CN104961122A - Graphene organic functional modification methods and application - Google Patents
Graphene organic functional modification methods and application Download PDFInfo
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- CN104961122A CN104961122A CN201510226433.3A CN201510226433A CN104961122A CN 104961122 A CN104961122 A CN 104961122A CN 201510226433 A CN201510226433 A CN 201510226433A CN 104961122 A CN104961122 A CN 104961122A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention discloses a graphene organic functional modification method and application, the method comprises the following steps: S1, using a strong oxidizing agent for oxidizing graphite powder, then by ultrasonically treating to obtain graphene oxide; S2, performing covalent bond functionalization treatment on the graphene oxide; and S3, performing different degrees of reduction processing on the functionally treated graphene oxide to obtain different types of organically modified graphene. By use of high conductivity and stability of the structure of the graphene, graphene-based full-solid-state and gel state polymer electrolytes can be obtained, graphene-polymer lithium-ion batteries can be obtained, the graphene-polymer lithium-ion batteries can be widely applied in mobile phones, computers and other electronic products, automobiles, electric bicycles and other vehicles, and also can be used in aerospace fields and the like which requires high energy density, long cycle life and small volume.
Description
Technical field
The invention belongs to polymer Li-ion battery field, relate in particular to a kind of described Graphene organic functional method of modifying and obtain and application in polymer dielectric.
Background technology
Metallic lithium is the lightest in all metals, and redox potential is minimum, and mass energy density is maximum, lithium cell one of substitute energy becoming oil gradually from eighties of last century sixties.Along with the development of society, more and more higher to the requirement of environmental protection low-carbon (LC), green energy resource, lithium ion battery obtains in short decades and develops rapidly, and experienced by different developmental stage, developed into the lithium secondary battery of recharging by the lithium primary cell at initial stage, then be further development of polymer Li-ion battery; Wherein polymer Li-ion battery is except the feature having lithium ion battery, also has the following advantages: external form handiness, can make battery and the ultra-thin battery of different shape; High safety reliability, nonflammable, there is no the leakage of liquid; Have longer work-ing life, capacitance loss is little; Volume utilization is high, than liquid lithium battery height 10-20%; Do not need series connection just can make large battery; Traditional diaphragm material need not be used; Easier large-scale industrial production and Application Areas is wider.
The electrolytical kind of existing polymer Li-ion battery is a lot, can be divided into according to bulk composition: polyethers system (being mainly polyoxyethylene PEO), polyacrylonitrile based (PAN), polymethylmethacrylate system (PMMA), solvent-freely not solvent-laden full solid state polymer electrolyte (Solid polymer Electrolyte can be divided into according to having, referred to as SPE) and containing gel-type polymer electrolyte (the Gel Polymer Electrolyte of organic plasticizers, referred to as GPE), different shortcomings is there is separately in above-mentioned polymer dielectric, as: based on PEO, PAN, although the SPE of PMMA improves the defect such as leakage and volume change, but specific conductivity is not high, and not high based on the GPE physical strength of PEO, PMMA, PAN because of-CN base and metallic lithium poor compatibility, seriously also limit it with lithium electrode interface passivation phenomenon and apply.Visible, the defect that the polymer dielectric based on above-mentioned organic main body composition is had nothing in common with each other, have impact on use value, therefore develops the research emphasis that new full solid state polymer electrolyte is present stage.
Summary of the invention
For this reason, technical problem to be solved by this invention is that existing polymer dielectric exists that specific conductivity is not high, physical strength is not enough, organic group and metallic lithium poor compatibility, use value is affected, thus proposes a kind of high conductivity, high-capacitance, the functional modification method of novel polymer electrolyte component that use range is wider and application thereof.
For solving the problems of the technologies described above, technical scheme of the present invention is:
The invention provides a kind of Graphene organic functional method of modifying, it comprises the steps:
S1, employing strong oxidizer graphite oxide powder, obtain graphene oxide;
S2, covalent linkage functionalization is carried out to described graphene oxide;
S3, the reduction treatment carrying out in various degree to the graphene oxide after functionalization, obtain dissimilar organic modification Graphene.
Further, the described strong oxidizer in described step S1 is H
2sO
4, HNO
3, HCl, KMnO
4, H
2o
2in one or more.
Further, in described step S2, the functionalizers in described functionalization process is diamine or dibasic alcohol.
Further, described diamine is one or more in quadrol, butanediamine, hexanediamine, dicyclohexylcarbodiimide; Described dibasic alcohol is one or more in ethylene glycol, propylene glycol, glycol ether.
Further, in described step S3, the reductive agent in described reduction treatment process is H
2,n
2h
4h
2o, NaBH
4in one or more.
Further, in described step S1 before graphite oxide, also comprise the step mixed with anhydrous nitric acid sodium by described powdered graphite.
Further, also comprising by volumetric concentration after graphene oxide in described step S1 is the H of 3%-5%
2o
2reduce excessive KMnO
4with by KMnO
4the MnSO obtained
4step.
