CN105226249A - A kind of 3 SiC 2/graphite alkene core-shell material and Synthesis and applications thereof with gap - Google Patents
A kind of 3 SiC 2/graphite alkene core-shell material and Synthesis and applications thereof with gap Download PDFInfo
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- CN105226249A CN105226249A CN201510580493.5A CN201510580493A CN105226249A CN 105226249 A CN105226249 A CN 105226249A CN 201510580493 A CN201510580493 A CN 201510580493A CN 105226249 A CN105226249 A CN 105226249A
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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Abstract
The present invention proposes a kind of 3 SiC 2/graphite alkene core-shell material with gap, and be the material of nucleocapsid structure, kernel is silicon grain, and shell is Graphene, has the gap that distance is 0.1nm ~ 10 μm between kernel and shell.The present invention also proposes the preparation method of described 3 SiC 2/graphite alkene core-shell material, and this material is as the application of lithium ion battery negative material.The silicon materials that the present invention proposes as the de-first lithium capacity of the lithium ion battery of negative active core-shell material up to 3015mAh/g; Described silicon materials possess high high rate performance as lithium ion battery prepared by negative active core-shell material, and the de-lithium capacity under 5C multiplying power is up to 2440mAh/g.The volumetric expansion that the nucleocapsid interstitial structure of silicon materials that the present invention proposes can effectively be held and alleviate in lithium ion battery charge and discharge process and contraction and because of volumetric expansion and the mechanical stress of shrinking generation, eliminate bulk effect, make prepared lithium ion battery possess outstanding cyclical stability.
Description
Technical field
The invention belongs to field of energy source materials, be specifically related to a kind ofly have electrode material of graphene coated layer and preparation method thereof.
Background technology
Graphite material is the negative material that lithium ion battery mainly uses, and its theoretical capacity is 372mAh/g, and current battery is close to the limit of its energy density.What require battery energy density along with market improves constantly, and uses high power capacity negative pole (theoretical capacity is respectively 4200mAh/g, 1600mAh/g and 994mAh/g for such as silicon, germanium and tin) material substitution graphite material to be inexorable trend.
But above-mentioned high-capacity cathode material is not also really applied in lithium ion battery owing to there is following deficiency: (1) discharge and recharge is with larger change in volume, and cause granule atomization, battery life is extremely short, cannot reach real requirement; (2) multiplying power property is inferior to graphite material; (3) electrode slice porosity is higher than graphite material electrode slice, and conventional lithium ion battery preparation technology cannot realize.
In sum, this area is in the urgent need to developing a kind of negative material with height ratio capacity and good circulation stability overcoming above-mentioned defect.
The proposition amorphous carbon such as S.-H.Ng are directly the negative pole (Angew.Chem.Int.Ed. of lithium ion battery at the nanocomposite that silicon face is coated, 45:6896 – 6899), in 20 circulations of the combination electrode that weight portion 44%Si and 56%C is formed, specific capacity is 3257 MAhs/g to the maximum, namely reaches 77% of theoretical value.Above-mentioned on silicon coated or growth amorphous carbon, the rate charge-discharge performance of material is increased.But the cycle performance caused because of change in volume in cycle charge discharge electric process for silicon materials declines, stability is not enough, still needs and wants better solution.
Summary of the invention
The present inventor, through long-term and deep research, is surprised to find that by carrying out surface multi-layer time multi-functional step-by-step processing and modification to silicon grain, can obtains a kind of silicon/Graphene nucleocapsid, and between nucleocapsid, have the negative material in gap.Particularly, the present inventor is by adopting silicon grain, formed on silicon grain surface afterwards and sacrifice template, afterwards at template surface coated graphite alkene, remove moulding plate series technique afterwards, one can be prepared there is silicon core, not containing the silica-base material in the gap of any material between Graphene shell and nucleocapsid, the lithium ion battery prepared for electrode active material with described silica-base material provides the additional volumes needed for silicon in charge and discharge process intermediate gap, Graphene shell provides when silicon change in volume the effect of clamping down on, buffer volumes changes the material stress caused, silicon structure is kept to stablize, and battery has height ratio capacity, high-rate characteristics, good cyclical stability.In addition, described silicon materials can use traditional standard cathode membrane preparation method, and diaphragm porosity is similar to traditional negative pole diaphragm hole gap rate, and preparation technology's cost is low, be beneficial to large-scale production.Based on above-mentioned discovery, inventor completes the present invention.
Particularly, the object of the present invention is to provide a kind of 3 SiC 2/graphite alkene nucleocapsid lithium ion battery negative material with gap with height ratio capacity and good circulation stability.
Second object of the present invention is the preparation method proposing described 3 SiC 2/graphite alkene core-shell material.
3rd object of the present invention proposes this 3 SiC 2/graphite alkene core-shell material application in lithium ion battery.
The technical scheme realizing above-mentioned purpose of the present invention is:
Have the 3 SiC 2/graphite alkene core-shell material in gap, be the material of nucleocapsid structure, kernel is silicon grain, and shell is Graphene, has the gap that distance is 0.1nm ~ 10 μm between kernel and shell.
Further, described silicon grain is of a size of 4nm ~ 19 μm, and Graphene has 1 ~ 100 layer, has the gap that distance is 1nm ~ 2.5 μm between kernel and shell, is preferably the gap of 1nm ~ 250nm.
Wherein, described 3 SiC 2/graphite alkene core-shell material particle size is 5nm ~ 20 μm, and the percentage by weight of described graphene layer in 3 SiC 2/graphite alkene core-shell material is 0.1% ~ 75%, is preferably 1% ~ 20%.
