CN105206802A - Lithium-rich sulfonated graphene-nanometer SiOx negative electrode material and preparation method and application thereof - Google Patents
Lithium-rich sulfonated graphene-nanometer SiOx negative electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a lithium-rich sulfonated graphene-nanometer SiOx (0<=x<=1) negative electrode material. The negative electrode material is prepared from sulfonated graphene, nanometer SiOx and a lithium compound, wherein the molar ratio of silicon to sulfur is 1:1-16:1, the molar ratio of lithium to sulfur is 1:1-1:5, the grain size of nanometer SiOx is 3 nm-500 nm, the radial size of sulfonated graphene is 0.05 micrometer-100 micrometers, the thickness of sulfonated graphene is 0.5 nm-20 nm, and represented as the molar ratio of silicon to sulfur, the sulfonic group content in sulfonated graphene is 12:1-3:1. The invention further discloses a preparation method of the negative electrode material. The lithium-rich sulfonated graphene-nanometer SiOx negative electrode material has the advantages of being large in specific discharge capacity, high in initial coulomb efficiency, good in cycle performance and the like and is suitable for being widely applied to lithium ion batteries and other devices. The preparation technology is simple, easy to implement, low in cost, good in controllability and suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of negative material that can be applicable to the energy storage devices such as lithium ion battery, particularly a kind of rich lithium sulfonated graphene-nano silicon oxide negative material and preparation method thereof and application.
Background technology
Along with day by day highlighting of energy and environment problem, New Energy Industry obtains increasing attention.Lithium ion battery, because of features such as its energy density is high, good cycle, is widely used as a kind of important Novel energy storage apparatus in recent years.Such as, instead of the chemical power sources such as traditional lead-acid battery gradually at hybrid vehicle and electric automobile industry.
Lithium ion battery negative material is the important component part of battery, and its Structure and Properties directly affects capacity and the cycle performance of lithium ion battery.The lithium ion battery negative material of current commercialization is based on graphite, and due to the low wide material sources of graphite cost, be suitable for commercialization, but its capacity is lower, theoretical capacity is only 372mAh/g, and the application in the field exported needing high-energy is restricted.
Silicon based anode material is owing to having very high theoretical capacity, and intercalation potential is low, and electrochemical reversible capacity is high, and security performance is good, the advantages such as aboundresources, is the study hotspot of lithium ion battery material of new generation.But silica-base material is the same with other metal_based materials, in the deintercalation process of lithium ion, along with serious bulk effect, cause the powder of detached of active material in charge and discharge process, capacity attenuation is serious, reduces efficiency and the cycle performance of battery, and there is serious potential safety hazard.
In order to improve the power of silicium cathode, energy density and cycle performance, industry has attempted kinds of schemes.Such as, current comparatively common a kind of mode utilizes the nanometer of active material to reduce the absolute volume change in reversible process, utilizes the Composite of active material simultaneously, utilize other materials to fetter the change in volume of active material in cyclic process.
Such as, consult CN101346834A, CN102064322B, CN103050672A, CN103972484A, relate separately in the patents such as CN101924211A and utilized modification or unmodified carbon nano-tube, modification or unmodified graphene oxide etc. form with the compound such as modification or unmodified nano silicon material the technical scheme being applicable as lithium ion battery negative material, these negative materials are than traditional silicon based anode material, at power, although the aspect such as energy density and cycle performance all more or less have certain lifting, but it is still very limited that it promotes amplitude, still be difficult to the demand meeting practical application.
Summary of the invention
Main purpose of the present invention is to provide a kind of rich lithium sulfonated graphene-nano silicon oxide (SiO
x, 0≤x≤1) and negative material and preparation method thereof and application, thus overcome deficiency of the prior art.
