CN106684245B - A kind of electrical storage device and preparation method thereof based on one-dimensional organic-inorganic hybrid polymer chain - Google Patents
A kind of electrical storage device and preparation method thereof based on one-dimensional organic-inorganic hybrid polymer chain Download PDFInfo
- Publication number
- CN106684245B CN106684245B CN201611219319.9A CN201611219319A CN106684245B CN 106684245 B CN106684245 B CN 106684245B CN 201611219319 A CN201611219319 A CN 201611219319A CN 106684245 B CN106684245 B CN 106684245B
- Authority
- CN
- China
- Prior art keywords
- organic
- inorganic hybrid
- hybrid polymer
- electrical storage
- storage device
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- -1 amine salt Chemical class 0.000 claims abstract description 13
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000012047 saturated solution Substances 0.000 claims abstract description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 9
- 230000036571 hydration Effects 0.000 claims abstract description 9
- 238000006703 hydration reaction Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 230000033228 biological regulation Effects 0.000 claims abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000004528 spin coating Methods 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- ANUAIBBBDSEVKN-UHFFFAOYSA-N benzene-1,2,4,5-tetramine Chemical compound NC1=CC(N)=C(N)C=C1N ANUAIBBBDSEVKN-UHFFFAOYSA-N 0.000 claims description 6
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 239000011232 storage material Substances 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 150000003840 hydrochlorides Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 230000005611 electricity Effects 0.000 abstract description 15
- 150000002736 metal compounds Chemical class 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 230000006399 behavior Effects 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 239000010409 thin film Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a kind of electrical storage devices and preparation method thereof based on one-dimensional organic-inorganic hybrid polymer chain；Preparation includes the following steps：Six hydration Nickel Chloride aqueous solutions are instilled in amine salt organic solution, then regulation system pH value is 7；Then it is stirred to react 6 hours, prepares organic-inorganic hybrid polymer；Organic-inorganic hybrid polymer saturated solution is applied in substrate, organic film is prepared；Then electrode is prepared on organic film, obtains the electrical storage device based on one-dimensional organic-inorganic hybrid polymer chain.The present invention forms one-dimensional organic-inorganic hybrid polymer using organic molecule and inorganic metal compound by coordination, it is prepared into organic electrical storage device of sandwich structure, it is successfully realized Organic Electricity storage behavior, preparation process is simple, and device environment and high-temperature stability are good；Therefore the application the invention also discloses above-mentioned organic-inorganic hybrid polymer in preparing electrical storage device.
Description
Technical field
The invention belongs to organic semiconducting materials technical fields, and in particular to one kind is polymerize based on one-dimensional organic inorganic hybridization
The electrical storage device and preparation method thereof of object chain.
Background technology
With the fast development of modern information technologies, human society has come into the epoch of information explosion, especially mutually
The fast development of networking technology so that explosive growth is presented in information content.Bulk information is cannot be satisfied in conventional storage technologies
Under the background of storage demand, Organic Electricity memory technology causes more and more concerns, and the generation of ternary memory technology makes
The memory capacity of information is from 2nIt is promoted to 3n, the growth of power side's grade is realized, is had for the promotion of information storage capacity great
Meaning.For organic material, organic molecular structure designability is strong, is easy to purify, and can be applied to flexible device, still
Environment and high-temperature stability are poor；On the other hand, inorganic material need mostly carry out high-temperature process, to experiment condition require compared with
Height, and inorganic material type itself is very limited.Therefore, it just needs to provide when solving electrical storage device problem encountered
New material solution.
Invention content
It is complicated for the preparation process of current Organic Electricity storage material, the problems such as environment and poor high temperature stability, the present invention
Disclose a kind of electrical storage device and preparation method thereof based on one-dimensional organic-inorganic hybrid polymer chain, preparation process letter
Single, device environment and high-temperature stability are good, are of great significance for the practicality of moving towards of Organic Electricity memory technology.
