CN105719842A - All-solid-state battery-capacitor hybrid device and preparation method thereof - Google Patents
All-solid-state battery-capacitor hybrid device and preparation method thereof Download PDFInfo
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- CN105719842A CN105719842A CN201610058570.5A CN201610058570A CN105719842A CN 105719842 A CN105719842 A CN 105719842A CN 201610058570 A CN201610058570 A CN 201610058570A CN 105719842 A CN105719842 A CN 105719842A
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- 239000003990 capacitor Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 70
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 56
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 29
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 29
- 229910017052 cobalt Inorganic materials 0.000 claims description 29
- 239000010941 cobalt Substances 0.000 claims description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 29
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 26
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000006260 foam Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007784 solid electrolyte Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229940097267 cobaltous chloride Drugs 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 239000011572 manganese Substances 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002120 nanofilm Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical class [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 229910001753 sapphirine Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- H01G11/04—Hybrid capacitors
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention discloses an all-solid-state battery-capacitor hybrid device and a preparation method thereof. The all-solid-state battery-capacitor hybrid device comprises a positive electrode, a negative electrode, a diaphragm, a solid-state electrolyte and a current collector, wherein the positive electrode is made of nickel cobaltate/manganese oxide composite material, and the negative electrode is made of molybdenum oxide/polypyrrole composite material. The preparation method comprises the following steps of 1, preparing the nickel cobaltate/manganese oxide composite material and the molybdenum oxide/polypyrrole composite material, growing the composite materials or applying the composite materials on a certain substrate; 2, preparing the electrolyte, and controlling a temperature to be 80-100 DEG C; 3, respectively immersing the nickel cobaltate/manganese and the molybdenum oxide/polypyrrole in the electrolyte which is prepared already for 5-20 minutes; and 4, finally, separating the two materials with the diaphragm, separately packaging the two materials into a button device and a soft-package device, and placing the button device and the soft-package device in a drying oven for drying for 8-15 hours at 60-80 DEG C. The all-solid-state battery-capacitor hybrid device has the advantages of simple in synthesis process, saving, environmental friendliness, cheap cost and controllable product morphology, and is also endowed with excellent performance on specific capacity, cycle density, energy density and power density.
Description
Technical field
The invention belongs to field of material technology, relate to a kind of all-solid-state battery based on novel electrode material-capacitor hybrid device and preparation method thereof, particularly relate to a kind of using cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole as the battery of both positive and negative polarity-capacitor hybrid device and preparation method thereof.
Background technology
Along with the day by day serious of environmental pollution and the consumption of the energy, the most increasing research worker is devoted to work out some sustainable and environmentally friendly energy storage devices, in numerous research, ultracapacitor is shown one's talent because having the advantages such as high power density, fast charging and discharging and long cycle life, these advantages also make ultracapacitor have huge potentiality in short time high power discharge field, compensate for the deficiency of accumulator and electrostatic condenser.The appearance of ultracapacitor is the demand of era development, and will demonstrate unprecedented great potential in fields such as information electronics, electric automobile, science and techniques of defence and Aero-Space.But existing ultracapacitor remains drawback, such as, can not meet the requirement of high-energy-density and compare the most single in material selection, majority is all carbon-to-carbon, metal oxide-carbon, the device of metal hydroxides-carbon composition.Want to make the energy density of ultracapacitor improve thus to modify on single material up, and the material that this modification preferably uses a kind of cell type is carried out, because the material of cell type all has a high energy density.So, the device (existing high energy density also has high power density simultaneously) that just can make a mixed type meets people's demand to energy storage device, and its application prospect therefore can also be made wider.Additionally as capacitor often using material with carbon element as negative pole, such as Graphene, CNT etc..It is known that this kind of material has the highest expense compared with metal-oxide or conducting polymer.A kind of material with carbon element can be substituted and cheap negative pole is the most necessary so synthesizing.
Summary of the invention
It is an object of the invention to provide a kind of all-solid-state battery based on novel electrode material-capacitor hybrid device and preparation method thereof, have that synthesis technique is simple, economical environment-protective, the advantage that cheap, product morphology is controlled, specific capacity, circulation, energy density and power density have also embodied superior performance.
