CN109768261A - A kind of novel cathode material for lithium ion battery N doping porous graphene preparation method and application - Google Patents
A kind of novel cathode material for lithium ion battery N doping porous graphene preparation method and application Download PDFInfo
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Abstract
The invention belongs to field of material preparation, propose a kind of novel cathode material for lithium ion battery N doping porous graphene preparation method and application.It first has to produce graphene oxide, solution temperature is risen to 95 degree after temperature 60 C reaction 6h or more when concentrated acid aoxidizes, heats half an hour.Next solution is cooled down, GO solution is placed on cooling in the large beaker equipped with ice water, and 20ml deionized water is added into solution, is cooled to 0 degree or so.Appropriate hydrogen peroxide is added, graphene oxide is made.After being ultrasonically treated 30min, add (NH4)2CO3Volume 1.1:1 is diluted neutrality, is placed in reaction kettle and carries out the last centrifugal drying of heating water bath.It is final to obtain single layer N doping porous graphene material.The entire preparation process flow of the present invention is simple, the cost of material is low, nitrogenous graphene easily operated, obtained has porosity, large specific surface area, film relatively preferable and good conductivity, after lithium ion battery, the transporting rate of lithium ion significantly improves, and battery capacity is greatly enhanced.
Description
Technical field
The invention belongs to field of material preparation, are related to a kind of novel cathode material for lithium ion battery N doping porous graphene
The preparation method and application that is combined with water bath heating of oxidation-reduction method.
Background technique
With the development of the times, the size of population constantly increases and demand of the development to the energy of society is increasing, and
Instantly fossil energy is constantly exhausted, such as biomass energy, wind energy, ocean energy, nuclear energy and the new energy development of solar energy have been compeled
In the eyebrows and eyelashes.However the good energy storage material of development becomes particularly important, the material of preparation can be applied in many energy storage devices
Such as supercapacitor, lithium ion battery, fuel cell.Battery is as the energy carrier for storing these energy.On how to manufacture
The battery of enough large capacities has initiated new challenge to meet people's routine use out.
Battery industry is the industry intimately developed, the development of lithium ion battery appoint be so it is most promising,
Carbon-based material and silicon class material are the nowadays most common electrode materials of negative electrode of lithium ion battery.The development in carbon-based material future will be led
Concentrate on high power graphite negative electrodes and non-graphite high capacity Carbon anode.This kind of materials theory capacity is larger, but is using
During would tend to occur that the production cycle is long, prepare the problem of low layer number graphene difficulty, thus constrain its development.It grinds
Study carefully the performance of graphene and realize its extensive use, required porous graphite is prepared in a manner of reliable, inexpensive, high yield
Alkene.On how to improve grapheme material performance synthesis condition problem, academia expands a series of research.
It is found from research that graphene is that a kind of highest material of most thin and hardness, graphene are in current material in recent years
A kind of sp2 hydridization monolayer honeycomb shape material, good, large specific surface area, good energy storage material with toughness.But also have simultaneously scarce
It falls into, doped graphene can not only make up graphene defect " zero band gap " but also be a good research direction, but implementation steps
Have much room for improvement and perfect.N doping porous graphene can open band gap, and it is steady effectively to alleviate specific surface area, conductivity, circulation
The problems such as qualitative and simplified technique, shortens the reaction time and improves yield, improves the cyclicity of graphite cathode material and quickly fills
Discharge capability.Thus, the material of porous graphene containing N doping is widely used in negative electrode of lithium ion battery, develops function admirable
Doping porous graphene material it is most important to the development of lithium ion battery.It can be applied in the ideal material of energy storage device
And supercapacitor.
Have much preparation methods about the dilute material of graphite, but different preparation methods and preparation condition both at home and abroad at present
The properity dilute to graphite has a great impact, and can limit its application due to different preparation methods.Currently prepare graphite
Dilute main method has graphite oxide (GO) reduction method, chemical vapour deposition technique (CVD), SiC epitaxial growth method and organic conjunction
At method etc..Although CVD method is applied in currently preparation large-area graphene film the most generally, since the stone that the method obtains is dilute
Film is usually deposited in metallic substrates, not can be used directly in microelectronic component.There is complicated operation in three kinds of methods afterwards
The defects of step is complicated, at high cost, condition requires harsh and product performance bad.And oxidation-reduction method and water bath heating knot
Close that preparation doping porous graphene is at low cost, and yield is high, product can be stable in the presence of in water or organic solvent be not necessarily to it is subsequent
Substrate transfer, provides a kind of good preparation method for the exploitation of grapheme material and industrial applications.