The present invention adopts the following technical scheme that, a kind of electrical storage device based on one-dimensional organic-inorganic hybrid polymer chain
Preparation method includes the following steps：
（1）Under the conditions of ice-water bath, six hydration Nickel Chloride aqueous solutions are instilled in amine salt organic solution, then regulation system
PH values are 7；Then it is stirred to react 6 hours, prepares organic-inorganic hybrid polymer；The amine salt is 1,2,4,5- benzene tetramine four
Four hydrochloride of hydrochloride or 3,3'-diaminobenzidine；
（2）Organic-inorganic hybrid polymer saturated solution is applied in substrate, organic film is prepared；Then in organic film
On prepare electrode, obtain the electrical storage device based on one-dimensional organic-inorganic hybrid polymer chain.
In above-mentioned technical proposal, step（1）In, the molar ratio of six hydration Nickel Chlorides and amine salt is 1:1；The amine salt has
In machine solution, solvent DMF；It is 7 with ammonia water conditioning system pH values.
In above-mentioned technical proposal, step（1）In, after reaction, reaction solution is by centrifuging, being filtered to remove solvent, then
Solid is separately added into deionized water, acetone, is cleaned by ultrasonic；Then it is dried in vacuo, obtains organic-inorganic hybrid polymer, go
Except unreacting material, it is conducive to the raising of device performance.
In above-mentioned technical proposal, step（2）In, in organic-inorganic hybrid polymer saturated solution, solvent DMSO；Using
Organic-inorganic hybrid polymer saturated solution is applied in substrate by spin-coating method；Electrode is prepared on organic film using vapour deposition method.
In above-mentioned technical proposal, step（2）In, the condition for preparing organic film is 150 DEG C of 4 h of vacuum annealing；Spin coating item
Part is 1000~3000 r/min of rotating speed, and the time is 6~20s；Evaporation condition is 5 × 10-4 Under Pa vacuum conditions, evaporation rate
For 2 A/s.
In above-mentioned technical proposal, step（2）In, the substrate is ito glass；The thickness of the organic film be 80~
100 nm；The thickness of the electrode is 80~100 nm.
The thickness of organic film prepared by the present invention is reasonable, and organic electrical storage device, device institute are prepared in conjunction with other component
The performance shown is better；Evaporation rate remains constant, the electrode of preparation than more uniform, be conducive to electricity can stabilization.
The invention also discloses a kind of preparation methods of organic-inorganic hybrid polymer, include the following steps, ice-water bath item
Under part, six hydration Nickel Chloride aqueous solutions are instilled in amine salt organic solution, then regulation system pH values are 7；Then 6 are stirred
Hour, prepare organic-inorganic hybrid polymer；The amine salt is that four hydrochloride of 1,2,4,5- benzene tetramine or 3,3'- diamino join
Four hydrochloride of aniline；Product preparation process is simple, and final products separation is relatively convenient.
The present invention forms one-dimensional organic inorganic hybridization using organic molecule and inorganic metal compound by coordination
Polymer is prepared into organic electrical storage device of sandwich structure, is successfully realized Organic Electricity storage behavior, preparation process letter
Single, device environment and high-temperature stability are good；Therefore the invention also discloses above-mentioned organic-inorganic hybrid polymers deposits preparing electricity
Application in memory device.
Application the present invention further discloses above-mentioned organic-inorganic hybrid polymer as electrical storage device storage material.
Compared with prior art, using above-mentioned technical proposal the invention has the advantages that：
（1）The present invention is prepared for a series of Sanming City using organic-inorganic hybrid polymer chain material as organic active layer
Control organic electrical storage device of type, the preparation method of active layer material and device is simple, convenient, easily operated；
（2）Organic electrical storage device in the present invention is successfully realized ternary electric storage behavior；
（3）Compared with traditional device, organic electrical storage device in the present invention shows preferable environment and high temperature is steady
Qualitative, moving towards practical for organic electrical storage device has great meaning.