For realizing aforementioned invention object, among an embodiment of the present invention, provide a kind of rich lithium sulfonated graphene-nano silicon oxide (SiO
x, 0≤x≤1) and negative material, it comprises sulfonated graphene, nano silicon oxide (SiO
x, 0≤x≤1) and lithium compound, and among described negative material, the mol ratio of element silicon and element sulphur is 1:1 ~ 16:1, the mol ratio of elemental lithium and element sulphur is 1:1 ~ 1:5.
Wherein, described nano silicon oxide (SiO
x, 0≤x≤1) particle diameter be 3nm ~ 500nm.
Wherein, the radial dimension of described sulfonated graphene is 0.05 μm ~ 100 μm, and thickness is 0.5nm ~ 20nm, and in described sulfonated graphene, sulfonic content is expressed as 12:1 ~ 3:1 with the mol ratio of carbon and element sulphur.
Further, described rich lithium sulfonated graphene-nano silicon oxide (SiO
x, 0≤x≤1) and negative material reacts primarily of sulfonated graphene formed with containing amino silane, siloxanes and lithium compound.
A kind of rich lithium sulfonated graphene-nano silicon oxide (SiO is provided among an embodiment of the present invention
x, 0≤x≤1) and the preparation method of negative material, comprising:
Sulfonated graphene is fully mixed with amino silane, positive esters of silicon acis in aqueous phase system, and the part sulfonic group in sulfonated graphene is reacted with containing the amino in amino silane, form Graphene-nano silicon oxide SiO
xprecursor water solution;
In an inert atmosphere to described Graphene-nano silicon oxide SiO
xadd lithium compound in precursor water solution, and at room temperature make the part sulfonic group in sulfonated graphene and lithium compound react, obtain rich lithium precursor water solution;
Remove the moisture in described rich lithium precursor water solution, and high temperature sintering in an inert atmosphere, obtain described rich lithium sulfonated graphene-nano silicon oxide negative material.
Among a comparatively preferred embodiment, described preparation method can comprise:
Sulfonated graphite aqueous solution is fully mixed with the aqueous solution containing amino silane and positive esters of silicon acis, and the part sulfonic group in sulfonated graphene is reacted with containing the amino in amino silane, form Graphene-nano silicon oxide (SiO
x, 0≤x≤1) and precursor water solution.
Wherein, the radial dimension of described sulfonated graphene is 0.05 μm ~ 100 μm, and thickness is 0.5nm ~ 20nm, and wherein sulfonic content is expressed as 12:1 ~ 3:1 with the mol ratio of carbon and element sulphur.
Among a comparatively preferred embodiment, described is 1:1 ~ 1:10 containing amino silane and the aqueous solution of positive esters of silicon acis and the mass ratio of described sulfonated graphite aqueous solution.
Comparatively preferred, the described mol ratio containing amino silane and positive esters of silicon acis is 1:1 ~ 1:30.
Comparatively preferred, the concentration of described sulfonated graphite aqueous solution is 0.1500g/L ~ 500g/L.
Comparatively preferred, described containing amino silane be selected from comprise 1 ~ 5 amino containing amino silane, such as can be selected from but be not limited to 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxy dimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxy diethoxy silane, diethylenetriamine base propyl trimethoxy silicane, diethylenetriamine base propyl-triethoxysilicane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl alkyl diethoxy silane, 3-aminopropyl alkyl one Ethoxysilane, 3-aminopropyl alkyl-dimethyl TMOS, any one or two or more combinations in 3-aminopropyl alkyl one methoxy silane.
Comparatively preferred, described positive esters of silicon acis is selected from the ester group comprising 1 ~ 6 carbon atom, described in comprise 1 ~ 6 carbon atom ester group comprise methyl silicate, tetraethoxysilane, positive silicic acid propyl ester, butyl silicate, positive silicic acid pentyl ester, any one or two or more combinations in the own ester of positive silicic acid
Comparatively preferred, aforementioned sulfonated graphene is 1h ~ 12h with the time of reacting containing amino silane.
Further, described lithium compound comprises lithia and/or lithium hydroxide, but is not limited thereto.
