CN109346681A - A kind of nuclear shell structure nano silicon-MXene composite negative pole material and preparation method thereof - Google Patents
A kind of nuclear shell structure nano silicon-MXene composite negative pole material and preparation method thereof Download PDFInfo
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- CN109346681A CN109346681A CN201810939968.9A CN201810939968A CN109346681A CN 109346681 A CN109346681 A CN 109346681A CN 201810939968 A CN201810939968 A CN 201810939968A CN 109346681 A CN109346681 A CN 109346681A
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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Abstract
The present invention discloses a kind of nuclear shell structure nano silicon-MXene composite negative pole material and preparation method thereof, when preparation, includes following steps: (1) using ceramic phase precursor MAX as raw material, MXene material is obtained after being washed with deionized after HCl+LiF is etched；(2) MXene material is added in nanometer silicon suspension, disperses to obtain the compound suspension of nano-silicon-MXene by high-energy ball milling, obtains nano-silicon/MXene composite granule after dry；(3) nano-silicon-MXene composite granule is coated with pitch, the nano-silicon-MXene composite negative pole material of core-shell structure is prepared after charing.The present invention is combined nano-silicon with the MXene of two-dimensional layered structure by the method for high-energy ball milling, and design the core-shell structure of porous network, the volume expansion in silicon nanoparticle charge and discharge process can effectively be buffered, electrolyte is prevented to contact with the direct of silicon interface, the electric conductivity of active material is improved simultaneously, and then cooperates with the specific capacity and cyclical stability for improving lithium ion battery.
Description
Technical field
The present invention relates to negative electrode material field technologies, refer in particular to a kind of nuclear shell structure nano silicon-MXene composite negative pole material
Material and preparation method thereof.
Background technique
In recent years, two-dimensional material with its large specific surface area, ion transmission path is short the features such as show in energy storage field it is huge
Big advantage, MXene are a kind of two-dimentional transition metal carbides with class graphene-structured, and general formula is represented by Mn+1XnTx(n=
1,2,3, M is transition metal element, and X is carbon or nitrogen, and T represents functional group produced during the preparation process), MXene has
Good hydrophilic property, large specific surface area, good conductivity, charge response speed is fast, the feature with fake capacitance and cycle life are stable
Advantage has huge potentiality in energy storage.
MXene contains atomic layer magnitude thickness carbon-coating, and surface-active site is more, has the good conductive of similar graphene
Property, and have transition metal layer, it can express the performance of similar transition metal oxide.Meanwhile the officials such as surface-F abundant ,-OH
It can roll into a ball and assign its excellent chemical reactivity and hydrophily, be the ideal host material for constructing nano combined energy storage material.But
It is that pure MXene is easy to happen to collapse and stacking, influences its performance as electrode material, it is necessary to intercalation is carried out to MXene and changed
Property, doping treatment or compound with other materials, prevent its stacking, reduce ion diffusional resistance, improve its chemical property.
The theoretical capacity of silicium cathode is up to 4200mAh/g, but silicon is semiconductor, poorly conductive, and silicium cathode material makes
Lead to material dusting with middle volume expansion, causes battery cycle life to be deteriorated, capacity attenuation is fast.Huge bulk effect and lower
Conductivity limit the commercial applications of silicium cathode technology.The study found that nano Si particle is dispersed in the matrix of carbon, Si
Volume change during embedding de- lithium can be absorbed by flexible carbon, so as to improve the cycle performance of electrode.But it receives
Rice grain material specific surface area is huge, increases in the side reaction occurred between electrolyte in cyclic process, limits its electrification
Learn the promotion of performance.
Summary of the invention
In view of this, in view of the deficiencies of the prior art, the present invention aims to provide a kind of core-shell structures to receive
Rice silicon-MXene composite negative pole material and preparation method thereof, simple process, production cost is low, the nano composite anode material of preparation
Material has preferable cycle performance and capacity retention ratio.
