CN107026263A - Sea urchin shape bismuth sulfide/macropore graphene composite material, preparation method and applications - Google Patents
Sea urchin shape bismuth sulfide/macropore graphene composite material, preparation method and applications Download PDFInfo
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- CN107026263A CN107026263A CN201710408052.6A CN201710408052A CN107026263A CN 107026263 A CN107026263 A CN 107026263A CN 201710408052 A CN201710408052 A CN 201710408052A CN 107026263 A CN107026263 A CN 107026263A
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- H—ELECTRICITY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- 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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- H—ELECTRICITY
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- 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
- H01M4/62—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of sea urchin shape bismuth sulfide/macropore graphene composite material, preparation method and applications.Using simple hydro-thermal method, using bismuth nitrate as bismuth source, sulphur source is used as using thiocarbamide, trimellitic acid is used as binding agent, cetyl trimethylammonium bromide prepares described sea urchin shape bismuth sulfide/macropore graphene complex as surfactant, redistilled water as solvent.The present invention is simple to operate, and reaction condition is controllable, and prepared bismuth sulfide pattern is homogeneous, and is successfully loaded in macropore graphene hole；Macropore graphene preferably shortens lithium ion and electron diffusion path during effectively buffering volumetric expansion pressure of the bismuth sulfide in charge and discharge process, cycle charge-discharge, greatly improves the cycle performance of battery.
Description
Technical field
The invention belongs to lithium ion battery negative material field, more particularly to a kind of sea urchin shape bismuth sulfide/macropore graphite
Alkene composite, preparation method and applications.
Background technology
Current commercialized lithium ion battery negative material is mainly carbon-based material, but the relatively low specific volume of carbon-based material
Amount and safety issue, which have become, restricts its technical bottleneck further developed.
Bismuth sulfide（Bi2S3）It is a kind of important semi-conducting material, in terms of lithium is stored up, Bi2S3Nano material theoretical specific capacity
Reach 625 mAh/g, and the electrochemical reaction characteristic with completely reversibility.On the other hand, Bi2S3The raw material of negative material
Aboundresources, it is with low cost, have a safety feature, it is pollution-free, the advantages of prepare easy, have a good application prospect.But Bi2S3
There is larger bulk effect during embedding de- lithium, cause its cyclical stability in charge and discharge process poor, its work is constrained
For the application of lithium ion battery negative material.Although in recent years, by preparing the Bi of different-shape2S3, its cyclical stability has
Improved, but it does not obtain basic solution also.
For lithium cell cathode material, the specific surface area of material is bigger, and its contact area with electrolyte is bigger, more
Be conducive to lithium ion it is embedding take off into.Therefore, preparing the larger material of specific surface area turns into direction and the difficult point of research, mixes conduction
Property higher material improve its conductance, further improve the high rate performance of composite.
The content of the invention
It is an object of the invention to propose a kind of simple bismuth sulfide of with low cost, technique/macropore graphene composite material
Lithium ion battery negative material.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of sea urchin shape bismuth sulfide/macropore graphene composite material, by the way that sea urchin shape bismuth sulfide is attached into macropore graphene
Hole constitutes the composite, wherein, the mass ratio of sea urchin shape bismuth sulfide and macropore graphene is 1:10.
Further, macropore graphene refers to the graphene for having irregular holes in surface distributed.
The preparation method of above-mentioned composite, comprises the following steps：
1）The preparation of macropore graphene：Prepare certain mass concentration graphene oxide solution, it is ultrasonically treated after, carry out hydro-thermal it is anti-
Should, after after gained sample natural cooling, it is freeze-dried；
2）The preparation of composite：Using bismuth nitrate as bismuth source, using thiocarbamide as sulphur source, trimellitic acid is used as binding agent, ten
Six alkyl trimethyl ammonium bromides are as surfactant, and redistilled water is as solvent, and all raw material ultrasonic mixings make its uniform
Afterwards, by the solution and step 1）Obtained macropore graphene carries out hydro-thermal reaction together, after reaction terminates after cleaning, vacuum drying
Obtain the composite.
Further, step 1）In, the mass concentration of graphene oxide is 3 mg/mL;Sonication treatment time is 2 h, work(
The kHz of rate 55.
Further, step 1）In, hydrothermal temperature is 180 ± 10 DEG C, and the hydro-thermal reaction time is 12 h.
Further, step 2）In, the ratio between amount of material of the bismuth nitrate and thiocarbamide is 1: 50.
Further, step 2）In, hydrothermal temperature is 120 ± 5 DEG C, and the hydro-thermal reaction time is 12 h.
Further, step 2）In, the vacuum drying temperature is 60 DEG C, and vacuum drying time is 10 ~ 12h.
Above-mentioned composite as the negative material of lithium ion battery application.
