CN105633386A - Graphene-supported silicon quantum dot negative electrode material and preparation method and application thereof - Google Patents
Graphene-supported silicon quantum dot negative electrode material and preparation method and application thereof Download PDFInfo
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- CN105633386A CN105633386A CN201410612312.8A CN201410612312A CN105633386A CN 105633386 A CN105633386 A CN 105633386A CN 201410612312 A CN201410612312 A CN 201410612312A CN 105633386 A CN105633386 A CN 105633386A
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Abstract
The invention relates to a graphene-supported silicon quantum dot negative electrode material and a preparation method and application thereof. The preparation method comprises the following steps of (1) synthesizing silicon quantum dots which are highly uniform in size by a solvothermal method based on an organic silicon precursor; (2) highly uniformly loading the silicon quantum dots on graphene oxide by a non-covalent self-assembly method to prepare graphene oxide supported silicon quantum dots; and (3) reducing the graphene oxide by a thermal treatment method to prepare the graphene-supported silicon quantum dot negative electrode material. The preparation method has the advantages of low cost, simplicity in process, controllability and low energy consumption, and can be scalable, and moreover, the obtained graphene-supported silicon quantum dot negative material is high in charging/discharging and rate performance and very stable in circulation.
Description
Technical field
The invention belongs to electrode material field, particularly to silicon quantum dot negative material that a kind of Graphene supports and its production and use.
Background technology
Lithium ion battery is the ideal source of portable electric appts and electric automobile, development have high-energy-density, high power density, long circulation life new type lithium ion battery electrode be the focus in current Study on Li-ion batteries field. Silicon is a kind of novel lithium ion battery negative material, its storage lithium response voltage platform is relatively low, theoretical capacity high (4200mAh/g), it is significantly larger than the graphite cathode of existing market, and, silicon is rich reserves in nature, is the lithium ion battery negative material of a great development prospect of class. But the electronics of silicon own and lithium ion conductivity are all relatively low, and it is attended by huge change in volume (more than 300%) in storage lithium process, the stress that this change in volume process produces causes lead rupture efflorescence, material inactive, and then causes that cycle performance declines rapidly.
At present, nano-structured by silicon materials, and then prepare silicon-carbon nano composite material, the instability problem that silicon volume deformation causes is able to effective solution to a certain extent, and electrode storage lithium characteristic obtains and is greatly improved. But, silicon-carbon nano composite material (complex of such as Graphene and silicon nano) base lithium ion battery cathode, on the one hand, wherein the dimensional homogeneity of silicon components is very poor, this significantly impacts cyclical stability (the Rolesofnanosizeinlithiumreactivenanomaterialsforlithiumi onbatteries of designing material, NanoToday2011,6,28); On the other hand, the preparation of this kind of material relies primarily on the gaseous state silicon sources such as costliness, the monosilane of high risk, or is unfavorable for the hf etching process of environment, or harsh (such as, fine vacuum, high temperature etc.) building-up process (Large-scalefabrication, 3Dtomography, the andlithium-ionbatteryapplicationofporoussilicon that consume energy, NanoLetters2014,14,261), method itself seriously restricts the practical application of such material.
Summary of the invention
For overcoming the defect of prior art, the preparation method that an object of the present invention is in that the silicon quantum dot negative material providing a kind of Graphene to support. Method provided by the invention prepares, by the graphene oxide process of the non-covalent self assembly of solvent thermal reaction and graphene oxide, the reducing loaded silicon quantum dot of Low Temperature Heat Treatment, the silicon quantum dot negative material that Graphene supports for raw material with the organosilicon precursor of business. The advantages such as the preparation method of the present invention has with low cost, and preparation technology is simple, it is low to consume energy, can amplify.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that
The preparation method of the silicon quantum dot negative material that a kind of Graphene supports, comprises the steps:
(1) based on organosilicon precursor, the silicon quantum dot being controlled the homogeneous 1-30nm of synthesis dimensional height by solvent-thermal method;
(2) based on the amino group (-NH on above-mentioned silicon quantum dot surface2) and the oxygen-containing functional group (such as hydroxy-acid group-COOH) of surface of graphene oxide between electrostatic interaction carry out non-covalent self assembly, realize the highly homogeneously load on graphene oxide of above-mentioned silicon quantum dot, thus preparing the silicon quantum dot that graphene oxide supports;
(3) adopt the graphene oxide of the reducing loaded silicon quantum dot of heat treating process, prepare the silicon quantum dot negative material that Graphene supports.
