CN105719842B - 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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- CN105719842B CN105719842B CN201610058570.5A CN201610058570A CN105719842B CN 105719842 B CN105719842 B CN 105719842B CN 201610058570 A CN201610058570 A CN 201610058570A CN 105719842 B CN105719842 B CN 105719842B
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Abstract
The invention discloses a kind of all-solid-state battery capacitor hybrid device and preparation method thereof, the all-solid-state battery capacitor hybrid device is made up of positive pole, negative pole, barrier film, solid electrolyte and collector, wherein：Just extremely cobalt acid nickel/manganese oxide composite material, negative pole are molybdenum oxide/Pt/Polypyrrole composite material, and preparation method is as follows：First, cobalt acid nickel/manganese oxide and molybdenum oxide/Pt/Polypyrrole composite material are prepared, it is grown or is coated on certain substrate；2nd, electrolyte is prepared, temperature control is at 80 ~ 100 DEG C；3rd, cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are immersed in 5 ~ 20 min in the electrolyte prepared respectively；4th, finally two kinds of materials are separated with barrier film, is packaged into button-shaped device and Soft Roll formula device respectively, be put into 60 ~ 80 DEG C of 8 ~ 15 h of drying of baking oven.The present invention have synthesis technique simple, economical environment-protective, it is cheap, product morphology is controllable the advantages of, superior performance has also been embodied in specific capacity, circulation, energy density and power density.
Description
Technical field
The invention belongs to field of material technology, is related to a kind of all-solid-state battery-capacitor based on novel electrode material and mixes
Clutch part and preparation method thereof, more particularly to it is a kind of using cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole as both positive and negative polarity
Battery-capacitor hybrid device and preparation method thereof.
Background technology
With the getting worse of environmental pollution and the consumption of the energy, more and more researcher is directed to working out now
Some sustainable and environmentally friendly energy storage devices, in numerous research, ultracapacitor is close because having high power
Degree, fast charging and discharging and length cycle life the advantages that and show one's talent, these advantages also cause ultracapacitor in the short time
There are huge potentiality in high power discharge field, compensate for the deficiency of battery and electrostatic condenser.Ultracapacitor is
The demand of era development, and institute is not before being shown in fields such as information electronics, electric automobile, science and techniques of defence and Aero-Space
Some great potentials.But existing ultracapacitor remains drawback, such as the requirement of high-energy-density can not be met simultaneously
And it is relatively simple in material selection, majority is all carbon-to-carbon, metal oxide-carbon, the device of metal hydroxides-carbon composition.
Thus want to make the energy density of ultracapacitor to improve to have to be modified on single material up, and this repair
Decorations are preferably carried out using a kind of material of cell type, because the material of cell type all has a high energy density.This
Sample one, can be to make the device of a mixed type（Existing high energy density, while also there is high power density）Come
Meet the needs of people are to energy storage device, and its application prospect therefore can also be made wider.Additionally as capacitor often with carbon
Material is as negative pole, such as graphene, CNT etc..It is well known that this kind of material and metal oxide or conducting polymer
Compared to very high expense.So synthesizing a kind of can substitute carbon material and cheap negative pole is also necessary
's.
The content 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
Its preparation method, have synthesis technique simple, economical environment-protective, it is cheap, product morphology is controllable the advantages of, in specific capacity, follow
Also superior performance has been embodied in ring, energy density and power density.
The purpose of the present invention is achieved through the following technical solutions：
A kind of all-solid-state battery-capacitor hybrid device, by positive pole, negative pole, barrier film, solid electrolyte and collector structure
Into, wherein：Just extremely cobalt acid nickel/manganese oxide composite material, negative pole are molybdenum oxide/Pt/Polypyrrole composite material.
A kind of method that electrode material based on novelty prepares above-mentioned all-solid-state battery-capacitor hybrid device, including with
Lower step：
First, cobalt acid nickel/manganese oxide and molybdenum oxide/Pt/Polypyrrole composite material are prepared using the precipitation method, hydro-thermal method or ice bath method,
It is set to grow or be coated on certain substrate；
2nd, electrolyte is prepared, temperature control is at 80 ~ 100 DEG C；
3rd, cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are immersed in 5 ~ 20 in the electrolyte prepared respectively
min；
4th, finally two kinds of materials are separated with barrier film, is packaged into button-shaped device and Soft Roll formula device respectively, is put into baking oven
60 ~ 80 DEG C of 8 ~ 15 h of drying.