Compared with prior art, the invention has the advantages that：（1）, the present invention made with cetyl trimethylammonium bromide
For surfactant, it is easy to bismuth nitrate, thiocarbamide, trimellitic acid in aqueous scattered, effectively prevents product bismuth sulfide group
The generation of poly- phenomenon；（2）, control hydrothermal temperature, sea urchin shape pattern is made in bismuth sulfide, larger specific surface area is made it have,
Increase and the contact area of electrolyte, so as to improve its chemical property；（3）, macropore graphene there is abundant macroporous structure
And multi-dimensional electronic pipeline, its intrinsic property, such as larger specific surface area, stable structure, promote the leaching of electrolyte
Profit, accelerates the migration rate of lithium ion；（4）, macropore graphene pore structure can more effectively alleviate bismuth sulfide in embedding de- lithium
During volumetric expansion pressure；（5）, the present invention prepares it is with low cost, equipment requirement simply, short preparation period.
Brief description of the drawings
Fig. 1 is the XRD of the bismuth sulfide/macropore graphene composite material prepared using the embodiment of the present invention 1.
Fig. 2 is the SEM figures of the macropore graphene prepared using the embodiment of the present invention 1.
Fig. 3 is the bismuth sulfide prepared using the embodiment of the present invention 1（a、b）With bismuth sulfide/macropore graphene（c、d）SEM
Figure.
Fig. 4 is that the TEM and first vegetarian noodles of the bismuth sulfide/macropore graphene composite material prepared using the embodiment of the present invention 1 are swept
Tracing.
Fig. 5 is the discharge and recharge of the bismuth sulfide and bismuth sulfide/macropore graphene composite material that are prepared using the embodiment of the present invention 1
Cycle performance figure.
Fig. 6 is the bismuth sulfide/macropore graphene synthesized using the embodiment of the present invention 1（a）With comparative example 1, it is 2-in-1 into vulcanization
Bismuth/macropore graphene（b、c）Charge-discharge performance figure.
Embodiment
The experimentation of the present invention is described in detail below, it is intended to make design cycle, the purpose of design of the present invention
And its innovative point and advantage more understand.
Idea of the invention is that：The composite wood is constituted by the hole that sea urchin shape bismuth sulfide is attached to macropore graphene
Material, sea urchin shape structure makes it have great specific surface area, considerably increases its contact area with electrolyte, be conducive to charge and discharge
The embedding of lithium ion is taken off into significantly improving battery charging and discharging performance in electric process.Graphene is that a kind of preferable two dimension is conductive
Property matrix, due to its preferable chemical stability, fabulous electronic conductivity and larger specific surface area, is prepared into macropore
Graphene can be buffered more effectively during volumetric expansion pressure of the bismuth sulfide in charge and discharge process, cycle charge-discharge preferably
Shorten lithium ion and electron diffusion path, its composite greatly improves the cycle performance of battery.
First, preparation technology：
Embodiment 1
1st, 0.2 mol/L aqueous bismuth nitrate solution is prepared：
Weigh 9.7020 g Bi (NO3)3·5H2O is placed in small beaker, is added after deionized water dissolving, is drained to glass bar
In 100 mL volumetric flask, deionized water constant volume is then used, 0.2 mol/L aqueous bismuth nitrate solution is obtained.
2nd, macropore graphene is prepared
Weigh 60 mg graphene oxide and be configured to 3 mg mL-1The dilute suspension of graphite oxide, it is ultrasonically treated after（It is super
The sonication time is 2 h, the kHz of power 55）, in the inner liner of reaction kettle that the suspension is transferred to polytetrafluoroethylene (PTFE) material, by liner
It is put into the reactor of steel material and tightens and covered on reactor, then reactor is placed in constant temperature blast drying oven temperature is set
Spend for 180oC, reacts 12 h, and prepared macropore graphene pattern is preferable under the conditions of this concentration, temperature and time, Kong Jie
Structure enriches.After after gained sample natural cooling, it is freeze-dried；
3rd, bismuth sulfide/macropore graphene composite material is prepared：
In 50 mL beakers, 0.0210 g trimellitic acids [mol ratio C is separately added into9H6O6/Bi(NO3)3 R1=1:1]、
0.0365 gCTAB [mol ratio CTAB/Bi (NO3)3 R2=1:1], 0.3806 g thiocarbamides（5.0×10-3mol）[mol ratio sulphur
Urea/Bi (NO3)3 R3=50:1]、0.50 mL（0.20 M）Aqueous bismuth nitrate solution and 9.50 mL redistilled water, by system
Ultrasonic mixing obtains yellow solution after making its uniform, the ultrasound condition is 55 kHz, and ultrasonic time is 2 h.Ultrasonic bar herein
Under part, macropore graphene is uniformly dispersed in system is gone, the product good dispersion of preparation.By the solution with it is well prepared in advance big
Hole graphene is transferred in the inner liner of reaction kettle of polytetrafluoroethylene (PTFE) material together, and liner is put into the reactor of steel material and twisted
Covered on tight reactor, then reactor is placed in constant temperature blast drying oven and sets temperature to be 120oC, reacts 12 h, warm herein
Under degree and time, the pattern of synthesized bismuth sulfide is homogeneous sea urchin shape and is successfully loaded in macropore graphene hole.Instead
Taken out after should terminating by the black precipitate bismuth sulfide of inner liner of reaction kettle bottom/macropore graphene taking-up after reactor, natural cooling,
And successively with respectively washing 3 times of distilled water and absolute ethyl alcohol, most after 60o12 h are dried in vacuo under the conditions of C and obtain black powder,
Dried at a temperature of this, the structure of macropore graphene can be effectively retained.Gained sample remains subsequent treatment or sign.
