CN107275628B - A kind of preparation method and lithium ion battery of two dimension bismuth alkene - Google Patents
A kind of preparation method and lithium ion battery of two dimension bismuth alkene Download PDFInfo
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- CN107275628B CN107275628B CN201710588276.XA CN201710588276A CN107275628B CN 107275628 B CN107275628 B CN 107275628B CN 201710588276 A CN201710588276 A CN 201710588276A CN 107275628 B CN107275628 B CN 107275628B
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Abstract
The invention belongs to new energy correlative technology fields, and it discloses a kind of preparation methods of two-dimentional bismuth alkene, method includes the following steps: the ultrasonic vibration predetermined time in removing solvent is added in bismuth meal by (1), to obtain mixed solvent；(2) centrifugation removes the unstripped bismuth meal of the in the mixed solvent, to obtain supernatant；(3) the obtained supernatant is subjected to more high-revolving centrifugal vacuum drying, to obtain two-dimentional bismuth alkene.The invention further relates to the lithium ion batteries that electrode constituent includes above-mentioned two-dimentional bismuth alkene.The two-dimentional bismuth meal volume and capacity ratio with higher and good cycle performance, and stablize, environment friendly and pollution-free, preparation process is simple.
Description
Technical field
The invention belongs to new energy correlative technology fields, more particularly, to the preparation method and lithium of a kind of two-dimentional bismuth alkene
Ion battery.
Background technique
The energy is most important for human social development, but most energy consumption is fossil combustion every year in the world at present
Material, bring greenhouse effects and environmental pollution is serious threatens our sustainable development.Change existing energy resource structure, greatly develops
These problems can be effectively relieved in the clean energy resourcies such as wind energy, solar energy.But these clean energy resourcies randomness inherently,
The disadvantages of having a rest property, causes to be difficult to meet portable electronic device requirement, such as the solar energy only ability in the case where there is light
It can smoothly generate electricity, but be difficult to obtain energy at night or in the bad situation of light, developing let us can use whenever and wherever possible
The energy storage technology of the upper energy is most important.
The energy storage technology of mainstream includes the energy storage of physics class and electrochemical energy storage two major classes, electrochemical energy storage technology tool at this stage
Efficient height, small investment, using the advantages that safe, flexible in application, be very suitable to the developing direction of the current energy.Lithium ion battery
Have many advantages, such as that light-weight, capacity is big, memory-less effect, the especially portable electronic devices such as mobile phone, laptop are in society
Universal and large-scale use in life, is greatly facilitated the exploitation and use of the electrochemical energy storages such as lithium ion battery.But lithium
Although ion battery energy density is very high, the theoretical volumetric capacity of the negative electrode material graphite really used only has 837 mAh/cm3,
Which has limited the development of the portable energy-storing equipment of smaller volume.Bismuth metal theoretical capacity 3765mAh/cm with higher3, this
Almost graphite (837mAh/cm3) 4.5 times, be that high energy density per unit volume electrode material selects well, in addition bismuth metal green
It is pollution-free, it has a good application prospect.However, application of the bismuth metal in terms of new energy energy storage is very few, electrode material is
Doped with bismuth metal to improve electrode.
The color of bismuth metal be from silvery white to pink, pure bismuth be it is soft, it is more crisp when impure.The chemical property of bismuth
More stable at room temperature, bismuth is not reacted with oxygen or water, stable in the air.The bismuth resource of China occupies first place in the world, China
Existing 70 many places of bismuth mineral, so that China becomes the absolute predominance country of world's bismuth.Bismuth as " green metal " that can be used safely,
At present in addition to for pharmaceuticals industry, also it is widely used in the fields such as semiconductor, superconductor, fire retardant, pigment, cosmetics, is expected to
Replace the elements such as toxic lead, antimony, cadmium mercury.In addition, bismuth is the strongest metal of diamagnetism, resistivity increases and hot under magnetic fields
Conductance reduces, and also has good application prospect in terms of thermoelectricity and superconduction.
