CN108682812A - A kind of combination electrode material and preparation method thereof of MXene coated Sis - Google Patents
A kind of combination electrode material and preparation method thereof of MXene coated Sis Download PDFInfo
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- CN108682812A CN108682812A CN201810444215.0A CN201810444215A CN108682812A CN 108682812 A CN108682812 A CN 108682812A CN 201810444215 A CN201810444215 A CN 201810444215A CN 108682812 A CN108682812 A CN 108682812A
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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Abstract
The present invention relates to a kind of MXene coated Sis combination electrode materials and preparation method thereof, belong to the preparing technical field of cell negative electrode material.The combination electrode material is made of MXene phase materials and silicon, and MXene phase materials are coated on the surface of silicon;The preparation method includes the following steps:(1)The aqueous solution for first configuring MXene phase materials, is then added cationic surfactant, stirs;(2)To step(1)In solution in be added silica flour, it is stirring, filtering, dry, you can MXene coated Sis compound.MXene materials have been coated on silicon face by the present invention, the problem of overcoming silicon poorly conductive, are kept silicon electric conductivity, cyclical stability prepared by the present invention more preferable, are effectively improved chemical property and the safety of battery.
Description
Technical field
The invention belongs to the preparing technical fields of cell negative electrode material, and in particular to a kind of compound electric of MXene coated Sis
Pole material and preparation method thereof.
Background technology
Lithium battery is due to its high ratio energy, self discharge is small, environmentally protective, the advantages that having extended cycle life, and has been used as electricity
Electrical automobile and the most promising power supply system of battery product;The common cathode of lithium battery is mainly graphite type material at present, reason
There was only 372mAh/g by capacity, this severely limits the entirety of the performance of lithium battery to improve, so it is high to develop novel ratio energy
Negative material it is particularly important.
Metallic silicon and lithium can form silicon lithium alloy (Li4.4Si), theoretical specific capacity has reached 4212mAh/g, and
The rich reserves of silicon, derive from a wealth of sources, and are a kind of ideal lithium cell cathode materials.But silicon as negative material there are also lack
Point:(1) expensive, it prepares difficult.The silicon of usual nanometer is typically the device therefor made from high-energy ball milling method or CVD method
Costliness, low yield are of high cost.(2) metallic silicon volume expansion during storing up lithium leads to electricity to cause pole piece powder of detached
Pond performance degradation.(3) silicon is a kind of semi-conducting material, and electric conductivity is poor, limits its high rate performance.
By silicon and some high conductivity materials it is compound be the effective ways to solve the above problems.For example, patent
201410064482.7 disclose a kind of carbon silicon combination electrode material and preparation method thereof, in carbon contg particle and silicon-containing particle
Surface is respectively coated by organic polymer modified membrane, to promote effective dispersibility of the silicon-containing particle on carbon contg particle surface.Although this
Kind of method can solve the problems, such as that silicon has and improve the electric conductivity of silicon, and it is at low cost, there is good chemical property, energy
Enough effective energy densities for improving battery.But above patent document is limited to the electric conductivity promotion of silicon.Therefore, one is developed
The cell negative electrode material of kind high conductivity is particularly important.
Invention content
For the above-mentioned prior art the problem of, the present invention is intended to provide a kind of combination electrode of MXene coated Sis
Material and preparation method thereof.MXene materials have been coated on silicon face by the present invention, the problem of overcoming silicon poorly conductive, make this
It is more preferable to invent the silicon electric conductivity prepared, cyclical stability, effectively improves chemical property and the safety of battery.
An object of the present invention is to provide a kind of MXene coated Sis combination electrode material.
The second object of the present invention is to provide a kind of preparation method of MXene coated Sis combination electrode material.
The third object of the present invention is to provide a kind of a kind of lithium ion battery including combination electrode material of the present invention.
The fourth object of the present invention is to provide MXene coated Si combination electrode materials and preparation method thereof, comprising the present invention
A kind of application of lithium ion battery of combination electrode material.