The ratio between amount for the material that feeds intake of bismuth nitrate and thiocarbamide is 1 in this example：50, it is synthesized under the ratio between amount of the material
Bismuth sulfide pattern is homogeneous sea urchin shape and is successfully loaded in macropore graphene hole.
Comparative example 1
It is identical with operating procedure in embodiment 1, but the ratio between amount for the material that feeds intake of bismuth nitrate and thiocarbamide is 2 in this example：50, water
Hot temperature is 120oC, the hydro-thermal time is 12 h.
Comparative example 2
It is identical with operating procedure in embodiment 1, but the ratio between amount for the material that feeds intake of bismuth nitrate and thiocarbamide is 1 in this example：50, water
Hot temperature is 100oC, the hydro-thermal time is 12 h.
Application examples 1
1）Using NMP as solvent, by bismuth sulfide/macropore graphene, Kynoar（PVDF）, acetylene black according to mass ratio be 8:
1:Slurry, is then uniformly coated on aluminium foil, is dried on coating machine by 1 ratio uniform mixing with coating machine, after tabletting, warp
Positive plate is made in punching, then is placed in vacuum drying chamber dry.
2）To prepare electrode slice as negative pole, metal lithium sheet is positive pole, and microporous polypropylene membrane is used as barrier film, 1 M LiPF6/EC
+DMC+EMC（Volume ratio 1:1:1）As button battery electrolyte, assembled battery simultaneously carries out electrochemical property test
Fig. 1 is the XRD of the bismuth sulfide/macropore graphene composite material prepared using the embodiment of the present invention 1, as seen from Figure 1：
Fig. 1 is the XRD spectrum of obtained bismuth sulfide and bismuth sulfide/macropore graphene.We can be clearly from bismuth sulfide collection of illustrative plates
Strong diffraction maximum is occurred in that to 23.72 °, 24.93 °, 28.61 ° and 31.80 °, they are corresponded respectively to（101）、（130）、
（211）、（221）Crystal face, contrast standard card can show that all diffraction maximums can distinguish index to orthorhombic phase bismuth sulfide
(JCPDS No.17-0320).In addition, not finding other impurity diffraction maximums, it is very pure sulphur to show the product prepared by us
Change bismuth sample.Collection of illustrative plates contrast from bismuth sulfide and bismuth sulfide/macropore graphene to bismuth sulfide with macropore graphene as can be seen that repaiied
Obvious change does not occur for main peak after decorations, and this shows that formation of the method for in-situ modification on bismuth sulfide does not influence.
Fig. 2 is the SEM figures of macropore graphene prepared by the embodiment of the present invention 1, and macropore graphene has rich as seen from Figure 2
Rich pore space structure
Fig. 3 is the SEM figures of the bismuth sulfide/macropore graphene composite material prepared using the embodiment of the present invention 1, as seen from Figure 3：
It can clearly find out that bismuth sulfide is sea urchin shape structure by Fig. 3 a and Fig. 3 b, and the structure is by long 1-2 μm of Bi2S3Thin rod
Composition, the tip diameter of thin rod is about 70 nm.Fig. 3 c and Fig. 3 d are the scanning figures of the composite after macropore graphene coated,
This it appears that the bismuth sulfide of sea urchin shape is successfully supported in macropore graphene hole in figure.
The distribution shape of bismuth sulfide and macropore graphene in bismuth sulfide/macropore graphene is obtained in order to further characterize us
Condition, we have done the test of element Surface scan, as shown in Figure 4.Analyzed by element Surface scan, it will be seen that composite
In comprise only tri- kinds of elements of Bi, S, C, and C is distributed in Bi2S3Periphery.
