CN102760871A - Metallic antimony/graphene composite material, and preparation method and application thereof - Google Patents
Metallic antimony/graphene composite material, and preparation method and application thereof Download PDFInfo
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- CN102760871A CN102760871A CN2012102548473A CN201210254847A CN102760871A CN 102760871 A CN102760871 A CN 102760871A CN 2012102548473 A CN2012102548473 A CN 2012102548473A CN 201210254847 A CN201210254847 A CN 201210254847A CN 102760871 A CN102760871 A CN 102760871A
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Abstract
The invention discloses a metallic antimony/graphene composite material which is composed of nano metallic antimony and graphene. Under the dispersion and loading action of the graphene, the metallic antimony can be distributed uniformly, the stability of the metallic antimony in the charging/discharging process can be effectively enhanced, and the composite material can be used as a lithium ion battery negative pole material. The invention also discloses a preparation method of the composite material by a one-step hydrothermal process or one-step solvothermal process, which has the advantages of simple technique, low cost, short cycle, low energy consumption and the like.
Description
Technical field
The present invention relates to lithium ion battery and use field of compound material, be specifically related to a kind of metallic antimony/graphene composite material.
Background technology
Lithium ion battery has advantages such as operating voltage height, energy density is big, security performance is good; Therefore in portable type electronic products such as digital camera, mobile phone and notebook computer, be used widely, also have application prospect for electric bicycle and electric automobile.The negative material of present commercial lithium ion battery is the material with carbon element of graphite and other form.Because the theoretical capacity of graphite has only 372mAhg
-1, and embedding lithium current potential is lower, has limited its scope of application.Compare with material with carbon element such as graphite, metallic antimony has comparatively ideal embedding lithium current potential and higher quality volume and capacity ratio when, and application prospect is very wide.But because metallic antimony change in volume in charge and discharge process is bigger, and by the big and skewness of metallic antimony particle size of conventional method preparation, so the electrochemical stability of metallic antimony is relatively poor.The method that improves metal negative pole cyclical stability at present has material nanoization and compoundization.
Composite material (Composite materials) is by two or more materials with different properties, through the method for physics or chemistry, the material of on macroscopic view, forming with new capability.Various materials in the composite material generally can make up for each other's deficiencies and learn from each other on performance, produce cooperative effect, make the combination property of composite material be superior to former composition material and satisfy various requirement.Graphene is because its conductivity is high, and intensity is high, and specific area is big, and the carrier that is widely used as nano particle prepares composite material.Be to disclose a kind of graphene-supported cobaltosic oxide nano composite material and preparation method thereof in 201010158087.7 the one Chinese patent application like application number; Form by Graphene and cobaltosic oxide; Cobaltosic oxide loads on the graphene nanometer sheet, and the mass fraction of graphene nanometer sheet is 2%-95%wt, and the thickness of graphene nanometer sheet is 0.3～50 nanometer; The particle diameter of cobaltosic oxide is 1～200 nanometer, and cobaltosic oxide is spherical or sheet; The preparation method is: get graphene oxide solution and divalent cobalt, high molecular surfactant mixing; Stir or ultrasonic 0.2～5 hour with the aqueous slkali mixing back that adds oxidant then, transfer in the pyroreaction still, annealing down at 100～250 ℃ obtained product in 3～30 hours, through washing, drying, promptly got graphene-supported cobaltosic oxide nano composite material.One Chinese patent application CN201110083740.2 discloses a kind of transition metal three antimonides/graphene composite material, has M
xSb
3The composition of/G, wherein M represents VIIIB group 4 transition metal element, 0.95≤x≤1.05, G represents Graphene; Transition metal three antimonides in this composite material can effectively improve the stability of transition metal three antimonides in charge and discharge process because the dispersion and the carrying effect of Graphene can evenly distribute; The preparation method of this a composite material by adopting one step hydro thermal method or a step solvent-thermal method has that technology is simple, cost is low, the cycle is short, low power consumption and other advantages.Therefore, the composite material of exploitation nano-scale is with a wide range of applications.
Summary of the invention
The invention provides a kind of electrochemical stability good metal antimony/graphene composite material.
The present invention also provides an a kind of one step preparation method of metallic antimony/graphene composite material, and this method technology is simple, and energy consumption is low, cost is low, and the products therefrom particle size is tiny and be evenly distributed.
A kind of metallic antimony/graphene composite material, both are composited by nano level metal antimony (Sb) and Graphene (G).