Preferably, the degree of crystallinity of described silicon grain is 20 ~ 100%, and more preferably degree of crystallinity is 50 ~ 99%.
Wherein, in the XRD collection of illustrative plates of described 3 SiC 2/graphite alkene core-shell material, there are at least 3 the 2 θ characteristic peaks being selected from lower group: 28.44 ± 0.2 °, 47.31 ± 0.2 °, 56.13 ± 0.2 °, 69.14 ± 0.2 °, 76.38 ± 0.2 °, 88.04 ± 0.2 °.
The thickness of described graphene layer can, within the scope of 0.3 ~ 30nm, be preferably 0.3nm ~ 10nm.
Further, described Graphene has 2 ~ 15 layers, and the thickness of described graphene layer is 0.6 ~ 5nm.
The 3 SiC 2/graphite alkene core-shell material that the present invention proposes, its BET specific surface area is 1 ~ 500m
2/ g is preferably 10 ~ 200m
2/ g is more preferably 50 ~ 200m
2/ g.
Graphene shell diameter in described nucleocapsid structure is 10nm ~ 10 μm, is preferably 20nm ~ 5 μm, is more preferably 20nm ~ 500nm.In described graphene layer, the Graphene of individual layer forms complete spherical shell shape or forming section spherical shell shape.The volume in the space between described silicon core and Graphene shell is 1nm
3~ 4000 μm
3, be preferably 10nm
3~ 400 μm
3, be more preferably 20nm
3~ 1 μm
3.
The preparation method of the 3 SiC 2/graphite alkene core-shell material that the present invention proposes, comprises step:
1) silicon grain having and sacrifice template is provided: described sacrifice template is the Si/O composite layer that silicon grain outer surface exists naturally, or for silicon grain is by the coated sacrifice layer of oxidizing thermal treatment, or for silicon grain is by the coated sacrifice layer of sol-gal process, or pass through the coated sacrifice layer of chemical vapour deposition (CVD) for silicon grain;
2) at sacrifice template Surface coating Graphene: coated method is chemical vapour deposition (CVD) or wet chemistry method;
3) sacrifice template is removed with etchant solution: described etchant solution is selected from hydrofluoric acid, water, NaOH, potassium hydroxide, ethanol, H
2sO
4, HCl, HNO
3in one or more, removing template required time is 5 minutes to 10 hours.
The present invention also provides the concrete preparation method of sacrifice layer as follows:
Wherein, described step 1) in, the condition of oxidizing thermal treatment is: furnace atmosphere is air, oxygen, carbon dioxide or its combination, and heat treatment temperature is 500 ~ 1000 DEG C, heat treatment time is 1min ~ 48h, and the programming rate rising to described heat treatment temperature from room temperature is 5 ~ 80 DEG C/min; After heat treatment, naturally cool with furnace temperature or control rate of temperature fall 0.2 ~ 20 DEG C/min and be down to normal temperature.
Described heat treatment can be carried out in Muffle furnace, also can carry out in tube furnace.In heat treatment process, atmosphere pressures is 0.1 ~ 100psi, is preferably 1 ~ 50psi, is more preferably 5 ~ 20psi.In another preference, in described heat treatment process, atmosphere flow is 1 ~ 200sccm, is preferably 5 ~ 100sccm, is more preferably 20 ~ 80sccm.
The condition of described sol-gal process is: presoma be selected from methyl silicate, tetraethoxysilane, positive silicic acid propyl ester, butyl silicate, aluminic acid trimethyl, aluminic acid three isopropyl ester, aluminic acid three benzyl ester, tetraisopropyl titanate, butyl titanate, trimethylborate, triethyl borate, triisopropyl borate ester one or more, solvent be selected from water, ethanol, ammoniacal liquor one or more.
The pulp furnish of sol-gal process can be: the silicon grain of 1 gram is dispersed in mixed solution, and mixed solution is by 400 ~ 600mlH
2o and 3 ~ 4ml1 ~ 2MNaOH, 0 ~ 2 gram of surfactant composition, then add 4 ~ 8ml presoma in whipping process.
In sol-gel deposition process, pH value is preferably 3 ~ 10, is more preferably 5 ~ 9.PH value is regulated by lower group of chemicals: NaOH, potassium hydroxide, hydrochloric acid, nitric acid, aluminic acid, ammoniacal liquor or its combination.
In sol-gal process, surfactant can add or not add.Surfactant can be selected from softex kw, non-ionic surface active agent P123, F127, polyethylene glycol oxide ~ PPOX ~ polyethylene oxide block copolymer one or more, the described sol-gel deposition reaction time is 30 minutes ~ 24 hours, and reaction temperature is 20 ~ 80 DEG C.
In described chemical vapor deposition processes, presoma be selected from trimethyl aluminium, three (dimethylamino) silane, methyl silicate, silicon tetrachloride, four (diethyl) titanium, four (dimethylamino) titanium, titanium tetrachloride, isopropyl titanate, diethyl zinc, zirconium (IV) tert-butyl alcohol, four (dimethylamino) zirconium, water one or more, reaction pressure in vapor deposition processes is atmosphere pressures, described atmosphere pressures is 1mpsi ~ 100psi, being preferably 1mpsi ~ 10psi, is more preferably 1mpsi ~ 1psi.Vapor deposition times is 1 ~ 60 second at every turn, and circulation carries out 10 ~ 100 times.
Wherein, in described chemical vapor deposition processes, temperature is 100 ~ 500 DEG C.