Comparatively preferred, the addition of described lithium compound in described precursor water solution is 0.3g/L ~ 30g/L.
Comparatively preferred, this preparation method comprises: employing heating evaporate to dryness mode removes the moisture in described rich lithium precursor water solution, and evaporate to dryness temperature is 80 DEG C ~ 250 DEG C, time is 4h ~ 24h, carry out high temperature sintering afterwards, sintering temperature is 450 DEG C ~ 1950 DEG C, and the time is 6h ~ 48h.
In the preparation process in accordance with the present invention, the water that aforementioned heating evaporation goes out reclaims by modes such as condensations and recycles, and to avoid causing environmental pollution, and realizes the efficiency utilization of resource.
The rich lithium sulfonated graphene-nano silicon oxide (SiO prepared by any one method aforementioned is additionally provided among an embodiment of the present invention
x, 0≤x≤1) and negative material.
Any one rich lithium sulfonated graphene-nano silicon oxide (SiO aforementioned is additionally provided among an embodiment of the present invention
x, 0≤x≤1) and negative material is in preparing the application in physics and/or chemical energy storage device.
Such as, among a comparatively typical application case, provide a kind of physics and/or chemical energy storage device, it comprises any one rich lithium sulfonated graphene-nano silicon oxide (SiO aforementioned
x, 0≤x≤1) and negative material.
Such as, a kind of physics and/or chemical energy storage device, its negative pole comprises any one rich lithium sulfonated graphene-nano silicon oxide (SiO aforementioned
x, 0≤x≤1) and negative material.
Further, described energy storage device comprises lithium ion battery etc., but is not limited thereto.
Compared with prior art, advantage of the present invention comprises:
(1) rich lithium sulfonated graphene-nano silicon oxide SiO of the present invention
xit is high that (0≤x≤1) negative material possesses specific discharge capacity, and coulombic efficiency is excellent first, and the advantages such as cycle performance is outstanding, are suitable for extensive use in the equipment such as lithium ion battery;
(2) preparation technology of the present invention is simple, and be easy to operation, cost is low, and controllability is good, is suitable for large-scale production.
Accompanying drawing explanation
Fig. 1 is the surface topography map (SEM observation) of the embodiment of the present invention 1 product;
Fig. 2 is the surface topography map (SEM observation) of reference examples 1 product;
Fig. 3 is the performance test figure becoming simulated battery with the embodiment of the present invention 1 assembling product;
Fig. 4 is the performance test figure becoming simulated battery with reference examples 1 assembling product.
Embodiment
One aspect of the present invention relates to a kind of rich lithium sulfonated graphene-nano silicon oxide SiO
x(0≤x≤1) negative material, it comprises sulfonated graphene, nano silicon oxide SiO
x(0≤x≤1) and lithium metal, wherein silicon sulphur is than being 1:1 ~ 16:1, and lithium sulphur is than being 1:1 ~ 1:5;
Described nano silicon oxide SiO
xthe particle diameter of (0≤x≤1) is 3-500nm;
The radial dimension of described sulfonated graphene is 0.05 ~ 100 μm, and thickness is 0.5 ~ 20nm, and wherein sulfonic content is expressed as 12:1 ~ 3:1 with carbon-sulfur ratio.
Another aspect of the present invention relates to one and prepares described rich lithium sulfonated graphene-nano silicon oxide SiO
xthe method of (0≤x≤1) negative material.
Among a comparatively typical case study on implementation, this preparation method can comprise the following steps:
(1) sulfonated graphene is dispersed in water;
(2) in sulfonated graphene solution, add the mixed aqueous solution containing amino silane and positive esters of silicon acis;
(3) fully stir, make the part sulfonic group in sulfonated graphene solution and react containing the amino of amino silane, obtaining Graphene-nano silicon oxide SiO
x(0≤x≤1) precursor water solution;
(4) in Graphene-nano silicon oxide precursor water solution, add lithium compound in an inert atmosphere, and at room temperature stir, the part sulfonic group in sulfonated graphene and lithium compound are reacted, obtains rich lithium precursor water solution;
(5) moisture of the rich lithium precursor water solution of evaporate to dryness, and high temperature sintering in an inert atmosphere, obtain rich lithium sulfonated graphene-nano silicon oxide SiO
x(0≤x≤1) negative material.