To achieve the above object, the present invention is using following technical solution:
A kind of nuclear shell structure nano silicon-MXene composite negative pole material, is core-shell structure, is with nano-silicon-MXene compound
Core, phenolic resin are shell.
A kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material, includes following steps:
(1) using ceramic phase precursor MAX as raw material, MXene material is obtained after being washed with deionized after HCl+LiF is etched
Material；
(2) MXene material is added in nanometer silicon suspension, disperses to obtain nano-silicon-MXene by high-energy ball milling compound suspended
Liquid obtains nano-silicon/MXene composite granule after dry；
(3) nano-silicon-MXene composite granule is coated with pitch, the nano-silicon-of core-shell structure is prepared after charing
MXene composite negative pole material.
As a preferred embodiment, in the step (1), ceramic phase precursor MAX raw material is immersed into HCl+LiF and are mixed
Etching is stirred in etching agent；Mixing time 5-15min, the mass volume ratio of stirring rate 200-800rpm, LiF and HCl
For 1 (g): 5-15 (mL), the additional amount of MAX phase and the mass ratio of LiF are 1:1.05；Sample after etching is transferred to plastic centrifuge
Pipe is centrifuged, then is washed with deionized 3 times, centrifugal filtration, and then the concussion processing 12h in 1mol/L KOH solution, is used
30% H2O2Solution impregnates 12h, the two-dimensional layer that deionized water washing, the interlamellar spacing that dry surface functional group is-OH are expanded
MXene material.
As a preferred embodiment, in the step (2), by nano-silicon be added to volume ratio be 8:2 ethyl alcohol and go from
In sub- water mixed solvent, ultrasonic disperse 0.5-5h obtains finely dispersed silicon suspension, is added into nanometer silicon suspension above-mentioned
The MXene material prepared in step, high-energy ball milling dispersion 12-24h obtain the compound suspension of nano-silicon-MXene, wherein nano-silicon
Mass ratio with MXene material is 1:(0 .1-1.0), compound suspension is dried in vacuo to obtain nano-silicon-MXene composite powder
Body.
As a preferred embodiment, in the step (3), pitch-coating amount is 5-15wt%, then carbonizes through 800-1100 DEG C
Nano-silicon-MXene the composite negative pole material of porous core-shell structure is prepared afterwards.
As a preferred embodiment, the MAX former material is Ti3AlC2, MXene material is Ti3C2、Ti2At least one in C
Kind.
As a preferred embodiment, the nano-silicon purity is 99.9%, partial size 10-50nm.
As a preferred embodiment, the pitch is oil system pitch, and fusing point is 245-250 DEG C.
The present invention has obvious advantages and beneficial effects compared with the existing technology, specifically, by above-mentioned technical proposal
Known to:
The present invention is combined nano-silicon with the MXene of two-dimensional layered structure by the method for high-energy ball milling, and designs porous web
The core-shell structure of network can effectively buffer the volume expansion in silicon nanoparticle charge and discharge process, prevent electrolyte and silicon interface
Direct contact, while improving the electric conductivity of active material, and then cooperate with the specific capacity for improving lithium ion battery and circulation steady
It is qualitative.
Detailed description of the invention
Fig. 1 is the preparation flow schematic diagram of the present invention；
Fig. 2 is MXene_Ti in the present invention3C2SEM figure；
Fig. 3 is nano-silicon in the present invention/MXene complex microsphere SEM figure.
Specific embodiment
Present invention discloses a kind of nuclear shell structure nano silicon-MXene composite negative pole materials, are core-shell structure, with nanometer
Silicon-MXene compound is core, and phenolic resin is shell.
