CN104332594B - A kind of silicon based anode material and its preparation method and application - Google Patents
A kind of silicon based anode material and its preparation method and application Download PDFInfo
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- CN104332594B CN104332594B CN201410531148.8A CN201410531148A CN104332594B CN 104332594 B CN104332594 B CN 104332594B CN 201410531148 A CN201410531148 A CN 201410531148A CN 104332594 B CN104332594 B CN 104332594B
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 49
- 239000010703 silicon Substances 0.000 title claims abstract description 49
- 239000010405 anode material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 85
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000011259 mixed solution Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000013528 metallic particle Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- -1 Step a Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 20
- 239000002923 metal particle Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002210 silicon-based material Substances 0.000 abstract description 3
- 230000008719 thickening Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 241000209094 Oryza Species 0.000 description 9
- 235000007164 Oryza sativa Nutrition 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 235000009566 rice Nutrition 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000009831 deintercalation Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002388 carbon-based active material Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of silicon based anode material and its preparation method and application, belong to lithium ion battery negative material field.The silicon based anode material includes：Graphene, silicon nanoparticle and nano-metal particle with layer structure, the silicon nanoparticle and the nano-metal particle are embedded in the layer structure of the Graphene.The present invention is embedded in the layer structure of Graphene by by silicon nanoparticle, enable the Graphene with network that silicon nanoparticle is strapped in relatively-stationary space, so as to effectively buffer the bulk effect of silicon materials, constantly thickening for SEI films is avoided, the cyclical stability of negative material is improve.Meanwhile, it is embedded in the layer structure of Graphene by by nano-metal particle, improve electric transmission efficiency, it is to avoid the formation of junction resistance higher, the electric conductivity of the negative material is improve, and then improve its cyclical stability.
Description
Technical field
The present invention relates to lithium ion battery negative material field, more particularly to a kind of silicon based anode material and preparation method thereof
And application.
Background technology
Lithium battery (i.e. lithium ion battery) is a kind of with carbon active material as negative pole, and positive pole is made with the compound containing lithium
Can discharge and recharge battery.The insertion of its charge and discharge process, as lithium ion and deintercalation process：During charging, lithium ion is de- from positive pole
It is embedding, by electrolyte and barrier film, embedded negative pole, embedded lithium ion is more in negative pole, and the charge specific capacity of battery is higher；Instead
It, during electric discharge, lithium ion from negative pole deintercalation, by electrolyte and barrier film, insertion positive pole, get over from negative pole by the lithium ion of deintercalation
Many, the specific discharge capacity of battery is higher.It can be seen that, the discharge and recharge of the embedding lithium capacity (i.e. specific capacity) of lithium cell cathode material to battery
Performance has important influence.Graphitic conductive is good, with layer structure, is very suitable for the insertion and deintercalation of lithium ion, but its
Specific capacity is relatively low, only 372mAh/g, causes the specific capacity of lithium battery relatively low.
And silica-base material is with the up to height ratio capacity of 4200mAh/g, but the process of insertion and the deintercalation in lithium ion
In, there is very big bulk effect (cubical expansivity is up to 300%-400%) in this material, cause charging and discharging lithium battery process
The efflorescence of middle silica-base material and come off, connection so on the one hand between influence active material and collector is unfavorable for that electronics is passed
It is defeated；On the other hand solid electrolyte interface film (the solid electrolyte formed between silica-base material and electrolyte are caused
Interface, abbreviation SEI) film progressive additive, it is unfavorable for improving lithium battery capacity, under causing the cycle performance of lithium battery drastically
Drop.
Prior art (CN 102593418A) prepares carbon silicon composite cathode material by be combined carbon and silicon,
Make the carbon with relative resilient structure and the space to buffer the bulk effect of silicon, improve the cycle performance of silicon, its step is as follows：
(1) mix：Organic carbon matrix precursor is mixed with silica flour, the mixture of organic carbon matrix precursor and silica flour is obtained；(2) coat：Will be upper
Mixture high temperature cabonization in an inert atmosphere is stated, the composite of the tight coated Si of porous carbon layer is obtained；(3) corrode：With corrosion
Liquid removes the part silicon in the composite of the tight coated Si of porous carbon layer, obtains carbon silicon composite cathode material, the carbon silicon
There is space in composite negative pole material between carbon and silicon.
Inventor has found that prior art at least has problems with：
The silicon based anode material that prior art is provided easily forms junction resistance higher, causes its cyclical stability poor.