In above-mentioned preparation method, nickel salt used is one in nickel nitrate and nickel chloride in described hydro-thermal method and ice bath method
Kind, cobalt salt is one kind of cobalt nitrate and cobalt chloride, and molybdenum source is one kind of sodium molybdate and molybdenum powder.
In above-mentioned preparation method, described substrate is one or both of carbon cloth and nickel foam.
In above-mentioned preparation method, described electrolyte is one kind in polyvinyl alcohol, lithium chloride, sodium sulphate, potassium hydroxide
Or a variety of mixture.
In above-mentioned preparation method, the barrier film is in cellulosic separator, polypropylene screen, diaphragm paper and polymer matrix
It is a kind of.
The present invention devise it is a kind of it is novel based on cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole respectively as both positive and negative polarity
All-solid-state battery-capacitor hybrid device, there is advantages below：
1st, there is higher energy density and power density, the LED bulb of sapphirine can be put after being connected, is embodied
Preferable practicality, if improved and optimized, it is expected to turn into preferable energy storage device later.
2nd, the material chosen is the transition metal oxide and conducting polymer for having fine fake capacitance and battery performance, is filled
Divide the combining form for having broken routine.
3rd, there is cheap, environmental protection, recuperability.
4th, there is high theoretical capacitance and the good stability in neutral environment.
5th, there is good energy density and power density.
6th, synthesis technique and simple for assembly process, material and device as future ideality are expected in energy storage.
7th, can be drawn from electro-chemical test, cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole all exist one higher
Capacity, it is 842mAh g respectively-1With 312 mAh g-1, assemble them into after a device, still can reach one higher
Electric capacity, in addition, this device circulation 10000 circle after, the reservation efficiency of its electric capacity still can reach more than 80 percent,
Embody superior cycle life；And from the charging and discharging curve of device（Fig. 3）It is also seen that presenting one is similar to line
The triangle of property, shows that charge-discharge performance is very excellent.
Brief description of the drawings
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 and molybdenum oxide/polypyrrole all-solid-state battery-capacitor blender prepared by the present invention
The cycle performance curve of part and application；
Fig. 3 is cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole all-solid-state battery-capacitor blender prepared by the present invention
The charging and discharging curve of part.
Embodiment
Technical scheme is further described below in conjunction with the accompanying drawings, but is not limited thereto, it is every to this
Inventive technique scheme is modified or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, all should cover
In protection scope of the present invention.
Embodiment one：As shown in figure 1, all-solid-state battery-capacitor hybrid device master that present embodiment provides
To be made up of positive pole, negative pole, barrier film, solid electrolyte, collector, with two kinds of cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole not
Both positive and negative polarity of the same composite respectively as battery-capacitor hybrid device.
Embodiment two：Present embodiment prepares battery-capacitor hybrid device in accordance with the following steps：
First, cobalt acid nickel/oxidation manganese material is prepared：
（1）The urea for weighing 0.2 g nickel nitrates, 0.4 g cobalt nitrates, 1.2 g ammonium fluorides and 3 g is dissolved in 70 mL steaming
1 h is stirred in distilled water, then the nickel foam cleaned up is put into reactor.
（2）The solution prepared is poured into reactor, 3 h are reacted at 120 DEG C, obtains cobalt acid nickel nano film.
（3）100 mL reactions are put into after the cobalt acid nickel nano film made is dried into 12 h in 60 DEG C of baking oven
In kettle.
（4）The potassium permanganate for weighing 0.63 g is dissolved in 40 mL distilled water and stirs 30 min, then this solution is poured into
In the reactor for having put cobalt acid nickel nano film well, 180 DEG C reaction 30 min, obtain cobalt acid nickel/manganese oxide nanometer sheet, its with
Current density is 1.91 A g-1Under, quality specific capacitance may be up to 842mAh g-1, with 2.85 A g-1Charge and discharge under current density
After electricity circulation 6000 times, capability retention 97.5%.
2nd, molybdenum oxide/Pt/Polypyrrole composite material is prepared：
（1）Under conditions of ice bath, 40mL distilled water is slowly added into title has in the beaker of 4 g molybdenum powders, stirs 4 h
It is in orange to solution, then orange solution is put into 100 mL reactors, 180 DEG C of 24 h of reaction, is finally cooled to room temperature, obtains
Molybdenum trioxide nano band.
