CN103219515A - 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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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 the lithium ion battery field of compound material, be specifically related to a kind of PbSe isometric particle/graphene composite material and its production and application.
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 elements 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, by the method for physics or chemistry, the material of forming on macroscopic view 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 better than former composition material and satisfy various requirement.Graphene is because its conductivity height, the intensity height, and specific area is big, and the carrier that is widely used as nano particle prepares composite material.As disclosing a kind of graphene-supported cobaltosic oxide nano composite material and preparation method thereof among the Chinese patent ZL201010158087.7, form by Graphene and cobaltosic oxide, cobaltosic oxide loads on the 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; The preparation method is: get graphene oxide solution and divalent cobalt, high molecular surfactant mixing; Mix the back with the aqueous slkali that adds oxidant then and stir or ultrasonic 0.2～5 hour, transfer in the pyroreaction still, annealing obtained product in 3～30 hours under 100～250 ℃, through washing, drying, promptly got 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 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.
Lead selenide (PbSe) has cubic crystal structure, lattice constant 0.6122nm, and many semi-conducting materials as low energy gap generally are used to make photo resistance and infrared detector etc.
Summary of the invention
The invention provides the good PbSe isometric particle/graphene composite material of a kind of electrochemical stability.
The present invention also provides an a kind of one step preparation method of PbSe isometric particle/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 PbSe isometric particle/graphene composite material is composited by nanoscale PbSe isometric particle and Graphene (G).It is the composition that described composite material has PbSe/G.
The present invention finds with the existing PbSe isometric particle that is used to make photo resistance and infrared detector and Graphene to have good electrochemical after compound, and electrochemical stability is good, can be used as or prepare the negative material of lithium ion battery.
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, and more preferably 7.4%～17%.
Because the particle size of PbSe is more little, easy more covering is stated from the Graphene, and the electrochemical stability performance of composite material is good more, so the present invention selects nanoscale PbSe isometric particle for use, and preferred, the length of side of described nanoscale PbSe isometric particle is 100 nanometers～200 nanometers.
Preferably, nanoscale PbSe isometric particle is even dispersion in the described composite material.
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 may further comprise the steps:
1) with simple substance selenium (Se) or contain selenium compound and the compound of leaded (Pb) is a raw material, stoichiometric proportion (being the atomic ratio 1:1 of Pb and Se) according to PbSe is mixed in the reproducibility organic solvent, and obtaining in PbSe concentration is the mixed solution of 0.01mol/L～0.1mol/L;
2) in the mixed liquor of step 1), add graphene oxide (GO) through abundant ultrasonic dispersion, in sealed environment, cool off after 12 hours～72 hours then 120 ℃～250 ℃ reactions, 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 a PbSe theoretical weight, preferred 20%～50%.
In the step 1), the described selenium compound that contains can be selected the salt that contains selenium for use, preferred Na
2SeO
3Or K
2SeO
3
Described leaded compound can be selected leaded salt for use, preferred lead chloride, lead fluoride, plumbi nitras, lead sulfate, lead oxalate or lead acetate.
Owing to adopt the reproducibility organic solvent, can add other reducing agents in addition and come reduction-oxidation graphite, described reproducibility organic solvent not only can be used as reducing agent but also can be used as reaction dissolvent.Do not contain water in the described reproducibility organic solvent, select ethanol, methyl alcohol, ethylene glycol, N for use, dinethylformamide, ethylenediamine or oleyl amine.
Step 2) in, further preferred: as in sealed environment, to cool off after 24 hours～48 hours 140 ℃～240 ℃ reactions; General this reaction temperature is high more, and the time is long more, the easy more formation of PbSe, and the easy more Graphene that is reduced into of graphene oxide, but little to the particle size 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 PbSe isometric particle/the graphene composite material electrochemical stability is good, can be used as or prepare lithium ion battery negative material.
