CN110498410A - Utilize the method for one step preparing grapheme through oxidation reduction of graphite in old and useless battery - Google Patents
Utilize the method for one step preparing grapheme through oxidation reduction of graphite in old and useless battery Download PDFInfo
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- CN110498410A CN110498410A CN201910714968.3A CN201910714968A CN110498410A CN 110498410 A CN110498410 A CN 110498410A CN 201910714968 A CN201910714968 A CN 201910714968A CN 110498410 A CN110498410 A CN 110498410A
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- graphene
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- oxidation reduction
- useless battery
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
Abstract
The invention discloses the methods using one step preparing grapheme through oxidation reduction of graphite in old and useless battery, follow the steps below: Step 1: going out waste and old lithium ion battery by reduction ammonia-leaching obtains barren rock ink；Step 2: the obtained barren rock ink of step 1 is by oxidizing, intercalator intercalation, auxiliary reagent ancillary redox and removing prepares redox graphene；Step 3: the graphene after step 2 removing removes the metal ion on surface by cleaning agent；Step 4: drying the redox graphene that step 3 obtains to obtain graphene product.Advantages of the present invention: the barren rock ink after metal leaches prepares graphene, turns waste into wealth, low in cost；Oxidation system does not use traditional nitrate, improves quality of graphene, avoids environmental pollution；A step preparing grapheme through oxidation reduction is assisted by Peracetic acid, graphene preparation process is simplified, avoids the use of other Hazardous organics, the oxygen of generation is conducive to environment.
Description
Technical field
The present invention relates to a kind of methods for preparing graphene, in particular to a kind of to be aoxidized using one step of graphite in old and useless battery
The method that reduction prepares graphene, belongs to technical field of graphene.
Background technique
Lithium ion battery (LIB) have high-energy density, long life cycle, low self-discharge, and it is safe and reliable the advantages that
And it is widely used in mobile phone, and laptop, new-energy automobile and other modern appliances.However, since it only has
Several years service life (about 1000 charge/discharge cycles) will generate largely useless LIB.It is estimated that the year two thousand twenty China uses
LIB quantity and weight respectively more than 25,000,000,000 and 500,000 tons.In general, useless LIB includes cathode, anode, electrolyte, diaphragm
And shell, cathode include essential lithium metal oxide, anode includes graphite, the lithium salts electrolysis being dissolved in organic solvent
Matter.For LIB after service life, resource and harmfulness cause many concerns.However, in the recycling of useless LIB,
Presence due to transition metal oxide material and their validity in several applications of different field, cathode material
Recycling is got more attention than anode graphite.
A large amount of barren rocks ink can be left after leaching the valuable metal for recycling useless LIB by organic and inorganic acid or ammonia, this be it is low at
This prepares the favorable substitutes of graphene.Up to the present, many methods have been developed for synthesizing redox graphene
(rGO), such as the cracking of the micromechanics of graphite, chemical vapor deposition, liquid phase chemical aoxidize removing etc..Wherein, liquid phase chemical aoxidizes
Removing can a large amount of synthesis redox graphenes of low cost.Hummers graphene the preparation method is because of its high efficiency and satisfactorily
Reaction safety and by most concerns.However, there are still two to ask due to using nitric acid and sodium nitrate as oxidant
Topic: oxidation process releases toxic gas, such as NO2And N2O4;It is difficult to synthesize from graphene oxide and give up with what is formed in purification process
Remaining Na is removed in water+And NO3-.In addition, graphene oxide obtained usually requires to introduce additional chemical reagent, such as
NaBH4, N2H4·H2O, MnCl2, L-AA causes graphene preparation section complex and costly high for restoring GO.
Summary of the invention
The technical problem to be solved in the present invention, is to provide and a kind of is prepared using one step redox of graphite in old and useless battery
The method of graphene is realized extensive, the redox preparation of high-quality, is realized useless by changing oxidation system reagent composition
The resource utilization of old lithium ion battery barren rock ink.
The present invention is realized by following proposal: utilizing the side of one step preparing grapheme through oxidation reduction of graphite in old and useless battery
Method follows the steps below:
Step 1: leaching waste and old lithium ion battery obtains barren rock ink；
Step 2: the barren rock ink that step 1 obtains prepares redox graphene by redox and removing；
Step 3: the metal ion of the graphene surface after removal step 2 removing.