It is an object of the invention to be achieved through the following technical solutions:
A kind of all-solid-state battery-capacitor hybrid device, is made up of positive pole, negative pole, barrier film, solid electrolyte and collector, wherein: the most extremely cobalt acid nickel/manganese oxide composite material, and negative pole is molybdenum oxide/Pt/Polypyrrole composite material.
A kind of method preparing above-mentioned all-solid-state battery-capacitor hybrid device based on novel electrode material, comprises the following steps:
One, the sedimentation method, hydro-thermal method or ice bath method is utilized to prepare cobalt acid nickel/manganese oxide and molybdenum oxide/Pt/Polypyrrole composite material so that it is grow or be coated on certain substrate；
Two, preparation electrolyte, temperature controls at 80 ~ 100 DEG C；
Three, cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are immersed in 5 ~ 20 min in the electrolyte prepared respectively；
Four, finally bi-material barrier film is separated, be packaged into button-shaped device and Soft Roll formula device respectively, put into 60 ~ 80 DEG C of baking oven and be dried 8 ~ 15 h.
In above-mentioned preparation method, in described hydro-thermal method and ice bath method, nickel salt used is the one in nickel nitrate and Nickel dichloride., and cobalt salt is the one of cobalt nitrate and cobaltous chloride, and molybdenum source is the one of sodium molybdate and molybdenum powder.
In above-mentioned preparation method, described substrate is one or both in carbon cloth and nickel foam.
In above-mentioned preparation method, described electrolyte is the mixture of one or more in polyvinyl alcohol, lithium chloride, sodium sulfate, potassium hydroxide.
In above-mentioned preparation method, described barrier film is the one in cellulosic separator, polypropylene screen, diaphragm paper and polymer matrix.
The present invention devise a kind of novelty based on cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole respectively as the all-solid-state battery-capacitor hybrid device of both positive and negative polarity, have the advantage that
1, there is higher energy density and power density, the LED bulb of sapphirine after being connected, can be put, embody preferable practicality, if being improved and optimizing, be expected to become preferable energy storage device later.
2, the material chosen is to have fine fake capacitance and the transition metal oxide of battery performance and conducting polymer, has fully broken the combining form of routine.
3, have inexpensively, environmental protection, recuperability.
4, have high theoretical capacitance and in neutral environment good stability.
5, there is the advantages such as good energy density and power density.
6, synthesis technique and simple for assembly process, is expected to become the material of future ideality and device in energy storage.
7, can draw from electro-chemical test, all there is a higher capacity in cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole, is 842 respectivelymAh g-1With 312 mAh
g-1, after assembling them into a device, still can reach a higher electric capacity, additionally, this device is after circulation 10000 circle, the reservation efficiency of its electric capacity still can reach more than 80 percent, embodies superior cycle life；And it is similar to linear triangle from the charging and discharging curve (Fig. 3) of device it is also seen that present one, shows that charge-discharge performance is the most excellent.
Accompanying drawing explanation
Fig. 1 is the structural representation of all-solid-state battery of the present invention-capacitor hybrid device；
Fig. 2 is cobalt acid nickel/manganese oxide of preparing of the present invention and the cycle performance curve of molybdenum oxide/polypyrrole all-solid-state battery-capacitor hybrid device and application；
Fig. 3 is cobalt acid nickel/manganese oxide of preparing of the present invention and the charging and discharging curve of molybdenum oxide/polypyrrole all-solid-state battery-capacitor hybrid device.
Detailed description of the invention
Below in conjunction with the accompanying drawings technical scheme is further described; but it is not limited thereto; every technical solution of the present invention is modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention, all should contain in protection scope of the present invention.
Detailed description of the invention one: as shown in Figure 1, all-solid-state battery-capacitor hybrid device that present embodiment provides mainly is made up of positive pole, negative pole, barrier film, solid electrolyte, collector, using two kinds of different composites of cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole as the both positive and negative polarity of battery-capacitor hybrid device.
