CN106410128A - Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode - Google Patents
Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a graphene-bismuth oxide composite material for a lithium ion battery negative electrode. A bismuth oxide nanosphere is loaded on a surface of graphene for modification, a bismuth oxide-graphene composite material with ultrahigh loading capacity is formed, the morphology and structure stability of the material is favorably ensured, the conductivity of a metal oxide material is improved, and the performance of a lithium ion battery is further improved. According to the preparation method, ethylene glycol, urea, graphene oxide, polyvinylpyrrolidone and Bi(NO3)3 are added into a hydrothermal reaction kettle for hydrothermal reaction, and bismuth oxide nanoparticles with diameters of 5-10 nanometers are formed during the hydrothermal process by modification of a surfactant and are uniformly loaded on a graphene sheet layer. In the prepared bismuth oxide-graphene composite material, a good conductive network is provided for bismuth oxide due to the presence of the graphene, the volume expansion of the bismuth oxide material during the charge-discharge process is effectively prevented, the cycle lifetime of a lithium ion battery is prolonged, and the rate performance of the battery is improved.
Description
Technical field
The present invention relates to Material Field, more particularly, to a kind of system of used as negative electrode of Li-ion battery metal oxide composite
Preparation Method.
Background technology
With scientific and technological development, the new forms of energy of high-efficiency environment friendly replace traditional energy has become inevitable trend, and energy storage also becomes
For one of hot issue scientific and technological now.Lithium ion battery due to itself excellent performance, in portable
It is widely used, nowadays also into the market of electric motor car and electric automobile, people are continuously increased to the needs of function,
Business-like graphite cathode material theoretical capacity only has 372mAh/g currently on the market, and with capacity attenuation is fast, safety
The problems such as poor performance, it also is difficult to there is room for promotion more in use, seeking height ratio capacity negative material becomes the task of top priority.
Bismuth oxide nano material, generates Li changing to react with lithium2While O, can also be given birth to by alloy reaction
Become Li3Bi, stores more lithiums, and its theoretical capacity is up to 690mAh/g, removal lithium embedded current potential as little as 0.5V (vs Li+/ Li), valency
Lattice are cheap and nontoxic, are a kind of very promising metal-oxide negative materials.
However, for bismuth oxide, self-conductive is poor, easily reunite when granule reaches nanoscale, be unfavorable for lithium from
The deintercalation of son and the infiltration of electrolyte, and the volumetric expansion causing after embedding lithium easily causes the efflorescence of active material, and this is also
Current lithium ion battery decay several important the reason.
In view of above-mentioned defect, the design people, actively research and innovation in addition, to founding a kind of lithium ion battery negative
With the preparation method of Graphene-bismuth oxide composite so as to more the value in industry.
Content of the invention
For solving above-mentioned technical problem, it is an object of the invention to provide a kind of used as negative electrode of Li-ion battery Graphene-oxidation
The preparation method of bismuth composite, bismuth oxide nanoparticles are uniformly grown on graphene sheet layer, and the presence of material with carbon element can
Improve the electric conductivity of bismuth oxide, can simultaneously serve as the substrate of material, effectively suppress the little reunion to 5-10nm granule, graphite
The flexibility of alkene be also possible to prevent the embedding lithium of active material after the structural deterioration that causes of volumetric expansion, these features can ensure that battery follows
The stability of ring, effectively improves chemical property.
The preparation method of the used as negative electrode of Li-ion battery Graphene-bismuth oxide composite of the present invention, comprises the steps：
1) graphene oxide is placed in beaker, adding ethylene glycol solution to carry out the ultrasonic concentration that obtains is 0.2g/L-1.0g/
The graphene suspension of L；
2) graphene suspension is transferred in hydrothermal reaction kettle, and adds carbamide and polyvinylpyrrolidine in a kettle.