Preparation method for the present invention, in step (1), the process of the silicon quantum dot of synthesis 1-30nm is: be mixed in solvent thermal reaction still by organosilicon precursor and predissolve reducing agent in water, at 120-400 DEG C, constant temperature is placed 0.5-12 hour, obtains the silicon quantum dot of the homogeneous 1-30nm of dimensional height.
Preferably, described organosilicon precursor is one or more the mixing in APTES (APTES), triphenylsilyl amine, diethylenetriamine base propyl trimethoxy silicane, 3-(2-aminoethylamino) propyl trimethoxy silicane.
Preferably, described reducing agent is one or more the mixing in sodium citrate, sodium hypophosphite, glutathion, sodium sulfite, sodium sulfocynanate, white phosphorus, sodium borohydride, chitosan.
Preferably, described organosilicon precursor and the preferred mass ratio of reducing agent are 1:1-10:1.
Preferably, constant temperature is dialysed after terminating, to remove unreacted raw material.
Preparation method for the present invention, the process preparing the silicon quantum dot that graphene oxide supports in step (2) is: mixed under the pH of 1-7 by the silicon quantum dot that graphene oxide is prepared with step (1), can ensure that the amino group positively charged on silicon quantum dot surface, surface of graphene oxide oxygen-containing functional group electronegative, realize silicon quantum dot highly homogeneously load on graphene oxide thereby through electrostatic interaction therebetween, prepare the silicon quantum dot that graphene oxide supports.
For the preparation method of the present invention, heat treatment described in step (3) carries out under an inert atmosphere.
Preferably, described inert atmosphere is one or more the mixing in helium, neon, argon, Krypton, xenon, radon gas or hydrogen, it is preferred to argon and/or hydrogen.
Preferably, described heat treated temperature is 150-900 DEG C, and the heat treated time is 0.5-12 hour.
An object of the present invention also resides in the silicon quantum dot negative material that the Graphene provided obtained by the preparation method of the present invention supports.
An object of the present invention also resides in the purposes of the silicon quantum dot negative material providing described Graphene to support, and uses it in lithium rechargeable battery.
Preferably, negative material of the present invention mixes use as ion secondary battery cathode material lithium with other negative materials.
Preferably, negative material consumption of the present invention is not less than the 1% of total negative material.
Preferably, other active cathode material described are that Delanium, native graphite, SWCN, few layer CNT, multi-walled carbon nano-tubes, Graphene, the graphene oxide of reduction, hard carbon material and lithium can occur the metal of alloying reaction and precursor (such as stannum, germanium, aluminum, cobalt etc.) thereof and lithium that one or more the mixing in the transistion metal compound (such as cobalt oxide, ferrum oxide etc.) of conversion reaction or embedding lithium type transition metal oxide (such as lithium titanate etc.) can occur.
The present invention has the advantage that
(1) preparing the cheaper starting materials of the silicon quantum dot that Graphene supports, be easy to get, preparation technology is simple, it is low to consume energy, and can be substantially reduced the production cost of the silicon quantum dot that Graphene supports, have good can amplification;
(2) when the silicon quantum dot that the Graphene prepared by supports is as lithium ion battery negative material, size and the load of high uniformity on Graphene due to silicon quantum dot height homogeneous, extra small (1-30nm), the each transmission range of silicon quantum dot unit electronics and the diffusion length of lithium ion that count during electrode material is tested significantly shorten, its storage lithium kinetics is obviously improved, so consisting of electrode show fabulous discharge and recharge, high rate performance and extremely excellent cyclical stability.
Accompanying drawing explanation
Fig. 1 is the STEM picture of the silicon quantum dot that embodiment 1 gained Graphene supports;
Fig. 2 is the TEM picture of the silicon quantum dot that embodiment 1 gained Graphene supports;
Fig. 3 is the size statistic figure of the silicon quantum dot that embodiment 1 gained Graphene supports;
Fig. 4 is the Raman spectrum of the silicon quantum dot that embodiment 1 gained Graphene supports;
Fig. 5 is the cycle performance curve chart (electric current density is 2A/g) of the silicon quantum dot that embodiment 1 gained Graphene supports.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment. Those skilled in the art understand the present invention it will be clearly understood that described embodiment is used only for help, are not construed as the concrete restriction to the present invention.
Embodiment 1
(1) by 3-aminopropyl triethoxysilane and predissolve, the sodium citrate in water mixes according to the mass ratio of 5:1, then proceed in solvent thermal reaction still, after 180 DEG C of constant temperature are placed 2 hours, unreacted raw material is removed in dialysis, obtains the silicon quantum dot of homogeneous 3nm;
(2) after being mixed with graphene oxide by homogeneous silicon quantum dot, regulate the pH value of solution to 3, further after stirring, obtain the silicon quantum dot that graphene oxide supports;
(3) silicon quantum dot that above-mentioned graphene oxide is supported 300 DEG C, process 5 hours under hydrogen atmosphere, prepare the silicon quantum dot that Graphene supports.
The prepared silicon quantum dot of Graphene support, binding agent polyvinylidene fluoride (PVDF), conductive agent acetylene black Homogeneous phase mixing in N-Methyl pyrrolidone (NMP) are configured to slurry, then it is applied on Copper Foil collector body, is pressed into cathode pole piece in 12 hours back roller of 120 DEG C of vacuum dryings; With cathode pole piece for test electrode, with metallic lithium foil for electrode, electrolyte is 1MLiPF6/ EC:DEC (1:1; V/v), being namely dissolved with the ethylene carbonate of lithium hexafluoro phosphate and the mixed solvent of diethyl carbonate, barrier film is Celgard2400, is respectively less than in the glove box of 1ppm at oxygen and water content and is assembled into button-shaped lithium ion battery. Under the electric current density of 20A/, it still has the specific capacity up to 566mAh/g; After circulating 500 times under the electric current density of 2A/g, capability retention is up to 98%.
Fig. 1 is the STEM picture of the silicon quantum dot that the present embodiment gained Graphene supports, and Fig. 2 is the TEM picture of the silicon quantum dot that the present embodiment gained Graphene supports, and Fig. 1 and Fig. 2 shows silicon quantum dot load of high uniformity on Graphene; Fig. 3 is the size statistic figure of the silicon quantum dot that the present embodiment gained Graphene supports, it was shown that the size of the silicon quantum dot being carried on Graphene has high level of homogeneity; Fig. 4 is the Raman spectrum of the silicon quantum dot that the present embodiment gained Graphene supports, it was shown that the component of the silicon quantum dot that Graphene supports is silicon and graphited carbon; Fig. 5 is the cycle performance curve chart (electric current density is 2A/g) of the silicon quantum dot that the present embodiment gained Graphene supports, it was shown that the silicon quantum dot that Graphene supports has extremely stable cycle performance.
Embodiment 2
(1) by triphenylsilyl amine and predissolve, the sodium borohydride in water mixes according to the mass ratio of 1:1, then proceed in solvent thermal reaction still, after 400 DEG C of constant temperature are placed 0.5 hour, unreacted raw material is removed in dialysis, obtains the silicon quantum dot of homogeneous 30nm;
(2) after being mixed with graphene oxide by homogeneous silicon quantum dot, regulate the pH value of solution to 1, further after stirring, obtain the silicon quantum dot that graphene oxide supports;
(3) silicon quantum dot that above-mentioned graphene oxide is supported 900 DEG C, process 0.5 hour under argon gas atmosphere, prepare the silicon quantum dot that Graphene supports.
Follow-up test is embodiment 1 such as. Under the electric current density of 10A/, the silicon quantum dot that described Graphene supports still has the specific capacity up to 655mAh/g; After circulating 300 times under the electric current density of 2A/g, capability retention is up to 99%.
Embodiment 3
(1) by diethylenetriamine base propyl trimethoxy silicane and predissolve, the sodium sulfite in water mixes according to the mass ratio of 10:1, then proceed in solvent thermal reaction still, after 120 DEG C of constant temperature are placed 12 hours, unreacted raw material is removed in dialysis, obtains the silicon quantum dot of homogeneous 15nm;
(2) after being mixed with graphene oxide by homogeneous silicon quantum dot, regulate the pH value of solution to 7, further after stirring, obtain the silicon quantum dot that graphene oxide supports;
(3) silicon quantum dot supported by above-mentioned graphene oxide processes 12 hours under 150 DEG C, argon and hydrogen mixed gas atmosphere, prepares the silicon quantum dot that Graphene supports.
Follow-up test is embodiment 1 such as. Under the electric current density of 20A/, the homogeneous extra small silicon quantum dot that described Graphene supports still has the specific capacity up to 595mAh/g; After circulating 450 times under the electric current density of 2A/g, capability retention is up to 99%.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, but the invention is not limited in above-mentioned detailed process equipment and technological process, namely do not mean that the present invention has to rely on above-mentioned detailed process equipment and technological process could be implemented. The equivalence of each raw material of product of the present invention, it will be clearly understood that any improvement in the present invention, is replaced and the interpolation of auxiliary element, concrete way choice etc. by person of ordinary skill in the field, all falls within protection scope of the present invention and open scope.
Claims (10)
1. a preparation method for the silicon quantum dot negative material that Graphene supports, comprises the steps:
(1) based on organosilicon precursor, by the silicon quantum dot of the homogeneous 1-30nm of solvent structure dimensional height;
(2) realize silicon quantum dot load highly equably on graphene oxide by non-covalent self-assembly method, prepare the silicon quantum dot that graphene oxide supports;
(3) adopt the graphene oxide of the reducing loaded silicon quantum dot of heat treating process, prepare the silicon quantum dot negative material that Graphene supports.
2. preparation method according to claim 1, it is characterized in that, in step (1), the process of the silicon quantum dot of synthesis 1-30nm is: be mixed in solvent thermal reaction still by organosilicon precursor and predissolve reducing agent in water, at 120-400 DEG C, constant temperature is placed 0.5-12 hour, obtains the silicon quantum dot of the homogeneous 1-30nm of dimensional height.
3. preparation method according to claim 1 and 2, it is characterized in that, described organosilicon precursor is one or more the mixing in APTES (APTES), triphenylsilyl amine, diethylenetriamine base propyl trimethoxy silicane, 3-(2-aminoethylamino) propyl trimethoxy silicane.
4. preparation method according to claim 2, it is characterised in that described reducing agent is one or more the mixing in sodium citrate, sodium hypophosphite, glutathion, sodium sulfite, sodium sulfocynanate, white phosphorus, sodium borohydride, chitosan;
Preferably, described organosilicon precursor and the preferred mass ratio of reducing agent are 1:1-10:1;
Preferably, constant temperature is dialysed after terminating.
5. preparation method according to claim 1 and 2, it is characterized in that, the process preparing the silicon quantum dot that graphene oxide supports in step (2) is: mixed under the pH of 1-7 by the silicon quantum dot that graphene oxide is prepared with step (1), carry out non-covalent self assembly based on electrostatic interaction therebetween, prepare the silicon quantum dot that graphene oxide supports.
6. preparation method according to claim 1 and 2, it is characterised in that heat treatment described in step (3) carries out under an inert atmosphere;
Preferably, described inert atmosphere is one or more the mixing in helium, neon, argon, Krypton, xenon, radon gas or hydrogen, it is preferred to argon and/or hydrogen;
Preferably, described heat treated temperature is 150-900 DEG C, and the heat treated time is 0.5-12 hour.
7. the silicon quantum dot negative material that a Graphene supports, it is characterised in that prepared by the preparation method described in any one of claim 1-6.
8. the silicon quantum dot negative material that Graphene described in claim 7 supports purposes in lithium rechargeable battery.
9. purposes according to claim 8, it is characterised in that the silicon quantum dot negative material that described Graphene supports mixes use as ion secondary battery cathode material lithium with other negative materials;
Preferably, the silicon quantum dot negative material consumption that described Graphene supports is not less than the 1% of total negative material.
10. purposes according to claim 8 or claim 9, it is characterized in that, other active cathode material described are that Delanium, native graphite, SWCN, few layer CNT, multi-walled carbon nano-tubes, Graphene, the graphene oxide of reduction, hard carbon material and lithium can occur the metal of alloying reaction and precursor thereof and lithium that one or more the mixing in the transistion metal compound of conversion reaction or embedding lithium type transition metal oxide can occur.
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| CN111029586A (en) * | 2019-03-21 | 2020-04-17 | 东北师范大学 | High-rate lithium ion battery anode slurry |
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| CN110511745B (en) * | 2019-08-26 | 2022-05-27 | 河南师范大学 | Preparation method of water-soluble fluorescent silicon quantum dots and application of water-soluble fluorescent silicon quantum dots in selective detection of p-nitrophenol |
| CN111678954A (en) * | 2020-06-05 | 2020-09-18 | 苏州科技大学 | Si-RGO composite material and application thereof in detection of nitrogen dioxide gas |
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