For achieving the above object, specifically, the invention discloses following technical proposals:
First, the invention discloses a kind of MXene coated Sis combination electrode material, the combination electrode material is by MXene
Phase material and silicon are constituted, and MXene phase materials are coated on the surface of silicon.
The molecular formula of the MXene phase materials is Ma+1Xa, wherein M atomic layer hexagonal closs packings, X atoms are filled in octahedral
Body vacancy forms MX layers, and M is selected from the mixture of one or more of Ti, Zr, Nb, Cr, Mo, V, Ta;X is C or/and N.
Preferably, the MXene phase materials include:Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、
Nb4C3、Ti3CN、Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Nb4C3、Ti3One or both of CN
Above mixture.
Secondly, the invention discloses a kind of preparation methods of MXene coated Sis combination electrode material, include the following steps:
(1) aqueous solution for first configuring MXene phase materials, is then added cationic surfactant, stirs;
(2) silica flour, stirring, filtering, drying, you can obtain the compound of MXene coated Sis are added in the solution into step (1)
Object.
In step (1), the molecular formula of the MXene phase materials is Ma+1Xa, wherein M atomic layer hexagonal closs packings, X atoms
It is filled in octahedral voids and forms MX layers, M is selected from the mixture of one or more of Ti, Zr, Nb, Cr, Mo, V, Ta;X
For C or/and N.
Preferably, the MXene phase materials include Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、
Nb4C3、Ti3CN、Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Nb4C3、Ti3CN etc..
In step (1), the concentration of the MXene aqueous solutions is 0.1-50wt%.
In step (1), the cationic surfactant is tetrabutylammonium hydroxide, myristyl-lutidines bromine
Change ammonium, cetyl benzenesulfonic acid sodium, dialkyl ethanolamine ester methyl Methylsulfate amine, tri alkyl ammomium chloride, hexatriacontane Ji Jia
Ammonium chloride, trialkyl methyl ammonium chloride, dimethyl diallyl ammonium chloride, acrylic acid diethylaminoethyl ammonium chloride, three second
The mixture of one or more of the double stearate methylsulfuric acid ammonium methyls of hydramine.
In step (2), the silica flour accounts for the 1-90wt% of compound quality.
In step (2), the drying is vacuum drying, and drying temperature is 60-150 DEG C.
Again, the invention discloses a kind of lithium ion batteries, including anode, cathode, electrolyte, it is characterised in that:It is described
Cathode is the combination electrode material of MXene coated Sis prepared by the present invention.
The anode includes cobalt acid lithium, LiMn2O4, LiFePO4, lithium-nickel-cobalt-oxygen, lithium nickel cobalt manganese oxygen etc..
The electrolyte is ethylene carbonate, dimethyl carbonate, ethylene carbonate, diethyl carbonate, biphenyl (BP), carbonic acid
Vinylene (VC), vinylethylene carbonate (VEC), fluorinated ethylene carbonate (FEC), 1,3-N-morpholinopropanesulfonic acid lactone (PS), 1,4-
Butyl sultone (BS), 1,3- (1- propylene) sultone (PST), ethylene sulfite (ESI), sulfuric acid vinyl ester (ESA), hexamethylene
In base benzene (CHB), tert-butyl benzene (TBB), tert-amyl benzene (TPB) and fourth dicyan (SN) it is arbitrary one or several with lithium salts composition
Mixed liquor;
The lithium salts is LiBF4 (LiBF4), lithium hexafluoro phosphate (LiPF6), double trifluoro sulfonamide lithium (LiN
(SO2CF3)2), double fluorine sulfonamide lithiums (LiFSI), biethyl diacid lithium borate (LiBOB), trifluoromethanesulfonic acid lithium (LiSO3CF3) in
One or more of mixtures.
Finally, the invention also discloses MXene coated Si combination electrode materials and preparation method thereof, lithium ion batteries in vapour
Application in vehicle, electric vehicle.