Ketone, carries out magnetic agitation, so that all of material is dissolved completely in ethylene glycol solution；
3) by Bi (NO3)3·5H2O is dissolved in dilute acid soln, after dissolving, according to Bi (NO3)3·5H2O and Graphene
Mass ratio is 50:1-10:1 is added drop-wise to 2) in the solution handled well, carry out magnetic agitation, make material mixing uniform；
4) mixed solution is loaded box hat, air dry oven carries out solvent thermal reaction, reaction is natural after terminating
It is cooled to room temperature；
5) product after hydro-thermal reaction is transferred in centrifuge tube, add 20-30ml water in centrifuge tube, through ultrasonic place
After reason, it is centrifuged, is outwelled supernatant, and repeated 2-3 time；
6) again in centrifuge tube add 20-30ml dehydrated alcohol, sonicated after, be centrifuged, outwelled supernatant, and
Repeat 2-3 time；
7) by step 6) in material after obtained cleaning put into 6-8h in freeze dryer, be dried, remove in material
Moisture, dried material is ground the bismuth oxide-graphene composite material that can get superelevation load capacity, and load capacity >=
94%.
Further, in the Graphene of described preparation-bismuth oxide composite, bismuth oxide nanoparticles size is received for 5-10
Rice, is dispersed on graphene film.
Further, described graphene oxide improved Hummers method preparation, modified Hummers method preparation oxidation stone
The concretely comprising the following steps of black alkene：
A, weigh 0.5g flaky graphite solid and 0.5g sodium nitrate solid in round-bottomed flask, round-bottomed flask is fixed on
On magnetic stirring apparatuss and carry out ice bath；
B, measure 24mL concentrated sulphuric acid and be added in the round-bottomed flask in A, stirring and evenly mixing, it is then transferred in Ultrasound Instrument, ice
Bathe ultrasonic 1h；
C, weigh 3g potassium permanganate solid, after step B terminates, round-bottomed flask is transferred on magnetic stirring apparatuss in ice bath bar
Continue stirring under part, in 0.5h, 3g potassium permanganate solid is slowly added in round-bottomed flask, after being added completely into, continue stirring
1.5h；
D, round-bottomed flask is transferred in Ultrasound Instrument, ultrasonic 1h under the conditions of 40 DEG C；
After E, ultrasonic end, round-bottomed flask is transferred to and is stirred on magnetic stirring apparatuss, under normal temperature condition, by 25mL
Distilled water is slowly dropped in round-bottomed flask, then raises temperature to 80 DEG C, continues stirring 1h；
F, temperature is reduced to 40 DEG C, continuously stirred, the appropriate hydrogenperoxide steam generator of Deca during stirring, until
There are a large amount of bubbles to produce, solution is changed into yellow, stop stirring, solution is transferred in small beaker, naturally cools to room temperature；
G, carry out centrifuge washing 5 times with 0.05mol/L dilute hydrochloric acid solution, subsequently carrying out centrifuge washing with distilled water to PH is
Stop when neutral, lyophilization can get graphene oxide composite material.
Further, described dilute acid soln is the dilute nitric acid solution of 0.4M.
Further, described step 2) at a temperature of 120-180 DEG C hydro-thermal reaction 3-6h.
By such scheme, the present invention at least has advantages below：
1st, after loading to bismuth oxide on Graphene, the particle diameter that can effectively reduce bismuth oxide (subtracts from about 100nm
Little to 5-10nm), the reduction of active material particle diameter can be conducive to the performance of the capacity of battery material；
2nd, the presence of Graphene can provide good conductive network for bismuth oxide material, improves the electric conductivity of material, with
When also utilize the flexibility of itself, effectively prevent the structural deterioration that active material process of intercalation volumetric expansion leads to, this can be effective
Improve circulating battery during stability and reversibility；
3rd, in the bismuth oxide/graphene composite material of preparation, the content of bismuth oxide is up to 94.5% (mass fraction), realizes
The superelevation amount load of material, so in charge and discharge process, battery just has higher theoretical capacity (about 690mAh/g).