Description of the drawings
Fig. 1 is the structural schematic diagram of one organic electrical storage device of embodiment；
Fig. 2 is electric storage behavior and the stability test result figure of one organic electrical storage device of embodiment；
Fig. 3 is the X-ray diffractogram of one organic electrical storage device of embodiment；
Fig. 4 is the transmission electron microscope (a) and scanning electron microscope (c) figure of two organic electrical storage device of embodiment；
Fig. 5 is that the SEM of two organic electrical storage device of embodiment schemes；
Fig. 6 is electric storage behavior and the stability test result figure of three organic electrical storage device of embodiment；
Fig. 7 is the X-ray diffractogram of three organic electrical storage device of embodiment；
Fig. 8 is the transmission electron microscope and scanning electron microscope diagram of the organic electrical storage device of example IV；
Fig. 9 is that the SEM of the organic electrical storage device of example IV schemes；
Figure 10 is the thermal weight loss test chart of TAP and BPA molecules.
Specific implementation mode
The technical solution further illustrated the present invention below in conjunction with the drawings and specific embodiments.Unless otherwise indicated,
Reagent, material, instrument used in the following example etc. can be obtained by commercial means.
Embodiment one
A kind of preparation method of organic-inorganic hybrid polymer, specific synthesis step are as follows：
Four hydrochloride of 1,2,4,5- benzene tetramine（2.84 g, 10 mmol）It is dissolved in DMF (50 mL), two is hydrated by six
Nickel chloride（2.38 g, 10 mmol）It is dissolved in deionized water（50 mL）In, and above-mentioned solution is added drop-wise under the conditions of ice-water bath
In.Reaction system is then adjusted to neutrality by the way that ammonium hydroxide is added dropwise（pH = 7）.6 h are finally stirred at room temperature.After reaction
There is black solid generation, the solvent for centrifuging, being filtered to remove in system is then respectively adding deionized water, and acetone is clear in ultrasonic wave
Washed product in device is washed, and solvent is removed by way of centrifuging, filtering, after repeating the above steps three times, product is put into
In vacuum drying chamber, dry 40 hours, final to obtain black powder product under conditions of 70 DEG C, is denoted as TAP；
Electrical storage device is followed successively by ito glass basal layer, organic as shown in Figure 1, device is divided into three layers substantially from bottom to top
Film layer and aluminium electrode layer, preparation method are as follows：
1, in ultrasonic washing instrument, deionized water, acetone, washes of absolute alcohol ito glass substrate are used successively；
2,2 mg TAP are dissolved in the saturated solution that TAP is prepared into 10 mL DMSO solvents；
3, TAP solution is spun in ito glass substrate by spin-coating method, forms the organic thin film layer that thickness is 80 nm,
4 h that anneal are subsequently placed in 150 DEG C of vacuum drying ovens；Spincoating conditions are as follows：Low speed（1000 r/min）6 s, high speed（3000 r/
min）20 s；
4, aluminium electrode is vaporized on organic thin film layer, until aluminium electrode thickness reaches 80 nm, obtains corresponding Organic Electricity
Memory device A；Evaporation condition is as follows：5 × 10-4 Under Pa vacuum conditions, the rate of vapor deposition is 2 A/s；It finally obtains and is based on one
Tie up organic electrical storage device of organic-inorganic hybrid polymer chain material.
Attached drawing 2 is above-mentioned organic electrical storage device electricity storage behavior and stability test, a to d are respectively fresh device
Ternary WORM type electricity stores behavior；It is fresh, place three months after and 100 DEG C of high temperature under three electricity of device lead state in -1 V
Read voltage under stability result, it can be seen that device place three months after and fresh device under 100 DEG C of high temperature
Show excellent stability.
Attached drawing 3 is above-mentioned organic electrical storage device X-ray diffractogram, including experimental result and fitting result.