Compared with prior art, the present invention has following advantage:
1, in the composite material of the present invention nano PbS e isometric particle since the dispersion of Graphene and carrying effect can in composite material, evenly distribute, can effectively improve the stability of PbSe in charge and discharge process, be significant for the electrochemical stability that improves PbSe.
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 nano PbS e.
3, the present invention adopts a step solvent-thermal method to prepare the PbSe isometric particle/graphene composite material of nano-scale, and original position is introduced Graphene in solvent-thermally synthesizing nano PbSe process, has 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, gained PbSe purity height, granularity are little, and cube length of side is 100 nanometers～200 nanometers, and it is more even to distribute.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of embodiment 1 gained PbSe/G composite material;
Fig. 2 is the ESEM 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
1) will analyze pure Pb (NO
3)
2With the Se powder, be mixed in the absolute ethyl alcohol after the ratio batching in Pb:Se atomic ratio 1:1, making in PbSe concentration is the mixed liquor of 0.01mol/L, mixeding liquid volume is 80 milliliters.
2) adding 114 milligrams of GO and abundant ultrasonic dispersion in the mixed liquor of step 1), to place capacity then be 100 milliliters autoclave (compactedness 80%, percent by volume), sealing immediately then.
3) reactor is heated to 180 ℃, and reacted 36 hours.
4) naturally cool to room temperature after having reacted, Powdered product at the bottom of the collection still, use deionized water successively, after the absolute ethyl alcohol alternate repetition cleans for several times, with powder 110 ℃ of following vacuumizes 12 hours, obtain composite powder 0.27 gram, the percentage by weight of Graphene is 17% in the composite material.
The X ray diffracting spectrum of the composite powder of gained and ESEM picture are respectively as Fig. 1 and Fig. 2, all diffraction maximums all can be classified as the diffraction maximum of PbSe among Fig. 1, do not find the diffraction maximum of Graphene among Fig. 1, show that graphene layer is disperseed by the PbSe uniform particles, the composite powder that can find out gained is plumbous selenium compound/Graphene (PbSe/G) composite material, wherein the PbSe particle is an isometric particle, particle size is nanoscale, the length of side is 100 nanometers～200 nanometers, and it is more even to distribute.
Be 100 nanometers～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 the preparation method of pure nano PbS e, difference is not add graphene oxide in the raw material) carry out the 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 shows, cycle-index are 1 o'clock, the capacity of PbSe/G composite material is 516mAhg
-1, cycle-index is 20 o'clock, the capacity of PbSe/G composite material is only reduced to 417mAhg
-1And cycle-index is 1 o'clock, and the capacity of pure nano PbS e is 439mAhg
-1, cycle-index is 20 o'clock, the capacity of pure nano PbS e is reduced to 164mAhg rapidly
-1As seen compare with pure nano PbS e, the cyclical stability of PbSe/G composite material obviously improves, and electrochemical stability is good.
Embodiment 2
1) will analyze pure PbCl
2And Na
2SeO
3, be mixed in N after the ratio batching in Pb:Se atomic ratio 1:1, dinethylformamide, making in PbSe concentration is the mixed liquor of 0.03mol/L, mixeding liquid volume is 80 milliliters.
2) adding 274 milligrams of GO and abundant ultrasonic dispersion in the mixed liquor of step 1), to place capacity then be 100 milliliters autoclave (compactedness 80%, percent by volume), sealing immediately then.
3) reactor is heated to 140 ℃, and reacted 48 hours.
4) naturally cool to room temperature after having reacted, Powdered product at the bottom of the collection still, use deionized water successively, after the absolute ethyl alcohol alternate repetition cleans for several times, with powder 110 ℃ of following vacuumizes 12 hours, obtain composite powder 0.75 gram, the percentage by weight of Graphene is 14% in the composite material.
The composite powder of gained is analyzed through X ray diffracting spectrum and ESEM picture, the composite powder that can find out gained is plumbous selenium compound/Graphene (PbSe/G) composite material, wherein the PbSe particle is an isometric particle, particle size is nanoscale, the length of side is 100 nanometers～200 nanometers, and it is more even to distribute.