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of description, below with presently preferred embodiments of the present invention and coordinate accompanying drawing describe in detail as after.
Brief description
Fig. 1 (a) is the SEM figure of bismuth oxide nanosphere in the present invention, and Fig. 1 (b) is bismuth oxide-graphene composite material
SEM schemes；
Fig. 2 is the SEM figure of the SEM figure of the bismuth oxide nanosphere of embodiment one preparation, bismuth oxide-graphene composite material；
Fig. 3 is the SEM figure of the SEM figure of the bismuth oxide nanosphere of embodiment two preparation, bismuth oxide-graphene composite material；
Fig. 4 is the SEM figure of the SEM figure of the bismuth oxide nanosphere of embodiment three preparation, bismuth oxide-graphene composite material.
Specific embodiment
With reference to the accompanying drawings and examples, the specific embodiment of the present invention is described in further detail.Hereinafter implement
Example is used for the present invention is described, but is not limited to the scope of the present invention.
The preparation method of the used as negative electrode of Li-ion battery Graphene-bismuth oxide composite of the present invention, comprises the steps：
1) graphene oxide of preparation is placed in beaker, adds ethylene glycol solution to carry out the ultrasonic Graphene that obtains and suspend
Liquid；
2) graphene suspension is transferred in hydrothermal reaction kettle, and adds carbamide (hydrolysis hydroxyl is provided) in a kettle.
With Polyvinylpyrrolidone (as surfactant), carry out magnetic agitation, make all of material be dissolved completely in ethylene glycol and (carry
For reduction system) in solution；
3) by Bi (NO3)3·5H2O is dissolved in dilute acid soln, after dissolving, is added drop-wise to 2) in the solution handled well, enter
Row magnetic agitation, makes material mixing uniform；
4) mixed solution is loaded box hat, air dry oven carries out solvent thermal reaction, reaction is natural after terminating
It is cooled to room temperature；
5) product after hydro-thermal reaction is transferred in centrifuge tube, add 20-30ml water in centrifuge tube, through ultrasonic place
After reason, it is centrifuged, is outwelled supernatant, and repeated 2-3 time；
6) again in above-mentioned centrifuge tube add 20-30ml dehydrated alcohol, sonicated after, be centrifuged, outwelled supernatant
Liquid, and repeat 2-3 time；
7) by step 6) in material after obtained cleaning put into 6-8h in freeze dryer, be dried, remove in material
Moisture, dried material is ground the bismuth oxide-graphene composite material that can get superelevation load capacity, and load capacity >=
94%, such as shown in Fig. 1 (b).
In Graphene prepared by the present invention-bismuth oxide composite, bismuth oxide nanoparticles size is 5-10 nanometer, all
Even it is dispersed on graphene film, shown in such as Fig. 1 (a).
Specifically, the graphene oxide in the present invention passes through to improve the preparation of Hummers method.Using modified Hummers legal system
For concretely comprising the following steps of graphene oxide：
A, weigh 0.5g flaky graphite solid and 0.5g sodium nitrate solid in 50mL round-bottomed flask, subsequently round bottom is burnt
Bottle is fixed on magnetic stirring apparatuss and carries out ice bath；
B, measure 24mL concentrated sulphuric acid and be added in the round-bottomed flask in A, stirring and evenly mixing (mixing speed first slowly after fast), subsequently
It is transferred in Ultrasound Instrument, ice-bath ultrasonic 1h is it is ensured that flaky graphite is scattered more uniform；
C, weigh 3g potassium permanganate solid, after step B terminates, round-bottomed flask is transferred on magnetic stirring apparatuss in ice bath bar
Continue stirring under part, in 0.5h, 3g potassium permanganate solid is slowly added in round-bottomed flask, after being added completely into, continue stirring
1.5h；
D, subsequently round-bottomed flask is transferred in Ultrasound Instrument, ultrasonic 1h under the conditions of 40 DEG C；
After E, ultrasonic end, round-bottomed flask is transferred to and is stirred on magnetic stirring apparatuss, under normal temperature condition, by 25mL
Distilled water is slowly dropped in round-bottomed flask (required time about 30min), then raises temperature to 80 DEG C, continues stirring 1h；
F, subsequently temperature is reduced to 40 DEG C, continuously stirred, the appropriate hydrogenperoxide steam generator of Deca during stirring,
Until there being a large amount of bubbles to produce, solution is changed into yellow, stops stirring, solution is transferred in small beaker, naturally cools to room temperature；
G, carry out centrifuge washing 5 times with 0.05mol/L dilute hydrochloric acid solution, subsequently carrying out centrifuge washing with distilled water to PH is
Stop when neutral, lyophilization can get graphene oxide composite material.