Oxidation-reduction method is a kind of traditional material surface modifying technology, is produced during graphene obtains using oxidation-reduction method
Between the surface of graphene oxide of object contain certain oxygen-containing group, these oxygen-containing groups can assign the special property such as its surface-active
Can, it can preferably be contacted with organic material, to produce some special functional materials.And then it can realize conventional treatment method institute
The non-equilibrium microstructure structure and performance that can not be obtained.In water bath heating, using water as reaction medium, in high-temperature high-pressure reaction kettle
High-temperature high-voltage reaction is carried out, indissoluble or insoluble substance is made to dissolve (oxide or hydroxide), makes to synthesize nitrogen-doped graphene
It reacts more abundant, allows nitrogen to enter in graphene layer structure, nitrogen element content is higher, this will more be conducive to carbon material energy storage
The raising of performance.
Research oxidation-reduction method is combined with water bath heating, compared with conventional industrial process, its production cost of the method
Lower, principle is simple, and it is strong that behaviour does feasibility, the advantages that capable of largely preparing, there is extensive prospects for commercial application.The method at present
The research work for causing the microstructure and properties of material to change etc. is carried out also relatively fewer, in terms of modified to graphene
Research be mostly in exploration state, and the research of actual application aspect then relatively slowly.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of oxidation-reduction method and prepares in conjunction with water bath heating
The method of N doping porous graphene obtains the doped graphene material with single layered porous, applies it to lithium ion battery
In.
The specific technical proposal of the invention is:
One kind having novel cathode material for lithium ion battery N doping porous graphene preparation method, includes the following steps:
(1) prepared by graphene oxide:
200mLH2SO4Middle addition 2g graphite powder, after 20min with 20mLHNO3Mixing, then it is slowly added into 12gKMnO4, temperature
Degree is about 45 degree, stirs 40min~50min.Then temperature is increased to 60 degree, stirring 6h or more (theoretically the time is longer,
React more abundant) after, solution temperature is risen to 90 degree, heats half an hour, no color change.Next solution temperature is down to 10
Degree is hereinafter, be placed on cooling in the large beaker equipped with ice water for graphite oxide GO solution, and be added into graphene oxide solution
20ml deionized water is cooled to 0 degree or so.It is added appropriate hydrogen peroxide, solution is immediately emerged a large amount of bubbles, and solution is in golden yellow.
Solution is graphene oxide at this time.
(2) synthesis of N doping porous graphene:
The graphene oxide solution that upper step is obtained carries out ultrasonication 30min, is then added into solution appropriate
(NH4)2CO3It is diluted, makes the PH=7 of solution, solution is put into progress water-bath in the autoclave of tetrafluoroethene liner and is added
Hot 12h finally sets 8min for solution with 1100rpm centrifugation time, repeated centrifugation 7 to 8 times, dry after centrifugation is good.It obtains
N doping porous graphene product.(NH is added4)2CO3For saturated solution, ammonium carbonate volume and reaction solution are than being about 1.1:1.
It is 190 DEG C that the heating water bath carries out temperature in pyroreaction kettle.
Further, it is 325 or more that graphite used in above-mentioned steps (1), which is suitable for mesh number,.
Further, be used in above-mentioned steps (1) acid solution concentration be 98% H2SO4Solution and concentration 50%-
70% nitric acid.
Further, hydrogen peroxide concentration used in above-mentioned steps (1) be 30%, potassium permanganate content be greater than
99.5%.
The above method is obtained to have the application of N doping porous graphene, is used for manufacture negative electrode of lithium ion battery, packet
Include following steps:
(1) electrode slice processed: carrying out electrode preparation using coating method, and by active material nitrogen-doped graphene, acetonitrile is black, bonding
Agent PVDF is dissolved in NMP according to the ratio of mass ratio 8:1:1, and stir about 30min is slurried, then carefully with blade
By being applied on carrying object copper foil for electrode material slurries even uniform.Then 80 DEG C of processing 8h in vacuum drying box, drying
After be pressed into electrode slice.