Detailed description of the invention two: present embodiment prepares battery-capacitor hybrid device in accordance with the following steps:
One, cobalt acid nickel/manganese oxide material is prepared:
(1) weigh the carbamide of 0.2 g nickel nitrate, 0.4 g cobalt nitrate, 1.2 g ammonium fluorides and 3 g to be dissolved in the distilled water of 70 mL and stir 1 h, then the nickel foam cleaned up is put in reactor.
(2) solution prepared is poured into reactor, at 120 DEG C, react 3 h, obtain cobalt acid nickel nano film.
(3) put in 100 mL reactors after the cobalt acid nickel nano film made being dried 12 h in the baking oven of 60 DEG C.
(4) weigh the potassium permanganate of 0.63 g to be dissolved in the distilled water of 40 mL and stir 30 min, again this solution is poured in the reactor having put cobalt acid nickel nano film well, 180 DEG C of reaction 30 min, obtain cobalt acid nickel/manganese oxide nanometer sheet, and it is being 1.91 A g with electric current density-1Under, quality may be up to 842 than electric capacitymAh g-1, with 2.85 A g-1Under electric current density after charge and discharge cycles 6000 times, capability retention is 97.5%.
Two, molybdenum oxide/Pt/Polypyrrole composite material is prepared:
(1) under conditions of ice bath, being slowly added into by 40mL distilled water in the beaker claiming there are 4 g molybdenum powders, it is orange for stirring 4 h to solution, again orange solution is put in 100 mL reactors, 180 DEG C of reaction 24 h, are finally cooled to room temperature, obtain molybdenum trioxide nano band.
(2) the molybdenum trioxide nano band weighing 0.1g is dissolved in 20mL distilled water, the pyrroles of 0.2mL is added again in this solution, after stirring 30 min, the Ammonium persulfate. having been dissolved in 10mL distilled water 0.4g is slowly dropped in above-mentioned solution and stirs 4 h, last centrifugal drying, obtains molybdenum oxide/polypyrrole nano belt.It is being 1.33 A g with electric current density-1Under, quality may be up to 312 mAh g than electric capacity-1, with 2A g-1Under electric current density after charge and discharge cycles 6000 times, capability retention is 86.2%.
Three, device is prepared:
(1) cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are immersed in respectively 10min in the polyvinyl alcohol/sodium sulfate prepared, wherein: the concentration of sodium sulfate is 1 mol.
(2) being taken out after, molybdenum oxide/polypyrrole does negative pole, and cobalt acid nickel/manganese oxide does positive pole, and centre cellulosic separator separates, and control membrane thicknesses, in 40 μm, is packaged into all solid state button-shaped and Soft Roll formula device.
(3) put into 80 DEG C of baking oven and be dried 10 h.
(4) taking out after being dried, connect wired in series and carry out a LED, individual devices is carried out electro-chemical test, the device that test result is single has good cycle performance, and after circulation 10000 circle, capacity retention rate is 88.2%(Fig. 2).
Detailed description of the invention three: present embodiment is unlike detailed description of the invention two: cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are immersed in respectively 5min in the polyvinyl alcohol/potassium sulfate prepared, wherein: the concentration of potassium sulfate is 1 mol.Being taken out afterwards, molybdenum oxide/polypyrrole does negative pole, and cobalt acid nickel/manganese oxide does positive pole, and centre cellulosic separator separates, and thickness, in 40 μm, is packaged into all solid state button-shaped and Soft Roll formula device.Put into 80 DEG C of baking oven and be dried 8 h.Take out after being dried, obtain battery-capacitor hybrid device.
Detailed description of the invention four: present embodiment is unlike detailed description of the invention two: cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are immersed in respectively 8min in the polyvinyl alcohol/potassium sulfate prepared, wherein: the concentration of potassium sulfate is 2mol.Being taken out afterwards, molybdenum oxide/polypyrrole does negative pole, and cobalt acid nickel/manganese oxide does positive pole, and centre diaphragm paper separates, and thickness, in 40 μm, is packaged into all solid state button-shaped and Soft Roll formula device.Put into 60 DEG C of baking oven and be dried 15 h.Take out after being dried, obtain battery-capacitor hybrid device.