The present invention also provides the concrete grammar of coated Graphene as follows:
Described step 2) in, the method for chemical vapour deposition (CVD) coated graphite alkene is: atmosphere be selected from methane, ethene, acetylene, hydrogen, argon gas, nitrogen, carbon dioxide one or more, chemical vapour deposition (CVD) temperature is 800 ~ 1000 DEG C.In described chemical vapor deposition processes, be first warming up to predetermined heat treatment temperature, wherein heating rate is 1 ~ 100 DEG C/min, is preferably 5 ~ 80 DEG C/min, is more preferably 10 ~ 70 DEG C/min.After reaching chemical vapour deposition (CVD) temperature, sedimentation time is 1 minute to 1 hour, is more preferably 1 minute to 30 minutes.Atmosphere pressures is 1 ~ 50psi, and be preferably 5 ~ 20psi, atmosphere flow is 5 ~ 100sccm, is preferably 20 ~ 80sccm.Described chemical vapor deposition processes can carry out in tube furnace.
Described step 2) in, the method for wet chemistry method coated graphite alkene is: reactant is selected from H
2sO
4, graphite, KMnO
4, H
2o
2, HCl, water, poly-[(phenylacetylene)-co-(2,5-bis-octyloxy is to phenylacetylene)], one or more in ethylene glycol monoemethyl ether.In described wet-chemical process, temperature is 0 ~ 100 DEG C, is preferably 0 ~ 50 DEG C, is more preferably 0 ~ 35 DEG C.
Further, in described wet-chemical process, use ultrasonic disperse.
In described wet-chemical process, silicon grain can be placed in water, then graphite and potassium permanganate is added, silicon grain, graphite and potassium permanganate weight portion are 1:0.1 ~ 0.3:0.5 ~ 1.0, reaction time is 1 minute to 5 hours, be preferably 10 minutes to 2 hours, be more preferably 10 minutes to 1 hour, potassium permanganate preferably divides and adds for two to five times; Then the ratio adding 5ml according to 1g silicon grain adds the H of 30 ~ 35%
2o
2, continue reaction 10 ~ 20 minutes.
Described step 3) in, removing template required time can 1 minute to 24 hours, and be more effectively 5 minutes to 10 hours, be more preferably 5 minutes to 1 hour, the temperature removing template is 0 ~ 100 DEG C, and being preferably 0 ~ 50 DEG C, is more preferably 0 ~ 35 DEG C.The solution removing template can be specifically HF:H
2o volume ratio is the solution of 1:2 ~ 20, or the sodium hydroxide solution of 1 ~ 5M, or the salpeter solution of mass fraction 1 ~ 20%.
The lithium ion battery that the 3 SiC 2/graphite alkene core-shell material proposed with the present invention is negative material.
Particularly, described negative material also comprises conductive agent and/or binding agent.Described conductive agent includes but not limited to: carbon nano-tube, carbon nanocoils, Nano carbon balls, Graphene, acetylene black, SuperP-Li, carbon fiber, coke, graphite, carbonaceous mesophase spherules, hard carbon or its combination.Described bonding agent includes but not limited to: Kynoar (PVDF), polypropylene lithium (Li-PAA), butadiene-styrene rubber (SBR), sodium carboxymethylcellulose (CMC) or its combination.
Particularly, in described negative material, with the total weight of negative material, the content of the 3 SiC 2/graphite alkene core-shell material that the present invention proposes is 10 ~ 99wt%, and the content of conductive agent is 0.1 ~ 80wt%, and the content of binding agent is 0.1 ~ 20wt%.
In an optimal technical scheme, in described negative material, the mass ratio of described silicon materials, conductive agent, bonding agent three is (80 ± 10): (10 ± 2): (10 ± 2).
Lithium ion battery comprises positive pole, negative pole, barrier film, electrolyte and shell.Described shell is metal material, composite material or its combination.Barrier film is ceramic porous membrane, prepared by synthetic resin perforated membrane, fibreglass diaphragm.Positive electrode comprises one or more reactive metal oxides as positive electrode active materials, wherein, also comprise inactive metal element in described reactive metal oxides, wherein said inactive metal element includes, but are not limited to: manganese, iron, cobalt, vanadium, nickel, chromium or its combination.Described positive electrode active materials includes but not limited to: the metal oxide of inactive metal, metal sulfide, transition metal oxide, transient metal sulfide or its combination.
Such as, described positive electrode active materials is be selected from the component of lower group:
LiMnO
2, LiMn
2o
4, LiCoO
2, Li
2crO
7, LiNiO
2, LiFeO
2, LiNixCo
1-xo
2(0<x<1), LiFePO
4, LiMn
zni
1-zo
2(0<z<1; As LiMn
0.5ni
0.5o
2), LiMn0
.33co
0.33ni
0.33o
2, LiMc
0.5mn
1.5o
4(wherein Mc is divalent metal), LiNi
xco
yme
zo
2(wherein Me represents one in Al, Mg, Ti, B, Ga, Si or several element, x>0; Y<1, z<1), transition metal oxide, transient metal sulfide or its combination.
Described electrolyte comprises one or more electrolytic salts; And described electrolyte comprises one or more organic solvents.Described electrolytic salt is lithium salts.Described organic solvent comprises the cyclic carbonate derivative that at least one is replaced by a kind of or multiple halogen atom; Preferably, described organic solvent is fluoro-1, the 3-dioxane penta-2-ketone of 4-.
The test condition of cycle performance of battery test is:
Specific capacity is pressed 4200mAh/g and is calculated, with C/n, charge-discharge magnification represents that (namely by theoretical calculation of capacity, discharge and recharge respectively needs n hour.Such as: C/5 means 5 hours), charging/discharging voltage scope is 0.05V ~ 0.8V.