In order further to improve the application performance of composite material, the weight percentage of Graphene is preferably 0.4%～20% in the described composite material, further is preferably 0.4%～16%.
The particle diameter of metallic antimony is more little, and easy more covering is stated from the Graphene, and the electrochemical stability performance of composite material is good more, so the present invention selects nano level metal antimony for use, and preferred, the particle diameter of described nano level metal antimony is 30 nanometers～100 nanometers.
Preferably, nano level metal antimony is even dispersion in the described composite material.
The preparation method of described metallic antimony/graphene composite material is an one step hydro thermal method or a step solvent-thermal method.
In order to reach better invention effect, preferably:
The preparation method of described metallic antimony/graphene composite material may further comprise the steps:
1) is raw material to contain antimonious compound, it is dissolved in deionized water or the organic solvent, obtain antimony ion (Sb
3+) concentration is the solution of 0.05mol/L～0.5mol/L;
2) in the solution of step 1), add behind graphene oxide (GO) and the reducing agent in sealed environment in 100 ℃～250 ℃ reactions cooling after 6 hours～72 hours; Collect solid product; Through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains metallic antimony/graphene composite material;
The addition of described GO is 1%～50% of a metallic antimony theoretical weight, further is preferably 1%～40%;
The addition of described reducing agent is adjusted by two parts, confirms by following method: every mole of Sb
3+Add 4 moles～6 moles reducing agents, every gram GO adds 0.2 mole～1 mole reducing agent again.
Describedly contain the hydrate that antimonious compound can be selected trichloride antimony, antimony oxide, nitric acid antimony, antimony sulfate, carbonic acid antimony, antimony oxalate, antimony acetate or said any one salt for use.
Described organic solvent is ethanol, methyl alcohol, ethylene glycol, acetone, N, dinethylformamide, pyridine, ethylenediamine, benzene or toluene.
Described reducing agent is used for graphene oxide is reduced into Graphene, selects alkali-metal boron hydride for use, preferred NaBH
4Or KBH
4
Step 2) in, further preferably in 180 ℃～240 ℃ reactions cooling after 24 hours～72 hours; Reaction temperature is high, and the time is long, and graphene oxide is prone to be reduced into Graphene, but little to antimony particle size and pattern influence.
The qualification that the temperature of described cooling is not strict is operating as the master with suitable, generally can be cooled to 15 ℃～30 ℃ ambient temperature.
Described metallic antimony/graphene composite material can be used as lithium ion battery negative material.
Compared with prior art, the present invention has following advantage:
1, metallic antimony (Sb) can effectively improve the stability of metallic antimony in charge and discharge process because the dispersion of Graphene and carrying effect can evenly distribute in the composite material of the present invention in composite material, is significant for improving the antimony electrochemical stability.
2, the composite material of the present invention advantage that is used for lithium ion battery negative is: the combination property, particularly electrochemical stability of utilizing the high conductivity of Graphene, high mechanical strength, big specific area agent and porosity to improve metallic antimony.
3, the present invention adopts a step hydro-thermal or solvent-thermal method to prepare the metallic antimony/graphene composite material of nano-scale; Promptly carry the metal Sb with the dispersing nanometer size, have that technology is simple, cost is low, the cycle is short, low power consumption and other advantages, because the dispersion and the carrying effect of Graphene with Graphene; Gained metallic antimony purity is high, granularity is little; Particle size is nanoscale, and diameter is about 30 nanometers～100 nanometers, and it is more even to distribute; Can effectively improve its stability in charge and discharge process, be significant for the electrochemical stability of metallic antimony.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of embodiment 1 gained Sb/G composite material;
Fig. 2 is the transmission electron microscope photo of embodiment 1 gained Sb/G composite material;
Fig. 3 is embodiment 1 gained Sb/G composite material and pure Sb chemical property figure.
Embodiment
Embodiment 1
1) will analyze pure SbCl
3Be dissolved in the absolute ethyl alcohol, make Sb
3+Concentration is the solution of 0.2mol/L, and the volume of solution is 80 milliliters.
2) in the solution of step 1), adding 400 milligrams of GO capacity of being placed on is (compactedness 80%, percent by volume) in 100 milliliters the autoclave, and in solution, adds 6.8 gram reducing agent NaBH
4, sealing immediately then.
3) agitated reactor is heated to 200 ℃, and reacted 24 hours.