Further, in abovementioned steps 3, the reaction time is preferably 1h ~ 12h.
Further, in abovementioned steps 5, the temperature of evaporating water is preferably 80 DEG C ~ 250 DEG C, and the time is 4h ~ 24h, and the temperature of high temperature sintering is 450 DEG C ~ 1950 DEG C, and sintering time is 6h ~ 48h.
At rich lithium sulfonated graphene nano silicon oxide SiO of the present invention
xamong (0≤x≤1) negative material, sulfonated graphene is homodisperse state, and lithium compound through ionic bond uniform load on sulfonated graphene, and most nano oxidized silicon grain is evenly incorporated on sulfonated graphene through covalent bond, separately there is part nano silicon oxide Dispersed precipitate between sulfonated graphene.Among this kind of structure, nano-silicon and active lithium and sulfonated graphene are combined closely, both its conductivity can significantly be promoted, also can alleviate the destruction of the internal stress anticathode material structure even avoiding the volumetric expansion in removal lithium embedded process to produce, lithium ion battery negative material provided by the invention is made to have higher specific discharge capacity, more excellent coulombic efficiency first and better cycle performance.Experimental result shows, lithium ion battery negative material first discharge specific capacity provided by the invention is up to 2236mAh/g, and coulombic efficiency is up to 93.4% first, and after 100 circulations, capacitance loss is below 8.5%%.
Below in conjunction with some embodiments, the technical solution of the present invention is further explained illustrates, but the present invention is not limited to these embodiments.The radial dimension of the sulfonated graphene adopted in following embodiment is 0.05 ~ 100 μm, and thickness is 0.5 ~ 20nm, and wherein sulfonic content is expressed as 12:1 ~ 3:1 with carbon, sulphur mol ratio.The various approach that these sulfonated graphenes can adopt industry known obtain (such as consults CN103539105A; CN103359728A; NanoLetters, 2008,8 (6): 1679 documents such as – 1682 grade), and all kinds of testing equipments related to, all can select industry know and usual model.
Embodiment 1
A kind of rich lithium sulfonated graphene-Nano-meter SiO_2
x(x=0) preparation method of lithium ion battery negative material, it comprises:
S1: be dispersed in by sulfonated graphene in water, forms the sulfonated graphite aqueous solution that concentration is 200g/L;
S2: the aqueous solution adding 3-aminopropyl triethoxysilane and tetramethoxy-silicane in sulfonated graphene solution, the solution of this 3-aminopropyl triethoxysilane and tetramethoxy-silicane and the mass ratio of sulfonated graphite aqueous solution are the mol ratio of 1:10,3-aminopropyl triethoxysilane and tetramethoxy-silicane is 1:1;
S3: fully stir, makes the amino of the part sulfonic acid in sulfonated graphene solution and 3-aminopropyl triethoxysilane fully react 8 ~ 12h, obtains Graphene-Nano-meter SiO_2
xprecursor water solution;
S4: in an inert atmosphere to Graphene-Nano-meter SiO_2
xadd lithia in precursor water solution, and the addition of lithia in precursor water solution is 30g/L, at room temperature stirs and the part sulfonic acid in sulfonated graphene and lithia are reacted, obtain rich lithium precursor water solution;
S5: by rich lithium precursor water solution at 150 DEG C of heating 24h with evaporate to dryness moisture wherein, high temperature sintering in an inert atmosphere afterwards, sintering temperature is 1550 DEG C, and the time is 10h, obtains rich lithium sulfonated graphene-Nano-meter SiO_2
xmaterial.