Compared with prior art, the present invention has following major advantage:
(1) the de-first lithium capacity of the lithium ion battery that the 3 SiC 2/graphite alkene core-shell material using the present invention to propose is prepared as negative active core-shell material is up to 3015mAh/g;
(2) use 3 SiC 2/graphite alkene core-shell material proposed by the invention to possess high high rate performance as lithium ion battery prepared by negative active core-shell material, under 5C multiplying power de-lithium capacity up to 2440mAh/g;
(3) use material proposed by the invention to have excellent cyclical stability as lithium ion battery prepared by negative active core-shell material, its specific capacity that to circulate under C/5 multiplying power after 300 times is still up to 2145mAh/g, and its coulombic efficiency remains on about 100%;
(4) with the lithium ion battery of material of the present invention assembling after 300 charge and discharge cycles, the structure of described silicon materials is substantially constant;
(5) volumetric expansion that the nucleocapsid interstitial structure of material that the present invention proposes can effectively be held and alleviate in lithium ion battery charge and discharge process and contraction and because of volumetric expansion and the mechanical stress of shrinking generation, eliminate bulk effect, make prepared lithium ion battery possess outstanding cyclical stability;
(6) the Graphene shell of the 3 SiC 2/graphite alkene core-shell material of the present invention's proposition has excellent conductive structure, is beneficial to high power charging-discharging;
(7) use material of the present invention close with traditional negative pole material hole gap rate, existing lithium ion battery preparation technology can be used;
(8) preparation method's process costs of material of proposing of the present invention low, be beneficial to large-scale production.
Accompanying drawing explanation
Fig. 1 is preparation technology's flow chart of silicon materials of the present invention.
Fig. 2 is the XRD collection of illustrative plates of the silicon materials 1 of embodiment 1.
Fig. 3 is the SEM figure of the silicon materials 1 of embodiment 1.
Fig. 4 is the TEM figure of the silicon materials 1 of embodiment 1.
Fig. 5 is the TEM figure of the silicon materials C1 of comparative example 1.
Fig. 6 is the SEM figure of the silicon materials C2 of embodiment 2.
Fig. 7 is the SEM figure of the silicon materials C3 of embodiment 3.
Fig. 8 is the TEM figure that the silicon materials 2 of embodiment 4 sacrifice template.
Fig. 9 is the TEM figure of the silicon materials C4 sacrifice template of embodiment 5.
Figure 10 is the TEM figure of the silicon materials C5 of comparative example 2.
Figure 11 is the TEM figure that the silicon materials 3 of embodiment 6 sacrifice template.
Figure 12 is the SEM figure of the silicon materials 3 of embodiment 6.
Figure 13 is the TEM figure that the silicon materials C6 of comparative example 3 removes before template.
Figure 14 is the change of silicon specific capacity with cycle-index of the lithium battery 1 of embodiment 7.
Figure 15 is that the silicon specific capacity of the lithium battery 1 of embodiment 7 is with the change under charge/discharge different multiplying.
Figure 16 is the change of silicon specific capacity with cycle-index of the lithium battery C1 of comparative example 4.
Figure 17 is the change of silicon specific capacity with cycle-index of the lithium battery C2 of embodiment 8.
Figure 18 is the change of silicon specific capacity with cycle-index of the lithium battery C3 of embodiment 9.
Figure 19 is that the silicon specific capacity of the lithium battery 2 of embodiment 10 is with the change under charge/discharge different multiplying.
Figure 20 is that the silicon specific capacity of the lithium battery C4 of embodiment 11 is with the change under charge/discharge different multiplying.
Figure 21 is that the silicon specific capacity of the lithium battery C5 of comparative example 5 is with the change under charge/discharge different multiplying.
Figure 22 is the change of silicon specific capacity with cycle-index of the lithium battery 3 of embodiment 12.
Figure 23 is the change of silicon specific capacity with cycle-index of the lithium battery C6 of comparative example 6.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, the usually conveniently conditioned disjunction condition of advising according to manufacturer.Unless otherwise indicated, otherwise percentage and number calculate by weight.
Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the meaning be familiar with identical.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Embodiment 1:
Prepare 3 SiC 2/graphite alkene core-shell material, flow process is as Fig. 1.
Be positioned in Muffle furnace by the silicon grain raw material of 1 gram of about 100 nanometer, atmosphere is air, and pressure is 15psi, and flow is 70sccm.Programming rate is 20 degrees/min, and holding temperature is 950 degree, and temperature retention time is 1 minute, and insulation terminates rear naturally cooling, in silicon grain surface formation sacrifice template.
Be positioned in tube furnace by the silicon grain of sacrificing template that has of gained, intensification atmosphere is argon gas, and pressure is 12.5psi, flow is 50sccm, and programming rate is 100 degrees/min, and holding temperature is 900 degree, temperature retention time is 5 minutes, and insulation atmosphere is methane, and pressure is 12.5psi, flow is 100sccm, then with stove cooling, cooling atmosphere is argon gas, and pressure is 12.5psi, flow is 50sccm, at template surface coated graphite alkene.
The sample of coated graphite alkene is placed in the hydrofluoric acid solution (HF:H of 1:10
2o), keep 10 minutes, temperature is room temperature, removes template.Through filtering, washing and drying, obtain 3 SiC 2/graphite alkene core-shell material, be designated as silicon materials 1.
Comparative example 1
Prepare silicon materials C1
With embodiment 1, difference is: at silicon grain outer cladding carbon, and coated process is that (water of 2:1: alcohol) is undertaken by reactor reaction in glucose solution.Reaction temperature is 190 DEG C.Reaction time is 15 hours.Sacrifice the preparation of template and remove with embodiment 1.
Embodiment 2
Prepare silicon materials C2
With embodiment 1, difference is: forming the holding temperature of sacrificing template is 1100 DEG C.