4) naturally cool to room temperature after having reacted, collect the Powdered product at the bottom of the still, use deionized water successively; After the absolute ethyl alcohol alternate repetition cleaning many times; Powder 110 ℃ of following vacuumizes 12 hours, is obtained composite powder, and the percentage by weight of Graphene is 8% in the composite material.
The X ray diffracting spectrum of the composite powder of gained and transmission electron microscope photo are respectively like Fig. 1 and Fig. 2, and all diffraction maximums all can be classified as the diffraction maximum of Sb among Fig. 1, do not find the diffraction maximum of Graphene among Fig. 1, show that graphene layer is disperseed by the Sb uniform particles; Can find out that from Fig. 1 and Fig. 2 the composite powder of gained is metallic antimony/Graphene (Sb/G) composite material, wherein the Sb particle size is nanoscale, and diameter is 30 nanometers～100 nanometers, and it is more even to distribute.
(its particle diameter is 30 nanometers～100 nanometers with gained Sb/G composite material and pure nanometer Sb respectively; The same Sb/G of the preparation method of pure nanometer Sb; Difference is not add graphene oxide in the raw material) carry out electrochemical property test (constant current charge-discharge in the certain voltage scope) as lithium ion battery negative material; Gained Sb/G composite material and pure nanometer Sb chemical property figure such as Fig. 3, constant current charge-discharge (current density 40mA/g, voltage range 0.05～1.5V) test shows; Cycle-index is 1 o'clock, and the capacity of Sb/G composite material is 510mAhg
-1, cycle-index is 30 o'clock, the capacity of Sb/G composite material only is reduced to 400mAhg
-1And cycle-index is 1 o'clock, and the capacity of pure nanometer Sb is 280mAhg
-1, cycle-index is 30 o'clock, the capacity of pure nanometer Sb reduction rapidly is merely 40mAhg
-1It is thus clear that compare with pure nanometer Sb, the cyclical stability of Sb/G composite material obviously improves, electrochemical stability is good.
Embodiment 2
1) will analyze pure Sb (NO
3)
3Be dissolved in the deionized water, make Sb
3+Concentration is the solution of 0.05mol/L, and liquor capacity is 80 milliliters.
2) in the solution of step 1), adding 195 milligrams of GO capacity of being placed on is (compactedness 80%, percent by volume) in 100 milliliters the autoclave, and in solution, adds 6.2 gram reducing agent KBH
4, sealing immediately then.
3) agitated reactor is heated to 180 ℃, and reacted 36 hours.
4) naturally cool to room temperature after having reacted, collect the Powdered product at the bottom of the still, use deionized water successively; After the absolute ethyl alcohol alternate repetition cleaning many times; Powder 110 ℃ of following vacuumizes 12 hours, is obtained composite powder, and the percentage by weight of Graphene is 16% in the composite material.
The composite powder of gained is through X ray diffracting spectrum and transmission electron microscope photo analysis; The composite powder that can find out gained is metallic antimony/Graphene (Sb/G) composite material; Wherein the Sb particle size is nanoscale, and diameter is 30 nanometers～100 nanometers, and it is more even to distribute.
(its particle diameter is 30 nanometers～100 nanometers with gained Sb/G composite material and pure nanometer Sb respectively; The same Sb/G of the preparation method of pure nanometer Sb, difference is not add graphene oxide in the raw material) carry out electrochemical property test as lithium ion battery negative material, method of testing is with embodiment 1, constant current charge-discharge (current density 40mAg
-1, voltage range 0.05～1.5V) test is compared with pure nanometer Sb, and the cyclical stability of Sb/G composite material obviously improves, and electrochemical stability is good.
Embodiment 3
1) will analyze pure SbCl
3Be dissolved in the no water glycol, make Sb
3+Concentration is the solution of 0.3mol/L, and liquor capacity is 80 milliliters.
2) in the solution of step 1), adding 290 milligrams of GO capacity of being placed on is (compactedness 80%, percent by volume) in 100 milliliters the autoclave, and in solution, adds 13.8 gram reducing agent KBH
4, sealing immediately then.
3) agitated reactor is heated to 220 ℃, and reacted 48 hours.
4) naturally cool to room temperature after having reacted, collect the Powdered product at the bottom of the still, use deionized water successively; After the absolute ethyl alcohol alternate repetition cleaning many times; Powder 110 ℃ of following vacuumizes 12 hours, is obtained composite powder, and the percentage by weight of Graphene is 4% in the composite material.