Using the method for one step preparing grapheme through oxidation reduction of graphite in old and useless battery, follow the steps below:
Step 1: going out waste and old lithium ion battery by reduction ammonia-leaching obtains barren rock ink；
Step 2: the barren rock ink that step 1 obtains is by oxidizing, intercalator intercalation, auxiliary reagent ancillary redox is simultaneously
Removing prepares redox graphene；
Step 3: the graphene after step 2 removing removes the metal ion on surface by cleaning agent；
Step 4: drying the redox graphene that step 3 obtains to obtain graphene product.
The group of the step 1 reduction ammonia becomes ammonium hydroxide, ammonium sulfite and ammonium hydrogen carbonate.
The ammonia concn used is 1.5mol/L, and ammonium sulfite concentration is 1mol/L, the concentration of ammonium hydrogen carbonate is 1mol/L.
Oxidant is potassium permanganate in the step 2, and intercalator is the concentrated sulfuric acid, and ancillary redox reagent is peroxide second
Acid.
Cleaning agent is dilute hydrochloric acid and deionized water in the step 3.
Graphene in the step 3 removes metal ion by the cleaning of 5% dilute hydrochloric acid, is cleaned with deionized water into
Property.
Drying temperature in the step 4 is 105oC.
The invention has the benefit that
1, the present invention can be turned waste into wealth using the method for one step preparing grapheme through oxidation reduction of graphite in old and useless battery, prepare stone
Black alkene it is low in cost；
2, the present invention is using the oxidation system of the method for one step preparing grapheme through oxidation reduction of graphite in old and useless battery without using biography
The nitrate of system, improves quality of graphene, avoids environmental pollution；
3, the present invention assists one by Peracetic acid using the method for one step preparing grapheme through oxidation reduction of graphite in old and useless battery
Preparing grapheme through oxidation reduction is walked, graphene preparation process is simplified, avoids the use of other Hazardous organics, the oxygen of generation
Gas is conducive to environment；
4, the present invention goes out to obtain using the method for one step preparing grapheme through oxidation reduction of graphite in old and useless battery by reduction ammonia-leaching
After barren rock ink, in ternary system, oxidant potassium permanganate is commonly used in aoxidizing and opening graphite edge, to make sulfuric acid conduct
Intercalator is embedded in graphite, and Peracetic acid then assists oxidation and redox graphene, is decomposed in reaction process and is discharged O2, cause
Increase the instantaneous pressure in graphite sandwich passage, it, can when pressure, which rises to, can overcome the Van der Waals force between graphite linings
Removing obtains stratiform redox graphene.The graphene C/O of preparation is 8.52, and quality is higher, yield 61.2%, therefore logical
Redox graphene can be mass produced by crossing the present invention, by application extension to various carbon-based materials.
Detailed description of the invention
Fig. 1 is that the present invention is illustrated using the process of the method for one step preparing grapheme through oxidation reduction of graphite in old and useless battery
Figure.
Fig. 2 is graphene (b) the SEM figure of the barren rock black (a) obtained after leaching and preparation.
Specific embodiment
Below with reference to Fig. 1, the present invention is further described, but the scope of the present invention does not limit to the content.
Wherein identical components are presented with like reference characters.It should be noted that word used in the following description
Language "front", "rear", "left", "right", "up" and "down" refer to that the direction in attached drawing, word "inner" and "outside" refer respectively to court
To or far from geometric center of specific component direction, and attached drawing is all made of very simplified form and uses non-accurate ratio
Rate, only for the purpose of facilitating and clarifying the purpose of the embodiments of the invention.
For clarity, not describing whole features of practical embodiments, in the following description, it is not described in detail well known function
And structure, because they can make the present invention chaotic due to unnecessary details, it will be understood that opening in any practical embodiments
In hair, it is necessary to make a large amount of implementation details to realize the specific objective of developer, such as according to related system or related business
Limitation, changes into another embodiment by one embodiment, additionally, it should think that this development may be complicated and expend
Time, but to those skilled in the art it is only routine work.