Embodiment 3
Prepare silicon materials C3
With embodiment 1, difference is: silicon grain raw material particle size is 40nm.
The tests such as XRD, thermal weight loss, SEM and TEM are carried out to embodiment 1-3, comparative example 1 resulting materials.
Fig. 2 is the XRD collection of illustrative plates of silicon materials 1.As can be seen from Figure 2: silicon materials 1 have very high degree of crystallinity, be 95%, main peak value, in 28.44 ° (111 faces), 47.31 ° (220 face), 56.13 ° (311 face), 69.14 ° (400 face), 76.38 ° (331 face), 88.04 ° (422 face), does not have other impurity peaks to occur substantially.The preparation technology of known silicon materials 1 does not change the crystal structure of silicon grain raw material.
Fig. 3 is the SEM figure of silicon materials 1.Can find out, silicon materials have the silicon core that diameter is 100nm.Outside silicon core, there is Graphene shell, diameter is 140nm.Gap is there is, not containing any material in gap between nucleocapsid.Between nucleocapsid, the distance in gap is about 20 nanometers.The volume ratio of space and silicon core is 1.9:1.Graphene shell is rigidity, is not collapsed upon silicon core surface.Be conducive to stablizing its structure when silicon discharge and recharge change in volume.
Fig. 4 is the TEM figure of silicon materials 1.The layer structure of Graphene in display Graphene shell, as shown by arrows.The Graphene number of plies is about 10, and thickness is about 3.4nm.Interlamellar spacing is 0.34nm, coincide with the spacing in Graphene (002) face.
In thermal weight loss test display silicon materials 1, the content of Graphene is 13%.
Fig. 5 is the TEM figure of the silicon materials C1 of comparative example 1.Can find out that not there is in shell the layer structure of Graphene.Shell is amorphous carbon layer.Thickness is about 10nm, as shown by arrows in FIG..So the shell formed by reactor reaction by glucose solution (water of 2:1: alcohol) is amorphous carbon, cannot form Graphene shell.
Fig. 6 is the SEM figure of the silicon materials C2 of embodiment 2.This material can be found out also for having the nucleocapsid structure in space.Between nucleocapsid, the average distance in space is 60 nanometers.1100 DEG C of sacrificial mold plate thickness formed are used to be greater than the sacrifice template of use 950 DEG C formation.High temperature improves the oxidation rate of silicon grain.Silicon core, the size in Graphene shell and gap and volume ratio can be controlled by the method.
Fig. 7 is the SEM figure of the silicon materials C3 of embodiment 3.This material can be found out also for having the nucleocapsid structure in space.Silicon nuclear diameter is about 40nm, and Graphene shell diameter is about 40nm, and between nucleocapsid, the average distance in space is 20 nanometers.The average distance in space is that the silicon materials 1 of embodiment 1 are similar.The temperature of identical formation sacrifice template can form the sacrifice template of comparable thickness on the silicon grain of different size.
Embodiment 4 prepares silicon materials 2
By silicon grain stock dispersion (480mlH in mixed solution of 1 gram of about 100 nanometer
2o adds 3.5ml2MNaOH), add 1g surfactant softex kw.In whipping process, 5ml tetraethoxysilane dropwise adds.Reaction temperature is in room temperature.Stirring after 6 hours, collecting product, cleaning-drying by stirring, formed on silicon grain surface and sacrifice template.
By vapour deposition at template surface coated graphite alkene.Be positioned in tube furnace by the silicon grain of sacrificing template that has of gained, atmosphere is argon gas, and pressure is 12.5psi, flow is 50sccm, and programming rate is 100 degrees/min, and holding temperature is 950 degree, temperature retention time is 5 minutes, and insulation atmosphere is methane, and pressure is 12.5psi, flow is 100sccm, then with stove cooling, cooling atmosphere is argon gas, and pressure is 12.5psi, flow is 50sccm, at template surface coated graphite alkene.
The sample of coated graphite alkene is placed in 2MNaOH solution (1:10HF:H
2o), keep 30 minutes, temperature is room temperature, removes template.Through filtering, washing and drying, obtain 3 SiC 2/graphite alkene core-shell material, be designated as silicon materials 2.
Embodiment 5 prepares silicon materials C4
With embodiment 4, difference is: utilize the natural oxide surface of silicon grain raw material as sacrifice template, skip over teos hydrolysis and produce the step of sacrificing template.
Comparative example 2 prepares silicon materials C5
With embodiment 4, difference is: omit to produce and sacrifice template step, at silicon grain (not containing the oxide surface of self-assembling formation) surperficial Direct precipitation Graphene (technique is with embodiment 4).Omit and remove template step.
The test such as thermal weight loss, SEM and TEM is carried out to embodiment 4,5 and comparative example 2 resulting materials.
Fig. 8 is the TEM figure that silicon materials 2 sacrifice template.Can find out, sacrifice template and be about 20nm at the thickness on surface, sacrifice the surface that template covers silicon grain, as shown by arrows in FIG..The diameter of silicon grain is about 100nm.The template formed by teos hydrolysis can be evenly complete the surface covering silicon grain.
In thermal weight loss test display silicon materials 2, the content of Graphene is 8.5%.The degree of crystallinity of silicon materials 2 is 99%.
Fig. 9 is the TEM figure of the silicon materials C4 sacrifice template of embodiment 5.Can find out, sacrifice template and be about 3nm at the thickness on surface, sacrifice the surface that template covers silicon grain, as shown by arrows in FIG..The surface oxide layer of the self-assembling formation of silicon grain raw material own can as the sacrifice template obtaining silicon materials C4.