Detailed description of the invention five: present embodiment is unlike detailed description of the invention two: cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are immersed in respectively 15min in the polyvinyl alcohol/sodium sulfate prepared, wherein: the concentration of sodium sulfate is 1.5mol.Being taken out afterwards, molybdenum oxide/polypyrrole does negative pole, and cobalt acid nickel/manganese oxide does positive pole, and centre cellulose membrane separates, and thickness, in 40 μm, is packaged into all solid state button-shaped and Soft Roll formula device.Put into 80 DEG C of dry 12h of baking oven.Take out after being dried, obtain battery-capacitor hybrid device.
Detailed description of the invention six: present embodiment is unlike detailed description of the invention two: cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are immersed in respectively 15min in the polyvinyl alcohol/lithium sulfate prepared, wherein: the concentration of lithium sulfate is 2mol.Being taken out afterwards, molybdenum oxide/polypyrrole does negative pole, and cobalt acid nickel/manganese oxide does positive pole, and centre cellulose membrane separates, and thickness, in 40 μm, is packaged into all solid state button-shaped and Soft Roll formula device.Put into 80 DEG C of dry 12h of baking oven.Take out after being dried, obtain battery-capacitor hybrid device.
Detailed description of the invention seven: present embodiment is unlike detailed description of the invention two: cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are grown respectively and is coated on carbon cloth substrate, both are immersed in 15min in the polyvinyl alcohol/lithium sulfate prepared again, wherein: the concentration of lithium sulfate is 2mol.Being taken out afterwards, molybdenum oxide/polypyrrole does negative pole, and cobalt acid nickel/manganese oxide does positive pole, and centre cellulose membrane separates, and thickness, in 40 μm, is packaged into all solid state button-shaped and Soft Roll formula device.Put into 80 DEG C of dry 12h of baking oven.Take out after being dried, obtain battery-capacitor hybrid device.
Claims (6)
1. all-solid-state battery-capacitor hybrid device, is made up of positive pole, negative pole, barrier film, solid electrolyte and collector, it is characterised in that described the most extremely cobalt acid nickel/manganese oxide composite material, negative pole is molybdenum oxide/Pt/Polypyrrole composite material.
2. the preparation method of all-solid-state battery-capacitor hybrid device described in a claim 1, it is characterised in that described method step is as follows:
One, the sedimentation method, hydro-thermal method or ice bath method is utilized to prepare cobalt acid nickel/manganese oxide and molybdenum oxide/Pt/Polypyrrole composite material so that it is grow or be coated on substrate；
Two, preparation electrolyte, temperature controls at 80 ~ 100 DEG C；
Three, cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are immersed in 5 ~ 20 min in the electrolyte prepared respectively；
Four, finally bi-material barrier film is separated, be packaged into button-shaped device and Soft Roll formula device respectively, put into 60 ~ 80 DEG C of baking oven and be dried 8 ~ 15 h, obtain all-solid-state battery-capacitor hybrid device.
The preparation method of all-solid-state battery the most according to claim 2-capacitor hybrid device, it is characterized in that in described hydro-thermal method and ice bath method, nickel salt used is the one in nickel nitrate and Nickel dichloride., and cobalt salt is the one of cobalt nitrate and cobaltous chloride, and molybdenum source is the one of sodium molybdate and molybdenum powder.
The preparation method of all-solid-state battery the most according to claim 2-capacitor hybrid device, it is characterised in that described substrate is one or both in carbon cloth and nickel foam.
The preparation method of all-solid-state battery the most according to claim 2-capacitor hybrid device, it is characterised in that described electrolyte is the mixture of one or more in polyvinyl alcohol, lithium chloride, sodium sulfate, potassium hydroxide.
The preparation method of all-solid-state battery the most according to claim 2-capacitor hybrid device, it is characterised in that described barrier film is the one in cellulosic separator, polypropylene screen, diaphragm paper and polymer matrix.
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| CN110165303A (en) * | 2019-06-10 | 2019-08-23 | 天津瑞晟晖能科技有限公司 | Secondary cell and preparation method thereof, electrical equipment |
| CN112863897A (en) * | 2020-12-24 | 2021-05-28 | 华南理工大学 | Based on A-CNTs/KxMnO2And Ti3C2Ty/MoO3Flexible super capacitor and its making method |
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