Embodiment 2
A kind of rich lithium sulfonated graphene-Nano-meter SiO_2
x(x=0.3) preparation method of lithium ion battery negative material, it comprises:
S1: be dispersed in by sulfonated graphene in water, forms the sulfonated graphite aqueous solution that concentration is 140g/L;
S2: the aqueous solution adding N-(2-aminoethyl)-3-aminopropyl triethoxysilane and tetraethoxysilane in sulfonated graphene solution, this N-(2-aminoethyl)-3-aminopropyl triethoxysilane and the solution of tetraethoxysilane and the mass ratio of sulfonated graphite aqueous solution are the mol ratio of 1:7, N-(2-aminoethyl)-3-aminopropyl triethoxysilane and tetramethoxy-silicane is 1:12;
S3: fully stir, makes the amino of the part sulfonic acid in sulfonated graphene solution and N-(2-aminoethyl)-3-aminopropyl triethoxysilane fully react 1 ~ 6h, obtains Graphene-Nano-meter SiO_2
xprecursor water solution;
S4: in an inert atmosphere to Graphene-Nano-meter SiO_2
xadd lithium hydroxide in precursor water solution, and the addition of lithium hydroxide in precursor water solution is 21g/L, at room temperature stirs and the part sulfonic acid in sulfonated graphene and lithium hydroxide are reacted, obtain rich lithium precursor water solution;
S5: by rich lithium precursor water solution at 150 DEG C of heating 20 ~ 24h with evaporate to dryness moisture wherein, high temperature sintering in an inert atmosphere afterwards, sintering temperature is 1240 DEG C, and the time is 8h, obtains rich lithium sulfonated graphene-Nano-meter SiO_2
xmaterial.
Embodiment 3
A kind of rich lithium sulfonated graphene-Nano-meter SiO_2
x(x=0.6) preparation method of lithium ion battery negative material, it comprises:
S1: be dispersed in by sulfonated graphene in water, forms the sulfonated graphite aqueous solution that concentration is 60g/L;
S2: the aqueous solution adding 3-aminopropyl alkyl one methoxy silane and tetrapropoxysilane in sulfonated graphene solution, this 3-aminopropyl alkyl one methoxy silane and the solution of tetrapropoxysilane and the mass ratio of sulfonated graphite aqueous solution are the mol ratio of 1:4,3-aminopropyl alkyl one methoxy silane and tetramethoxy-silicane is 1:21;
S3: fully stir, makes the amino of the part sulfonic acid in sulfonated graphene solution and 3-aminopropyl alkyl one methoxy silane fully react 5 ~ 6h, obtains Graphene-Nano-meter SiO_2
xprecursor water solution;
S4: in an inert atmosphere to Graphene-Nano-meter SiO_2
xadd lithia in precursor water solution, and the addition of lithia in precursor water solution is 9g/L, at room temperature stirs and the part sulfonic acid in sulfonated graphene and lithia are reacted, obtain rich lithium precursor water solution;
S5: by rich lithium precursor water solution at 150 DEG C of heating 18 ~ 20h with evaporate to dryness moisture wherein, high temperature sintering in an inert atmosphere afterwards, sintering temperature is 1020 DEG C, and the time is 7h, obtains rich lithium sulfonated graphene-Nano-meter SiO_2
xmaterial.