Embodiment two
A kind of preparation method of organic-inorganic hybrid polymer, specific synthesis step are as follows：
Four hydrochloride of 1,2,4,5- benzene tetramine（2.84 g, 10 mmol）It is dissolved in DMF (50 mL), two is hydrated by six
Nickel chloride（2.38 g, 10 mmol）It is dissolved in deionized water（50 mL）In, and above-mentioned solution is added drop-wise under the conditions of ice-water bath
In.Reaction system is then adjusted to neutrality by the way that ammonium hydroxide is added dropwise（pH = 7）.6 h are finally stirred at room temperature.After reaction
There is black solid generation, the solvent for centrifuging, being filtered to remove in system is then respectively adding deionized water, and acetone is clear in ultrasonic wave
Washed product in device is washed, and solvent is removed by way of centrifuging, filtering, after repeating the above steps three times, product is put into
In vacuum drying chamber, dry 40 hours, final to obtain black powder product under conditions of 70 DEG C, is denoted as TAP；
The preparation method of electrical storage device, is as follows：
1, in ultrasonic washing instrument, deionized water, acetone, washes of absolute alcohol ito glass substrate are used successively；
2,2 mg TAP are dissolved in the saturated solution that TAP is prepared into 10 mL DMSO solvents；
3, TAP solution is spun in ito glass substrate by spin-coating method, forms the organic film that thickness is 100 nm
Layer, is subsequently placed in 150 DEG C of vacuum drying ovens 4 h that anneal；Spincoating conditions are as follows：Low speed（1000 r/min）6 s, high speed（3000
r/min）20 s；
4, aluminium electrode is vaporized on organic thin film layer, until aluminium electrode thickness reaches 100 nm, is obtained corresponding organic
Electrical storage device A；Evaporation condition is as follows：5 × 10-4 Under Pa vacuum conditions, the rate of vapor deposition is 2 A/s；It finally obtains and is based on
Organic electrical storage device of one-dimensional organic-inorganic hybrid polymer chain material.
Fig. 4 is the transmission electron microscope (a) and scanning electron microscope (c) figure of above-mentioned organic electrical storage device；Fig. 5 is
The SEM of above-mentioned organic electrical storage device schemes.
Embodiment three
A kind of preparation method of organic-inorganic hybrid polymer, specific synthesis step are as follows：
Four hydrochloride of 3,3'-diaminobenzidine（3.60 g, 10 mmol）It is dissolved in DMF (50 mL), by six hydrations
Nickel Chloride（2.38 g, 10 mmol）It is dissolved in deionized water（50 mL）In, and be added drop-wise under the conditions of ice-water bath above-mentioned molten
In liquid.Reaction system is then adjusted to neutrality by the way that ammonium hydroxide is added dropwise（pH = 7）.6 h are finally stirred at room temperature.Reaction terminates
After have black solid generation, the solvent for centrifuging, being filtered to remove in system is then respectively adding deionized water, and acetone is in ultrasonic wave
Washed product in washer, and solvent is removed by way of centrifuging, filtering, after repeating the above steps three times, product is put
Enter in vacuum drying chamber, dry 40 hours, final to obtain black powder product under conditions of 70 DEG C, is denoted as BPA.
The preparation method of electrical storage device, is as follows：
1, in ultrasonic washing instrument, deionized water, acetone, washes of absolute alcohol ito glass substrate are used successively；
2,2 mg BPA are dissolved in the saturated solution that TAP is prepared into 10 mL DMSO solvents；
3, BPA solution is spun in ito glass substrate by spin-coating method, forms the organic thin film layer that thickness is 80 nm,
4 h that anneal are subsequently placed in 150 DEG C of vacuum drying ovens；Spincoating conditions are as follows：Low speed（1000 r/min）6 s, high speed（3000 r/
min）20 s；
4, aluminium electrode is vaporized on organic thin film layer, until aluminium electrode thickness reaches 80 nm, obtains corresponding Organic Electricity
Memory device A；Evaporation condition is as follows：5 × 10-4 Under Pa vacuum conditions, the rate of vapor deposition is 2 A/s；It finally obtains and is based on one
Tie up organic electrical storage device of organic-inorganic hybrid polymer chain material.
Attached drawing 6 is above-mentioned organic electrical storage device electricity storage behavior and stability test, e to h are respectively fresh device
Ternary WORM type electricity stores behavior；It is fresh, place three months after and 100 DEG C of high temperature under three electricity of device lead state in -1 V
Read voltage under stability result, it can be seen that device place three months after and fresh device under 100 DEG C of high temperature
Show excellent stability.
Attached drawing 7 is above-mentioned organic electrical storage device X-ray diffractogram, including experimental result and fitting result.