The composite powder of gained is through X ray diffracting spectrum and transmission electron microscope photo analysis; The composite powder that can find out gained is metallic antimony/Graphene (Sb/G) composite material; Wherein the Sb particle size is nanoscale, and diameter is 30 nanometers～100 nanometers, and it is more even to distribute.
(its particle diameter is 30 nanometers～100 nanometers with gained Sb/G composite material and pure nanometer Sb respectively; The same Sb/G of the preparation method of pure nanometer Sb, difference is not add graphene oxide in the raw material) carry out electrochemical property test as lithium ion battery negative material, method of testing is with embodiment 1, constant current charge-discharge (current density 40mAg
-1, voltage range 0.05～1.5V) test is compared with pure nanometer Sb, and the cyclical stability of Sb/G composite material obviously improves, and electrochemical stability is good.
Embodiment 4
1) will analyze pure Sb (CH
3COO)
3Be dissolved in the toluene, make Sb
3+Concentration is the solution of 0.5mol/L, and liquor capacity is 80 milliliters.
2), in the solution of step 1), to add 50 milligrams of GO capacity of being placed on be (compactedness 80%, percent by volume) in 100 milliliters the autoclave, and in solution, adds 7.8 gram reducing agent NaBH
4, sealing immediately then.
3), agitated reactor is heated to 240 ℃, and reacted 72 hours.
4), naturally cool to room temperature after having reacted, collect the Powdered product at the bottom of the still, use deionized water successively; After the absolute ethyl alcohol alternate repetition cleaning many times; Powder 110 ℃ of following vacuumizes 12 hours, is obtained composite powder, and the percentage by weight of Graphene is 0.4% in the composite material.
The composite powder of gained is through X ray diffracting spectrum and transmission electron microscope photo analysis; The composite powder that can find out gained is metallic antimony/Graphene (Sb/G) composite material; Wherein the Sb particle size is nanoscale, and diameter is 30 nanometers～100 nanometers, and it is more even to distribute.
(its particle diameter is 30 nanometers～100 nanometers with gained Sb/G composite material and pure nanometer Sb respectively; The same Sb/G of the preparation method of pure nanometer Sb, difference is not add graphene oxide in the raw material) carry out electrochemical property test as lithium ion battery negative material, method of testing is with embodiment 1, constant current charge-discharge (current density 40mAg
-1, voltage range 0.05～1.5V) test is compared with pure nanometer Sb, and the cyclical stability of Sb/G composite material obviously improves, and electrochemical stability is good.
Claims (10)
1. a metallic antimony/graphene composite material is characterized in that, described composite material is composited by nano level metal antimony and Graphene.
2. metallic antimony/graphene composite material according to claim 1 is characterized in that, the weight percentage of Graphene is 0.4%～20% in the described composite material.
3. metallic antimony/graphene composite material according to claim 1 is characterized in that, the particle diameter of described nano level metal antimony is 30 nanometers～100 nanometers.
4. metallic antimony/graphene composite material according to claim 1 is characterized in that nano level metal antimony is even dispersion in the described composite material.
5. according to the preparation method of each described metallic antimony/graphene composite material of claim 1～4, it is characterized in that, may further comprise the steps:
1) is raw material to contain antimonious compound, is dissolved in deionized water or the organic solvent, obtain Sb
3+Concentration is the solution of 0.05mol/L～0.5mol/L;
2) in the solution of step 1), in sealed environment, cool off after 6 hours～72 hours behind adding GO and the reducing agent 100 ℃～250 ℃ reactions; Collect solid product; Through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains metallic antimony/graphene composite material;
The addition of described GO is 1%～50% of a metallic antimony theoretical weight;
The addition of described reducing agent is adjusted by two parts, confirms by following method: every mole of Sb
3+Add 4 moles～6 moles reducing agents, every gram GO adds 0.2 mole～1 mole reducing agent again.
6. preparation method according to claim 5 is characterized in that, saidly contains the hydrate that antimonious compound is trichloride antimony, antimony oxide, nitric acid antimony, antimony sulfate, carbonic acid antimony, antimony oxalate, antimony acetate or said any one salt.
7. preparation method according to claim 5 is characterized in that, described organic solvent is ethanol, methyl alcohol, ethylene glycol, acetone, N, dinethylformamide, pyridine, ethylenediamine, benzene or toluene.
8. preparation method according to claim 5 is characterized in that, described reducing agent is alkali-metal boron hydride.