Fig. 5 be bismuth sulfide/macropore graphene and bismuth sulfide low current activation after in the mA g of current density 200-1Circulate respectively
60 circles, loop test when voltage range is 0.01-3 V.For bismuth sulfide, due to the presence of irreversible capacity, specific volume
Measure the 295 mAh g by first lap-1Then stablize in 240 mAh g-1, 38.4 % of theoretical specific capacity are accounted for after stablizing.Vulcanization
The improvement maximum compared to bismuth sulfide of bismuth/macropore graphene is the raising of cycle performance, and bismuth sulfide/macropore graphene is in 200 mA
g-1Current density under first discharge specific capacity reach 469 mAh g-1, it is then stable in 415 mAh g-1.Compared to vulcanization
Bismuth, 72.9 % of capacity boost, therefore its chemical property handled by carbon coating be significantly improved.
Fig. 6 is bismuth sulfide/macropore graphene that the embodiment of the present invention 1 is synthesized（a）With comparative example 1, it is 2-in-1 into bismuth sulfide/
Macropore graphene（b、c）In the mA g of current density 200 after low current activation-1Circulation 60 is enclosed respectively, and voltage range is 0.01-3 V
When loop test.Although it is evident that bismuth sulfide/macropore graphene that comparative example 1 of the present invention is synthesized is circulated surely in figure
It is qualitative preferable, but circulation specific capacity is relatively low；In addition, comparative example it is 2-in-1 into bismuth sulfide/macropore graphene not only stability
Poor, specific capacity declines comparatively fast, and circulation specific capacity is low.As a result show, bismuth sulfide/macropore stone that the embodiment of the present invention 1 is synthesized
Black alkene has more outstanding chemical property.
Claims (9)
1. a kind of sea urchin shape bismuth sulfide/macropore graphene composite material, it is characterised in that by the way that sea urchin shape bismuth sulfide is attached to
The hole of macropore graphene is constituted, wherein, the mass ratio of sea urchin shape bismuth sulfide and macropore graphene is 1:10.
2. composite as claimed in claim 1, it is characterised in that macropore graphene refers to there is irregular hole in surface distributed
The graphene in hole.
3. the preparation method of composite as claimed in claim 1 or 2, it is characterised in that comprise the following steps：
1）The preparation of macropore graphene：Prepare graphene oxide solution, it is ultrasonically treated after, carry out hydro-thermal reaction, treat gained sample
After natural cooling, freeze-drying；
2）The preparation of composite：Using bismuth nitrate as bismuth source, using thiocarbamide as sulphur source, trimellitic acid is used as binding agent, ten
Six alkyl trimethyl ammonium bromides are as surfactant, and redistilled water is as solvent, and all raw material ultrasonic mixings make its uniform
Afterwards, by the solution and step 1）Obtained macropore graphene carries out hydro-thermal reaction together, after reaction terminates after cleaning, vacuum drying
Obtain the composite.
4. method as claimed in claim 3, it is characterised in that step 1）In, the mass concentration of graphene oxide is 3 mg/
mL;Sonication treatment time is 2 h, the kHz of power 55.
5. method as claimed in claim 3, it is characterised in that step 1）In, hydrothermal temperature is 180 ± 10 DEG C, hydro-thermal
Reaction time is 12 h.
6. method as claimed in claim 3, it is characterised in that step 2）In, the amount of the material of the bismuth nitrate and thiocarbamide it
Than for 1: 50.
7. method as claimed in claim 3, it is characterised in that step 2）In, hydrothermal temperature is 120 ± 5 DEG C, hydro-thermal
Reaction time is 12 h.
8. method as claimed in claim 3, it is characterised in that step 2）In, the vacuum drying temperature is 60 DEG C, and vacuum is done
The dry time is 10 ~ 12h.
9. composite as claimed in claim 1 or 2 is used as the application of the negative material of lithium ion battery.
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| CN110336022A (en) * | 2019-07-25 | 2019-10-15 | 广东工业大学 | A kind of preparation method of bismuth compound sulphur combination electrode material |
| CN114899388A (en) * | 2022-05-11 | 2022-08-12 | 商丘师范学院 | Bismuth-graphene/graphene composite material and preparation method and application thereof |
| CN115286388A (en) * | 2022-08-29 | 2022-11-04 | 昆明理工大学 | Method for simply synthesizing bismuthyl trisulfide-graphene oxide composite thermoelectric material |
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| CN110336022A (en) * | 2019-07-25 | 2019-10-15 | 广东工业大学 | A kind of preparation method of bismuth compound sulphur combination electrode material |
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| CN114899388A (en) * | 2022-05-11 | 2022-08-12 | 商丘师范学院 | Bismuth-graphene/graphene composite material and preparation method and application thereof |
| CN114899388B (en) * | 2022-05-11 | 2023-11-21 | 商丘师范学院 | Bismuth alkene/graphene composite material and preparation method and application thereof |
| CN115286388A (en) * | 2022-08-29 | 2022-11-04 | 昆明理工大学 | Method for simply synthesizing bismuthyl trisulfide-graphene oxide composite thermoelectric material |
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| CN107026263B (en) | 2020-07-07 |
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