Dilute acid soln employed in the present invention is the dilute nitric acid solution of 0.4M.
Step 2) hydro-thermal reaction 3-6h specifically at a temperature of 120-180 DEG C.
The modification by surfactant for the present invention, the bismuth oxide that can form diameter about 5-10nm in water-heat process is received
Rice grain, uniform load is on graphene sheet layer；Preparation bismuth oxide-graphene composite material in, Graphene exist for oxygen
Changing bismuth provides good conductive network, also effectively inhibits volumetric expansion in charge and discharge process for the bismuth oxide material simultaneously,
So not only extend the cycle life of lithium ion battery, and improve the high rate performance of battery.
In order to be better understood from the present invention, it is further elucidated with present disclosure with reference to example, but the present invention's is interior
Hold and do not limit to example given below.
Embodiment one
1) the graphene oxide 5mg weighing preparation is placed in 50mL beaker, adds 25mL ethylene glycol solution ultrasonic disperse
30min, can get the graphene suspension that mass concentration is 0.2g/L；
2) graphene suspension is transferred in 50mL hydrothermal reaction kettle, and adds carbamide (to provide hydrolysis in a kettle.
Hydroxyl) and Polyvinylpyrrolidone (as surfactant), carry out magnetic agitation, make all of material be dissolved completely in second two
In alcohol (offer reduction system) solution；
3) 243mg Bi (NO will be weighed3)3·5H2O is dissolved in 5mL0.4M dilute nitric acid solution, after dissolving, is added drop-wise to 2)
In in the solution handled well, carry out magnetic agitation, make material mixing uniform；
4) mixed solution is loaded box hat, under 150 DEG C of conditionals of air dry oven, react 4h, naturally cold after terminating
But to room temperature；
5) product after hydro-thermal reaction is transferred in 50mL centrifuge tube, centrifuge tube adds 30mL distilled water, warp
After supersound process, it is centrifuged, is outwelled supernatant, and repeated 2-3 time；
6) again in above-mentioned centrifuge tube add 30ml dehydrated alcohol, sonicated after, be centrifuged, outwelled supernatant,
And repeat 2-3 time；
7) by step 6) in material after obtained cleaning put into 8h in freeze dryer, be dried, remove the water in material
Point, dried material is ground the bismuth oxide-graphene composite material that can get superelevation load capacity.Manufactured in the present embodiment
The SEM figure of bismuth oxide nanosphere, the SEM of bismuth oxide-graphene composite material scheme as shown in Figure 2.
Embodiment two
1) the graphene oxide 10mg weighing preparation is placed in 50mL beaker, adds 25mL ethylene glycol solution ultrasonic disperse
30min, can get the graphene suspension that mass concentration is 0.4g/L；
2) graphene suspension is transferred in 50mL hydrothermal reaction kettle, and adds carbamide (to provide hydrolysis in a kettle.