Figure 10 is the TEM figure of the silicon materials C5 of comparative example 2.Can find out, Graphene directly overlays the surface of silicon grain.The Graphene number of plies is about 15 layers, and thickness is about 5nm.Be directly crystalline silicon below Graphene shell, lattice is mutually high-visible.
Embodiment 6 prepares silicon materials 3
The silicon grain raw material of 1 gram of about 40 nanometer is loaded sample room.Sacrifice the technique of formation by vapour deposition of template.Reaction temperature is 200 degree.Each deposition process comprises the steps: 1) sample room is vacuumized; 2) introduce steam, continue 20 seconds, atmosphere pressures is 500mpsi; 3). sample room is vacuumized; 4) introduce trimethyl aluminium, continue 20 seconds, atmosphere pressures is 1psi.Carry out 50 circulations altogether.Formed on silicon grain surface and sacrifice template.
The silicon grain of sacrificing template that has of gained is dispersed in water, adds 0.2g graphite simultaneously.Then, 0.3gKMnO
4slowly join in suspension.Temperature remains on less than 10 DEG C.Reaction time is 30 minutes.Afterwards, 0.6gKMnO
4slowly join in suspension, temperature remains on less than 30 DEG C.Reaction time is 30 minutes.Then, the H of 5ml30%
2o
2slowly join in reactant liquor.Reaction time is 10 minutes.Product is by centrifugal, washing, dry acquisition.Obtain at template surface coated graphite alkene.
The sample of coated graphite alkene is placed in 1%HNO
3in solution, keep 20 minutes, temperature is room temperature, removes template.Through filtering, washing and drying, obtain 3 SiC 2/graphite alkene core-shell material, be designated as silicon materials 3.
Comparative example 3
Prepare silicon materials C6
With embodiment 6, difference is: carry out coated by chemical vapour deposition (CVD) at template surface.Be positioned in tube furnace by the silicon grain of sacrificing template that has of gained, atmosphere is argon gas, and pressure is 7psi, flow is 50sccm, and programming rate is 100 degrees/min, and holding temperature is 700 degree, temperature retention time is 15 minutes, and insulation atmosphere is acetylene, and pressure is 7psi, flow is 100sccm, then with stove cooling, cooling atmosphere is argon gas, and pressure is 7psi, flow is 20sccm, at the coated amorphous carbon of template surface.
The test such as thermal weight loss, SEM and TEM is carried out to embodiment 6, comparative example 3 resulting materials.
Figure 11 is the TEM figure that silicon materials 3 sacrifice template.Can find out, sacrifice template and be about 5nm at the thickness on surface, sacrifice the surface that template covers silicon grain.The diameter of silicon grain is about 40nm.The template formed by vapour deposition can be evenly complete the surface covering silicon grain.
Figure 12 is the SEM figure of silicon materials 3.Can find out, silicon materials have the silicon core that diameter is 40nm.Outside silicon core, there is Graphene shell, diameter is about 50nm.Gap is there is between nucleocapsid.Between nucleocapsid, the distance in gap is about 5 nanometers.Graphene shell is rigidity, is not collapsed upon silicon core surface.Be conducive to stablizing its structure when silicon discharge and recharge change in volume.
In thermal weight loss test display silicon materials 3, the content of Graphene is 9.5%.
Figure 13 is the TEM figure that the obtained silicon materials C6 of comparative example 3 removes before template.Display is sacrificed template surface and be there is one deck carbon-coating.Carbon-coating is amorphous carbon, there is not layer structure.Thickness is about 3nm, as shown by arrows in FIG..
Embodiment 7 prepares lithium ion battery 1
Silicon materials 1 prepared by embodiment 1, conductive carbon (Super-P) and Lithium polyacrylate (Li-PAA) are blended in water according to the mass ratio of 80:10:10, stir, obtaining electrode slurry, is to electrode with lithium sheet, and assembling obtains lithium ion battery 1.
Comparative example 4 prepares lithium ion battery C1
With embodiment 7, difference is: with the silicon materials C1 in comparative example 1 for electrode active material.
Embodiment 8 prepares lithium ion battery C2
With embodiment 7, difference is: with silicon materials C2 in embodiment 2 for electrode active material.
Embodiment 9 prepares lithium ion battery C3
With embodiment 7, difference is: with silicon materials C3 in embodiment 3 for electrode active material.
Charge-discharge performance test is carried out to embodiment 7 ~ 9, comparative example 4 gained lithium battery.
Figure 14 is the change of silicon specific capacity with cycle-index of the lithium battery 1 of embodiment 7.The speed that first time circulates is C/20.Specific capacity is 3015mAh/g.The speed of following cycle is C/5.Specific capacity rises to 2972mAh/g from 2616mAh/g, then reduces gradually.The specific capacity of the 300th circulation is 2147mAh/g, is 82% of first time C/5 circulation.Lithium battery 1 demonstrates good cyclical stability.
Figure 15 is that the silicon specific capacity of the lithium battery 1 of embodiment 7 is with the change under charge/discharge different multiplying.Specific capacity under C/10, C/5, C/2,1C, 2C and 5C multiplying power is respectively 3081mAh/g, 3115mAh/g, 3050mAh/g, 3057mAh/g, 2986mAh/g and 2440mAh/g.Lithium battery 1 demonstrates good high rate performance.
Figure 16 is the change of silicon specific capacity with cycle-index of the lithium battery C1 of comparative example 4.The speed that first time circulates is C/20.Specific capacity is 2603mAh/g.The speed of following cycle is C/5.Specific capacity reduces gradually from 2581mAh/g.The specific capacity of the 120th circulation is 1882mAh/g, is 73% of first time C/5 circulation.Adopt the amorphous carbon shell of breakdown of glucose formation compared to Graphene shell, the capacity of silicon materials and cyclical stability reduce.