Example IV
A kind of preparation method of organic-inorganic hybrid polymer, specific synthesis step are as follows：
Four hydrochloride of 3,3'-diaminobenzidine（3.60 g, 10 mmol）It is dissolved in DMF (50 mL), by six hydrations
Nickel Chloride（2.38 g, 10 mmol）It is dissolved in deionized water（50 mL）In, and be added drop-wise under the conditions of ice-water bath above-mentioned molten
In liquid.Reaction system is then adjusted to neutrality by the way that ammonium hydroxide is added dropwise（pH = 7）.6 h are finally stirred at room temperature.Reaction terminates
After have black solid generation, the solvent for centrifuging, being filtered to remove in system is then respectively adding deionized water, and acetone is in ultrasonic wave
Washed product in washer, and solvent is removed by way of centrifuging, filtering, after repeating the above steps three times, product is put
Enter in vacuum drying chamber, dry 40 hours, final to obtain black powder product under conditions of 70 DEG C, is denoted as BPA.
The preparation method of electrical storage device, is as follows：
1, in ultrasonic washing instrument, deionized water, acetone, washes of absolute alcohol ito glass substrate are used successively；
2,2 mg BPA are dissolved in the saturated solution that TAP is prepared into 10 mL DMSO solvents；
3, BPA solution is spun in ito glass substrate by spin-coating method, forms the organic film that thickness is 100 nm
Layer, is subsequently placed in 150 DEG C of vacuum drying ovens 4 h that anneal；Spincoating conditions are as follows：Low speed（1000 r/min）6 s, high speed（3000
r/min）20 s；
4, aluminium electrode is vaporized on organic thin film layer, until aluminium electrode thickness reaches 100 nm, is obtained corresponding organic
Electrical storage device A；Evaporation condition is as follows：5 × 10-4 Under Pa vacuum conditions, the rate of vapor deposition is 2 A/s；It finally obtains and is based on
Organic electrical storage device of one-dimensional organic-inorganic hybrid polymer chain material.
Fig. 8 is the transmission electron microscope (b) and scanning electron microscope (d) figure of above-mentioned organic electrical storage device；Fig. 9 is
The SEM of above-mentioned organic electrical storage device schemes.
Figure 10 is the thermal weight loss test chart of TAP and BPA molecules, and it is good to illustrate that the organic-inorganic polymer of the present invention has
Hot property.
In conclusion the present invention utilizes the sandwich structure based on one-dimensional organic-inorganic hybrid polymer chain material preparation
Electrical storage device is successfully realized the electric storage behavior of ternary WORM types, and device is after a long time placement and in height
Good stability is shown under the conditions of temperature, solves asking for current organic electrical storage device environment and poor high temperature stability
Topic.Electrical storage device based on one-dimensional organic-inorganic hybrid polymer chain material preparation has high application value.
Claims (10)
1. a kind of preparation method of the electrical storage device based on one-dimensional organic-inorganic hybrid polymer chain, which is characterized in that including
Following steps：
（1）Under the conditions of ice-water bath, six hydration Nickel Chloride aqueous solutions are instilled in amine salt organic solution, then regulation system pH
Value is 7；Then it is stirred to react 6 hours, prepares organic-inorganic hybrid polymer；The amine salt is four hydrochloric acid of 1,2,4,5- benzene tetramine
Four hydrochloride of salt or 3,3'-diaminobenzidine；
（2）Organic-inorganic hybrid polymer saturated solution is applied in substrate, organic film is prepared；Then it is made on organic film
Standby electrode, obtains the electrical storage device based on one-dimensional organic-inorganic hybrid polymer chain.
2. the preparation method of the electrical storage device according to claim 1 based on one-dimensional organic-inorganic hybrid polymer chain,
It is characterized in that, step（1）In, the molar ratio of six hydration Nickel Chlorides and amine salt is 1: 1；In the amine salt organic solution, solvent
For DMF；It is 7 with ammonia water conditioning system pH values.
3. the preparation method of the electrical storage device according to claim 1 based on one-dimensional organic-inorganic hybrid polymer chain,
It is characterized in that, step（2）In, in organic-inorganic hybrid polymer saturated solution, solvent DMSO；Using spin-coating method by organic nothing
Machine hybridized polymer saturated solution is applied in substrate；Electrode is prepared on organic film using vapour deposition method.