Currently, the related technical personnel of this field have prepared the low-dimensional nanometer bismuth of different-shape using different methods
Material, bismuth nano-wire, bismuth nanotube etc., but related technology of preparing, part are former not yet for the two-dimensional ultrathin material bismuth alkene of bismuth
Because may be that bismuth presoma or hydrothermal synthesizing condition are difficult to control.Many hexagonal crystal system materials are made of two-dimensional material stacking
The crystal structure of macroscopic view, and chemical bond is very strong in two-dimensional material plane, interlayer Robert Van de Walle interaction is then very weak, this makes
The interaction force that two-dimensional material can overcome by various methods interlayer weak is obtained, removes to obtain two wieners from its corresponding block of material
Rice piece.At this stage high-volume and capacity ratio, stable circulation alloy reached bottleneck as the technology of cathode, liquid phase removes graphite
Alkene, black phosphorus existing research, phosphorus alkene is in spite of higher capacity, but phosphorus alkene is very easy to oxidation in air, is afraid of that oxygen is afraid of water.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of preparation method of two-dimentional bismuth alkene and
The ultrasonic vibration predetermined time in removing solvent is added in bismuth meal by lithium ion battery, and to obtain mixed solvent, centrifugation removal is described mixed
Unstripped bismuth meal in bonding solvent prepares two-dimentional bismuth alkene, preparation process letter using the method for liquid phase removing to obtain supernatant
Two-dimentional bismuth alkene volume and capacity ratio with higher and cyclical stability single, and prepare.
To achieve the above object, according to one aspect of the present invention, a kind of preparation method of two-dimentional bismuth alkene, the system are provided
Preparation Method the following steps are included:
(1) the ultrasonic vibration predetermined time in removing solvent is added in bismuth meal, during ultrasonic vibration, the bismuth meal is in institute
It states and is partially stripped into sheet under the action of removing solvent, the mixed solvent with sheet bismuth alkene is obtained with this；
(2) centrifugation removes the unstripped bismuth meal of the in the mixed solvent and is remained in the supernatant with obtaining supernatant
The sheet bismuth alkene；
(3) the obtained supernatant is subjected to centrifugal vacuum drying, to obtain the two-dimentional bismuth alkene of sheet.
Further, the removing solvent is one of alcohol, isopropanol, N-Methyl pyrrolidone, water or several
Combination.
Further, the removing solvent is water and the alcohol solvent that 1:1 is mixed to get by volume.
Further, the predetermined time was 5~6 (hours).
Further, the revolving speed when supernatant being carried out centrifugal vacuum drying is greater than centrifugation and removes the mixed solvent
In unstripped bismuth meal when revolving speed.
It is another aspect of this invention to provide that providing a kind of lithium ion battery, the lithium ion battery includes electrode, described
The constituent of electrode includes two-dimentional bismuth alkene as described above.
Further, the two-dimentional bismuth alkene with a thickness of 3~5 nanometers.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, provided by the invention two
The preparation method and lithium ion battery for tieing up bismuth alkene mainly have the advantages that
1. the ultrasonic vibration predetermined time in removing solvent is added in bismuth meal, to obtain mixed solvent, centrifugation removal is described mixed
Unstripped bismuth meal in bonding solvent prepares two-dimentional bismuth alkene, preparation process letter using the method for liquid phase removing to obtain supernatant
Two-dimentional bismuth alkene volume and capacity ratio with higher and cyclical stability single, and prepare；
2. two-dimentional bismuth alkene is used as the lithium ion battery of electrode material in 0.5C (1883mA/cm3, 190mA/g) and electric current is close
Degree is lower to carry out constant current charge-discharge, still keeps 90% or so of initial capacity after circulation 150 times, has preferable cycle characteristics；
3. two-dimentional bismuth alkene with a thickness of 3 nanometers~5 nanometers, it was proved that, two-dimentional bismuth alkene is under different current densities
Volume capacity almost without obvious decaying, there is preferable high rate performance.