Figure 17 is the change of silicon specific capacity with cycle-index of the lithium battery C2 of embodiment 8.The speed that first time circulates is C/20.Specific capacity is 2696mAh/g.The speed of following cycle is C/5.Specific capacity rises to 2519mAh/g from 2451mAh/g, then reduces gradually.The specific capacity of the 100th circulation is 2128mAh/g, is 87% of first time C/5 circulation.Cyclical stability is better than the lithium battery C1 of breakdown of glucose method.
Figure 18 is the change of silicon specific capacity with cycle-index of the lithium battery C3 of embodiment 9.The speed that first time circulates is C/20.Specific capacity is 2917mAh/g.The speed of following cycle is C/5.Specific capacity rises to 2743mAh/g from 2640mAh/g, then reduces gradually.The specific capacity of the 300th circulation is 1612mAh/g, is 61% of first time C/5 circulation.
Embodiment 10 prepares lithium ion battery 2
Silicon materials 2 prepared by embodiment 4, conductive carbon (Super-P) and Lithium polyacrylate (Li-PAA) are blended in water according to the mass ratio of 85:7:8, stir, obtaining electrode slurry, is to electrode with lithium sheet, and assembling obtains lithium ion battery 2.
Embodiment 11 prepares lithium ion battery C4
With embodiment 10, difference is: with silicon materials C4 for electrode active material.
Comparative example 5 prepares lithium ion battery C5
With embodiment 10, difference is: with silicon materials C5 for electrode active material.
Under different multiplying, charge/discharge performance test is carried out to the lithium battery of embodiment 10,11 and comparative example 5.
Figure 19 is that the silicon specific capacity of the lithium battery 2 of embodiment 10 is with the change under charge/discharge different multiplying.Specific capacity under C/10, C/5, C/2,1C, 2C and 5C multiplying power is respectively 3200mAh/g, 3184mAh/g, 3150mAh/g, 3085mAh/g, 2956mAh/g and 2409mAh/g.Lithium battery 2 demonstrates good high rate performance.
Figure 20 is that the silicon specific capacity of the lithium battery C4 of embodiment 11 is with the change under charge/discharge different multiplying.Specific capacity under C/10, C/5, C/2,1C, 2C and 5C multiplying power is respectively 3076mAh/g, 3042mAh/g, 2961mAh/g, 2784mAh/g, 2404mAh/g and 1192mAh/g.Lithium battery C4 demonstrates good high rate performance, but the high rate performance of contrast lithium battery 2 declines to some extent.Illustrate that the thickness of sacrificing template has impact to high rate performance.
Figure 21 is that the silicon specific capacity of the lithium battery C5 of comparative example 5 is with the change under charge/discharge different multiplying.Specific capacity under C/10, C/5, C/2,1C, 2C and 5C multiplying power is respectively 2615mAh/g, 2632mAh/g, 2589mAh/g, 2518mAh/g, 2271mAh/g and 964mAh/g.Specific capacity and the high rate performance of lithium battery C5 contrast lithium battery 2 decline to some extent.Illustrate that the specific capacity of the silicon-carbon nucleocapsid negative pole without gap and high rate performance are not as having the silicon-carbon nucleocapsid negative pole in gap.
Embodiment 12 prepares lithium ion battery 3
Silicon materials 3 prepared by embodiment 7, conductive carbon (Super-P) and Lithium polyacrylate (Li-PAA) are blended in water according to the mass ratio of 75:13:12, stir, obtaining electrode slurry, is to electrode with lithium sheet, and assembling obtains lithium ion battery 3.
Comparative example 6 prepares lithium ion battery C6
With embodiment 12, difference is: with silicon materials C6 for electrode active material.
Under different multiplying, charge/discharge performance test is carried out to the lithium battery of embodiment 12 and comparative example 6.
Figure 22 is the change of silicon specific capacity with cycle-index of the lithium battery 3 of embodiment 12.The speed that first time circulates is C/20.Specific capacity is 3180mAh/g.The speed of following cycle is C/5.Specific capacity reduces gradually from 2746mAh/g.The specific capacity of the 240th circulation is 2103mAh/g, is 75% of first time C/5 circulation.Lithium battery 3 demonstrates good cyclical stability.
Figure 23 is the change of silicon specific capacity with cycle-index of the lithium battery C6 of comparative example 6.The speed that first time circulates is C/20.Specific capacity is 1676mAh/g.The speed of following cycle is C/5.Specific capacity rises to 1589mAh/g from 1470mAh/g, then reduces gradually.The specific capacity of the 240th circulation is 1162mAh/g, is 79% of first time C/5 circulation.The capacity of lithium battery C6, lower than lithium battery 3, illustrates that the capacity of the amorphous carbon layer formed by acetylene cracking is lower than the silicon-based anode of Graphene as carbon-coating.
Above embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various modification that the common engineers and technicians in this area make technical scheme of the present invention and improvement, all should fall in protection range that claims of the present invention determine.
Claims (10)
1. have the 3 SiC 2/graphite alkene core-shell material in gap, it is characterized in that, be the material of nucleocapsid structure, kernel is silicon grain, and shell is Graphene, has the gap that distance is 0.1nm ~ 10 μm between kernel and shell.
2. 3 SiC 2/graphite alkene core-shell material according to claim 1, it is characterized in that, described silicon grain is of a size of 4nm ~ 19 μm, and Graphene has 1 ~ 100 layer, there is the gap that distance is 1nm ~ 2.5 μm between kernel and shell, be preferably the gap of 1nm ~ 250nm.