Embodiment 4
A kind of rich lithium sulfonated graphene-Nano-meter SiO_2
x(x=1) preparation method of lithium ion battery negative material, it comprises:
S1: be dispersed in by sulfonated graphene in water, forms the sulfonated graphite aqueous solution that concentration is 2g/L;
S2: the aqueous solution adding diethylenetriamine base propyl trimethoxy silicane and four butoxy silanes in sulfonated graphene solution, the solution of diethylenetriamine base propyl trimethoxy silicane and four butoxy silanes and the mass ratio of sulfonated graphite aqueous solution are 1:1, and the mol ratio of diethylenetriamine base propyl trimethoxy silicane and four butoxy silanes is 1:30;
S3: fully stir, makes the amino of the part sulfonic acid in sulfonated graphene solution and diethylenetriamine base propyl trimethoxy silicane fully react 5 ~ 6h, obtains Graphene-Nano-meter SiO_2
xprecursor water solution;
S4: in an inert atmosphere to Graphene-Nano-meter SiO_2
xadd lithia in precursor water solution, and the addition of lithia in precursor water solution is 0.3g/L, at room temperature stirs and the part sulfonic acid in sulfonated graphene and lithia are reacted, obtain rich lithium precursor water solution;
S5: by rich lithium precursor water solution at 125 DEG C of heating 12h with evaporate to dryness wherein moisture, high temperature sintering in an inert atmosphere afterwards, sintering temperature is 740 DEG C, and the time is 6h, obtains rich lithium sulfonated graphene-Nano-meter SiO_2
xmaterial.
In previous embodiment 1-4 containing amino silane can also previously described other containing amino silane substitute.
Reference examples 1: this reference examples is substantially the same manner as Example 1, so difference substituted for sulfonated graphene with graphene oxide.
With SEM, the surface topography of embodiment 1-4 and reference examples 1 product is observed respectively, can know: embodiment 1-4 obtains among negative material, sulfonated graphene is homogeneously dispersed state, most nano silicon oxide uniform particles is combined on sulfonated graphene, separately has part nano silicon oxide Dispersed precipitate between sulfonated graphene.And functionalization graphene exists agglomeration in various degree in reference examples 1, most nano silicon oxide grain silicon Dispersed precipitate is between graphene oxide.More intuitively, refer to the surface topography map that Figure 1 shows that embodiment 1 product, Figure 2 shows that the surface topography map of reference examples 1 product.
Become simulated battery with embodiment 1-4 and reference examples 1 assembling product respectively again, and carry out constant current charge-discharge test on LAND tester, charge-discharge magnification is 0.1A/g, and charging/discharging voltage interval is 0.001-2.5V.
Wherein, the test result of first charge-discharge specific capacity, first coulombic efficiency and the cycle performance etc. of embodiment 1-4 and reference examples 1 product is listed in table 1, can know: it is high that negative material of the present invention possesses first charge-discharge specific capacity, coulombic efficiency is excellent first, the advantages such as cycle performance is outstanding.
In addition, refer to the concrete test result being respectively shown in Fig. 3-Fig. 4 and becoming simulated battery with embodiment 1 with reference examples 1 assembling product, can find, than the product of embodiment 1, the first charge-discharge specific capacity of reference examples 1 product is relatively low, and coulombic efficiency is not high first.
In addition, inventor also utilizes the corresponding raw material in the alternate embodiment 1-4 such as other listed raw material and other process conditions and process conditions to carry out similar test above, to obtain the performance of product also all ideal.
Be to be understood that; the foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification of the present invention and accompanying drawing content to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
First charge-discharge specific discharge capacity, the first coulombic efficiency of the simulated battery that table 1 embodiment 1-4 and reference examples 1 assembling product become and 100 circulate rear capacitance loss rates and coulombic efficiency test results
Claims (10)
1. rich lithium sulfonated graphene-nano silicon oxide negative material, is characterized in that described negative material comprises sulfonated graphene, nano silicon oxide SiO
xand lithium compound, and among described negative material, the mol ratio of element silicon and element sulphur is 1:1 ~ 16:1, the mol ratio of elemental lithium and element sulphur is 1:1 ~ 1:5;
Wherein, described nano silicon oxide SiO
xparticle diameter be 3nm ~ 500nm, 0≤x≤1,
The radial dimension of described sulfonated graphene is 0.05 μm ~ 100 μm, and thickness is 0.5nm ~ 20nm,
In described sulfonated graphene, sulfonic content is expressed as 12:1 ~ 3:1 with the mol ratio of carbon and element sulphur.