Present invention further teaches a kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material, include with
Lower step:
(1) using ceramic phase precursor MAX as raw material, MXene material is obtained after being washed with deionized after HCl+LiF is etched
Material.Etching is stirred specifically, ceramic phase precursor MAX raw material are immersed in HCl+LiF mixing etching agent；When stirring
Between 5-15min, the mass volume ratio of stirring rate 200-800rpm, LiF and HCl is 1 (g): 5-15 (mL), the addition of MAX phase
The mass ratio of amount and LiF are 1:1.05；Sample after etching is transferred to plastic centrifuge tube to be centrifuged, then is washed with deionized
3 times, centrifugal filtration, then concussion handles 12h in 1mol/L KOH solution, with 30% H2O2Solution impregnates 12h, deionized water
The two-dimensional layer MXene material that washing, the interlamellar spacing that dry surface functional group is-OH are expanded.The MAX former material is
Ti3AlC2, MXene material are Ti3C2、Ti2At least one of C.
(2) MXene material is added in nanometer silicon suspension, disperses to obtain nano-silicon-MXene by high-energy ball milling compound
Suspension obtains nano-silicon/MXene composite granule after dry.Specifically, nano-silicon is added to the second that volume ratio is 8:2
Pure and mild deionized water in the mixed solvent, ultrasonic disperse 0.5-5h obtain finely dispersed silicon suspension, into nanometer silicon suspension
The MXene material prepared in above-mentioned steps is added, high-energy ball milling dispersion 12-24h obtains the compound suspension of nano-silicon-MXene,
The mass ratio of middle nano-silicon and MXene material is 1:(0.1-1.0), compound suspension is dried in vacuo to obtain nano-silicon-MXene
Composite granule.The nano-silicon purity is 99.9%, partial size 10-50nm.
(3) nano-silicon-MXene composite granule is coated with pitch, the nanometer of core-shell structure is prepared after charing
Silicon-MXene composite negative pole material.Specifically, pitch-coating amount is 5-15wt%, then preparation is more after 800-1100 DEG C of charing
Nano-silicon-MXene the composite negative pole material of the core-shell structure in hole, the pitch are oil system pitch, and fusing point is 250 DEG C.
The present invention carries out intercalation modifying and doping treatment to MXene interlayer using nano-silicon, and nano-silicon prevents MXene heap
It is folded, the high capacity of silicon has been played, ion diffusional resistance has been reduced, improves its chemical property；The two-dimensional layer structure of MXene is skilful simultaneously
The wonderful buffer function for playing silicon expansion, and enhance electric conductivity, the two mutually " learning from other's strong points to offset one's weaknesses ", brings out the best in each other.Nano-silicon and MXene
Composite material as core, outer layer coats the shell of Carbon Materials again, and the shell of Carbon Materials enhances the mechanical strength of entire material, reduces
The solvent reaction of electrolyte, improves the interface behavior of material, reduces irreversible capacity loss, improve material cycle performance and
Safety, to promote the overall performance of composite negative pole material.
With multiple embodiments, invention is further described in detail below:
Embodiment 1:
A kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material, includes following steps:
(1) using ceramic phase precursor MAX as raw material, MXene material is obtained after being washed with deionized after HCl+LiF is etched
Material.Etching is stirred specifically, ceramic phase precursor MAX raw material are immersed in HCl+LiF mixing etching agent；When stirring
Between 15min, the mass volume ratio of stirring rate 600rpm, LiF and HCl is 1 (g): 12 (mL), the additional amount of MAX phase and LiF's
Mass ratio is 1:1.05；Sample after etching is transferred to plastic centrifuge tube to be centrifuged, then is washed with deionized 3 times, is centrifuged
Filtering, then concussion handles 12h in 1mol/L KOH solution, with 30% H2O2Solution impregnates 12h, and deionized water washing is done
The dry two-dimensional layer MXene material for obtaining the interlamellar spacing that surface functional group is-OH and expanding.The MAX former material is Ti3AlC2, MXene
Material is Ti3C2。
(2) MXene material is added in nanometer silicon suspension, disperses to obtain nano-silicon-MXene by high-energy ball milling compound
Suspension obtains nano-silicon/MXene composite granule after dry.Specifically, nano-silicon is added to the second that volume ratio is 8:2
Pure and mild deionized water in the mixed solvent, ultrasonic disperse 1h obtain finely dispersed silicon suspension, are added into nanometer silicon suspension
The MXene material prepared in above-mentioned steps, high-energy ball milling dispersion 12h obtain the compound suspension of nano-silicon-MXene, wherein nanometer
The mass ratio of silicon and MXene material is 1:0.8, and compound suspension is dried in vacuo to obtain nano-silicon-MXene composite granule.Institute
Stating nano-silicon purity is 99.9%, partial size 25nm.