3. 3 SiC 2/graphite alkene core-shell material according to claim 1 and 2, it is characterized in that, described 3 SiC 2/graphite alkene core-shell material particle size is 5nm ~ 20 μm, and the percentage by weight of described graphene layer in 3 SiC 2/graphite alkene core-shell material is 0.1% ~ 75%, is preferably 1% ~ 20%.
4. 3 SiC 2/graphite alkene core-shell material according to claim 1 and 2, is characterized in that, the degree of crystallinity of described silicon grain is 20 ~ 100%, and preferred degree of crystallinity is 50 ~ 99%.
5. 3 SiC 2/graphite alkene core-shell material according to claim 1 and 2, it is characterized in that there are at least 3 the 2 θ characteristic peaks being selected from lower group: 28.44 ± 0.2 °, 47.31 ± 0.2 °, 56.13 ± 0.2 °, 69.14 ± 0.2 °, 76.38 ± 0.2 °, 88.04 ± 0.2 ° in the XRD collection of illustrative plates of described 3 SiC 2/graphite alkene core-shell material.
6. 3 SiC 2/graphite alkene core-shell material according to claim 1 and 2, it is characterized in that, described Graphene has 2 ~ 15 layers, and the thickness of described graphene layer is 0.6 ~ 5nm.
7. the preparation method of the arbitrary described 3 SiC 2/graphite alkene core-shell material of claim 1 ~ 6, is characterized in that, comprise step:
1) silicon grain having and sacrifice template is provided: described sacrifice template is the Si/O composite layer that silicon grain outer surface exists naturally, or for silicon grain is by the coated sacrifice layer of oxidizing thermal treatment, or for silicon grain is by the coated sacrifice layer of sol-gal process, or pass through the coated sacrifice layer of chemical vapour deposition (CVD) for silicon grain;
2) at sacrifice template Surface coating Graphene: coated method is chemical vapour deposition (CVD) or wet chemistry method;
3) sacrifice template is removed with etchant solution: described etchant solution is selected from hydrofluoric acid, water, NaOH, potassium hydroxide, ethanol, H
2sO
4, HCl, HNO
3in one or more, removing template required time is 5 minutes to 10 hours.
8. preparation method according to claim 7, it is characterized in that, described step 1) in, the condition of oxidizing thermal treatment is: furnace atmosphere is air, oxygen, carbon dioxide or its combination, heat treatment temperature is 500 ~ 1000 DEG C, heat treatment time is 1min ~ 48h, and the programming rate rising to described heat treatment temperature from room temperature is 5 ~ 80 DEG C/min; After heat treatment, naturally cool with furnace temperature or control rate of temperature fall 0.2 ~ 20 DEG C/min and be down to normal temperature;
The condition of described sol-gal process is: presoma be selected from methyl silicate, tetraethoxysilane, positive silicic acid propyl ester, butyl silicate, aluminic acid trimethyl, aluminic acid three isopropyl ester, aluminic acid three benzyl ester, tetraisopropyl titanate, butyl titanate, trimethylborate, triethyl borate, triisopropyl borate ester one or more, solvent be selected from water, ethanol, ammoniacal liquor one or more, the described sol-gel deposition reaction time is 30 minutes ~ 24 hours, and reaction temperature is 20 ~ 80 DEG C;
In described chemical vapor deposition processes, presoma be selected from trimethyl aluminium, three (dimethylamino) silane, methyl silicate, silicon tetrachloride, four (diethyl) titanium, four (dimethylamino) titanium, titanium tetrachloride, isopropyl titanate, diethyl zinc, zirconium (IV) tert-butyl alcohol, four (dimethylamino) zirconium, water one or more, reaction pressure in vapor deposition processes is atmosphere pressures, described atmosphere pressures is 1mpsi ~ 100psi, is preferably 1mpsi ~ 1psi; Vapor deposition times is 1 ~ 60 second at every turn, and circulation carries out 10 ~ 100 times, and vapour deposition temperature is 100 ~ 500 DEG C.
9. the preparation method according to claim 7 or 8, it is characterized in that, described step 2) in, the method of chemical vapour deposition (CVD) coated graphite alkene is: atmosphere is selected from methane, ethene, acetylene, hydrogen, argon gas, nitrogen, one or more in carbon dioxide, chemical vapour deposition (CVD) temperature is 800 ~ 1000 DEG C, the heating rate being warming up to chemical vapour deposition (CVD) temperature from normal temperature is 1 ~ 100 DEG C/min, after reaching chemical vapour deposition (CVD) temperature, sedimentation time is 1 minute to 1 hour, atmosphere pressures is 1 ~ 50psi, be preferably 5 ~ 20psi, atmosphere flow is 5 ~ 100sccm, be preferably 20 ~ 80sccm,
The method of wet chemistry method coated graphite alkene is: reactant is selected from H
2sO
4, graphite, KMnO
4, H
2o
2, HCl, water, poly-[(phenylacetylene)-co-(2,5-bis-octyloxy is to phenylacetylene)], one or more in ethylene glycol monoemethyl ether; The wet-chemical reaction time is 10 minutes to 2 hours, is preferably 10 minutes to 1 hour.
10. with the lithium ion battery that the arbitrary described 3 SiC 2/graphite alkene core-shell material of claim 1 ~ 6 is negative material.
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| CN112366299B (en) * | 2020-10-28 | 2022-04-22 | 浙江大学 | Preparation method of graphite-silicon-based lithium ion battery negative electrode material and product thereof |
| CN113437251A (en) * | 2021-06-21 | 2021-09-24 | 宁德新能源科技有限公司 | Negative electrode active material, electrochemical device, and electronic device |
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