Further, the step described graphene oxide being dissolved in solvent NMP is also comprised before functionalization.
Present invention also offers the application of modified graphene in full solid state polymer electrolyte that the organic functional method of modifying described in employing obtains.
Present invention also offers the application of modified graphene in gel polymer electrolyte that the organic functional method of modifying described in employing obtains.
Technique scheme of the present invention has the following advantages compared to existing technology:
The bright Graphene organic functional method of modifying provided of this law, make use of graphene-structured to stablize, connection between each carbon atom is very soft again, the feature of the phenomenon that there will not be carbon atom to lack, when an external force is applied, carbon atom is with regard to flexural deformation, need not rearrange to adapt to external force, this stable crystalline network makes carbon atom have excellent electroconductibility, when electronics in Graphene moves in track, or foreign atom can not be introduced and scattering occurs because of the defect of lattice, because interatomic force is very strong, at normal temperatures, even if around carbon atom telescopes, the interference that electronics in Graphene is subject to is very little, the movement velocity of electronics can reach 1/300 of the light velocity simultaneously, considerably beyond the movement velocity in general conductor, this makes Graphene have superconductive characteristic.Graphene two-dimensional network structure also has the specific surface area of super large, can the various atom of adsorption and desorption and molecule, and these character make Graphene combine by chemistry and physical method and ion conductive material, reach desirable high conductivity.Modified Graphene can better and other macromolecular material compound, possessed all solid state or gel polymer electrolyte of good mechanical properties and high conduction performance simultaneously, and the lithium ion battery that can obtain further based on modified graphene polymer dielectric, gained battery can be widely used in the electronic product such as mobile phone, computer, the vehicles such as automobile, electric bicycle, also can be used for requirement energy density high, have extended cycle life, aerospace field etc. that volume is little.
Embodiment
In order to make content of the present invention be more likely to be clearly understood, below according to a particular embodiment of the invention, the present invention is further detailed explanation.
Embodiment 1
The present embodiment provides a kind of modified graphene, and it is prepared by following steps:
The Hunmers method of S1, employing classics, in the four-hole boiling flask of the stirring of 500ml band, thermometer, adds the dense H of 100ml by 10g Graphite Powder 99 and the mixing of 4g anhydrous nitric acid sodium
2sO
4in, and 0.5h is stirred under condition of ice bath, under strong stirring, add 10gKMnO
4, at 0 DEG C, react 4h, and be the H of 3% by volumetric concentration
2o
2reduce excessive KMnO
4with part KMnO
4the MnO that reduction obtains
2, make the two become colourless solvable MnSO
4, finally obtain jonquilleous suspension, by described suspension filtered, washing also vacuum hydro-extraction, obtain graphene oxide;
S2, in the NMP of 200g, add graphene oxide described in 10g, supersound process 2h, in the nmp solution of graphene oxide, add 1g quadrol, and at 80 DEG C stirring reaction 4h, obtain the graphene oxide of functionalization;
S3, in the graphene oxide of described functionalization, add 10g N
2h
4h
2o reductive agent, is warming up to 90 DEG C, reduction reaction 4h, and filter, washing precipitate, obtains amination modified Graphene.
The reaction formula of described modified graphene preparation process is as follows:
Embodiment 2
The Hunmers method of S1, employing classics, in the four-hole boiling flask of the stirring of 500ml band, thermometer, adds the dense HNO of 150ml by 15g Graphite Powder 99 and the mixing of 8g anhydrous nitric acid sodium
3in, and 1h is stirred under condition of ice bath, under strong stirring, add 12gKMnO
4, at 2 DEG C, react 5h, and be the H of 4% by volumetric concentration
2o
2reduce excessive KMnO
4with part KMnO
4the MnO that reduction obtains
2, make the two become colourless solvable MnSO
4, finally obtain jonquilleous suspension, by described suspension filtered, washing also vacuum hydro-extraction, obtain graphene oxide;
S2, in the NMP of 300g, add graphene oxide described in 13g, supersound process 2.5h, in the nmp solution of graphene oxide, add 1g hexanediamine, 1g dicyclohexylcarbodiimide, and at 85 DEG C stirring reaction 4.5h, obtain the graphene oxide of functionalization;
S3, pass into reductive agent H again
2, be warming up to 95 DEG C, reduction reaction 5h, filter, washing precipitate, obtains amination modified Graphene.