4. the preparation method of the electrical storage device according to claim 3 based on one-dimensional organic-inorganic hybrid polymer chain,
It is characterized in that, step（2）In, the condition for preparing organic film is 150 DEG C of 4 h of vacuum annealing；When spin coating rotating speed be 1000~
3000 r/min, time are 6~20s；Pressure is 5 × 10 when vapor deposition-4 Pa, rate are 2 A/s.
5. the preparation method of the electrical storage device according to claim 1 based on one-dimensional organic-inorganic hybrid polymer chain,
It is characterized in that, step（2）In, the substrate is ito glass；The thickness of the organic film is 80~100 nm；The electrode
Thickness be 80~100 nm.
6. prepared by the preparation method of the electrical storage device according to claim 1 based on one-dimensional organic-inorganic hybrid polymer chain
The electrical storage device based on one-dimensional organic-inorganic hybrid polymer chain.
7. a kind of preparation method of organic-inorganic hybrid polymer, which is characterized in that include the following steps, under the conditions of ice-water bath,
Six hydration Nickel Chloride aqueous solutions are instilled in amine salt organic solution, then regulation system pH values are 7；Then it stirs 6 hours,
Prepare organic-inorganic hybrid polymer；The amine salt is four hydrochloride of 1,2,4,5- benzene tetramine or 3,3'-diaminobenzidine
Four hydrochlorides.
8. organic-inorganic hybrid polymer prepared by preparation method according to claim 7.
9. application of the organic-inorganic hybrid polymer described in claim 8 in preparing electrical storage device.
10. application of the organic-inorganic hybrid polymer described in claim 8 as electrical storage device storage material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611219319.9A CN106684245B (en) | 2016-12-26 | 2016-12-26 | A kind of electrical storage device and preparation method thereof based on one-dimensional organic-inorganic hybrid polymer chain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611219319.9A CN106684245B (en) | 2016-12-26 | 2016-12-26 | A kind of electrical storage device and preparation method thereof based on one-dimensional organic-inorganic hybrid polymer chain |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106684245A CN106684245A (en) | 2017-05-17 |
| CN106684245B true CN106684245B (en) | 2018-08-14 |
Family
ID=58870672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611219319.9A Active CN106684245B (en) | 2016-12-26 | 2016-12-26 | A kind of electrical storage device and preparation method thereof based on one-dimensional organic-inorganic hybrid polymer chain |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106684245B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108511604B (en) * | 2018-04-11 | 2021-12-10 | 苏州大学 | Dopamine-based self-polymerization electric storage material, preparation method thereof and application of dopamine-based self-polymerization electric storage material in electric storage device |
| CN108615813B (en) * | 2018-04-19 | 2021-07-16 | 苏州大学 | Electric storage device based on one-dimensional organic-inorganic hybrid polymer chain and preparation method thereof |
| CN109037441B (en) * | 2018-08-01 | 2022-06-21 | 苏州大学 | Semiconductor electric storage material, flexible electric storage device prepared from semiconductor electric storage material and preparation method of flexible electric storage device |
| CN109659432B (en) * | 2018-10-29 | 2020-09-08 | 南京工业大学 | Write-once read-many memory based on coordination polymer film of benzene tetramine and preparation method thereof |
| CN109659431A (en) * | 2018-10-29 | 2019-04-19 | 南京工业大学 | The flash memories of coordination polymer film and preparation method thereof based on benzene tetramine |
| WO2020204838A2 (en) * | 2019-04-04 | 2020-10-08 | Nanyang Technological University | Π-d conjugated coordination polymer for electrochromic energy storage |
| CN115472815B (en) * | 2022-09-23 | 2024-04-26 | 天津大学 | Vanadium-based positive electrode material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214900A (en) * | 2013-04-24 | 2013-07-24 | 南京邮电大学 | Waste-based organic nano-ink applied to film device process, and preparation and application of waste-based organic nano-ink |
| CN103497176A (en) * | 2013-10-21 | 2014-01-08 | 苏州大学 | Ternary system electric storage material and preparation and application thereof |
