CN107394180B - Two-dimensional transition group metal carbide (nitride) -nano silicon particle composite material, preparation and application - Google Patents

Two-dimensional transition group metal carbide (nitride) -nano silicon particle composite material, preparation and application Download PDF

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CN107394180B
CN107394180B CN201710661360.XA CN201710661360A CN107394180B CN 107394180 B CN107394180 B CN 107394180B CN 201710661360 A CN201710661360 A CN 201710661360A CN 107394180 B CN107394180 B CN 107394180B
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nitride
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dimensional transition
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CN107394180A (en
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杨建�
熊街
潘丽梅
陈一铭
谢书峰
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Nanjing Tech University
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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
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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
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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Abstract

The invention belongs to the technical field of nano composite materials, and relates to a two-dimensional transition group metal carbide (nitride) and nano silicon particle composite material, and preparation and application thereof. The composite material is formed by uniformly dispersing and compounding two-dimensional transition metal carbide (nitride) nanosheets and nano silicon particles, a two-dimensional transition metal carbide (nitride) nanosheet suspension and a nano silicon suspension are mixed in proportion, the two-dimensional transition metal carbide (nitride) nanosheet suspension and the nano silicon suspension are ultrasonically mixed uniformly, a flexible composite film is obtained through vacuum filtration or is freeze-dried to obtain composite powder, the conductivity of the composite material can be regulated and controlled by changing the proportion of the two, and the flexible composite film can be directly used as a negative electrode of a lithium ion battery without introducing a binder and a conductive agent. The composite material obviously improves the defect of conductivity of the nano silicon particles and relieves the volume change of lithium ion insertion and extraction in the circulation process. The preparation method is simple, safe and efficient, and low in cost, and the two-dimensional transition metal carbide (nitride) and nano silicon particle composite material has a good application prospect as a lithium ion battery cathode material.