Be 100 nanometers～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 the preparation method of pure nano PbS e, 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 50mAg
-1, voltage range 0.05～2.5V) test shows, cycle-index are 1 o'clock, the capacity of PbSe/G composite material is 530mAhg
-1, cycle-index is 20 o'clock, the capacity of PbSe/G composite material is only reduced to 402mAhg
-1And cycle-index is 1 o'clock, and the capacity of pure nano PbS e is 462mAhg
-1, cycle-index is 20 o'clock, the capacity of pure nano PbS e is reduced to 160mAhg rapidly
-1As seen compare with pure nano PbS e, the cyclical stability of PbSe/G composite material obviously improves, and electrochemical stability is good.
Embodiment 3
1) will analyze pure PbSO
4And K
2SeO
3Be mixed in the absolute ethyl alcohol after the ratio batching in Pb:Se atomic ratio 1:1, making in PbSe concentration is the mixed liquor of 0.06mol/L, and mixeding liquid volume is 80 milliliters.
2) adding 412 milligrams of GO and abundant ultrasonic dispersion in the mixed liquor of step 1), to place capacity then be 100 milliliters autoclave (compactedness 80%, percent by volume), sealing immediately then.
3) reactor is heated to 220 ℃, and reacted 36 hours.
4) naturally cool to room temperature after having reacted, Powdered product at the bottom of the collection still, use deionized water successively, after the absolute ethyl alcohol alternate repetition cleans for several times, with powder 110 ℃ of following vacuumizes 12 hours, obtain composite powder 1.53 grams, the percentage by weight of Graphene is 11% in the composite material.
The composite powder of gained is analyzed through X ray diffracting spectrum and ESEM picture, the composite powder that can find out gained is plumbous selenium compound/Graphene (PbSe/G) composite material, wherein the PbSe particle is an isometric particle, particle size is nanoscale, the length of side is 100 nanometers～200 nanometers, and it is more even to distribute.
Be 100 nanometers～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 the preparation method of pure nano PbS e, 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 50mAg
-1, voltage range 0.05～2.5V) test shows, cycle-index are 1 o'clock, the capacity of PbSe/G composite material is 524mAhg
-1, cycle-index is 20 o'clock, the capacity of PbSe/G composite material is only reduced to 387mAhg
-1And cycle-index is 1 o'clock, and the capacity of pure nano PbS e is 443mAhg
-1, cycle-index is 20 o'clock, the capacity of pure nano PbS e is reduced to 144mAhg rapidly
-1As seen compare with pure nano PbS e, the cyclical stability of PbSe/G composite material obviously improves, and electrochemical stability is good.
Embodiment 4
1) will analyze pure PbC
2O
4Be mixed in the ethylenediamine after in the ratio of Pb:Se atomic ratio 1:1 batching with the Se powder, making in PbSe concentration is the mixed liquor of 0.1mol/L, and mixeding liquid volume is 80 milliliters.
2), adding 457 milligrams of GO and abundant ultrasonic dispersion in the mixed liquor of step 1), to place capacity then be 100 milliliters autoclave (compactedness 80%, percent by volume), sealing immediately then.
3), reactor is heated to 240 ℃, and reacted 24 hours.
4), naturally cool to room temperature after having reacted, Powdered product at the bottom of the collection still, use deionized water successively, after the absolute ethyl alcohol alternate repetition cleans for several times, with powder 110 ℃ of following vacuumizes 12 hours, obtain composite powder 2.4 grams, the percentage by weight of Graphene is 7.4% in the composite material.
The composite powder of gained is analyzed through X ray diffracting spectrum and ESEM picture, the composite powder that can find out gained is plumbous selenium compound/Graphene (PbSe/G) composite material, wherein the PbSe particle is an isometric particle, particle size is nanoscale, the length of side is 100 nanometers～200 nanometers, and it is more even to distribute.