Compared with prior art, the advantageous effect that the present invention obtains is:
(1) the problem of MXene materials have been coated on silicon face, have overcome silicon poorly conductive by the present invention, makes system of the present invention
Standby silicon electric conductivity, cyclical stability are more preferable, after tested, silicon/Ti prepared by the present invention3C2Compound capacity after recycling 50 weeks
Remaining 2486mAh g-1, capacity retention ratio 91.4%, and simple Si powder is in 200mA g-1Current density under, cycle 50
Capacity only residue 456mAh g after week-1, capacity retention ratio 16.7%, it can be seen that present invention greatly enhances Si powder
Cycle performance can effectively promote chemical property and the safety of battery.
(2) preparation process of the invention is simple, at low cost, and the production efficiency for greatly improving negative material is high, can be more
Meet the needs of industrialized production well, realizes large-scale production, great application prospect.
(3) preparation method of the invention is simple, electrical efficiency is high, highly practical, easy to spread.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation do not constitute the improper restriction to the application for explaining the application.
Fig. 1 is Ti in embodiment 13C2XRD diagram.
Fig. 2 is the XRD diagram of Si powder in embodiment 1.
Fig. 3 is silicon/Ti in embodiment 13C2The XRD diagram of compound.
Fig. 4 is Ti in embodiment 13C2SEM figure.
Fig. 5 is the SEM figures of Si powder in embodiment 1.
Fig. 6 is silicon/Ti in embodiment 13C2The SEM of compound schemes.
Fig. 7 is the cycle figure of Si powder in embodiment 1.
Fig. 8 is silicon/Ti in embodiment 13C2The cycle figure of compound.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
As background technology is introduced, existing method promotes the electric conductivity of silicon limited, can not make the potential of silicon
It brings into play, therefore, the present invention proposes a kind of MXene coated Sis combination electrode material and preparation method thereof, with reference to attached
The present invention is described further with specific implementation mode for figure.
Embodiment 1
A kind of preparation method of MXene coated Sis combination electrode material, includes the following steps:
(1) it is 10% Ti to take 10g mass fractions3C2Aqueous solution, be added 0.1g tetrabutylammonium hydroxide, stir evenly;
(2) and then in the solution of step (1) 1g silica flours are added, stir, filtering, 70 DEG C of vacuum tank dryings, you can obtain
Silicon/Ti3C2Combination electrode material.
Embodiment 2
A kind of preparation method of MXene coated Sis combination electrode material, includes the following steps:
(1) it is 20% Ti to take 10g mass fractions2The aqueous solution of C is added 1g tetrabutylammonium hydroxide, stirs evenly;
(2) and then in the solution of step (1) 0.5g silica flours are added, stir, filtering, 80 DEG C of vacuum tank dryings, you can
To silicon/Ti2C combination electrode materials.
Embodiment 3
A kind of preparation method of MXene coated Sis combination electrode material, includes the following steps:
(1) it is 40% Ti to take 10g mass fractions30.1g myristyls-lutidines bromination is added in the aqueous solution of CN
Ammonium stirs evenly;
(2) and then in the solution of step (1) 1g silica flours are added, stir, filtering, 100 DEG C of vacuum tank dryings, you can obtain
Silicon/Ti3CN combination electrode materials.
Embodiment 4
A kind of preparation method of MXene coated Sis combination electrode material, includes the following steps:
(1) it is the aqueous solution of 40% TiC to take 10g mass fractions, and 1g cetyl benzenesulfonic acid sodiums are added, stir evenly;
(2) and then in the solution of step (1) 1g silica flours are added, stir, filtering, 100 DEG C of vacuum tank dryings, you can obtain
Silicon/TiC combination electrode materials.
Embodiment 5
A kind of preparation method of MXene coated Sis combination electrode material, includes the following steps:
(1) it is 50% Nb to take 10g mass fractions4C3Aqueous solution, be added 0.5g dialkyl ethanolamine ester methyl sulfuric acid first
Ester amine stirs evenly;
(2) and then in the solution of step (1) 1g silica flours are added, stir, filtering, 90 DEG C of vacuum tank dryings, you can obtain
Silicon/Nb4C3Combination electrode material.