Detailed description of the invention
Fig. 1 is the flow diagram of the preparation method for the two-dimentional bismuth alkene that better embodiment of the present invention provides；
Fig. 2 is the atomic structure simulation schematic diagram using the two-dimentional bismuth alkene of the preparation method preparation of the two-dimentional bismuth alkene in Fig. 1；
Fig. 3 is the presoma bismuth meal section scanning electron microscope (SEM) that the preparation method of the two-dimentional bismuth alkene in Fig. 1 is related to
Figure；
Fig. 4 is two-dimentional bismuth alkene transmission electron microscope (TEM) figure using the preparation method preparation of the two-dimentional bismuth alkene in Fig. 1
Piece；
Fig. 5 is two-dimentional bismuth alkene atomic force microscope (AFM) figure using the preparation method preparation of the two-dimentional bismuth alkene in Fig. 1
Piece；
Fig. 6 is the Tyndall effect light using the bismuth alkene dispersion liquogel of the preparation method preparation of the two-dimentional bismuth alkene in Fig. 1
Learn photo；
Fig. 7 is X-ray diffraction (XRD) schematic diagram for the bismuth being related to using the preparation method of the two-dimentional bismuth alkene in Fig. 1；
Fig. 8 is the bismuth alkene and presoma bismuth meal Raman light of bismuth meal and the preparation method preparation using the two-dimentional bismuth alkene in Fig. 1
Spectrogram；
Fig. 9 is applied in lithium ion battery using the bismuth alkene of the preparation method preparation of the two-dimentional bismuth alkene in Fig. 1, the 1st, 4,
5 CV curves.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The preparation method for the two-dimentional bismuth alkene that better embodiment of the present invention provides referring to FIG. 1 to FIG. 4, the preparation side
Method is liquid phase strip preparation method, has high quality, high yield and ultra-thin design feature, the thickness of the two-dimentional bismuth alkene of preparation is 3
Nanometer~5 nanometers, having a size of 500nm or so.
The preparation method of the two-dimentional bismuth alkene mainly comprises the steps that
The ultrasonic vibration predetermined time in removing solvent is added, to obtain mixed solvent, wherein described in bismuth meal by step 1
Removing solvent is for removing the bismuth meal, to obtain the bismuth alkene of sheet.Specifically, the removing solvent is alcohol, different
One of propyl alcohol, N-Methyl pyrrolidone, water or several combinations；The predetermined time is 5~6 hours；The mixing
Solvent has sheet bismuth alkene.
In present embodiment, the removing solvent is the mixed solvent of water and the alcohol composition of 1:1 mixing by volume；It can be with
Understand, in other embodiments, the removing solvent can be other solvents, such as isopropanol, N-Methyl pyrrolidone.
Step 2, centrifugation removes the bismuth meal that the in the mixed solvent is not peeled off, to obtain supernatant.Present embodiment
In, the unstripped bismuth meal of the in the mixed solvent is removed using low-speed centrifugal, to obtain supernatant, is remained in the supernatant
The obtained supernatant is carried out centrifugal drying at a high speed by the sheet bismuth alkene, to obtain two-dimentional bismuth alkene, is turned when vacuum drying
Revolving speed when fast bismuth meal unstripped greater than the centrifugation removal in the mixed solvent.
Fig. 5 to Fig. 9 is please referred to, the obtained supernatant is carried out centrifugal vacuum drying, to obtain two dimension by figure step 3
Bismuth alkene.Specifically, the two-dimentional bismuth alkene with a thickness of 3 nanometers~5 nanometers, having a size of 500 rans.Wherein, in Fig. 8
Solid line indicates the light intensity of commercial bismuth meal with the change curve of wavelength shift；Dotted line indicates the system of two-dimentional bismuth alkene provided by the invention
Preparation Method preparation two-dimentional bismuth alkene light intensity with wavelength shift change curve.
The two-dimentional bismuth alkene of the preparation method preparation of two dimension bismuth alkene provided by the invention has high quality and ultra-thin structure special
Point, and there is very high volume and capacity ratio and good cycle performance, and stablize, it is environment friendly and pollution-free.
The two dimension bismuth alkene can be used for preparing electrode.Specifically, by the two-dimentional bismuth alkene, conductive agent, binder according to
Certain proportion is just coated on copper foil after being modulated into uniform sizing material, and is dried in vacuo to obtain electrode slice；Later, using hand
The electrode slice is packaged by casing, to obtain lithium ion battery.
As shown in table 1, two-dimentional bismuth alkene, the quality of the bismuth meal are prepared using the bismuth meal of phase homogenous quantities, different removing solvents
It is 8 grams, the volume of the removing solvent is 800 milliliters.From table 1 as can be seen that in several removing solvents in table 1, when adopting
When removing solvent is the intermixture of alcohol and water, the quality of two dimension bismuth meal obtained is maximum.
Table 1
Table 2 shows the volume capacity of the two-dimentional bismuth alkene under different current densities, under different current densities, bismuth alkene body
Product capacity is generally greater than block bismuth alkene volume capacity, wherein two-dimentional bismuth alkene volume capacity is maximum in current density 0.1C.