The reaction formula of described modified graphene preparation process is as follows:
Embodiment 3
The Hunmers method of S1, employing classics, in the four-hole boiling flask of the stirring of 500ml band, thermometer, adds 20g Graphite Powder 99 and the mixing of 10g anhydrous nitric acid sodium in the dense HCl of 250ml, and stir 2h under condition of ice bath, under strong stirring, add 15gKMnO
4, at 2 DEG C, react 5h, and be the H of 5% by volumetric concentration
2o
2reduce excessive KMnO
4with part KMnO
4the MnO that reduction obtains
2, make it become colourless solvable MnSO
4, finally obtain jonquilleous suspension, by described suspension filtered, washing also vacuum hydro-extraction, obtain graphene oxide;
S2, in the NMP of 300g, add graphene oxide described in 13g, supersound process 2.5h, in the nmp solution of graphene oxide, add 2g butanediamine, 2g hexanediamine, and at 85 DEG C stirring reaction 4.5h, obtain the graphene oxide of functionalization;
S3, in the graphene oxide of described functionalization, add 15g NaBH
4, be warming up to 95 DEG C, reduction reaction 5h, filter, washing precipitate, obtains amination modified Graphene.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. a Graphene organic functional method of modifying, is characterized in that, it comprises the steps:
S1, employing strong oxidizer graphite oxide powder, obtain graphene oxide by ultrasonication;
S2, covalent linkage functionalization is carried out to described graphene oxide;
S3, the reduction treatment carrying out in various degree to the graphene oxide after functionalization, obtain dissimilar organic modification Graphene.
2. Graphene organic functional method of modifying according to claim 1, is characterized in that, the described strong oxidizer in described step S1 is H
2sO
4, HNO
3, HCl, KMnO
4, H
2o
2in one or more.
3. Graphene organic functional method of modifying according to claim 1 and 2, is characterized in that, in described step S2, the functionalizers in described functionalization process is diamine or dibasic alcohol.
4. Graphene organic functional method of modifying according to claim 3, is characterized in that, described diamine is one or more in quadrol, butanediamine, hexanediamine, dicyclohexylcarbodiimide; Described dibasic alcohol is one or more in ethylene glycol, propylene glycol, glycol ether.
5. Graphene organic functional method of modifying according to claim 4, is characterized in that, in described step S3, the reductive agent in described reduction treatment process is H
2,n
2h
4h
2o, NaBH
4in one or more.
6. Graphene organic functional method of modifying according to claim 5, is characterized in that, in described step S1 before graphene oxide, also comprises the step mixed with anhydrous nitric acid sodium by described powdered graphite.
7. Graphene organic functional method of modifying according to claim 6, is characterized in that, also comprising by volumetric concentration in described step S1 after graphene oxide is the H of 3%-5%
2o
2reduce excessive KMnO
4with by KMnO
4the MnSO obtained
4step.
8. the Graphene organic functional method of modifying according to any one of claim 4-7, is characterized in that, in described step S2, also comprises the step described graphene oxide being dissolved in solvent NMP before functionalization.
9. adopt the application of modified graphene in full solid state polymer electrolyte that the organic functional method of modifying described in any one of claim 1-8 obtains.
10. adopt the application of modified graphene in gel polymer electrolyte that the organic functional method of modifying described in any one of claim 1-8 obtains.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106477571A (en) * | 2016-09-29 | 2017-03-08 | 广西大学 | To the modified method of graphene oxide microplate under multiple external force fields |
| CN106981374A (en) * | 2017-05-12 | 2017-07-25 | 东南大学 | Functional graphene oxide modified polymer gel electrolyte and its preparation method and application |
| CN107394259A (en) * | 2017-09-07 | 2017-11-24 | 南京汉尔斯生物科技有限公司 | Graphen catalyst applied to the ionic conductivity for improving lithium polymer battery |
| CN107963969A (en) * | 2016-10-19 | 2018-04-27 | 株式会社半导体能源研究所 | Graphite ene compound and its manufacture method, electrolyte, electrical storage device |
| CN108539184A (en) * | 2018-05-15 | 2018-09-14 | 肇庆益晟商贸有限公司 | A kind of modified graphene composite lithium ion battery cathode material and preparation method thereof |
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| CN101830458A (en) * | 2010-05-06 | 2010-09-15 | 西安交通大学 | Preparation method of high purity and high concentration graphene suspension |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106477571A (en) * | 2016-09-29 | 2017-03-08 | 广西大学 | To the modified method of graphene oxide microplate under multiple external force fields |
| CN107963969A (en) * | 2016-10-19 | 2018-04-27 | 株式会社半导体能源研究所 | Graphite ene compound and its manufacture method, electrolyte, electrical storage device |
| US11495826B2 (en) | 2016-10-19 | 2022-11-08 | Semiconductor Energy Laboratory Co., Ltd. | Graphene compound and manufacturing method thereof, electrolyte, and power storage device |
| CN106981374A (en) * | 2017-05-12 | 2017-07-25 | 东南大学 | Functional graphene oxide modified polymer gel electrolyte and its preparation method and application |
| CN106981374B (en) * | 2017-05-12 | 2018-09-21 | 东南大学 | Functional graphene oxide modified polymer gel electrolyte and its preparation method and application |
| CN107394259A (en) * | 2017-09-07 | 2017-11-24 | 南京汉尔斯生物科技有限公司 | Graphen catalyst applied to the ionic conductivity for improving lithium polymer battery |
| CN108539184A (en) * | 2018-05-15 | 2018-09-14 | 肇庆益晟商贸有限公司 | A kind of modified graphene composite lithium ion battery cathode material and preparation method thereof |
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