(3) nano-silicon-MXene composite granule is coated with pitch, the nanometer of core-shell structure is prepared after charing
Silicon-MXene composite negative pole material.Specifically, pitch-coating amount is 10wt%, then prepares porous core after 800 DEG C of charings
Nano-silicon-MXene the composite negative pole material of shell structure, the pitch are oil system pitch, and fusing point is 245 DEG C.
Embodiment 2:
A kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material, includes following steps:
(1) using ceramic phase precursor MAX as raw material, MXene material is obtained after being washed with deionized after HCl+LiF is etched
Material.Etching is stirred specifically, ceramic phase precursor MAX raw material are immersed in HCl+LiF mixing etching agent；When stirring
Between 5min, the mass volume ratio of stirring rate 200rpm, LiF and HCl is 1 (g): 10 (mL), the additional amount of MAX phase and LiF's
Mass ratio is 1:1.05；Sample after etching is transferred to plastic centrifuge tube to be centrifuged, then is washed with deionized 3 times, is centrifuged
Filtering, then concussion handles 12h in 1mol/L KOH solution, with 30% H2O2Solution impregnates 12h, and deionized water washing is done
The dry two-dimensional layer MXene material for obtaining the interlamellar spacing that surface functional group is-OH and expanding.The MAX former material is Ti3AlC2, MXene
Material is Ti2C。
(2) MXene material is added in nanometer silicon suspension, disperses to obtain nano-silicon-MXene by high-energy ball milling compound
Suspension obtains nano-silicon/MXene composite granule after dry.Specifically, nano-silicon is added to the second that volume ratio is 8:2
Pure and mild deionized water in the mixed solvent, ultrasonic disperse 0.5h obtain finely dispersed silicon suspension, add into nanometer silicon suspension
Enter the MXene material prepared in above-mentioned steps, high-energy ball milling dispersion 20h obtains the compound suspension of nano-silicon-MXene, wherein receiving
The mass ratio of rice silicon and MXene material is 1:0.1, and compound suspension is dried in vacuo to obtain nano-silicon-MXene composite granule.
The nano-silicon purity is 99.9%, partial size 18nm.
(3) nano-silicon-MXene composite granule is coated with pitch, the nanometer of core-shell structure is prepared after charing
Silicon-MXene composite negative pole material.Specifically, pitch-coating amount is 5wt%, then prepares porous nucleocapsid after 900 DEG C of charings
Nano-silicon-MXene the composite negative pole material of structure, the pitch are oil system pitch, and fusing point is 250 DEG C.
