CN103219515B - PbSe cubic particle/graphene composite material as well as preparation method and application thereof - Google Patents
PbSe cubic particle/graphene composite material as well as preparation method and application thereof Download PDFInfo
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- CN103219515B CN103219515B CN201310105877.2A CN201310105877A CN103219515B CN 103219515 B CN103219515 B CN 103219515B CN 201310105877 A CN201310105877 A CN 201310105877A CN 103219515 B CN103219515 B CN 103219515B
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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 PbSe cubic particle/graphene composite material as well as a preparation method and the application of the PbSe cubic particle/graphene composite material. The PbSe cubic particle/graphene composite material is formed by compounding nanoscale PbSe cubic particles and graphene. The graphene has the functions of dispersing, bearing and insulating, so that the stability of PbSe is effectively improved in the charge-discharge process. The composite material can be used as or used for preparing lithium ion battery cathode material. The preparation method of the one-step solvent thermal method of the composite material has the advantages of being simple in technology, low in cost, short in period, low in energy consumption and the like.
Description
Technical field
The present invention relates to lithium ion battery field of compound material, be specifically related to a kind of PbSe isometric particle/graphene composite material and its preparation method and application.
Background technology
Lithium ion battery has the advantages such as operating voltage is high, energy density is large, security performance is good, therefore be used widely in the portable type electronic products such as digital camera, mobile phone and notebook computer, also there is application prospect for electric bicycle and electric automobile.The negative material of current commercial lithium ion battery is the material with carbon element of graphite and other form.Because the theoretical capacity of graphite only has 372mAhg
-1, and intercalation potential is lower, limits its scope of application.Compared with the material with carbon elements such as graphite, metallic antimony has comparatively ideal intercalation potential and higher quality when volume and capacity ratio, and application prospect is very wide.But because metallic antimony change in volume in charge and discharge process is comparatively large, and the comparatively large and skewness of the metallic antimony particle size prepared by conventional method, so the electrochemical stability of metallic antimony is poor.The method of current raising metal negative electrode cyclical stability has material nano and Composite.
Composite material (Composite materials) is by two or more material of different nature, by the method for physics or chemistry, and the material with new capability macroscopically formed.Various materials in composite material generally can make up for each other's deficiencies and learn from each other in performance, produce cooperative effect, make the combination property of composite material be better than former composition material and meet various different requirement.Graphene due to its conductivity high, intensity is high, and specific area is large, is widely used as the carrier of nano particle to prepare composite material.As disclosed a kind of graphene-supported cobaltosic oxide nano composite material and preparation method thereof in Chinese patent ZL201010158087.7, be made up of Graphene and cobaltosic oxide, cobaltosic oxide load is on graphene nanometer sheet, the mass fraction of graphene nanometer sheet is 2%-95%wt, 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; Preparation method is: get graphene oxide solution and divalent cobalt, high molecular surfactant mixing; Then and after the aqueous slkali mixing adding oxidant stir or ultrasonic 0.2 ~ 5 hour, transfer in pyroreaction still, at 100 ~ 250 DEG C, annealing obtains product in 3 ~ 30 hours, through washing, dry, obtains graphene-supported cobaltosic oxide nano composite material.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 Group VIIIB element, 0.95≤x≤1.05, and G represents Graphene; In this composite material, transition metal three antimonide can be uniformly distributed due to the dispersion of Graphene and carrying effect, effectively can improve the stability of transition metal three antimonide in charge and discharge process; This composite material adopts the preparation method of one step hydro thermal method or a step solvent-thermal method, has that technique is simple, cost is low, the cycle is short, low power consumption and other advantages.Therefore, the composite material developing nano-scale is with a wide range of applications.
Lead selenide (PbSe) has cubic crystal structure, lattice constant 0.6122nm, how as the semi-conducting material of low energy gap, is generally used for and manufactures photo resistance and infrared detector etc.
Summary of the invention
The invention provides PbSe isometric particle/graphene composite material that a kind of electrochemical stability is good.
Present invention also offers an one step preparation method of a kind of PbSe isometric particle/graphene composite material, the method technique is simple, and energy consumption is low, cost is low, and products therefrom particle size is tiny and be evenly distributed.
