (en) * | 2020-01-16 | 2020-06-09 | 厦门理工学院 | Cobalt oxide-aloe-derived porous carbon composite electrode material and synthesis method and application thereof |
| CN113113676B (en) * | 2021-03-29 | 2022-11-29 | 南京理工大学 | Method for expanding voltage of water system energy storage device by introducing competitive type oxidation-reduction reaction |
| CN113097463A (en) * | 2021-03-30 | 2021-07-09 | 重庆科技学院 | Preparation method of cobaltous oxide nanosheet array/carbon cloth composite lithium ion battery flexible negative electrode material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100015875A (en) * | 2007-04-25 | 2010-02-12 | 니뽄 고어-텍스 인크. | Method for producing polymer electrolyte membrane for solid polymer fuel cell, membrane electrode assembly for solid polymer fuel cell, and solid polymer fuel cell |
| CN101162650B (en) * | 2007-05-29 | 2010-06-30 | 中南大学 | Flexible thin film type solid-state super capacitor and its manufacture process |
| CN102509635A (en) * | 2011-10-31 | 2012-06-20 | 华中科技大学 | Preparation method of flexible super capacitor based on carbon cloth |
| US20130171502A1 (en) * | 2011-12-29 | 2013-07-04 | Guorong Chen | Hybrid electrode and surface-mediated cell-based super-hybrid energy storage device containing same |
| CN103854878A (en) * | 2014-01-28 | 2014-06-11 | 华中科技大学 | Supercapacitor based on polypyrrole / manganese dioxide / carbon cloth and manufacturing method thereof |
| CN105070511B (en) * | 2015-08-05 | 2017-09-26 | 清华大学 | A kind of fibrous ultracapacitor and preparation method thereof |
-
2019
- 2019-01-09 CN CN201811295160.8A patent/CN109637845B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109637845A (en) | 2019-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109637845B (en) | Method for constructing all-solid-state flexible supercapacitor based on double-solid-state redox electrolyte | |
| CN103500826B (en) | A kind of preparation method of positive composite material of graphene-lithium battery | |
| CN107221716A (en) | A kind of chargeable water system Zinc ion battery | |
| Cheng et al. | Proton-conducting polyoxometalates as redox electrolytes synergistically boosting the performance of self-healing solid-state supercapacitors with polyaniline | |
| CN105702483A (en) | Paper-base polypyrrole composite film and preparation method thereof | |
| Deng et al. | Flexible quasi-solid-state dual-ion asymmetric supercapacitor based on Ni (OH) 2 and Nb2O5 nanosheet arrays | |
| CN112614987B (en) | Positive electrode active material, preparation method thereof, positive electrode material, positive electrode and zinc ion battery | |
| Yuan et al. | Influencing Factors and Suppressing Strategies of the Self-Discharge for Carbon Electrode Materials in Supercapacitors | |
| CN107045948B (en) | NaxMnO2Positive electrode, preparation method and applications | |
| CN105406042A (en) | Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery | |
| CN109671946A (en) | Zinc ion battery positive electrode active materials, positive electrode, Zinc ion battery anode, Zinc ion battery and its preparation method and application | |
| CN103745833A (en) | Super capacitor battery and preparation method thereof | |
| CN105206429A (en) | Flexible thin film electrode material and preparation method thereof | |
| Zhang et al. | Designing better flow batteries: an overview on fifty years’ research | |
| CN103887076A (en) | Water system asymmetric super capacitor and preparation method thereof | |
| CN104124435B (en) | Multiple edge MoS2nanometer sheet/Graphene electrochemistry storage sodium combination electrode and preparation method | |
| CN109036861A (en) | Flexible solid paper base supercapacitor and forming method thereof | |
| Yang et al. | A hierarchical strategy for fabricating synergistic 3D network bio-based porous carbon and 0D niobium-based bimetallic oxides as counter electrodes for I-and Cu-mediated dye-sensitized solar cells with N719 and Y123 dyes | |
| CN103887085A (en) | High-voltage electrolyte for hybrid super tantalum capacitor and preparation method thereof | |
| CN109616616B (en) | Preparation method of vanadium oxide nanobelt/foamed nickel composite self-supporting electrode material | |
| CN116741548A (en) | TiCu-HHTP MOF material and preparation and application thereof | |
| Abdalla et al. | Rational design and prospects for advanced aqueous Zn–organic batteries enabled by multielectron redox reactions | |
| CN105575676B (en) | A kind of all-solid-state supercapacitor based on PBI KOH anion conducting polymer electrolyte and preparation method thereof | |
| CN106128780B (en) | A kind of preparation method and applications of mangano-manganic oxide/DWCNT nanocomposites | |
| CN108400308A (en) | A kind of method that in-stiu coating conducting polymer improves electrode capacity |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |