CN105633386B - The silicon quantum dot negative electrode material and its preparation method and application of graphene support - Google Patents
The silicon quantum dot negative electrode material and its preparation method and application of graphene support Download PDFInfo
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- CN105633386B CN105633386B CN201410612312.8A CN201410612312A CN105633386B CN 105633386 B CN105633386 B CN 105633386B CN 201410612312 A CN201410612312 A CN 201410612312A CN 105633386 B CN105633386 B CN 105633386B
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Abstract
A kind of silicon quantum dot lithium ion battery negative material and its preparation method and application of graphene support.Its preparation includes the following steps：(1) based on organosilicon precursor, the silicon quantum dot uniform by solvent structure dimensional height；(2) it realizes that silicon quantum dot height on graphene oxide equably loads by non-covalent self-assembly method, prepares the silicon quantum dot of graphene oxide support；(3) heat treating process redox graphene is used, the silicon quantum dot negative electrode material of graphene support is prepared.Preparation method of the invention is not only low in cost, simple process, controllable, low energy consumption, can scale, but also the silicon quantum dot negative electrode material charge and discharge of obtained graphene support, high rate performance is high, circulation is extremely stable.
Description
Technical field
The invention belongs to electrode material field, in particular to a kind of the silicon quantum dot negative electrode material and its system of graphene support
Preparation Method and purposes.
Background technique
Lithium ion battery is the ideal source of portable electronic device and electric car, and development has high-energy density, height
Power density, long circulation life new type lithium ion battery electrode be the hot spot in current Study on Li-ion batteries field.Silicon is one
The novel lithium ion battery negative material of kind, storage lithium response voltage platform is lower, and theoretical capacity is high (4200mAh/g), far
Much higher than the graphite cathode of existing market, moreover, silicon rich reserves in nature, be a kind of great development prospect lithium from
Sub- cell negative electrode material.But silicon electronics itself and lithium ion conductivity are all lower, and are accompanied by huge body in the lithium storage process
Product variation (300% or more), the stress which generates causes lead rupture dusting, material inactive, and then causes
Cycle performance declines rapidly.
Currently, by the nano-structured of silicon materials, and then silicon-carbon nanocomposite is prepared, what silicon volume deformation caused
Instability problem is effectively solved to a certain extent, and electrode storage lithium characteristic is greatly improved.However, silicon-carbon nanometer
Composite material (such as complex of graphene and silicon nano) base lithium ion battery cathode, on the one hand, wherein silicon components
Dimensional homogeneity is very poor, this significantly impacts cyclical stability (the Roles of nanosize in lithium of designing material
reactive nanomaterials for lithium ion batteries,Nano Today 2011,6,28)；Another party
Face, this kind of material preparation relies primarily on the gaseous states silicon sources such as expensive, high risk monosilane, or is unfavorable for the hydrofluoric acid of environment
Etching process, or synthesis process (the Large-scale fabrication, 3D of harsh (for example, high vacuum, high temperature etc.) energy consumption
tomography,and lithium-ion battery application of porous silicon,Nano Letters
2014,14,261), method itself seriously restricts the practical application of such material.
Summary of the invention
To overcome the shortcomings of existing technologies, one of the objects of the present invention is to provide a kind of silicon quantum dots of graphene support
The preparation method of negative electrode material.Method provided by the invention using the organosilicon precursor of business as raw material by solvent thermal reaction, with
The non-covalent self assembly of graphene oxide, the reducing loaded silicon quantum dot of Low Temperature Heat Treatment graphene oxide process prepare graphene branch
The silicon quantum dot negative electrode material of support.Preparation method of the invention has low in cost, and preparation process is simple, energy consumption is low, can amplify
The advantages that.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of the silicon quantum dot negative electrode material of graphene support, includes the following steps：
(1) silicon quantum dot of the uniform 1-30nm of synthesis dimensional height is controlled based on organosilicon precursor, by solvent-thermal method；
(2) the amino group (- NH based on above-mentioned silicon quantum dot surface2) and surface of graphene oxide oxygen-containing function base
Electrostatic interaction between group (such as carboxylic acid group-COOH) carries out non-covalent self assembly, realizes that above-mentioned silicon quantum dot is aoxidizing
It is highly homogeneously loaded on graphene, so that the silicon quantum dot of graphene oxide support be made；
(3) graphene oxide for using the reducing loaded silicon quantum dot of heat treating process, prepares the silicon quantum dot of graphene support
Negative electrode material.
For preparation method of the invention, the process of the silicon quantum dot of synthesis 1-30nm is in step (1)：Before organosilicon
The reducing agent of body and predissolve in water is mixed in solvent thermal reaction kettle, and constant temperature is placed 0.5-12 hours at 120-400 DEG C,
Obtain the silicon quantum dot of the uniform 1-30nm of dimensional height.
Preferably, the organosilicon precursor is 3-aminopropyltriethoxysilane (APTES), triphen silyl
One of amine, diethylenetriamine base propyl trimethoxy silicane, 3- (2- aminoethylamino) propyl trimethoxy silicane or
Two or more mixing.
Preferably, the reducing agent be sodium citrate, it is sodium hypophosphite, glutathione, sodium sulfite, sodium sulfocynanate, white
The mixing of one or more of phosphorus, sodium borohydride, chitosan.
Preferably, the organosilicon precursor and the preferred mass ratio of reducing agent are 1:1-10:1.
Preferably, it dialyses after constant temperature, to remove unreacted raw material.
For preparation method of the invention, the process that the silicon quantum dot of graphene oxide support is prepared in step (2) is：It will
Graphene oxide is mixed at the pH of 1-7 with silicon quantum dot prepared by step (1), it can be ensured that the amino group on silicon quantum dot surface
Positively charged, surface of graphene oxide oxygen-containing functional group is negatively charged, to be realized by electrostatic interaction between the two
Silicon quantum dot highly homogeneously loads on graphene oxide, prepares the silicon quantum dot of graphene oxide support.
For preparation method of the invention, it is heat-treated described in step (3) and carries out under an inert atmosphere.
Preferably, the inert atmosphere is one of helium, neon, argon gas, Krypton, xenon, radon gas or hydrogen or two
Kind or more mixing, preferably argon gas and/or hydrogen.
Preferably, the temperature of the heat treatment is 150-900 DEG C, and the time of heat treatment is 0.5-12 hours.
An object of the present invention, which also resides in, provides the silicon of the support of graphene obtained by preparation method according to the invention
Quantum dot negative electrode material.
An object of the present invention, which also resides in, provides the purposes of the silicon quantum dot negative electrode material of the graphene support, by it
For in lithium ion secondary battery.
Preferably, negative electrode material of the present invention and other negative electrode materials are used in mixed way as lithium ion secondary battery negative pole
Material.
Preferably, negative electrode material dosage of the present invention is not less than the 1% of total negative electrode material.
Preferably, other described active cathode materials are artificial graphite, natural graphite, single-walled carbon nanotube, layer carbon is received less
The metal of alloying reaction can occur for mitron, multi-walled carbon nanotube, graphene, the graphene oxide of reduction, hard carbon material and lithium
And its transistion metal compound (such as cobalt oxide, iron oxide of conversion reaction can occur for precursor (such as tin, germanium, aluminium, cobalt) and lithium
Deng) or one or more of embedding lithium type transition metal oxide (such as lithium titanate) mixing.
The present invention has following advantage：
(1) raw material for preparing the silicon quantum dot of graphene support is cheap, is easy to get, and preparation process is simple, energy consumption is low, can be significantly
Reduce graphene support silicon quantum dot production cost, have it is good can amplification；
(2) when the silicon quantum dot of the graphene support prepared by is as lithium ion battery negative material, due to silicon quantum dot
The size of highly uniform, extra small (1-30nm) and on graphene high uniformity load, to electrode material test in be included in
Each silicon quantum dot unit for the transmission range of electronics and the diffusion length of lithium ion significantly shorten, storage lithium dynamics is bright
Aobvious to be promoted, the electrode being so made from it shows fabulous charge and discharge, high rate performance and extremely excellent cyclical stability.
Detailed description of the invention
Fig. 1 is the STEM picture of the silicon quantum dot of 1 gained graphene of embodiment support；
Fig. 2 is the TEM picture of the silicon quantum dot of 1 gained graphene of embodiment support；
Fig. 3 is the size statistic figure of the silicon quantum dot of 1 gained graphene of embodiment support；
Fig. 4 is the Raman spectrum of the silicon quantum dot of 1 gained graphene of embodiment support；
Fig. 5 is the cycle performance curve graph (current density 2A/g) of the silicon quantum dot of 1 gained graphene of embodiment support.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is used only for helping to understand the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
(1) sodium citrate by 3- aminopropyl triethoxysilane and predissolve in water is according to 5：1 mass ratio mixing,
Then it is transferred in solvent thermal reaction kettle, after 180 DEG C of constant temperature are placed 2 hours, dialysis removes unreacted raw material, obtains uniform
The silicon quantum dot of 3nm；
(2) after mixing uniform silicon quantum dot with graphene oxide, the pH value of solution is adjusted to 3, after futher stirring,
Obtain the silicon quantum dot of graphene oxide support；
(3) silicon quantum dot for supporting above-mentioned graphene oxide is handled 5 hours under 300 DEG C, hydrogen atmosphere, and graphite is made
The silicon quantum dot of alkene support.
Silicon quantum dot, binder polyvinylidene fluoride (PVDF), conductive agent acetylene black that graphene obtained supports are existed
It is uniformly hybridly prepared into slurry in N-Methyl pyrrolidone (NMP), is then applied on copper foil collector, in 120 DEG C of vacuum
Dry 12 hours back rollers are pressed into cathode pole piece；It is test electrode with cathode pole piece, is to electrode with metallic lithium foil, electrolyte is
1M LiPF6/EC:DEC(1:1；V/v), i.e. the mixing of ethylene carbonate and diethyl carbonate dissolved with lithium hexafluoro phosphate is molten
Agent, diaphragm are Celgard 2400, and button-shaped lithium ion battery is assembled into the glove box that oxygen and water content are respectively less than 1ppm.
Under the current density of 20A/, still there is the up to specific capacity of 566mAh/g；It is recycled 500 times under the current density of 2A/g
Afterwards, capacity retention ratio is up to 98%.
Fig. 1 is the STEM picture of the silicon quantum dot of the support of graphene obtained by the present embodiment, and Fig. 2 is graphite obtained by the present embodiment
The TEM picture of the silicon quantum dot of alkene support, Fig. 1 and Fig. 2 show the load of silicon quantum dot high uniformity on graphene；Fig. 3 is
The size statistic figure of the silicon quantum dot of the support of graphene obtained by the present embodiment, shows the ruler for the silicon quantum dot being carried on graphene
It is very little that there is high level of homogeneity；Fig. 4 is the Raman spectrum of the silicon quantum dot of the support of graphene obtained by the present embodiment, shows graphene branch
The component of the silicon quantum dot of support is silicon and graphited carbon；Fig. 5 is following for the silicon quantum dot of the support of graphene obtained by the present embodiment
Ring performance chart (current density 2A/g) shows that the silicon quantum dot of graphene support has extremely stable cycle performance.
Embodiment 2
(1) sodium borohydride by triphen silyl amine and predissolve in water is according to 1：1 mass ratio mixing, then
It is transferred in solvent thermal reaction kettle, after 400 DEG C of constant temperature are placed 0.5 hour, dialysis removes unreacted raw material, obtains uniform
The silicon quantum dot of 30nm；
(2) after mixing uniform silicon quantum dot with graphene oxide, the pH value of solution is adjusted to 1, after futher stirring,
Obtain the silicon quantum dot of graphene oxide support；
(3) silicon quantum dot for supporting above-mentioned graphene oxide is handled 0.5 hour under 900 DEG C, argon atmosphere, and stone is made
The silicon quantum dot of black alkene support.
Follow-up test such as embodiment 1.Under the current density of 10A/, the silicon quantum dot of the graphene support still has height
Up to the specific capacity of 655mAh/g；After recycling 300 times under the current density of 2A/g, capacity retention ratio is up to 99%.
Embodiment 3
(1) sodium sulfite by diethylenetriamine base propyl trimethoxy silicane and predissolve in water is according to 10：1 matter
Then amount is transferred in solvent thermal reaction kettle than mixing, after 120 DEG C of constant temperature are placed 12 hours, dialysis removes unreacted raw material,
Obtain the silicon quantum dot of uniform 15nm；
(2) after mixing uniform silicon quantum dot with graphene oxide, the pH value of solution is adjusted to 7, after futher stirring,
Obtain the silicon quantum dot of graphene oxide support；
(3) it is small to handle 12 under 150 DEG C, argon gas and hydrogen mixed gas atmosphere for the silicon quantum dot for supporting above-mentioned graphene oxide
When, the silicon quantum dot of graphene support is made.