A kind of PbSe isometric particle/graphene composite material, is composited by nanoscale PbSe isometric particle and Graphene (G).Namely described composite material has the composition of PbSe/G.
The present invention finds to have good chemical property by after the existing PbSe isometric particle for the manufacture of photo resistance and infrared detector and Graphene compound, and electrochemical stability well, can be used as or prepare the negative material of lithium ion battery.
In order to improve the application performance of composite material further, in described composite material, the weight percentage of Graphene is preferably 0.4% ~ 20%, and more preferably 7.4% ~ 17%.
Because the particle size of PbSe is less, more easily cover and be loaded on Graphene, the electrochemical stability performance of composite material is better, and therefore the present invention selects nanoscale PbSe isometric particle, and preferably, the length of side of described nanoscale PbSe isometric particle is 100 nanometer ~ 200 nanometers.
Preferably, in described composite material, nanoscale PbSe isometric particle is dispersed.
The preparation method of described PbSe isometric particle/graphene composite material is a step solvent-thermal method.
In order to reach better invention effect, preferably:
The preparation method of described PbSe/ graphene composite material, comprises the following steps:
1) with elemental selenium (Se) or containing the compound of selenium compound and leaded (Pb) for raw material, be mixed in reproducibility organic solvent according to the stoichiometric proportion (i.e. the atomic ratio 1:1 of Pb and Se) of PbSe, the mixed solution that to obtain in PbSe concentration be 0.01mol/L ~ 0.1mol/L;
2) in the mixed liquor of step 1), graphene oxide (GO) is added through abundant ultrasonic disperse, then cool after 12 hours ~ 72 hours 120 DEG C ~ 250 DEG C reactions in sealed environment, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying, obtains PbSe isometric particle/graphene composite material;
The addition of described graphene oxide is 1% ~ 50% of PbSe theoretical weight, preferably 20% ~ 50%.
In step 1), described can select salt containing selenium, preferred Na containing selenium compound
2seO
3or K
2seO
3.
Described leaded compound can select leaded salt, preferred lead chloride, lead fluoride, plumbi nitras, lead sulfate, lead oxalate or lead acetate.
Owing to adopting reproducibility organic solvent, separately can add other reducing agents and carry out reduction-oxidation graphite, described reproducibility organic solvent not only can be used as reducing agent but also can be used as reaction dissolvent.Not containing water in described reproducibility organic solvent, select ethanol, methyl alcohol, ethylene glycol, DMF, ethylenediamine or oleyl amine.
Step 2) in, further preferably: in 140 DEG C ~ 240 DEG C reactions cooling after 24 hours ~ 48 hours in sealed environment; This reaction temperature general is higher, and the time is longer, and PbSe is more easily formed, and graphene oxide is more easily reduced into Graphene, but little on particle size impact.
The temperature of described cooling not strict restriction, based on adequate operation, generally can be cooled to the ambient temperature of 15 DEG C ~ 30 DEG C.
Described PbSe isometric particle/graphene composite material electrochemical stability is good, can be used as or prepare lithium ion battery negative material.
Compared with prior art, tool of the present invention has the following advantages:
1, in composite material of the present invention, nano PbS e isometric particle can be uniformly distributed in the composite due to the dispersion of Graphene and carrying effect, effectively can improve the stability of PbSe in charge and discharge process, the electrochemical stability improving PbSe was significant.
2, composite material of the present invention is for the advantage of lithium ion battery negative: the conductivity utilizing Graphene high, high mechanical strength, large specific area agent and porosity are to improve the combination property of nano PbS e, particularly electrochemical stability.
3, the present invention adopts a step solvent-thermal method to prepare the PbSe isometric particle/graphene composite material of nano-scale, introduces Graphene, have that technique is simple, cost is low, the cycle is short, low power consumption and other advantages at solvent-thermally synthesizing nano PbSe process situ.Due to dispersion and the carrying effect of Graphene, gained PbSe purity is high, granularity is little, and cube length of side is 100 nanometer ~ 200 nanometers, and distribution is more even.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum of embodiment 1 gained PbSe/G composite material;
Fig. 2 is the scanning electron microscopic picture of embodiment 1 gained PbSe/G composite material;
Fig. 3 is embodiment 1 gained PbSe/G composite material and pure PbSe chemical property figure.