The content of the invention
Embodiment of the present invention technical problem to be solved is, there is provided a kind of good silicon-based anode of cyclical stability
Material and its preparation method and application.Concrete technical scheme is as follows：
In a first aspect, a kind of silicon based anode material is the embodiment of the invention provides, including：Graphite with layer structure
Alkene, silicon nanoparticle and nano-metal particle, the silicon nanoparticle and the nano-metal particle are embedded in the Graphene
Layer structure on.
Preferably, the silicon based anode material includes the composition of following mass percent：Graphite with layer structure
Alkene 5-20%, nano-metal particle 1-5%, balance of silicon nanoparticle.
Specifically, preferably, the nano-metal particle is nano copper particle and/or nano-Ag particles.
Specifically, preferably, the particle diameter of the silicon nanoparticle is 5-80nm.
Second aspect, the embodiment of the invention provides a kind of above-mentioned silicon based anode material in lithium ion battery is prepared
Using.
The third aspect, the embodiment of the invention provides a kind of preparation method of above-mentioned silicon based anode material, including：
Step a, silicon nanoparticle is dissolved in the ethanol solution of the Graphene containing layer structure, stirred, obtained
To the first mixed solution；
Step b, centrifugal treating is carried out to first mixed solution, acquisition is embedded with the Graphene of nano-silicon, and to described
The Graphene for being embedded with nano-silicon is washed；
Step c, by washing after be embedded with the Graphene of nano-silicon add the solution containing slaine in, stir, so
Hydrofluoric acid is added in the backward solution containing slaine, makes the reducing metal ions in the slaine into metal, obtained
Second mixed solution；
Step d, suction filtration treatment is carried out to second mixed solution, acquisition is embedded with the graphite of nano-silicon and nano metal
Alkene, and the Graphene for being embedded with nano-silicon and nano metal is washed, dried process；
Step e, the dried Graphene for being embedded with nano-silicon and nano metal is calcined, obtain silicon-based anode
Material.
Specifically, it is described to stir by ultrasonic agitation or magnetic agitation come real preferably, in the step a
It is existing.
Specifically, preferably, in the step c, the metal salt solution is selected from the salting liquid of silver and/or copper.
Specifically, preferably, in the step e, the calcining is carried out at a temperature of 250-500 DEG C.
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：
Silicon based anode material provided in an embodiment of the present invention, by the layer structure that silicon nanoparticle is embedded in Graphene
On, enable the Graphene with network that silicon nanoparticle is strapped in relatively-stationary space, so as to effectively buffer
The bulk effect of silicon materials, it is to avoid constantly thickening for SEI films, improves the cyclical stability of negative material.Meanwhile, by that will receive
Rice metallic particles is embedded in the layer structure of Graphene, improves electric transmission efficiency, it is to avoid the formation of junction resistance higher, is carried
The electric conductivity of the negative material high, and then improve the cyclical stability of the negative material.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be to that will make needed for embodiment description
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for
For those of ordinary skill in the art, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
Fig. 1 is the structural representation of silicon based anode material provided in an embodiment of the present invention.
Reference is represented respectively：
1 Graphene,
2 silicon nanoparticles,
3 nano-metal particles.
Specific embodiment
To make technical scheme and advantage clearer, below in conjunction with accompanying drawing embodiment of the present invention is made into
One step ground is described in detail.
In a first aspect, the embodiment of the invention provides a kind of silicon based anode material, accompanying drawing 1 is the knot of the silicon based anode material
Structure schematic diagram.As shown in Figure 1, the silicon based anode material includes：Graphene 1, silicon nanoparticle 2 with layer structure and receive
Rice metallic particles 3, silicon nanoparticle 2 and nano-metal particle 3 are embedded in the layer structure of Graphene 1.
Silicon based anode material provided in an embodiment of the present invention, by the layer structure that silicon nanoparticle is embedded in Graphene
On, enable the Graphene with network that silicon nanoparticle is strapped in relatively-stationary space, so as to effectively buffer
The bulk effect of silicon materials, it is to avoid constantly thickening for SEI films, improves the cyclical stability of negative material.Meanwhile, by that will receive
Rice metallic particles is embedded in the layer structure of Graphene, improves electric transmission efficiency, it is to avoid the formation of junction resistance higher, is carried
The electric conductivity of the negative material high.
It is understood that the structure of the Graphene described in the embodiment of the present invention is lamellar structure, it has at least two
Layer graphene layer, silicon nanoparticle and nano-metal particle be distributed in the lamellar structure of Graphene, that is, silicon nanoparticle and
Nano-metal particle is dispersed between adjacent graphene layer, and is combined with graphene layer.