2. a method for making for rich lithium sulfonated graphene-nano silicon oxide negative material, is characterized in that comprising:
Sulfonated graphene is fully mixed with amino silane, positive esters of silicon acis in aqueous phase system, and the part sulfonic group in sulfonated graphene is reacted with containing the amino in amino silane, form Graphene-nano silicon oxide SiO
xprecursor water solution;
In an inert atmosphere to described Graphene-nano silicon oxide SiO
xadd lithium compound in precursor water solution, and at room temperature make the part sulfonic group in sulfonated graphene and lithium compound react, obtain rich lithium precursor water solution;
Remove the moisture in described rich lithium precursor water solution, and high temperature sintering in an inert atmosphere, obtain described rich lithium sulfonated graphene-nano silicon oxide negative material.
3. the method for making of rich lithium sulfonated graphene-nano silicon oxide negative material according to claim 2, it is characterized in that comprising: sulfonated graphite aqueous solution is fully mixed with the aqueous solution containing amino silane and positive esters of silicon acis, and the part sulfonic group in sulfonated graphene is reacted with containing the amino in amino silane, form Graphene-nano silicon oxide SiO
xprecursor water solution;
Preferably, described is 1:1 ~ 1:10 containing amino silane and the aqueous solution of positive esters of silicon acis and the mass ratio of described sulfonated graphite aqueous solution, the described mol ratio containing amino silane and positive esters of silicon acis is 1:1 ~ 1:30, and the concentration of described sulfonated graphite aqueous solution is 0.15g/L ~ 500g/L;
Preferably, the radial dimension of described sulfonated graphene is 0.05 μm ~ 100 μm, and thickness is 0.5nm ~ 20nm, and in described sulfonated graphene, sulfonic content is expressed as 12:1 ~ 3:1 with the mol ratio of carbon and element sulphur.
4. the method for making of rich lithium sulfonated graphene-nano silicon oxide negative material according to claim 2, is characterized in that described sulfonated graphene is 1h ~ 12h with the time of reacting containing amino silane.
5. the method for making of rich lithium sulfonated graphene-nano silicon oxide negative material according to Claims 2 or 3, is characterized in that:
Described containing amino silane be selected from comprise 1 ~ 5 amino containing amino silane, describedly comprise 1 ~ 5 and amino be at least selected from 3-aminopropyl triethoxysilane containing amino silane, 3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxy dimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxy diethoxy silane, diethylenetriamine base propyl trimethoxy silicane, diethylenetriamine base propyl-triethoxysilicane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl alkyl diethoxy silane, 3-aminopropyl alkyl one Ethoxysilane, 3-aminopropyl alkyl-dimethyl TMOS, more than any one in 3-aminopropyl alkyl one methoxy silane,
And/or described positive esters of silicon acis is selected from the ester group comprising 1 ~ 6 carbon atom, described in comprise 1 ~ 6 carbon atom ester group be at least selected from methyl silicate, tetraethoxysilane, positive silicic acid propyl ester, butyl silicate, positive silicic acid pentyl ester, more than any one in the own ester of positive silicic acid.
6. the method for making of rich lithium sulfonated graphene-nano silicon oxide negative material according to claim 2, is characterized in that:
Described lithium compound is at least selected from more than any one in lithia and lithium hydroxide;
Preferably, the addition of described lithium compound in described precursor water solution is 0.3g/L ~ 30g/L.
7. the method for making of rich lithium sulfonated graphene-nano silicon oxide negative material according to claim 2, it is characterized in that comprising: employing heating evaporate to dryness mode removes the moisture in described rich lithium precursor water solution, evaporate to dryness temperature is 80 DEG C ~ 250 DEG C, time is 4h ~ 24h, carry out high temperature sintering afterwards, sintering temperature is 450 DEG C ~ 1950 DEG C, and the time is 6h ~ 48h.
8. rich lithium sulfonated graphene-nano silicon oxide negative material that according to any one of claim 2-7 prepared by method.
9. rich lithium sulfonated graphene-nano silicon oxide negative material described in claim 1 or 8 is in preparing the application in physics and/or chemical energy storage device.