(2) it assembles button cell: in vacuum glove box, using battery case, using metal lithium sheet as positive electrode, it will be positive
Shell, electrode slice, diaphragm, spring leaf, lithium piece, gasket, appropriate electrolyte solution and negative electrode casing are assembled into button cell in this order,
Sealing treatment is carried out to battery using hand seamer.
In the prior art using chemical vapour deposition technique (CVD), SiC epitaxial growth method and organic synthesis method etc. during
It will appear that at high cost, operating process is complicated, the production cycle is long, organic solvent is harmful to body, it is incomplete to introduce impurity multiprocessing
Poorly conductive, this was a kind of defect originally, and this defect more than the positive good utilisation production cycle length of the present invention, step, utilized oxygen
Change reduction method and water bath heating is incorporated under new reaction condition and prepares graphene oxide and synthesis N doping porous graphite
Alkene obtains the doping porous graphene that there is structure level number to conduct electricity very well less.
In the prior art, what is obtained by oxidation-reduction method there is doped graphene its porous surface capacity can only be made to decline
Subtract obviously, not can fully ensure that graphene conductive.By (ammonium carbonate was both with ammonium carbonate after graphene oxide is made in the present invention
Can make carbon source or make nitrogen source) reaction, shorten the reaction time of half using doped graphene made from water bath heating,
Conventional centrifugal number needs 15~30 times, and now only needing 7~8 times can complete, and not introduce other impurities, ensure that
Higher conductivity, nitrogen-doped graphene shows the more excellent performances of purer graphene, in unordered, transparent, fold thin
Yarn shape, partial sheet is stacked together, forms layer structure, shows higher specific capacitance and good cycle life.Pass through
Research to oxidation-reduction method and water bath heating association reaction condition, solution preparation graphene number of plies height influence electric conductivity,
Zero band gap influences lithium ion through-rate problem, and the change by the method to graphene internal structure prepares large specific surface area
Single layer efficient N doping porous graphene film.This porosity can be improved matter transportation rate and can be effective
The band gap of graphene is opened, and this nitrogenous porous graphene is applied in negative electrode of lithium ion battery, lithium ion can be improved
Transporting rate can get large capacity, and chemical property and cycle performance are excellent, and the higher new type lithium ion battery of safety is
Heavy-duty battery of new generation makes certain contribution.
Entire preparation process flow is simple, the cost of material is low, nitrogenous graphene easily operated, obtained has porosity,
Large specific surface area, film relatively preferably and good conductivity, for after lithium ion battery, battery capacity to improve a lot, cyclicity
It can improve to some extent.
Specific embodiment
Embodiment 1
The preparation method of the N doping porous graphene of the present embodiment follows the steps below:
(1) prepared by graphene oxide:
It is 325 mesh graphite powders that 2g specification, which is added, in the 200mL concentrated sulfuric acid, is mixed after 20min with 20mL nitric acid, then be slowly added into
12g potassium permanganate, temperature is 45 degree at this time, stirs 45min.Then temperature is risen to 60 degree, stirring 7h (theoretically get over by the time
It is long, react more abundant) after, solution temperature is risen to 90 degree, heats half an hour, color change is unobvious.Next by solution temperature
Degree is down to 10 degree hereinafter, GO solution is placed on cooling in the large beaker equipped with ice water, and be added into graphene oxide solution
20ml deionized water is cooled to 0 degree, is added appropriate hydrogen peroxide, and solution is immediately emerged a large amount of bubbles, and solution is in golden yellow.At this time
Solution is graphene oxide.
(2) synthesis of N doping porous graphene:
The graphene oxide solution that upper step is obtained carries out ultrasonication 30min, is then added into solution appropriate
(NH4)2CO3It is diluted, makes the PH=7 of solution, solution is put into progress water-bath in the autoclave of tetrafluoroethene liner and is added
Hot 12h finally sets 8min for solution with 1100rpm centrifugation time, repeated centrifugation 7 times, dry after centrifugation is good.Nitrogen is obtained to mix
Miscellaneous porous graphene product.
Wherein, it is that 325 mesh graphite powder products are made through step (1) reaction that the graphite oxide, which is commercially available specification,.
The Solution H2SO4Concentration is 98%, nitric acid 65%, hydrogen peroxide concentration 30%, and potassium permanganate content is big
In 99.5%.