Further, a kind of preferred silicon based anode material, including following mass percent be the embodiment of the invention provides
Composition：Graphene 5-20% with layer structure, nano-metal particle 1-5%, balance of silicon nanoparticle.
Further, the mass percent of Graphene is preferably 10-15%, more preferably 15%；Nano-metal particle
Mass percent be preferably 3-5%, more preferably 5%.
In order to improve the electric conductivity of prepared volume silicon based anode material, specifically, above-mentioned nano-metal particle is to receive
Rice copper particle and/or nano-Ag particles.Preferably, the particle diameter of above-mentioned nano-metal particle is 10-60nm；Silicon nanoparticle
Particle diameter is 5-80nm.
Second aspect, the embodiment of the invention provides a kind of above-mentioned silicon based anode material in lithium ion battery is prepared
Using.That is, a kind of lithium ion battery is the embodiment of the invention provides, the lithium ion battery includes above-mentioned silicon-based anode material
Material.
It is understood that it is steady to have good circulation concurrently by the lithium ion battery that above-mentioned silicon based anode material is prepared
Qualitative and electric conductivity.
The third aspect, the embodiment of the invention provides a kind of preparation method of above-mentioned silicon based anode material, and the method can
To carry out at normal temperatures.Specifically, the method includes：
Step 101, silicon nanoparticle is dissolved in the ethanol solution of the Graphene with layer structure, stirred,
The silicon nanoparticle is embedded in the layer structure of the Graphene, obtain the first mixed solution.
Specifically, in step 101, make silicon nanoparticle dispersed by ultrasonic agitation or magnetic agitation and embedded
In the layer structure of Graphene.
The embodiment of the present invention is not especially limited to the concentration of the ethanol solution of above-mentioned Graphene, and its concentration is beneficial to be made to receive
Rice silicon grain is uniformly distributed therein and is advisable.
Step 102, the first mixed solution to being obtained in step 101 carry out centrifugal treating, and acquisition is embedded with the stone of nano-silicon
Black alkene, and the Graphene for being embedded with nano-silicon is washed.
The resulting Graphene for being embedded with nano-silicon refers to silicon nanoparticle dispersion in step 102, preferably uniformly divides
It is dispersed in the layer structure of Graphene, and is physically combined with graphene layer.
Specifically, it is possible to use clear water is washed to the Graphene for being embedded with nano-silicon, to remove the impurity for containing thereon,
Avoid adversely affecting the chemical property of negative material.
Step 103, by washing after be embedded with the Graphene of nano-silicon add the solution containing slaine in, stir,
The metal ion in slaine is dispersed in the layer structure of the Graphene, addition in the solution of slaine is then contained to this
Hydrofluoric acid, makes above-mentioned reducing metal ions into metal, obtains the second mixed solution.
In step 103, reducing metal ions in Graphene layer structure into nanometer will be dispersed in by using hydrofluoric acid
Metallic particles, the metallic particles obtained by making is combined with graphene layer.The amount of hydrofluoric acid so that metal ion is reduced completely, preferably
Just reduction is advisable.The mass concentration of hydrofluoric acid preferably 10%.
It is understood that the combination of metallic particles and Graphene can be realized by electrostatic adsorption.
Preferably, the metallic particles in order to obtain even-grained nanoscale, the metal used by the embodiment of the present invention
Salting liquid is selected from the salting liquid of silver and/or copper.For example, can be molten for silver nitrate solution, copper nitrate solution, copper citrate
Liquid.
It is understood that other metals, such as manganese, iron, aluminium, magnesium etc. can also be applied to the present invention.
Step 104, the second mixed solution obtained to step 103 carry out suction filtration treatment, and acquisition is embedded with nano-silicon and nanometer
The Graphene of metal, and Graphene to being embedded with nano-silicon and nano metal washed, dried process.
In step 104, washing process can be carried out by using clear water, to remove contain on Graphene undesirable miscellaneous
Matter.Heat drying that can be by spray drying or at 60-80 DEG C is dried treatment.
Step 105, the dried Graphene for being embedded with nano-silicon and nano metal is calcined, obtain desired silicon substrate
Negative material.
Increase silicon nanoparticle and nano metal by being calcined to the Graphene for being embedded with nano-silicon and nano metal
The combination dynamics of particle and Graphene, improves the stability of the negative material.Preferably, at 250-500 DEG C, preferably 300-
The calcining is carried out at a temperature of 450 DEG C.