10. physics and/or a chemical energy storage device, it is characterized in that the rich lithium sulfonated graphene-nano silicon oxide negative material comprised described in claim 1 or 8, described energy storage device comprises lithium ion battery.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935854A (en) * | 2015-12-31 | 2017-07-07 | 中国人民解放军63971部队 | A kind of carbon material for lithium battery and preparation method thereof |
| CN107068990A (en) * | 2016-12-26 | 2017-08-18 | 苏州高通新材料科技有限公司 | Graphene composite lithium iron phosphate cathode material and preparation method and application |
| CN109802126A (en) * | 2019-03-21 | 2019-05-24 | 苏州高通新材料科技有限公司 | A kind of negative electrode material, preparation method and application |
| CN109873144A (en) * | 2019-02-26 | 2019-06-11 | 宁德新能源科技有限公司 | Negative electrode material and the electrochemical appliance for using it |
| CN114613955A (en) * | 2022-03-08 | 2022-06-10 | 惠州亿纬锂能股份有限公司 | Graphene modified silicon negative electrode material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101924211A (en) * | 2010-08-19 | 2010-12-22 | 北京科技大学 | Graphene/silicon lithium ion battery cathode material and preparation method thereof |
| WO2014027845A1 (en) * | 2012-08-16 | 2014-02-20 | 충남대학교산학협력단 | Silicon composite anode active material for lithium secondary batteries, method for preparing same, and lithium secondary batteries including same |
| CN104795535A (en) * | 2015-04-01 | 2015-07-22 | 广东烛光新能源科技有限公司 | Electrochemical energy storing component and preparation method thereof |
| CN104844794A (en) * | 2015-05-20 | 2015-08-19 | 苏州高通新材料科技有限公司 | Heat conducting nylon material based on sulfonated graphene and preparation method thereof |
-
2015
- 2015-08-24 CN CN201510523535.1A patent/CN105206802B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101924211A (en) * | 2010-08-19 | 2010-12-22 | 北京科技大学 | Graphene/silicon lithium ion battery cathode material and preparation method thereof |
| WO2014027845A1 (en) * | 2012-08-16 | 2014-02-20 | 충남대학교산학협력단 | Silicon composite anode active material for lithium secondary batteries, method for preparing same, and lithium secondary batteries including same |
| CN104795535A (en) * | 2015-04-01 | 2015-07-22 | 广东烛光新能源科技有限公司 | Electrochemical energy storing component and preparation method thereof |
| CN104844794A (en) * | 2015-05-20 | 2015-08-19 | 苏州高通新材料科技有限公司 | Heat conducting nylon material based on sulfonated graphene and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HYEONG SUB OH等: ""Hierarchical Si hydrogel architecture with conductive polyaniline channels on sulfonated-graphene for high-performance Li ion battery anodes having a robust cycle life"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935854A (en) * | 2015-12-31 | 2017-07-07 | 中国人民解放军63971部队 | A kind of carbon material for lithium battery and preparation method thereof |
| CN107068990A (en) * | 2016-12-26 | 2017-08-18 | 苏州高通新材料科技有限公司 | Graphene composite lithium iron phosphate cathode material and preparation method and application |
| CN109873144A (en) * | 2019-02-26 | 2019-06-11 | 宁德新能源科技有限公司 | Negative electrode material and the electrochemical appliance for using it |
| CN109802126A (en) * | 2019-03-21 | 2019-05-24 | 苏州高通新材料科技有限公司 | A kind of negative electrode material, preparation method and application |
| CN114613955A (en) * | 2022-03-08 | 2022-06-10 | 惠州亿纬锂能股份有限公司 | Graphene modified silicon negative electrode material and preparation method and application thereof |
| CN114613955B (en) * | 2022-03-08 | 2023-10-03 | 惠州亿纬锂能股份有限公司 | Graphene modified silicon anode material and preparation method and application thereof |
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