（2）The molybdenum trioxide nano band for weighing 0.1g is dissolved in 20mL distilled water, then adds 0.2mL's into the solution
Pyrroles, after stirring 30 min, the ammonium persulfate for having been dissolved in 10mL distilled water 0.4g is slowly dropped in above-mentioned solution and stirred
4 h are mixed, last centrifugal drying, obtain molybdenum oxide/polypyrrole nanobelt.It is using current density as 1.33 A g-1Under, mass ratio
Electric capacity may be up to 312 mAh g-1, with 2A g-1Under current density after charge and discharge cycles 6000 times, capability retention is
86.2%。
3rd, device is prepared：
（1）Cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are immersed in the polyvinyl alcohol/sulfuric acid prepared respectively
10min in sodium, wherein：The concentration of sodium sulphate is 1 mol.
（2）Taken out afterwards, molybdenum oxide/polypyrrole does negative pole, and cobalt acid nickel/manganese oxide does positive pole, centre cellulose
Barrier film separates, and control membrane thicknesses are packaged into all solid state button-shaped and Soft Roll formula device at 40 μm.
（3）It is put into 80 DEG C of 10 h of drying of baking oven.
（4）Taken out after drying, connecting wire series connection carries out a LED, and individual devices are carried out with electro-chemical test, test
Result is that single device has good cycle performance, and after the circle of circulation 10000, capacity retention rate is 88.2%（Fig. 2）.
Embodiment three：Present embodiment is unlike embodiment two：By cobalt acid nickel/manganese oxide and oxygen
Change molybdenum/polypyrrole and be immersed in 5min in the polyvinyl alcohol/potassium sulfate prepared respectively, wherein：The concentration of potassium sulfate is 1
mol.Taken out afterwards, molybdenum oxide/polypyrrole does negative pole, and cobalt acid nickel/manganese oxide does positive pole, centre cellulosic separator every
Open, thickness is packaged into all solid state button-shaped and Soft Roll formula device at 40 μm.It is put into 80 DEG C of 8 h of drying of baking oven.Taken after drying
Go out, obtain battery-capacitor hybrid device.
Embodiment four：Present embodiment is unlike embodiment two：By cobalt acid nickel/manganese oxide and oxygen
Change molybdenum/polypyrrole and be immersed in 8min in the polyvinyl alcohol/potassium sulfate prepared respectively, wherein：The concentration of potassium sulfate is
2mol.Taken out afterwards, molybdenum oxide/polypyrrole does negative pole, and cobalt acid nickel/manganese oxide does positive pole, and centre is separated with diaphragm paper, thick
Degree is packaged into all solid state button-shaped and Soft Roll formula device at 40 μm.It is put into 60 DEG C of 15 h of drying of baking oven.Taken out after drying,
Obtain battery-capacitor hybrid device.
Embodiment five：Present embodiment is unlike embodiment two：By cobalt acid nickel/manganese oxide and oxygen
Change molybdenum/polypyrrole and be immersed in 15min in the polyvinyl alcohol/sodium sulphate prepared respectively, wherein：The concentration of sodium sulphate is
1.5mol.Taken out afterwards, molybdenum oxide/polypyrrole does negative pole, and cobalt acid nickel/manganese oxide does positive pole, centre cellulose membrane every
Open, thickness is packaged into all solid state button-shaped and Soft Roll formula device at 40 μm.It is put into the dry 12h of 80 DEG C of baking oven.Taken after drying
Go out, obtain battery-capacitor hybrid device.
Embodiment six：Present embodiment is unlike embodiment two：By cobalt acid nickel/manganese oxide and oxygen
Change molybdenum/polypyrrole and be immersed in 15min in the polyvinyl alcohol/lithium sulfate prepared respectively, wherein：The concentration of lithium sulfate is
2mol.To be taken out afterwards, molybdenum oxide/polypyrrole does negative pole, and cobalt acid nickel/manganese oxide does positive pole, and centre is separated with cellulose membrane,
Thickness is packaged into all solid state button-shaped and Soft Roll formula device at 40 μm.It is put into the dry 12h of 80 DEG C of baking oven.Taken out after drying,
Obtain battery-capacitor hybrid device.