Embodiment 3:
A kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material, includes following steps:
(1) using ceramic phase precursor MAX as raw material, MXene material is obtained after being washed with deionized after HCl+LiF is etched
Material.Etching is stirred specifically, ceramic phase precursor MAX raw material are immersed in HCl+LiF mixing etching agent；When stirring
Between 14min, the mass volume ratio of stirring rate 300rpm, LiF and HCl is 1 (g): 5 (mL), the additional amount of MAX phase and LiF's
Mass ratio is 1:1.05；Sample after etching is transferred to plastic centrifuge tube to be centrifuged, then is washed with deionized 3 times, is centrifuged
Filtering, then concussion handles 12h in 1mol/L KOH solution, with 30% H2O2Solution impregnates 12h, and deionized water washing is done
The dry two-dimensional layer MXene material for obtaining the interlamellar spacing that surface functional group is-OH and expanding.The MAX former material is Ti3AlC2, MXene
Material is Ti3C2。
(2) MXene material is added in nanometer silicon suspension, disperses to obtain nano-silicon-MXene by high-energy ball milling compound
Suspension obtains nano-silicon/MXene composite granule after dry.Specifically, nano-silicon is added to the second that volume ratio is 8:2
Pure and mild deionized water in the mixed solvent, ultrasonic disperse 2h obtain finely dispersed silicon suspension, are added into nanometer silicon suspension
The MXene material prepared in above-mentioned steps, high-energy ball milling dispersion obtain the compound suspension of nano-silicon-MXene for 24 hours, wherein nanometer
The mass ratio of silicon and MXene material is 1:1.0, and compound suspension is dried in vacuo to obtain nano-silicon-MXene composite granule.Institute
Stating nano-silicon purity is 99.9%, partial size 10nm.
(3) nano-silicon-MXene composite granule is coated with pitch, the nanometer of core-shell structure is prepared after charing
Silicon-MXene composite negative pole material.Specifically, pitch-coating amount is 15wt%, then prepares porous core after 1000 DEG C of charings
Nano-silicon-MXene the composite negative pole material of shell structure, the pitch are oil system pitch, and fusing point is 248 DEG C.
Embodiment 4:
A kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material, includes following steps:
(1) using ceramic phase precursor MAX as raw material, MXene material is obtained after being washed with deionized after HCl+LiF is etched
Material.Etching is stirred specifically, ceramic phase precursor MAX raw material are immersed in HCl+LiF mixing etching agent；When stirring
Between 10min, the mass volume ratio of stirring rate 400rpm, LiF and HCl is 1 (g): 14 (mL), the additional amount of MAX phase and LiF's
Mass ratio is 1:1.05；Sample after etching is transferred to plastic centrifuge tube to be centrifuged, then is washed with deionized 3 times, is centrifuged
Filtering, then concussion handles 12h in 1mol/L KOH solution, with 30% H2O2Solution impregnates 12h, and deionized water washing is done
The dry two-dimensional layer MXene material for obtaining the interlamellar spacing that surface functional group is-OH and expanding.The MAX former material is Ti3AlC2, MXene
Material is Ti3C2And Ti2The mixture of C.
(2) MXene material is added in nanometer silicon suspension, disperses to obtain nano-silicon-MXene by high-energy ball milling compound
Suspension obtains nano-silicon/MXene composite granule after dry.Specifically, nano-silicon is added to the second that volume ratio is 8:2
Pure and mild deionized water in the mixed solvent, ultrasonic disperse 3h obtain finely dispersed silicon suspension, are added into nanometer silicon suspension
The MXene material prepared in above-mentioned steps, high-energy ball milling dispersion 18h obtain the compound suspension of nano-silicon-MXene, wherein nanometer
The mass ratio of silicon and MXene material is 1:0.6, and compound suspension is dried in vacuo to obtain nano-silicon-MXene composite granule.Institute
Stating nano-silicon purity is 99.9%, partial size 22nm.
(3) nano-silicon-MXene composite granule is coated with pitch, the nanometer of core-shell structure is prepared after charing
Silicon-MXene composite negative pole material.Specifically, pitch-coating amount is 12wt%, then prepares porous core after 1100 DEG C of charings
Nano-silicon-MXene the composite negative pole material of shell structure, the pitch are oil system pitch, and fusing point is 250 DEG C.