Using the method for one step preparing grapheme through oxidation reduction of graphite in old and useless battery, follow the steps below:
Step 1: band plug conical flask is added in the cathode powder that 5g is obtained from 18650 type lithium ion batteries, addition contains
The leaching agent 250ml of the ammonium hydroxide of 1.5mol/L, 1mol/L ammonium sulfite and 1mol/L ammonium hydrogen carbonate, leach 5h after filter residue rinse to
Neutrality, 120oC drying 12h obtain barren rock ink；
Step 2: the barren rock ink that step 1 obtains is taken appropriate addition beaker, the concentrated sulfuric acid is first added, after mixing evenly, adds
Potassium permanganate, is added Peracetic acid later, and reaction to bubble-free generates to arrive redox graphene；
Step 3: the redox graphene that step 2 obtains first is cleaned removal metal ion with 5% hydrochloric acid, then use deionization
Water is cleaned to neutrality；
Step 4 will obtain finished product graphene after graphene 105oC freeze-day with constant temperature that step 3 obtains.
Finished product graphene C/O is 8.52, illustrates that Peracetic acid successfully restores graphene oxide.
By reduction ammonia-leaching go out obtain barren rock ink after, in ternary system, oxidant potassium permanganate commonly used in oxidation and
Graphite edge is opened, to make sulfuric acid as in intercalator insertion graphite, Peracetic acid then assists oxidation and reduction-oxidation graphite
Alkene decomposes in reaction process and discharges O2, cause the instantaneous pressure in graphite sandwich passage to increase, when pressure rise to can with gram
It is peelable to obtain stratiform redox graphene when taking the Van der Waals force between graphite linings.The graphene C/O of preparation is 8.52,
Quality is higher, yield 61.2%, therefore redox graphene can be mass produced through the invention, by application extension
To various carbon-based materials.
Although having done more detailed elaboration to technical solution of the present invention and having enumerated, it should be understood that for ability
For field technique personnel, modifications to the embodiments described above may be made or uses equivalent alternative solution, this is to those skilled in the art
It is it is clear that these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the present invention for member
Claimed range.
Claims (8)
1. utilizing the method for one step preparing grapheme through oxidation reduction of graphite in old and useless battery, it is characterised in that: it is according to following step
It is rapid to carry out:
Step 1: leaching waste and old lithium ion battery obtains barren rock ink；
Step 2: the barren rock ink that step 1 obtains prepares redox graphene by redox and removing；
Step 3: the metal ion of the graphene surface after removal step 2 removing.
2. the method according to claim 1 using one step preparing grapheme through oxidation reduction of graphite in old and useless battery, special
Sign is: it is followed the steps below:
Step 1: going out waste and old lithium ion battery by reduction ammonia-leaching obtains barren rock ink；
Step 2: the barren rock ink that step 1 obtains is by oxidizing, intercalator intercalation, auxiliary reagent ancillary redox is simultaneously
Removing prepares redox graphene；
Step 3: the graphene after step 2 removing removes the metal ion on surface by cleaning agent；
Step 4: drying the redox graphene that step 3 obtains to obtain graphene product.
3. the method according to claim 2 using one step preparing grapheme through oxidation reduction of graphite in old and useless battery, special
Sign is: the group of the step 1 reduction ammonia becomes ammonium hydroxide, ammonium sulfite and ammonium hydrogen carbonate.
4. the method according to claim 3 using one step preparing grapheme through oxidation reduction of graphite in old and useless battery, special
Sign is: the ammonia concn used is 1.5mol/L, and ammonium sulfite concentration is 1mol/L, the concentration of ammonium hydrogen carbonate is 1mol/L.
5. the method according to claim 2 using one step preparing grapheme through oxidation reduction of graphite in old and useless battery, special
Sign is: oxidant is potassium permanganate in the step 2, and intercalator is the concentrated sulfuric acid, and ancillary redox reagent is peroxide second
Acid.
6. the method according to claim 2 using one step preparing grapheme through oxidation reduction of graphite in old and useless battery, special
Sign is: cleaning agent is dilute hydrochloric acid and deionized water in the step 3.
7. the method according to claim 2 using one step preparing grapheme through oxidation reduction of graphite in old and useless battery, special
Sign is: the graphene in the step 3 removes metal ion by the cleaning of 5% dilute hydrochloric acid, is cleaned with deionized water to neutrality.
8. the method according to claim 2 using one step preparing grapheme through oxidation reduction of graphite in old and useless battery, special
Sign is: the drying temperature in the step 4 is 105oC.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116075479A (en) * | 2020-07-30 | 2023-05-05 | Nts株式会社 | Method for manufacturing radiating fin by using waste graphite |
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