The water bath heating temperature is 190 DEG C, and (NH is added4)2CO3For saturated solution, ammonium carbonate volume and reaction solution
It is mixed according to volume ratio 1.1:1.
There is good electric conductivity in the porous nitrogen-doped graphene of low layer number finally obtained after step (2),
When cell negative electrode material processed, battery capacity improves a lot.
The application of the N doping porous graphene of the present embodiment is to be used for manufacture button lithium battery, specifically according to following
Step carries out:
(1) electrode slice processed: carrying out electrode preparation using coating method, and by active material nitrogen-doped graphene, acetonitrile is black, bonding
Agent PVDF is dissolved in NMP according to the ratio of mass ratio 8:1:1, and stir about 30min is slurried, then carefully with blade
By being applied on carrying object copper foil for electrode material slurries even uniform.Then 80 DEG C of processing 8h in vacuum drying box, drying
After be pressed into electrode slice.
(2) it assembles button cell: in vacuum glove box, using battery case, using metal lithium sheet as positive electrode, it will be positive
Shell, electrode slice, diaphragm, spring leaf, lithium piece, gasket, appropriate electrolyte solution and negative electrode casing are assembled into button cell in this order,
Sealing treatment is carried out to battery using hand seamer.
Embodiment 2
The preparation method of the present embodiment N doping porous graphene follows the steps below:
(1) prepared by graphene oxide
It is 325 mesh graphite powders that 2g specification, which is added, in the 200mL concentrated sulfuric acid, is mixed after 20min with 20mL nitric acid, then be slowly added into
12g potassium permanganate, temperature is 45 degree at this time, stirs 45min.Then temperature is risen to 60 degree, stirring 8h (theoretically get over by the time
It is long, react more abundant) after, solution temperature is risen to 90 degree, heats half an hour, color change is unobvious.Next by solution temperature
Degree is down to 10 degree hereinafter, GO solution is placed on cooling in the large beaker equipped with ice water, and be added into graphene oxide solution
20ml deionized water is cooled to 0 degree, is added appropriate hydrogen peroxide, and solution is immediately emerged a large amount of bubbles, and solution is in golden yellow.At this time
Solution is graphene oxide.
(2) synthesis of N doping porous graphene
The graphene oxide solution that upper step is obtained carries out ultrasonication 30min, is then added into solution appropriate
(NH4)2CO3It is diluted, makes the PH=7 of solution, solution is put into progress water-bath in the autoclave of tetrafluoroethene liner and is added
Hot 12h finally sets 8min for solution with 1100rpm centrifugation time, repeated centrifugation 8 times, dry after centrifugation is good.Nitrogen is obtained to mix
Miscellaneous porous graphene product.
Wherein, it is that 325 mesh graphite powder products are made through step (1) reaction that the graphite oxide, which is commercially available specification,.
The Solution H2SO4Concentration is 98%, nitric acid 69%, hydrogen peroxide concentration 30%, and potassium permanganate content is big
In 99.5%.
The water bath heating temperature is 190 DEG C, and (NH is added4)2CO3For saturated solution, ammonium carbonate volume and reaction solution
It is mixed according to volume ratio 1.1:1.
There is good electric conductivity in the porous nitrogen-doped graphene of low layer number finally obtained after step (2),
When battery processed when negative electrode material, battery capacity improves a lot.
The N doping porous graphene of the present embodiment application be used for manufacture fastening lithium ionic cell, specifically according to
Following steps carry out:
(1) electrode slice processed: carrying out electrode preparation using coating method, and by active material nitrogen-doped graphene, acetonitrile is black, bonding
Agent PVDF is dissolved in NMP according to the ratio of mass ratio 8:1:1, and stir about 30min is slurried, then carefully with blade
By being applied on carrying object copper foil for electrode material slurries even uniform.Then 80 DEG C of processing 8h in vacuum drying box, drying
After be pressed into electrode slice.
(2) it assembles button cell: in vacuum glove box, using battery case, using metal lithium sheet as positive electrode, it will be positive
Shell, electrode slice, diaphragm, spring leaf, lithium piece, gasket, appropriate electrolyte solution and negative electrode casing are assembled into button cell in this order,
Sealing treatment is carried out to battery using hand seamer.