Table 2
It is 0.5C (1883mA/cm that table 3, which shows current density,3), different cycle-index when circulation volume, it is seen then that
When different cycle-index, the volume capacity of two-dimentional bismuth alkene is generally greater than the volume capacity of block bismuth meal.
Table 3
The volume capacity of two-dimentional bismuth alkene and commercial graphite in different cycle-indexes is set forth in table 4, it is seen then that in difference
Cycle-index under, the volume capacity of two bismuth alkene is generally greater than the volume capacity of commercial graphite, with the increasing of cycle-index
Add gradually with the reduction of lesser amplitude.
Table 4
The preparation method and lithium ion battery of two bismuth alkene provided by the invention, the preparation method simple process, preparation
Obtained two-dimentional bismuth alkene volume and capacity ratio, cyclical stability and high rate performance with higher, as electrode material lithium from
Sub- battery has preferable cycle characteristics.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (5)
1. a kind of preparation method of two dimension bismuth alkene, which is characterized in that this method includes lower step:
(1) the ultrasonic vibration predetermined time in removing solvent is added in bismuth meal, during ultrasonic vibration, the bismuth meal is in the stripping
It is partially stripped into sheet under the action of exsolution agent, the mixed solvent with sheet bismuth alkene is obtained with this；Wherein, the removing solvent
For one of isopropanol, N-Methyl pyrrolidone, water or several combinations and water and alcohol, 1:1 is mixed by volume
Obtained solvent；
(2) centrifugation removes the unstripped bismuth meal of the in the mixed solvent, to obtain supernatant, remains in the supernatant described
Sheet bismuth alkene；
(3) the obtained supernatant is subjected to centrifugal vacuum drying, to obtain the two-dimentional bismuth alkene of sheet.
2. the preparation method of two dimension bismuth alkene as described in claim 1, it is characterised in that: the predetermined time is 5~6 hours.
3. such as the preparation method of the described in any item two-dimentional bismuth alkene of claim 1-2, it is characterised in that: carry out the supernatant
Revolving speed when centrifugal vacuum is dry is greater than revolving speed when centrifugation removes the in the mixed solvent unstripped bismuth meal.
4. a kind of lithium ion battery, the lithium ion battery includes electrode, it is characterised in that: the constituent of the electrode includes
Two dimension bismuth alkene as described in any one of claims 1-3.
5. lithium ion battery as claimed in claim 4, it is characterised in that: 3~5 nanometers of thickness of the two dimension bismuth alkene.
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| CN108580908B (en) * | 2017-12-26 | 2020-11-27 | 深圳大学 | Bismuth quantum dot and preparation method thereof |
| CN108247069B (en) * | 2017-12-26 | 2020-02-28 | 深圳大学 | Preparation method of bismuth quantum dots |
| CN108284220B (en) * | 2017-12-26 | 2021-01-05 | 深圳大学 | Bismuth-alkene nanosheet and preparation method thereof |
| CN108145171B (en) * | 2017-12-26 | 2020-11-27 | 深圳大学 | Bismuth-alkene nanosheet and preparation method thereof |
| CN108339972B (en) * | 2018-01-30 | 2020-05-05 | 深圳大学 | Two-dimensional titanium nanosheet and preparation method and application thereof |
| CN108515186A (en) * | 2018-05-15 | 2018-09-11 | 中国工程物理研究院化工材料研究所 | The bismuth alkene of surfactant auxiliary, the liquid phase ultrasound stripping means of antimony alkene, black phosphorus |
| CN111933918B (en) * | 2020-06-28 | 2022-03-04 | 武汉理工大学 | Preparation method of two-dimensional metal bismuth and application of two-dimensional metal bismuth in sodium/potassium ion secondary battery |
| CN115020120B (en) * | 2022-05-26 | 2023-07-25 | 安徽大学 | Composite graphene-bismuth alkene aerogel with staggered stacked intercalation structure, preparation method and application |
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| CN105297133A (en) * | 2015-10-28 | 2016-02-03 | 南京理工大学 | Preparation method of single-crystal less-layer antimonene |
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| CN105297133A (en) * | 2015-10-28 | 2016-02-03 | 南京理工大学 | Preparation method of single-crystal less-layer antimonene |
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| "Elemental two-dimensional nanosheets beyond graphene";Xiangkai Kong等;《Chemical Society Reviews》;20170322;第46卷(第8期);introduction、3.4部分 * |
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