Hydroxyl) and Polyvinylpyrrolidone (as surfactant), carry out magnetic agitation, make all of material be dissolved completely in second two
In alcohol (offer reduction system) solution；
3) 243mg Bi (NO will be weighed3)3·5H2O is dissolved in 5mL0.4M dilute nitric acid solution, after dissolving, is added drop-wise to 2)
In in the solution handled well, carry out magnetic agitation, make material mixing uniform；
4) mixed solution is loaded box hat, 120 DEG C of reaction 6h, naturally cool to room after terminating in air dry oven
Temperature；
5) product after hydro-thermal reaction is transferred in 50mL centrifuge tube, centrifuge tube adds 30mL distilled water, warp
After supersound process, it is centrifuged, is outwelled supernatant, and repeated 2-3 time；
6) again in above-mentioned centrifuge tube add 30mL dehydrated alcohol, sonicated after, be centrifuged, outwelled supernatant,
And repeat 2-3 time；
7) by step 6) in material after obtained cleaning put into 8h in freeze dryer, be dried, remove the water in material
Point, dried material is ground the bismuth oxide-graphene composite material that can get superelevation load capacity.Manufactured in the present embodiment
The SEM figure of bismuth oxide nanosphere, the SEM of bismuth oxide-graphene composite material scheme as shown in Figure 3.
Embodiment three
1) the graphene oxide 25mg weighing preparation is placed in 50mL beaker, adds 25mL ethylene glycol solution ultrasonic disperse
30min, can get the graphene suspension that mass concentration is 1.0g/L；
2) graphene suspension is transferred in 50mL hydrothermal reaction kettle, and adds carbamide (to provide hydrolysis in a kettle.
Hydroxyl) and Polyvinylpyrrolidone (as surfactant), carry out magnetic agitation, make all of material be dissolved completely in second two
In alcohol (offer reduction system) solution；
3) 243mg Bi (NO will be weighed3)3·5H2O is dissolved in dilute nitric acid solution, after dissolving, is added drop-wise to 2) middle process
In good solution, carry out magnetic agitation, make material mixing uniform；
4) mixed solution is loaded box hat, 180 DEG C of reaction 3h, naturally cool to room after terminating in air dry oven
Temperature；
5) product after hydro-thermal reaction is transferred in 50mL centrifuge tube, centrifuge tube adds 30mL distilled water, warp
After supersound process, it is centrifuged, is outwelled supernatant, and repeated 2-3 time；
6) again in above-mentioned centrifuge tube add 30mL dehydrated alcohol, sonicated after, be centrifuged, outwelled supernatant,
And repeat 2-3 time；
7) by step 6) in material after obtained cleaning put into 8h in freeze dryer, be dried, remove the water in material
Point, dried material is ground the bismuth oxide-graphene composite material that can get superelevation load capacity.Manufactured in the present embodiment
The SEM figure of bismuth oxide nanosphere, the SEM of bismuth oxide-graphene composite material scheme as shown in Figure 4.
The above is only the preferred embodiment of the present invention, is not limited to the present invention it is noted that for this skill
For the those of ordinary skill in art field, on the premise of without departing from the technology of the present invention principle, can also make some improve and
Modification, these improve and modification also should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of preparation method of used as negative electrode of Li-ion battery Graphene-bismuth oxide composite is it is characterised in that include as follows
Step：
1) graphene oxide is placed in beaker, adding ethylene glycol solution to carry out the ultrasonic concentration that obtains is 0.2g/L-1.0g/L's
Graphene suspension；
2) graphene suspension is transferred in hydrothermal reaction kettle, and adds carbamide and Polyvinylpyrrolidone in a kettle.,
Carry out magnetic agitation, so that all of material is dissolved completely in ethylene glycol solution；
3) by Bi (NO3)3·5H2O is dissolved in dilute acid soln, after dissolving, according to Bi (NO3)3·5H2O and the quality of Graphene
Than for 50:1-10:1 is added drop-wise to 2) in the solution handled well, carry out magnetic agitation, make material mixing uniform；
4) mixed solution is loaded box hat, air dry oven carries out solvent thermal reaction, reaction terminates rear natural cooling
To room temperature；
5) product after hydro-thermal reaction is transferred in centrifuge tube, centrifuge tube adds 20-30ml water, sonicated
Afterwards, it is centrifuged, is outwelled supernatant, and repeated 2-3 time；
6) again in centrifuge tube add 20-30ml dehydrated alcohol, sonicated after, be centrifuged, outwelled supernatant, and repeated
2-3 time；
7) by step 6) in material after obtained cleaning put into 6-8h in freeze dryer, be dried, remove the water in material
Point, dried material is ground the bismuth oxide-graphene composite material that can get superelevation load capacity, load capacity >=94%.