Embodiment 6
A kind of preparation method of MXene coated Sis combination electrode material, includes the following steps:
(1) it is 20% Nb to take 10g mass fractions2The aqueous solution of C is added 0.2g tri alkyl ammomium chlorides, stirs evenly;
(2) and then in the solution of step (1) 1g silica flours are added, stir, filtering, 100 DEG C of vacuum tank dryings, you can obtain
Silicon/Nb2C combination electrode materials.
Embodiment 7
A kind of preparation method of MXene coated Sis combination electrode material, includes the following steps:
(1) it is 0.1% Ti to take 10g mass fractions3C2Aqueous solution, 0.1g tetrabutylammonium hydroxide is added, stirring is equal
It is even;
(2) and then in the solution of step (1) 0.09g silica flours are added, stir, filtering, 60 DEG C of vacuum tank dryings, you can
To silicon/Ti3C2Combination electrode material.
Embodiment 8
A kind of preparation method of MXene coated Sis combination electrode material, includes the following steps:
(1) it is 1% Ti to take 10g mass fractions2The aqueous solution of C is added 1g tetrabutylammonium hydroxide, stirs evenly;
(2) and then in the solution of step (1) 0.001g silica flours are added, stir, filtering, 150 DEG C of vacuum tank dryings, you can
Obtain silicon/Ti2C combination electrode materials.
Embodiment 9
A kind of preparation method of MXene coated Sis combination electrode material, includes the following steps:
(1) it is 30% Ti to take 10g mass fractions30.1g myristyls-lutidines bromination is added in the aqueous solution of CN
Ammonium stirs evenly;
(2) and then in the solution of step (1) 7g silica flours are added, stir, filtering, 120 DEG C of vacuum tank dryings, you can obtain
Silicon/Ti3CN combination electrode materials.
Embodiment 10
A kind of preparation method of MXene coated Sis combination electrode material, includes the following steps:
(1) it is the aqueous solution of 50% TiC to take 10g mass fractions, and 1g cetyl benzenesulfonic acid sodiums are added, stir evenly;
(2) and then in the solution of step (1) 5g silica flours are added, stir, filtering, 140 DEG C of vacuum tank dryings, you can obtain
Silicon/TiC combination electrode materials.
Performance test:
Combination electrode material prepared by embodiment 1 is prepared into negative material, is assembled into lithium battery, tests the cycle of cathode
Performance, it is half-cell to test used, is used as to electrode and reference electrode, electrolyte LiPF using lithium piece6/ EC+DEC,
As a comparison, the present invention also assembles another lithium battery, is uncoated Ti difference lies in negative material3C2Silicon
Powder.
Test result is as shown in FIG. 7 and 8, as can be seen from Figure 7:Silica flour is in 200mAg-1Current density under, cycle 50
Capacity residue 456mAhg after week-1, capacity retention ratio 16.7% illustrates that the cyclicity of Si powder is very poor.As seen from Figure 8:
Silicon/Ti3C2Compound 200mAg-1Current density under, cycle 50 weeks after capacity residue 2486mAhg-1, capacity retention ratio is
91.4%, cyclicity is relative to uncoated Ti3C2Silica flour improve 5.47 times, so that the cycle performance of silica flour has been obtained significantly
It is promoted.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for those skilled in the art
For member, the application can have various modifications and variations.Any modification made by within the spirit and principles of this application,
Equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of MXene coated Sis combination electrode material, it is characterised in that:The combination electrode material by MXene phase materials and
Silicon is constituted, and MXene phase materials are coated on the surface of silicon.
2. combination electrode material as described in claim 1, it is characterised in that:The molecular formula of the MXene phase materials is Ma+1Xa,
M is selected from the mixture of one or more of Ti, Zr, Nb, Cr, Mo, V, Ta;X is C or/and N;
Preferably, the MXene phase materials include Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Nb4C3、
Ti3CN、Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Nb4C3、Ti3One or more of CN
Mixture.