Embodiment
Embodiment 1
1) pure Pb (NO will be analyzed
3)
2with Se powder, in being mixed in absolute ethyl alcohol after the ratio batching of Pb:Se atomic ratio 1:1, obtain the mixed liquor being 0.01mol/L in PbSe concentration, mixeding liquid volume is 80 milliliters.
2) in the mixed liquor of step 1), add 114 milligrams of GO and fully then ultrasonic disperse is placed in the autoclave (compactedness 80%, percent by volume) that capacity is 100 milliliters, then seal immediately.
3) reactor is heated to 180 DEG C, and reacts 36 hours.
4) room temperature is naturally cooled to after having reacted, collect the Powdered product at the bottom of still, use deionized water successively, after the cleaning for several times of absolute ethyl alcohol alternate repetition, by powder vacuumize 12 hours at 110 DEG C, obtain composite powder 0.27 gram, in composite material, the percentage by weight of Graphene is 17%.
The X ray diffracting spectrum of the composite powder of gained and scanning electron microscopic picture are respectively as Fig. 1 and Fig. 2, diffraction maximums all in Fig. 1 all can be classified as the diffraction maximum of PbSe, the diffraction maximum of Graphene is not found in Fig. 1, show graphene layer by PbSe even particulate dispersion, can find out that the composite powder of gained is plumbous selenium compound/Graphene (PbSe/G) composite material, wherein PbSe particle is isometric particle, particle size is nanoscale, the length of side is 100 nanometer ~ 200 nanometers, and distribution is more even.
Be 100 nanometer ~ 200 nanometers with gained PbSe/G composite material and its particle length of side of pure nano PbS e(respectively; The same PbSe/G of preparation method of pure nano PbS e, difference does not add graphene oxide in raw material) carry out electrochemical property test (see figure 3) as lithium ion battery negative material, constant current charge-discharge (current density 50mAg
-1, voltage range 0.05 ~ 2.5V) test show, when cycle-index is 1, the capacity of PbSe/G composite material is 516mAhg
-1, when cycle-index is 20, the capacity of PbSe/G composite material is only down to 417mAhg
-1; And cycle-index is when being 1, the capacity of pure nano PbS e is 439mAhg
-1, when cycle-index is 20, the capacity of pure nano PbS e is reduced to 164mAhg rapidly
-1; Compared with visible and pure nano PbS e, the cyclical stability of PbSe/G composite material significantly improves, and electrochemical stability is good.
Embodiment 2
1) pure PbCl will be analyzed
2and Na
2seO
3, be mixed in DMF in after the ratio batching of Pb:Se atomic ratio 1:1, obtain the mixed liquor being 0.03mol/L in PbSe concentration, mixeding liquid volume is 80 milliliters.
2) in the mixed liquor of step 1), add 274 milligrams of GO and fully then ultrasonic disperse is placed in the autoclave (compactedness 80%, percent by volume) that capacity is 100 milliliters, then seal immediately.
3) reactor is heated to 140 DEG C, and reacts 48 hours.
4) room temperature is naturally cooled to after having reacted, collect the Powdered product at the bottom of still, use deionized water successively, after the cleaning for several times of absolute ethyl alcohol alternate repetition, by powder vacuumize 12 hours at 110 DEG C, obtain composite powder 0.75 gram, in composite material, the percentage by weight of Graphene is 14%.
The composite powder of gained is through X ray diffracting spectrum and scanning electron microscopic picture analysis, can find out that the composite powder of gained is plumbous selenium compound/Graphene (PbSe/G) composite material, wherein PbSe particle is isometric particle, particle size is nanoscale, the length of side is 100 nanometer ~ 200 nanometers, and distribution is more even.