Embodiment 5:
A kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material, includes following steps:
(1) using ceramic phase precursor MAX as raw material, MXene material is obtained after being washed with deionized after HCl+LiF is etched
Material.Etching is stirred specifically, ceramic phase precursor MAX raw material are immersed in HCl+LiF mixing etching agent；When stirring
Between 8min, the mass volume ratio of stirring rate 500rpm, LiF and HCl is 1 (g): 15 (mL), the additional amount of MAX phase and LiF's
Mass ratio is 1:1.05；Sample after etching is transferred to plastic centrifuge tube to be centrifuged, then is washed with deionized 3 times, is centrifuged
Filtering, then concussion handles 12h in 1mol/L KOH solution, with 30% H2O2Solution impregnates 12h, and deionized water washing is done
The dry two-dimensional layer MXene material for obtaining the interlamellar spacing that surface functional group is-OH and expanding.The MAX former material is Ti3AlC2, MXene
Material is Ti3C2。
(2) MXene material is added in nanometer silicon suspension, disperses to obtain nano-silicon-MXene by high-energy ball milling compound
Suspension obtains nano-silicon/MXene composite granule after dry.Specifically, nano-silicon is added to the second that volume ratio is 8:2
Pure and mild deionized water in the mixed solvent, ultrasonic disperse 5h obtain finely dispersed silicon suspension, are added into nanometer silicon suspension
The MXene material prepared in above-mentioned steps, high-energy ball milling dispersion 15h obtain the compound suspension of nano-silicon-MXene, wherein nanometer
The mass ratio of silicon and MXene material is 1:0.5, and compound suspension is dried in vacuo to obtain nano-silicon-MXene composite granule.Institute
Stating nano-silicon purity is 99.9%, partial size 50nm.
(3) nano-silicon-MXene composite granule is coated with pitch, the nanometer of core-shell structure is prepared after charing
Silicon-MXene composite negative pole material.Specifically, pitch-coating amount is 8wt%, then prepares porous nucleocapsid after 950 DEG C of charings
Nano-silicon-MXene the composite negative pole material of structure, the pitch are oil system pitch, and fusing point is 250 DEG C.
Embodiment 6:
A kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material, includes following steps:
(1) using ceramic phase precursor MAX as raw material, MXene material is obtained after being washed with deionized after HCl+LiF is etched
Material.Etching is stirred specifically, ceramic phase precursor MAX raw material are immersed in HCl+LiF mixing etching agent；When stirring
Between 12min, the mass volume ratio of stirring rate 800rpm, LiF and HCl is 1 (g): 13 (mL), the additional amount of MAX phase and LiF's
Mass ratio is 1:1.05；Sample after etching is transferred to plastic centrifuge tube to be centrifuged, then is washed with deionized 3 times, is centrifuged
Filtering, then concussion handles 12h in 1mol/L KOH solution, with 30% H2O2Solution impregnates 12h, and deionized water washing is done
The dry two-dimensional layer MXene material for obtaining the interlamellar spacing that surface functional group is-OH and expanding.The MAX former material is Ti3AlC2, MXene
Material is Ti2C。
(2) MXene material is added in nanometer silicon suspension, disperses to obtain nano-silicon-MXene by high-energy ball milling compound
Suspension obtains nano-silicon/MXene composite granule after dry.Specifically, nano-silicon is added to the second that volume ratio is 8:2
Pure and mild deionized water in the mixed solvent, ultrasonic disperse 4h obtain finely dispersed silicon suspension, are added into nanometer silicon suspension
The MXene material prepared in above-mentioned steps, high-energy ball milling dispersion 22h obtain the compound suspension of nano-silicon-MXene, wherein nanometer
The mass ratio of silicon and MXene material is 1:0.4, and compound suspension is dried in vacuo to obtain nano-silicon-MXene composite granule.Institute
Stating nano-silicon purity is 99.9%, partial size 40nm.
(3) nano-silicon-MXene composite granule is coated with pitch, the nanometer of core-shell structure is prepared after charing
Silicon-MXene composite negative pole material.Specifically, pitch-coating amount is 14wt%, then prepares porous core after 850 DEG C of charings
Nano-silicon-MXene the composite negative pole material of shell structure, the pitch are oil system pitch, and fusing point is 250 DEG C.