2. the preparation method of used as negative electrode of Li-ion battery Graphene-bismuth oxide composite according to claim 1, it is special
Levy and be：In the Graphene of described preparation-bismuth oxide composite, bismuth oxide nanoparticles size is 5-10 nanometer, dispersed
On graphene film.
3. the preparation method of used as negative electrode of Li-ion battery Graphene-bismuth oxide composite according to claim 1, it is special
Levy and be：Prepared by described graphene oxide improved Hummers method, modified Hummers method prepares the concrete of graphene oxide
Step is：
A, weigh 0.5g flaky graphite solid and 0.5g sodium nitrate solid in round-bottomed flask, round-bottomed flask is fixed on magnetic force
On agitator and carry out ice bath；
B, measure 24mL concentrated sulphuric acid and be added in the round-bottomed flask in A, stirring and evenly mixing, it is then transferred in Ultrasound Instrument, ice bath surpasses
Sound 1h；
C, weigh 3g potassium permanganate solid, after step B terminates, round-bottomed flask is transferred on magnetic stirring apparatuss under condition of ice bath
Continue stirring, in 0.5h, 3g potassium permanganate solid is slowly added in round-bottomed flask, after being added completely into, continue stirring 1.5h；
D, round-bottomed flask is transferred in Ultrasound Instrument, ultrasonic 1h under the conditions of 40 DEG C；
After E, ultrasonic end, round-bottomed flask is transferred to and is stirred on magnetic stirring apparatuss, under normal temperature condition, 25mL is distilled
Water is slowly dropped in round-bottomed flask, then raises temperature to 80 DEG C, continues stirring 1h；
F, temperature is reduced to 40 DEG C, continuously stirred, the appropriate hydrogenperoxide steam generator of Deca during stirring, until have big
Amount bubble produces, and solution is changed into yellow, stops stirring, solution is transferred in small beaker, naturally cools to room temperature；
G, carry out centrifuge washing 5 times with 0.05mol/L dilute hydrochloric acid solution, it is neutral for subsequently carrying out centrifuge washing with distilled water to PH
When stop, lyophilization can get graphene oxide composite material.
4. the preparation method of used as negative electrode of Li-ion battery Graphene-bismuth oxide composite according to claim 1, it is special
Levy and be：Described dilute acid soln is the dilute nitric acid solution of 0.4M.
5. the preparation method of used as negative electrode of Li-ion battery Graphene-bismuth oxide composite according to claim 1, it is special
Levy and be：Described step 2) at a temperature of 120-180 DEG C hydro-thermal reaction 3-6h.
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| CN112924534B (en) * | 2021-02-02 | 2022-05-03 | 广东省农业科学院农业质量标准与监测技术研究所 | Preparation method of nano bismuth/graphene composite material and application of nano bismuth/graphene composite material in MALDI-MS |
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| CN114420924B (en) * | 2022-01-11 | 2023-10-27 | 西北工业大学 | Bismuth telluride-based composite anode material of sodium/potassium ion battery and preparation method thereof |
| CN114735690A (en) * | 2022-04-19 | 2022-07-12 | 湖南铂威新能源科技有限公司 | Preparation method of artificial graphite composite negative electrode material for lithium ion battery |
| CN114735690B (en) * | 2022-04-19 | 2022-10-28 | 湖南铂威新能源科技有限公司 | Preparation method of artificial graphite composite negative electrode material for lithium ion battery |
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