Be 100 nanometer ~ 200 nanometers with gained PbSe/G composite material and its particle length of side of pure nano PbS e(respectively; The same PbSe/G of preparation method of pure nano PbS e, difference does not add graphene oxide in raw material) carry out electrochemical property test as lithium ion battery negative material, method of testing with embodiment 1, constant current charge-discharge (current density 50mAg
-1, voltage range 0.05 ~ 2.5V) test show, when cycle-index is 1, the capacity of PbSe/G composite material is 530mAhg
-1, when cycle-index is 20, the capacity of PbSe/G composite material is only down to 402mAhg
-1; And cycle-index is when being 1, the capacity of pure nano PbS e is 462mAhg
-1, when cycle-index is 20, the capacity of pure nano PbS e is reduced to 160mAhg rapidly
-1; Compared with visible and pure nano PbS e, the cyclical stability of PbSe/G composite material significantly improves, and electrochemical stability is good.
Embodiment 3
1) pure PbSO will be analyzed
4and K
2seO
3in being mixed in absolute ethyl alcohol after the ratio batching of Pb:Se atomic ratio 1:1, obtain the mixed liquor being 0.06mol/L in PbSe concentration, mixeding liquid volume is 80 milliliters.
2) in the mixed liquor of step 1), add 412 milligrams of GO and fully then ultrasonic disperse is placed in the autoclave (compactedness 80%, percent by volume) that capacity is 100 milliliters, then seal immediately.
3) reactor is heated to 220 DEG C, and reacts 36 hours.
4) room temperature is naturally cooled to after having reacted, collect the Powdered product at the bottom of still, use deionized water successively, after the cleaning for several times of absolute ethyl alcohol alternate repetition, by powder vacuumize 12 hours at 110 DEG C, obtain composite powder 1.53 grams, in composite material, the percentage by weight of Graphene is 11%.
The composite powder of gained is through X ray diffracting spectrum and scanning electron microscopic picture analysis, can find out that the composite powder of gained is plumbous selenium compound/Graphene (PbSe/G) composite material, wherein PbSe particle is isometric particle, particle size is nanoscale, the length of side is 100 nanometer ~ 200 nanometers, and distribution is more even.
Be 100 nanometer ~ 200 nanometers with gained PbSe/G composite material and its particle length of side of pure nano PbS e(respectively; The same PbSe/G of preparation method of pure nano PbS e, difference does not add graphene oxide in raw material) carry out electrochemical property test as lithium ion battery negative material, method of testing with embodiment 1, constant current charge-discharge (current density 50mAg
-1, voltage range 0.05 ~ 2.5V) test show, when cycle-index is 1, the capacity of PbSe/G composite material is 524mAhg
-1, when cycle-index is 20, the capacity of PbSe/G composite material is only down to 387mAhg
-1; And cycle-index is when being 1, the capacity of pure nano PbS e is 443mAhg
-1, when cycle-index is 20, the capacity of pure nano PbS e is reduced to 144mAhg rapidly
-1; Compared with visible and pure nano PbS e, the cyclical stability of PbSe/G composite material significantly improves, and electrochemical stability is good.
Embodiment 4
1) pure PbC will be analyzed
2o
4with Se powder in being mixed in ethylenediamine after the ratio batching of Pb:Se atomic ratio 1:1, obtain the mixed liquor being 0.1mol/L in PbSe concentration, mixeding liquid volume is 80 milliliters.
2), in the mixed liquor of step 1), add 457 milligrams of GO and fully then ultrasonic disperse is placed in the autoclave (compactedness 80%, percent by volume) that capacity is 100 milliliters, then seal immediately.
3), by reactor be heated to 240 DEG C, and react 24 hours.
4) room temperature is naturally cooled to after, having reacted, collect the Powdered product at the bottom of still, use deionized water successively, after the cleaning for several times of absolute ethyl alcohol alternate repetition, by powder vacuumize 12 hours at 110 DEG C, obtain composite powder 2.4 grams, in composite material, the percentage by weight of Graphene is 7.4%.
The composite powder of gained is through X ray diffracting spectrum and scanning electron microscopic picture analysis, can find out that the composite powder of gained is plumbous selenium compound/Graphene (PbSe/G) composite material, wherein PbSe particle is isometric particle, particle size is nanoscale, the length of side is 100 nanometer ~ 200 nanometers, and distribution is more even.