Claims (4)
1. one kind has novel cathode material for lithium ion battery N doping porous graphene preparation method, which is characterized in that including
Following steps:
(1) prepared by graphene oxide
2g graphite powder is added in the 200mL concentrated sulfuric acid, is mixed after 20min with 20mL nitric acid, then be slowly added into 12g potassium permanganate,
Temperature is about 45 degree, stirs 40min~50min.Then temperature is increased to 60 degree, after stirring 6h or more, by solution temperature
90 degree are risen to, half an hour is heated；Next solution temperature is down to 10 degree hereinafter, graphite oxide solution is cooling, and to oxidation
20ml deionized water is added in graphene solution, is cooled to 0 degree or so.Hydrogen peroxide is added, solution is graphene oxide at this time；Institute
Hydrogen peroxide concentration is 30%, and potassium permanganate content is greater than 99.5%；
(2) synthesis of N doping porous graphene
The graphene oxide solution that step (1) is obtained carries out ultrasonication 30min, and (NH is then added into solution4)2CO3
It is diluted, makes the PH=7 of solution, solution is put into and carries out heating water bath 12h in the autoclave of tetrafluoroethene liner, most
8min is set with 1100rpm centrifugation time by solution afterwards, it is repeated centrifugation 7~8 times, dry after centrifugation is good, it is more to obtain N doping
Hole graphene product；
(the NH4)2CO3For saturated solution, ammonium carbonate volume and reaction solution are than being about 1.1:1；
It is 190 DEG C that step (2) heating water bath carries out temperature in pyroreaction kettle.
2. according to claim 1 a kind of with N doping porous graphene preparation method, which is characterized in that stone used
It is 325 or more that ink powder, which is suitable for mesh number,.
3. according to claim 1 or 2 a kind of with N doping porous graphene preparation method, which is characterized in that acid is molten
It is 98% H that liquid, which uses concentration,2SO4With concentration 50%-70% nitric acid.
4. obtained with N doping porous graphene use with N doping porous graphene preparation method described in claim 1-3
In manufacture negative electrode of lithium ion battery, which comprises the steps of:
(1) electrode slice processed: electrode preparation is carried out using coating method, by active material nitrogen-doped graphene, acetonitrile is black, binder
PVDF is dissolved in NMP according to the ratio of mass ratio 8:1:1, and stir about 30min is slurried, and then carefully will with blade
Electrode material slurries even uniform is applied on carrying object copper foil；Then 80 DEG C of processing 8h in vacuum drying box, after drying
It is pressed into electrode slice；
(2) assemble button cell: in vacuum glove box, using battery case, using metal lithium sheet as positive electrode, by anode cover,
Electrode slice, diaphragm, spring leaf, lithium piece, gasket, appropriate electrolyte solution and negative electrode casing are successively subsequently assembled into button cell,
Sealing treatment is carried out to battery using hand seamer.
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| CN110526241A (en) * | 2019-07-31 | 2019-12-03 | 山西大同大学 | A kind of electrolytic oxidation prepares the device and method of graphene oxide |
| CN110902671A (en) * | 2019-10-18 | 2020-03-24 | 东北大学 | Preparation method of low-layer graphene |
| CN111646462A (en) * | 2020-04-21 | 2020-09-11 | 东北大学 | Method for preparing high-quality reduced graphene oxide by high-current pulsed electron beam |
| CN112216833A (en) * | 2020-11-11 | 2021-01-12 | 榆林学院 | WS (WS)2/TiO2Preparation method of/nitrogen-doped graphene nanocomposite |
| CN112588311A (en) * | 2020-12-15 | 2021-04-02 | 湖南工学院 | Cobalt-based oxide supported double-doped graphene catalyst and preparation method and application thereof |
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| CN111646462A (en) * | 2020-04-21 | 2020-09-11 | 东北大学 | Method for preparing high-quality reduced graphene oxide by high-current pulsed electron beam |
| CN112216833A (en) * | 2020-11-11 | 2021-01-12 | 榆林学院 | WS (WS)2/TiO2Preparation method of/nitrogen-doped graphene nanocomposite |
| CN112588311A (en) * | 2020-12-15 | 2021-04-02 | 湖南工学院 | Cobalt-based oxide supported double-doped graphene catalyst and preparation method and application thereof |
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Application publication date: 20190517 |