| CN105130988A (en) * | 2015-07-31 | 2015-12-09 | 南京邮电大学 | Ion type perylene imide material, preparation method, and organic storage device thereof |
| CN105742501A (en) * | 2016-05-03 | 2016-07-06 | 苏州大学 | Organic electric memory device based on phosphonic acid or trichlorosilane-modified ITO glass substrate and preparation method for organic electric memory device |
-
2016
- 2016-12-26 CN CN201611219319.9A patent/CN106684245B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214900A (en) * | 2013-04-24 | 2013-07-24 | 南京邮电大学 | Waste-based organic nano-ink applied to film device process, and preparation and application of waste-based organic nano-ink |
| CN103497176A (en) * | 2013-10-21 | 2014-01-08 | 苏州大学 | Ternary system electric storage material and preparation and application thereof |
| CN105130988A (en) * | 2015-07-31 | 2015-12-09 | 南京邮电大学 | Ion type perylene imide material, preparation method, and organic storage device thereof |
| CN105742501A (en) * | 2016-05-03 | 2016-07-06 | 苏州大学 | Organic electric memory device based on phosphonic acid or trichlorosilane-modified ITO glass substrate and preparation method for organic electric memory device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106684245A (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106684245B (en) | A kind of electrical storage device and preparation method thereof based on one-dimensional organic-inorganic hybrid polymer chain | |
| CN102723209B (en) | Preparation method for graphene nanosheet/conducting polymer nanowire composite material | |
| CN108597898A (en) | A kind of preparation method of cobalt sulfide zinc nano material | |
| CN106915735B (en) | Preparation method of nitrogen or metal doped carbon material | |
| CN107302055A (en) | A kind of preparation method of perovskite thin film | |
| CN105931855B (en) | The synthesis of nitrogen sulphur codope carbon-polyaniline composite material and be applied to supercapacitor | |
| CN108362741B (en) | Preparation method and use method of gas sensor based on metal phthalocyanine | |
| CN102175724A (en) | Composite resistance NH3 gas-sensitive gas sensor and preparation method thereof | |
| CN112280051A (en) | Preparation method and application of cobalt-based metal organic framework Co-MOF material | |
| CN106549105B (en) | A kind of conjugation fullerene/graphene film solar battery and preparation method thereof | |
| CN102122580A (en) | Method for preparing modified titanium dioxide nanotube dye-sensitized photoanode thin film | |
| CN105130988B (en) | It is a kind of Li sub- Xing perylene diimide class materials and preparation method and its organic memory device | |
| CN107275114B (en) | A kind of preparation method of graphene composite film | |
| CN109524244A (en) | Nitrogenous two dimension conjugation carbon material of one kind and the preparation method and application thereof | |
| CN110164710A (en) | A kind of supercapacitor binary metal compound composite material and preparation method thereof | |
| CN105885410A (en) | Molybdenum sulfide/polypyrrole/polyaniline ternary composite material as well as preparation method and application thereof | |
| CN109449299B (en) | Photoelectric active layer and application thereof in flexible photoelectric-piezoelectric hybrid energy battery | |
| CN107316939B (en) | A kind of two-dimentional perovskite electrical storage device and preparation method thereof based on pseudohalogen induction | |
| CN113410063A (en) | Carbon nano tube composite electrode material and preparation method thereof | |
| CN110683588A (en) | Self-supporting CoMoS4Super capacitor electrode material, preparation method and application | |
| CN109887766A (en) | Titanium dioxide/carbon/polyaniline composite electrode material preparation method | |
| CN110330523B (en) | Thiophene-3-formic acid-containing titanium oxide cluster monomer and preparation and application thereof | |
| CN109698280B (en) | Application of fullerene methylene derivative I in perovskite solar cell, perovskite solar cell and preparation method of perovskite solar cell | |
| CN107903427A (en) | A kind of preparation method of polyaniline nanofiber array material | |
| CN109499494B (en) | polypyrrole/UiO-66 composite aerogel and preparation method thereof |
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 |