Follow-up test such as embodiment 1.Under the current density of 20A/, the uniform extra small silicon quantum dot of the graphene support
Still there is the specific capacity of up to 595mAh/g；After recycling 450 times under the current density of 2A/g, capacity retention ratio is up to 99%.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of preparation method of the silicon quantum dot negative electrode material of graphene support, includes the following steps：
（1）The reducing agent of organosilicon precursor and predissolve in water is mixed in solvent thermal reaction kettle, it is permanent at 120-400 DEG C
Temperature is placed 0.5-12 hours, and the silicon quantum dot of the uniform 1-30 nm of dimensional height is obtained；The organosilicon precursor is 3- aminopropan
Ethyl triethoxy silicane alkane（APTES）, triphen silyl amine, diethylenetriamine base propyl trimethoxy silicane, 3- (2- amino
Ethylamino) one or more of propyl trimethoxy silicane mixing；The reducing agent is sodium citrate, secondary phosphorous
The mixing of one or more of sour sodium, glutathione, sodium sulfite, sodium sulfocynanate, white phosphorus, sodium borohydride, chitosan；
The mass ratio of the organosilicon precursor and reducing agent is 1:1-10:1；
（2）By graphene oxide and step（1）The silicon quantum dot of preparation is mixed at the pH of 1-7, based on electrostatic between the two
Interaction carries out non-covalent self assembly, prepares the silicon quantum dot of graphene oxide support；
（3）Using the graphene oxide of the reducing loaded silicon quantum dot of heat treating process, the silicon quantum dot cathode of graphene support is prepared
Material.
2. preparation method according to claim 1, which is characterized in that step（1）The constant temperature carries out saturating after placing
Analysis.
3. preparation method according to claim 1, which is characterized in that step（3）Described in be heat-treated under an inert atmosphere
It carries out.
4. preparation method according to claim 3, which is characterized in that the inert atmosphere is helium, neon, argon gas, krypton
The mixing of one or more of gas, xenon, radon gas or hydrogen.
5. preparation method according to claim 1, which is characterized in that the temperature of the heat treatment is 150-900 DEG C, at heat
The time of reason is 0.5-12 hours.
6. a kind of silicon quantum dot negative electrode material of graphene support, which is characterized in that described in any item by claim 1-5
Preparation method is made.
7. the purposes of the silicon quantum dot negative electrode material of the support of graphene described in claim 6 in a lithium ion secondary battery.
8. purposes according to claim 7, which is characterized in that the silicon quantum dot negative electrode material of graphene support and its
He is used in mixed way as ion secondary battery cathode material lithium negative electrode material.
9. purposes according to claim 7, which is characterized in that the silicon quantum dot negative electrode material dosage of the graphene support
Not less than the 1% of total negative electrode material.
10. purposes according to claim 8, which is characterized in that other described active cathode materials are artificial graphite, naturally
Graphite, single-walled carbon nanotube, few layer carbon nanotube, multi-walled carbon nanotube, graphene, the graphene oxide of reduction, hard carbon material,
The metal of alloying reaction can occur with lithium and its precursor, the transistion metal compound or embedding lithium type of conversion reaction can occur with lithium
The mixing of one or more of transition metal oxide.
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| CN107611394B (en) * | 2017-09-08 | 2020-04-14 | 成都硅宝科技股份有限公司 | Carbon-coated core-shell structure nano silicon/graphene composite negative electrode material and preparation method thereof |
| CN109137142A (en) * | 2018-07-26 | 2019-01-04 | 南京工业大学 | Spot film structure carbon quantum dot-graphene fiber and preparation and application |
| CN111370656B (en) * | 2018-12-26 | 2021-12-17 | 国家纳米科学中心 | Silicon-carbon composite material and preparation method and application thereof |
| CN111029586B (en) * | 2019-03-21 | 2022-03-22 | 吉林省东驰新能源科技有限公司 | High-rate lithium ion battery anode slurry |
| 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 |
| CN111678954B (en) * | 2020-06-05 | 2022-06-21 | 苏州科技大学 | Gas sensor and application of Si-RGO composite material in preparation of gas sensor |
| CN111825844B (en) * | 2020-08-03 | 2021-11-26 | 齐鲁工业大学 | Phosphorescent carbonized polymer dots with ultra-long service life, and preparation method and application thereof |
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