Be 100 nanometers～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 the preparation method of pure nano PbS e, 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 50mAg
-1, voltage range 0.05～2.5V) test shows, cycle-index are 1 o'clock, the capacity of PbSe/G composite material is 554mAhg
-1, cycle-index is 20 o'clock, the capacity of PbSe/G composite material is only reduced to 321mAhg
-1And cycle-index is 1 o'clock, and the capacity of pure nano PbS e is 467mAhg
-1, cycle-index is 20 o'clock, the capacity of pure nano PbS e is reduced to 187mAhg rapidly
-1As seen compare with pure nano PbS e, the cyclical stability of PbSe/G composite material obviously improves, and electrochemical stability is good.
In addition, in scope of the present invention, for example contain selenium compound and substitute selenium powder or selenium salt in the foregoing description with of the present invention other, with the leaded compound in the alternative the foregoing description of other leaded compound of the present invention, with the reproducibility organic solvent in the alternative the foregoing description of other reproducibility organic solvent of the present invention, with the condition in the alternative the foregoing description of condition of the present invention, the composite material that makes all has nano PbS e isometric particle/Graphene composite construction, and cyclical stability is good.
Claims (9)
1. a PbSe isometric particle/graphene composite material is characterized in that, is composited by nanoscale PbSe isometric particle and Graphene.
2. PbSe isometric particle/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. 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 nanometers～200 nanometers.
4. according to claim 1 or 3 described PbSe isometric particle/graphene composite materials, it is characterized in that nanoscale PbSe isometric particle is even dispersion in the described composite material.
5. according to the preparation method of each described PbSe isometric particle/graphene composite material of claim 1～4, it is characterized in that, may further comprise the steps:
1) with simple substance selenium or contain selenium compound and leaded compound is a raw material, be mixed in the reproducibility organic solvent according to the stoichiometric proportion of PbSe, obtaining in PbSe concentration is the mixed solution of 0.01mol/L～0.1mol/L;
2) in the mixed liquor of step 1), add graphene oxide through abundant ultrasonic dispersion, in sealed environment, cool off after 12 hours～72 hours then 120 ℃～250 ℃ reactions, collect solid product, through deionized water and the washing of absolute ethyl alcohol alternate repetition, drying obtains PbSe isometric particle/graphene composite material.
6. preparation method according to claim 5 is characterized in that, the described selenium compound that contains is Na
2SeO
3Or K
2SeO
3Described leaded compound is lead chloride, lead fluoride, plumbi nitras, lead sulfate, lead oxalate or lead acetate.
7. preparation method according to claim 5 is characterized in that, described reproducibility organic solvent is ethanol, methyl alcohol, ethylene glycol, N, dinethylformamide, ethylenediamine or oleyl amine.
8. preparation method according to claim 5 is characterized in that, the addition of described graphene oxide is 1%～50% of a PbSe theoretical weight.
9. according to the application of each described PbSe isometric particle/graphene composite material of claim 1～4, it is characterized in that the application of described PbSe isometric particle/graphene composite material in conduct or preparation lithium ion battery negative material.
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Cited By (4)
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| CN105293475A (en) * | 2015-10-26 | 2016-02-03 | 李修兵 | Graphene and nickel diselenide composite and preparation method thereof |
| CN105836716A (en) * | 2016-03-25 | 2016-08-10 | 武汉工程大学 | Lead selenide quantum dot/graphene composite material and preparation method thereof |
| CN112607714A (en) * | 2021-01-07 | 2021-04-06 | 安徽大学绿色产业创新研究院 | Preparation method of PbSe-based thermoelectric material |
| 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 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105293475A (en) * | 2015-10-26 | 2016-02-03 | 李修兵 | Graphene and nickel diselenide composite and preparation method thereof |
| CN105836716A (en) * | 2016-03-25 | 2016-08-10 | 武汉工程大学 | 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 |
| CN112607714A (en) * | 2021-01-07 | 2021-04-06 | 安徽大学绿色产业创新研究院 | Preparation method of PbSe-based thermoelectric material |
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Granted publication date: 20141217 Termination date: 20170328 |