Be 100 nanometer ~ 200 nanometers with gained PbSe/G composite material and its particle length of side of pure nano PbS e(respectively; The same PbSe/G of preparation method of pure nano PbS e, difference does not add graphene oxide in raw material) carry out electrochemical property test as lithium ion battery negative material, method of testing with embodiment 1, constant current charge-discharge (current density 50mAg
-1, voltage range 0.05 ~ 2.5V) test show, when cycle-index is 1, the capacity of PbSe/G composite material is 554mAhg
-1, when cycle-index is 20, the capacity of PbSe/G composite material is only down to 321mAhg
-1; And cycle-index is when being 1, the capacity of pure nano PbS e is 467mAhg
-1, when cycle-index is 20, the capacity of pure nano PbS e is reduced to 187mAhg rapidly
-1; Compared with visible and pure nano PbS e, the cyclical stability of PbSe/G composite material significantly improves, and electrochemical stability is good.
In addition, in scope of the present invention, such as substitute selenium powder in above-described embodiment or selenium salt with of the present invention other containing selenium compound, the leaded compound in above-described embodiment is substituted with other leaded compound of the present invention, the reproducibility organic solvent in above-described embodiment is substituted with other reproducibility organic solvent of the present invention, the condition in above-described embodiment is substituted by condition of the present invention, obtained composite material all has nano PbS e isometric particle/graphene composite structure, and cyclical stability is good.
Claims (7)
1. isometric particle/the graphene composite material of the PbSe as lithium ion battery negative material, it is characterized in that, be composited by nanoscale PbSe isometric particle and Graphene, in composite material, the weight percentage of Graphene is 7.4% ~ 17%, and preparation method comprises the following steps:
1) with elemental selenium or containing selenium compound and leaded compound for raw material, be mixed in reproducibility organic solvent according to the stoichiometric proportion of PbSe, the mixed solution that to obtain in PbSe concentration be 0.01mol/L ~ 0.1mol/L;
2) in step 1) mixed liquor in add graphene oxide through abundant ultrasonic disperse, then cool after 12 hours ~ 72 hours 120 DEG C ~ 250 DEG C reactions in sealed environment, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying, obtains PbSe isometric particle/graphene composite material.
2. PbSe isometric particle/graphene composite material according to claim 1, is characterized in that, the length of side of described nanoscale PbSe isometric particle is 100 nanometer ~ 200 nanometers.
3. PbSe isometric particle/graphene composite material according to claim 1 and 2, is characterized in that, in described composite material, nanoscale PbSe isometric particle is dispersed.
4. PbSe isometric particle/graphene composite material according to claim 1, is characterized in that, described is Na containing selenium compound
2seO
3or K
2seO
3; Described leaded compound is lead chloride, lead fluoride, plumbi nitras, lead sulfate, lead oxalate or lead acetate.
5. PbSe isometric particle/graphene composite material according to claim 1, is characterized in that, described reproducibility organic solvent is ethanol, methyl alcohol, ethylene glycol, DMF, ethylenediamine or oleyl amine.
6. PbSe isometric particle/graphene composite material according to claim 1, is characterized in that, the addition of described graphene oxide is 1% ~ 50% of PbSe weight.
7. the application of the PbSe isometric particle/graphene composite material according to any one of Claims 1 to 4, is characterized in that, described PbSe isometric particle/graphene composite material is as the application in lithium ion battery negative material.
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| CN105293475A (en) * | 2015-10-26 | 2016-02-03 | 李修兵 | Graphene and nickel diselenide composite and preparation method thereof |
| CN105836716B (en) * | 2016-03-25 | 2017-11-10 | 武汉工程大学 | A kind of lead selenide quantum dot graphene composite material and preparation method thereof |
| CN108328589B (en) * | 2018-01-11 | 2021-07-20 | 三峡大学 | PSe negative electrode material with high coulombic efficiency for the first time and preparation method thereof |
| CN112607714B (en) * | 2021-01-07 | 2023-07-25 | 安徽大学绿色产业创新研究院 | Preparation method of PbSe-based thermoelectric material |
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| GB201009519D0 (en) * | 2010-06-07 | 2010-07-21 | Nexeon Ltd | An additive for lithium ion rechargeable battery cells |
| CN102760829B (en) * | 2012-07-23 | 2014-11-05 | 浙江大学 | PbTe cubic particle/grapheme composite material and preparation method and application thereof |
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