Nuclear shell structure nano silicon-MXene composite negative pole material is made to above-mentioned each embodiment below and carries out cycle performance
With the test of capacity retention ratio, test method is the prior art, is not described in detail herein, test result is as follows shown in table:
Design focal point of the invention is: the present invention is by the method for high-energy ball milling by nano-silicon and two-dimensional layered structure
MXene is combined, and designs the core-shell structure of porous network, and the volume that can effectively buffer in silicon nanoparticle charge and discharge process is swollen
It is swollen, prevent directly contacting for electrolyte and silicon interface, while improving the electric conductivity of active material, and then cooperate with improve lithium from
The specific capacity and cyclical stability of sub- battery.
The above described is only a preferred embodiment of the present invention, be not intended to limit the scope of the present invention,
Therefore any subtle modifications, equivalent variations and modifications to the above embodiments according to the technical essence of the invention, still
Belong in the range of technical solution of the present invention.
Claims (8)
1. a kind of nuclear shell structure nano silicon-MXene composite negative pole material, it is characterised in that: it is core-shell structure, with nano-silicon-
MXene compound is core, and phenolic resin is shell.
2. a kind of a kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material as described in claim 1,
It is characterized in that: including following steps:
(1) using ceramic phase precursor MAX as raw material, MXene material is obtained after being washed with deionized after HCl+LiF is etched
Material；
(2) MXene material is added in nanometer silicon suspension, disperses to obtain nano-silicon-MXene by high-energy ball milling compound suspended
Liquid obtains nano-silicon/MXene composite granule after dry；
(3) nano-silicon-MXene composite granule is coated with pitch, the nano-silicon-of core-shell structure is prepared after charing
MXene composite negative pole material.
3. a kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material according to claim 2, special
Sign is: in the step (1), ceramic phase precursor MAX raw material being immersed in HCl+LiF mixing etching agent and are stirred quarter
Erosion；The mass volume ratio of mixing time 5-15min, stirring rate 200-800rpm, LiF and HCl are 1 (g): 5-15 (mL), MAX
The additional amount of phase and the mass ratio of LiF are 1:1.05；Sample after etching is transferred to plastic centrifuge tube to be centrifuged, then spend from
Sub- water washing 3 times, centrifugal filtration, then concussion handles 12h in 1mol/L KOH solution, with 30% H2O2Solution impregnates 12h,
The two-dimensional layer MXene material that deionized water washing, the interlamellar spacing that dry surface functional group is-OH are expanded.
4. a kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material according to claim 2, special
Sign is: in the step (2), nano-silicon being added to the ethyl alcohol and deionized water in the mixed solvent that volume ratio is 8:2, ultrasound
Dispersion 0.5-5h obtains finely dispersed silicon suspension, and the MXene material prepared in above-mentioned steps is added into nanometer silicon suspension
Material, high-energy ball milling dispersion 12-24h obtain the compound suspension of nano-silicon-MXene, wherein the mass ratio of nano-silicon and MXene material
For 1:(0 .1-1.0), compound suspension is dried in vacuo to obtain nano-silicon-MXene composite granule.
5. a kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material according to claim 2, special
Sign is: in the step (3), pitch-coating amount is 5-15wt%, then prepares porous nucleocapsid knot after 800-1100 DEG C of charing
Nano-silicon-MXene the composite negative pole material of structure.
6. a kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material according to claim 2, special
Sign is: the MAX former material is Ti3AlC2, MXene material is Ti3C2、Ti2At least one of C.
7. a kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material according to claim 2, special
Sign is: the nano-silicon purity is 99.9%, partial size 10-50nm.
8. a kind of preparation method of nuclear shell structure nano silicon-MXene composite negative pole material according to claim 2, special
Sign is: the pitch is oil system pitch, and fusing point is 245-250 DEG C.
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