Hereinafter the present invention will be further described through by specific embodiment.
Raw materials used specification is as follows in following examples：
Graphene model GR-003 is purchased from Suzhou Heng Qiu Graphenes Science and Technology Ltd.；
Silicon nanoparticle model YFG01-N30 is purchased from Shanghai Yun Fu nanosecond science and technology Co., Ltd.
Embodiment 1
Present embodiments provide a kind of silicon based anode material, including following mass percent composition：Graphene 5%, receive
Rice metallic particles 2%, silicon nanoparticle 93%.
Above-mentioned silicon based anode material is prepared by following preparation method：
According to the mass ratio of each composition in above-mentioned negative material, Graphene is dissolved in ethanol solution, after stirring
Silicon nanoparticle is added, ultrasonic agitation 1h makes silicon nanoparticle be embedded on Graphene, obtains the first mixed solution.To this
One mixed solution carries out centrifugal treating, and acquisition is embedded with the Graphene of nano-silicon, and is washed 3 times using clear water.It is embedding after by washing
The Graphene for having nano-silicon is added in silver nitrate solution, stirs 0.5h, then again to adding mass concentration in the silver nitrate solution
It is 10% hydrofluoric acid, makes silver ion reduction into nano-Ag particles, obtains the second mixed solution.Second mixed solution is taken out
Filter is processed, and acquisition is embedded with the Graphene of nano-silicon and nano metal, and to carrying out washing 3 times to it using clear water, then 50
It is dried at DEG C.The dried Graphene for being embedded with nano-silicon and nano metal is calcined at a temperature of 250 DEG C, is obtained
Take desired silicon based anode material.
Embodiment 2
Present embodiments provide a kind of silicon based anode material, including following mass percent composition：Graphene 10%, receive
Rice metallic particles 1%, silicon nanoparticle 89%.
Above-mentioned silicon based anode material is prepared by following preparation method：
According to the mass ratio of each composition in above-mentioned negative material, Graphene is dissolved in ethanol solution, after stirring
Silicon nanoparticle is added, ultrasonic agitation 1.5h makes silicon nanoparticle be embedded on Graphene, obtains the first mixed solution.To this
First mixed solution carries out centrifugal treating, and acquisition is embedded with the Graphene of nano-silicon, and is washed 2 times using clear water.After washing
It is embedded with the Graphene of nano-silicon addition copper nitrate solution, stirs 0.5h, it is then dense to addition quality in the copper nitrate solution again
The hydrofluoric acid for 10% is spent, copper ion is reduced into nano copper particle, obtain the second mixed solution.Second mixed solution is carried out
Suction filtration treatment, acquisition is embedded with the Graphene of nano-silicon and nano metal, and to carrying out washing 2 times, Ran Hou to it using clear water
It is dried at 45 DEG C.The dried Graphene for being embedded with nano-silicon and nano metal is calcined at a temperature of 300 DEG C,
Obtain desired silicon based anode material.
Embodiment 3
Present embodiments provide a kind of silicon based anode material, including following mass percent composition：Graphene 15%, receive
Rice metallic particles 3%, silicon nanoparticle 82%.
Above-mentioned silicon based anode material is prepared by following preparation method：
According to the mass ratio of each composition in above-mentioned negative material, Graphene is dissolved in ethanol solution, after stirring
Silicon nanoparticle is added, ultrasonic agitation 2h makes silicon nanoparticle be embedded on Graphene, obtains the first mixed solution.To this
One mixed solution carries out centrifugal treating, and acquisition is embedded with the Graphene of nano-silicon, and is washed 4 times using clear water.It is embedding after by washing
The Graphene for having nano-silicon is added in silver nitrate solution, stirs 1.5h, then again to adding mass concentration in the silver nitrate solution
It is 10% hydrofluoric acid, makes silver ion reduction into nano-Ag particles, obtains the second mixed solution.Second mixed solution is taken out
Filter is processed, and acquisition is embedded with the Graphene of nano-silicon and nano metal, and to carrying out washing 4 times to it using clear water, then 60
It is dried at a temperature of DEG C.The dried Graphene for being embedded with nano-silicon and nano metal is carried out at a temperature of 450 DEG C
Calcining, obtains desired silicon based anode material.
Embodiment 4
Present embodiments provide a kind of silicon based anode material, including following mass percent composition：Graphene 20%, receive
Rice metallic particles 5%, silicon nanoparticle 75%.