Embodiment seven：Present embodiment is unlike embodiment two：By cobalt acid nickel/manganese oxide and oxygen
Change molybdenum/polypyrrole to grow and be coated on carbon cloth substrate respectively, then both are immersed in the polyvinyl alcohol/sulfuric acid prepared
15min in lithium, wherein：The concentration of lithium sulfate is 2mol.Taken out afterwards, molybdenum oxide/polypyrrole does negative pole, cobalt acid nickel/oxygen
Change manganese and do positive pole, centre is separated with cellulose membrane, and thickness is packaged into all solid state button-shaped and Soft Roll formula device at 40 μm.Put
Enter the dry 12h of 80 DEG C of baking oven.Taken out after drying, obtain battery-capacitor hybrid device.
Claims (5)
1. a kind of all-solid-state battery-capacitor hybrid device, is made up of positive pole, negative pole, barrier film, solid electrolyte and collector,
It is characterized in that described, just extremely cobalt acid nickel/manganese oxide composite material, negative pole are molybdenum oxide/Pt/Polypyrrole composite material.
A kind of 2. preparation method of all-solid-state battery described in claim 1-capacitor hybrid device, it is characterised in that methods described
Step is as follows：
First, cobalt acid nickel/manganese oxide and molybdenum oxide/Pt/Polypyrrole composite material are prepared using the precipitation method, hydro-thermal method or ice bath method, makes it
Grow or be coated on substrate；
2nd, electrolyte is prepared, temperature control is at 80 ~ 100 DEG C；The electrolyte is polyvinyl alcohol and lithium chloride, sodium sulphate, hydrogen-oxygen
Change one or more mixtures in potassium；
3rd, cobalt acid nickel/manganese oxide and molybdenum oxide/polypyrrole are immersed in 5 ~ 20min in the electrolyte prepared respectively；
4th, finally two kinds of materials are separated with barrier film, are packaged into button-shaped device and Soft Roll formula device respectively, be put into baking oven 60 ~
80 DEG C of dry 8 ~ 15h, produce all-solid-state battery-capacitor hybrid device.
3. the preparation method of all-solid-state battery according to claim 2-capacitor hybrid device, it is characterised in that the water
In hot method and ice bath method, nickel salt used is one kind in nickel nitrate and nickel chloride, and cobalt salt is one kind of cobalt nitrate and cobalt chloride, molybdenum
Source is one kind of sodium molybdate and molybdenum powder.
4. the preparation method of all-solid-state battery according to claim 2-capacitor hybrid device, it is characterised in that the lining
Bottom is one or both of carbon cloth and nickel foam.
5. the preparation method of all-solid-state battery according to claim 2-capacitor hybrid device, it is characterised in that described
Barrier film is polymer matrix；Described polymer matrix is one kind in cellulosic separator, POLYPROPYLENE GLYCOL, diaphragm paper.
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| CN106219616B (en) * | 2016-07-18 | 2019-02-19 | 合肥工业大学 | A kind of molybdenum dioxide/cobalt acid nickel classification hybrid nanostructure array and preparation method thereof |
| CN108242342B (en) * | 2018-01-18 | 2020-01-03 | 太原理工大学 | NiCo2O4@MnO2Foamed nickel/MnO2Preparation method of supercapacitor composite electrode material |
| CN110165303B (en) * | 2019-06-10 | 2022-04-26 | 南京理工大学北方研究院 | Secondary battery, preparation method thereof and electric equipment |
| CN112863897B (en) * | 2020-12-24 | 2021-12-21 | 华南理工大学 | Based on A-CNTs/KxMnO2And Ti3C2Ty/MoO3Flexible super capacitor and its making method |
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| CN103606467A (en) * | 2013-11-21 | 2014-02-26 | 东华大学 | Preparation method for NiCo2O4/MnO2/AC water system asymmetric super capacitor |
| CN105097292A (en) * | 2015-08-17 | 2015-11-25 | 哈尔滨工业大学 | All-solid asymmetric supercapacitor and manufacturing method thereof |
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| CN103606467A (en) * | 2013-11-21 | 2014-02-26 | 东华大学 | Preparation method for NiCo2O4/MnO2/AC water system asymmetric super capacitor |
| CN105097292A (en) * | 2015-08-17 | 2015-11-25 | 哈尔滨工业大学 | All-solid asymmetric supercapacitor and manufacturing method thereof |
Non-Patent Citations (1)
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| 纳米MoO3复合物电极材料的制备及其在电化学电容器中的应用研究;刘昱;《中国优秀硕士学位论文全文数据库工程科技I辑》;20150315;正文第26-33页 * |
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