3. a kind of preparation method of MXene coated Sis combination electrode material, it is characterised in that:Include the following steps:
(1) aqueous solution for first configuring MXene phase materials, is then added cationic surfactant, stirs;
(2) silica flour, stirring, filtering, drying, you can obtain the compound of MXene coated Sis are added in the solution into step (1).
4. the preparation method of combination electrode material as claimed in claim 3, it is characterised in that:In step (1), the MXene
The molecular formula of phase material is Ma+1Xa, mixtures of the M selected from one or more of Ti, Zr, Nb, Cr, Mo, V, Ta;X is C
Or/and N;Preferably, the MXene phase materials include Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、
Nb4C3、Ti3CN、Ti3C2、Ti2C、Ta4C3、TiNbC、(V0.5Cr0.5)3C2、V2C、Nb2C、Nb4C3、Ti3CN。
5. the preparation method of combination electrode material as claimed in claim 3, it is characterised in that:In step (1), the cation
Surfactant is tetrabutylammonium hydroxide, myristyl-lutidines ammonium bromide, cetyl benzenesulfonic acid sodium, dialkyl group
Ethanol amine ester methyl Methylsulfate amine, tri alkyl ammomium chloride, hexatriacontane methyl ammonium, trialkyl methyl ammonium chloride, two
The double stearate methylsulfuric acid ammonium methyls of methyl diallyl ammonium chloride, acrylic acid diethylaminoethyl ammonium chloride, triethanolamine
One or more of mixture.
6. the preparation method of combination electrode material as claimed in claim 3, it is characterised in that:In step (2), the drying is
Vacuum drying, drying temperature are 60-150 DEG C.
7. the preparation method of combination electrode material as claimed in claim 3, it is characterised in that:In step (1), the MXene
The concentration of aqueous solution is 0.1-50wt%.
8. such as the preparation method of claim 3-7 any one of them combination electrode materials, it is characterised in that:In step (2), institute
State the 1-90wt% that silica flour accounts for compound quality.
9. a kind of lithium ion battery, including anode, cathode, electrolyte, it is characterised in that:The cathode is such as claims 1 or 2
The combination electrode material of the MXene coated Sis, or the system such as claim 3-8 any one of them combination electrode materials
Preparation Method;
Preferably, the anode includes cobalt acid lithium, LiMn2O4, LiFePO4, lithium-nickel-cobalt-oxygen, lithium nickel cobalt manganese oxygen etc.;
Preferably, the electrolyte is ethylene carbonate, dimethyl carbonate, ethylene carbonate, diethyl carbonate, biphenyl, carbonic acid
Vinylene, vinylethylene carbonate, fluorinated ethylene carbonate, 1,3-N-morpholinopropanesulfonic acid lactone, 1,4- butyl sultones, 1,3- (1-
Propylene) appointing in sultone, ethylene sulfite, sulfuric acid vinyl ester, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene and fourth dicyan
It anticipates the mixed liquor that one or several form with lithium salts;
Preferably, the lithium salts is LiBF4, lithium hexafluoro phosphate, double trifluoro sulfonamide lithiums, double fluorine sulfonamide lithiums, double second two
The mixture of one or more of sour lithium borate, trifluoromethanesulfonic acid lithium.
10. the combination electrode material of MXene coated Sis as claimed in claim 1 or 2 and/or any one of such as claim 3-8
Application of the preparation method of the combination electrode material in automobile, electric vehicle.
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WO2022205154A1 (en) * | 2021-03-31 | 2022-10-06 | 宁德新能源科技有限公司 | Negative electrode active material, electrochemical apparatus, and electronic apparatus |
CN117229756A (en) * | 2023-09-18 | 2023-12-15 | 兰州理工大学 | Preparation method of MXene-based nano composite wave-absorbing material with adjustable interlayer spacing |
WO2024078053A1 (en) * | 2022-10-10 | 2024-04-18 | 华为技术有限公司 | Negative electrode material, preparation method therefor, secondary battery, and electrical device |
WO2024077965A1 (en) * | 2022-10-12 | 2024-04-18 | 宁波容百新能源科技股份有限公司 | Positive electrode material and preparation method therefor, and lithium-ion battery |
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