Above-mentioned silicon based anode material is prepared by following preparation method：
According to the mass ratio of each composition in above-mentioned negative material, Graphene is dissolved in ethanol solution, after stirring
Silicon nanoparticle is added, ultrasonic agitation 2.5h makes silicon nanoparticle be embedded on Graphene, obtains the first mixed solution.To this
First mixed solution carries out centrifugal treating, and acquisition is embedded with the Graphene of nano-silicon, and is washed 4 times using clear water.After washing
It is embedded with during the Graphene of nano-silicon adds copper citrate solution, 1.5h is stirred, then again to adding matter in the copper citrate solution
Amount concentration is 10% hydrofluoric acid, copper ion is reduced into nano copper particle, obtains the second mixed solution.To the second mixed solution
Suction filtration treatment is carried out, acquisition is embedded with the Graphene of nano-silicon and nano metal, and to carrying out washing 2 times to it using clear water, so
It is dried at a temperature of 70 DEG C afterwards.To the dried graphite for being embedded with nano-silicon and nano metal at a temperature of 500 DEG C
Alkene is calcined, and obtains desired silicon based anode material.
Embodiment 5
The present embodiment prepares lithium ion battery using the silicon based anode material that embodiment 1-4 is provided, and to the lithium-ion electric
The chemical property in pond is tested.Wherein, the preparation method of the battery is as follows：
By each silicon based anode material in embodiment 1-4 with conductive agent acetylene black and binding agent sodium alginate according to 80：
10：10 mass ratio is well mixed, and is then uniformly coated on Copper Foil with scraper, is vacuum dried 24 hours at 100 DEG C, is obtained real
Electrical verification pond pole piece.It is that, to electrode, electrolyte is 1mol/L LiPF with lithium piece6EC (ethyl carbonate ester)+DMC (dimethyl carbon
Acid esters) (volume ratio 1:1) solution, barrier film is celgard2400 films, and CR2025 is assembled into the glove box full of argon gas atmosphere
Type button cell.
During being detected to the button cell for preparing, during less than or equal to 10 times, using the electric discharge of 0.1C
Mechanism, at 10 times to 30 times, using the discharge mechanism of 0.2C, at 30 times to 50 times, using the discharge mechanism of 0.5C, arrives for 50 times
At 100 times, using the discharge mechanism of 1C, 100 times afterwards using the discharge mechanism of 2C.Experimental result is as shown in table 1：
The electrochemical property test table of the lithium ion battery of table 1
As shown in Table 1, lithium ion is prepared using the silicon based anode material prepared by the above-mentioned method of the embodiment of the present invention
Battery, its cyclical stability of gained lithium ion battery is good, with excellent chemical property.Side provided in an embodiment of the present invention
Method is simple, easy to operate, is easy to large-scale industrial application.
Presently preferred embodiments of the present invention is the foregoing is only, the protection domain being not intended to limit the invention is all in this hair
Within bright spirit and principle, any modification, equivalent substitution and improvements made etc. should be included in protection scope of the present invention
Within.
Claims (4)
1. a kind of preparation method of silicon based anode material, including：
Step a, silicon nanoparticle is dissolved in the ethanol solution of the Graphene containing layer structure, stirred, obtain
One mixed solution；
Step b, centrifugal treating is carried out to first mixed solution, acquisition is embedded with the Graphene of nano-silicon, and is embedded with to described
The Graphene of nano-silicon is washed；
Step c, by washing after be embedded with the Graphene of nano-silicon add the solution containing slaine in, stir, Ran Houxiang
The hydrofluoric acid that mass concentration is 10% is added in the solution containing slaine, makes the reducing metal ions in the slaine
Into metal, the second mixed solution is obtained；
Step d, suction filtration treatment is carried out to second mixed solution, acquisition is embedded with the Graphene of nano-silicon and nano metal, and
The Graphene for being embedded with nano-silicon and nano metal is washed, dried process；
Step e, the dried Graphene for being embedded with nano-silicon and nano metal is calcined, obtain silicon-based anode material
Material；
The silicon based anode material includes the composition of following mass percent：Graphene 5-20% with layer structure, nanometer
Metallic particles 1-5%, balance of silicon nanoparticle.
2. method according to claim 1, it is characterised in that described to stir by ultrasonic agitation in the step a
Or magnetic agitation is realized.
3. method according to claim 2, it is characterised in that in the step c, the solution containing slaine is silver
And/or the salting liquid of copper.
4. the method according to claim any one of 1-3, it is characterised in that in the step e, in 250-500 DEG C of temperature
The calcining is carried out under degree.
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