9. according to claim 5 or 8 described preparation methods, it is characterized in that described reducing agent is NaBH
4Or KBH
4
According to claim 1,2,3 or 4 described metallic antimony/graphene composite materials as the application in the lithium ion battery negative material.
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| CN104916827A (en) * | 2013-11-28 | 2015-09-16 | 巴莱诺斯清洁能源控股公司 | Antimony based anode material for rechargeable batteries and preparation method |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005243508A (en) * | 2004-02-27 | 2005-09-08 | Jfe Chemical Corp | Composite graphite particles for rechargeable lithium-ion battery cathode material, negative pole and rechargeable lithium-ion battery |
| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
| CN102231436A (en) * | 2011-05-20 | 2011-11-02 | 浙江大学 | Preparation method of Sn-Sb/grapheme nano-composite material |
-
2012
- 2012-07-23 CN CN2012102548473A patent/CN102760871A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005243508A (en) * | 2004-02-27 | 2005-09-08 | Jfe Chemical Corp | Composite graphite particles for rechargeable lithium-ion battery cathode material, negative pole and rechargeable lithium-ion battery |
| CN101857221A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Method for preparing graphene compounds and graphene oxide compounds with high efficiency |
| CN102231436A (en) * | 2011-05-20 | 2011-11-02 | 浙江大学 | Preparation method of Sn-Sb/grapheme nano-composite material |
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| CN103219498A (en) * | 2013-04-08 | 2013-07-24 | 严百坤 | Preparation method of antimony-base graphene-lithium stannate composite negative electrode material |
| CN104916827A (en) * | 2013-11-28 | 2015-09-16 | 巴莱诺斯清洁能源控股公司 | Antimony based anode material for rechargeable batteries and preparation method |
| CN105161697A (en) * | 2015-07-18 | 2015-12-16 | 东北师范大学 | Micro-nano structure compound with stable chemical bond and preparation method of micro-nano structure compound |
| CN105018909A (en) * | 2015-07-31 | 2015-11-04 | 中国科学院烟台海岸带研究所 | Metal nanometer material with carbon-based material as template and synthesis method thereof |
| CN106129391A (en) * | 2016-07-01 | 2016-11-16 | 西北师范大学 | One carbon quantum dot reduces SbCl3the method preparing Sb simple substance |
| CN106129391B (en) * | 2016-07-01 | 2019-03-26 | 西北师范大学 | It is a kind of to restore SbCl with carbon quantum dot3The method for preparing Sb simple substance |
| CN107248569B (en) * | 2017-04-28 | 2020-04-03 | 南京师范大学 | Antimony/nitrogen-doped carbon composite prepared by taking 1-ethyl-3-methylimidazol dicyandiamide as carbon source and preparation method and application thereof |
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| CN108448072A (en) * | 2018-01-24 | 2018-08-24 | 东北电力大学 | A kind of preparation method and application based on two-dimentional antimony oxide nanometer sheet/redox graphene aeroge combination electrode material |
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| CN108649191A (en) * | 2018-03-30 | 2018-10-12 | 南京师范大学 | The preparation method and its resulting materials of a kind of antimony/nitrogen-doped graphene compound and application |
| CN108649191B (en) * | 2018-03-30 | 2020-09-18 | 南京师范大学 | Preparation method of antimony/nitrogen-doped graphene composite for sodium ion battery, and obtained material and application thereof |
| CN109768240A (en) * | 2018-12-24 | 2019-05-17 | 岭南师范学院 | A kind of Sb nitrogen-doped graphene composite material and preparation method and application |
| CN110137484A (en) * | 2019-06-20 | 2019-08-16 | 西北师范大学 | A kind of preparation method of antimony oxide/redox graphene composite material |
| CN110120516A (en) * | 2019-06-20 | 2019-08-13 | 西北师范大学 | A kind of preparation method of antimony/redox graphene composite material |
| CN110137484B (en) * | 2019-06-20 | 2022-02-22 | 西北师范大学 | Preparation method of antimony trioxide/redox graphene composite material |
| CN110911684A (en) * | 2019-11-22 | 2020-03-24 | 广东工业大学 | Antimony-doped cobalt disulfide-loaded graphene and preparation method and application thereof |
| CN110911684B (en) * | 2019-11-22 | 2022-05-13 | 广东工业大学 | Antimony-doped cobalt disulfide-loaded graphene and preparation method and application thereof |
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Application publication date: 20121031 |