Description

Two-dimensional transition group metal carbide (nitride) -nano silicon particle composite material, preparation and application
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a two-dimensional transition group metal carbide (nitride) and nano silicon particle composite material, and preparation and application thereof.
Background
Lithium ion batteries have the advantages of high energy density, long cycle life, and the like, and are widely used as power sources for portable electronic devices. The electrode material is an important factor influencing the performance of the lithium ion battery, the graphite is mainly used as a negative electrode of the current commercial lithium ion battery, but the theoretical capacity of the graphite is low (372mAh/g), so that the lithium ion battery is difficult to meet the application requirements in the fields of high energy density, high power density and the like, especially new energy electric vehicles. The simple substance silicon has extremely high theoretical capacity (4200mAh/g), low cost and environmental protection, and attracts researchers to pay extensive attention to the silicon as the negative electrode material of the lithium ion battery. However, the electrochemical performance is not ideal because the conductivity is poor, the volume change is large (300%) in the charging and discharging process, the electrode is cracked and crushed in the Li-Si alloying process, and the electric contact between the active material and the current collector is lost.
In order to solve the problems, researchers build composite cathodes by compounding carbon materials, conductive polymers and the like with silicon. For example: ma and the like adopt the compounding of Graphene and nano silicon to be used for lithium ion battery negative electrodes [ Ma Y, Yonnesi R, et al+Storage and Flexible Integrated Configuration,Advanced Functional Materials,2016,26(37):6796-6806.]. MXene is a new two-dimensional transition metal carbide (nitride) with the chemical formula Mn+1XnTx(M is an early transition metal element, X is carbon or/and nitrogen, n is 1, 2 or 3, T represents a surface functional group such as-F, -O or-OH, etc.)n+1XnThe nano-sheet is formed by alternately stacking n layers of X atoms and n +1 layers of M atoms, wherein the M atom layer is positioned on the outermost layer). It is prepared from ternary layered carbon (nitride) compound such as MAX phase (chemical formula is M)n+1AXnFrom Mn+1XnLayers are stacked alternately with A layers, wherein M, X, n means Mn+1XnTxWherein A is a group III or IV element) to selectively etch out the atoms of layer AThe obtained novel graphene-like two-dimensional material. MXene prepared at present has Ti3C2Tx、Ti2CTx、(Ti0.5,Nb0.5)2CTx、(V0.5,Cr0.5)3C2Tx、Ti3CNTx、Ta4C3Tx、V2CTx、Nb2CTx、Nb4C3Tx、(Nb0.8,Ti0.2)4C3Tx、(Nb0.8,Zr0.2)4C3Tx、Mo2TiC2Tx、Mo2Ti2C3Tx、Mo2CTx、Cr2TiC2Tx、Zr3C2Tx、Ti4N3Tx[Anasori B,Xie Y,Beidaghi M,et al.Two-Dimensional,Ordered,Double Transition Metals Carbides(MXenes),ACS Nano,2015,9(10):9507-9516.Zhou J,Zha X-H,Chen F-Y,et al.A Two-Dimensional Zirconium Carbide by Selective Etching of Al3C3from Nanolaminated Zr3Al3C5,Angew Chem Int Edit,2016,55(16):5008-5013.]In which Ti3C2TxIs currently the most studied MXene. MXene has unique two-dimensional morphology, larger specific surface area and good conductivity and mechanical properties, so the MXene has wide application prospects in the fields of energy storage, catalysis, composite Materials, environmental governance and the like [ Anasori B, Lukatsuya M R, Gogottsi Y, et al.2D metal carbonates and nitriles (MXenes) for energy storage, Nature Reviews Materials,2017,2:16098.]In particular, excellent performance has been shown as electrode Materials for electrochemical energy storage devices such as supercapacitors and lithium Ion Batteries [ Naguib M, Halim J, Lu J, et al.New-Dimensional Niobium and variable carbide as a developing material for Li-Ion Batteries, Journal of the American Chemical Society,2013,135(43): 15966-15969. Michael G, Lukatskaya M R, et al.conductive Two-Dimensional titanium carbide' cell with high volumetric capacitance,Nature,2014,516(7529):78-81.Lukatskaya M R,Mashtalir O,Ren C E,et al.Cation Intercalation and High Volumetric Capacitance of Two-dimensional Titanium Carbide,Science,2013,341(6153):1502-1505.]. At present, the corrosive agents used for synthesizing MXene are HF, LiF + HCl and NaHF2、KHF2、NH4HF2And the like, wherein the HF is most widely applied, the A atomic layer is selectively corroded by the HF to obtain a plurality of layers of MXene, the MXene nanosheet suspension can be obtained through intercalation and stripping, the LiF + HCl corrosive is adopted, the mixed intercalation of lithium ions and water molecules is generated while the A atomic layer is selectively corroded, the stripping can be realized without the intercalation process of an intercalation reagent, and the MXene suspension with high concentration [ Naguib M, Mochalin V N, et al, two-dimensional nanocrystals purified by y enrichment of Ti is obtained3AlC2,Adv.Mater,2011,23(37):4248–4253.Ng V M H,Huang H,et al.Recent progress in layered transition metal carbides and/or nitrides(MXenes)and their composites:synthesis and applications,Journal of Materials Chemistry A,2017,5(7):3039-3068.]。
Disclosure of Invention
The invention aims to provide a two-dimensional transition group metal carbide (nitride) and nano silicon particle composite material, a preparation method of the composite material and application of the composite material.
The technical scheme of the invention is as follows: a two-dimensional transition group metal carbide (nitride) and nano silicon particle composite material is characterized in that: the composite material is formed by uniformly dispersing and compounding two-dimensional transition metal carbide (nitride) nanosheets and nano silicon particles, and then a flexible composite film of the two-dimensional transition metal carbide (nitride) and the nano silicon particles is obtained through vacuum filtration or freeze drying is carried out to obtain composite powder of the two-dimensional transition metal carbide (nitride) and the nano silicon particles.
Preferably, the average size of the nano silicon particles is 10-100nm, and the percentage content of silicon in the total mass of the composite material is 20-85%; more preferably, the percentage content of silicon in the total mass of the composite material is 30-65%; the thickness of the flexible composite film is 5-30 μm.
Preferably, the two-dimensional transition group metal (nitride) is Ti3C2Tx、Ti3CNTx、Ti2CTx、(Ti0.5,Nb0.5)2CTx、(V0.5,Cr0.5)3C2Tx、Ta4C3Tx、V2CTx、Nb2CTx、Nb4C3Tx、(Nb0.8,Ti0.2)4C3Tx、(Nb0.8,Zr0.2)4C3Tx、Mo2TiC2Tx、Mo2Ti2C3Tx、Mo2CTx、Cr2TiC2Tx、Zr3C2TxOr Ti4N3TxAnd the like.
The invention also provides a preparation method of the two-dimensional transition group metal carbide (nitride) and nano silicon particle composite material, which comprises the following specific steps: adding the nano silicon particle suspension into the two-dimensional transition metal carbon (nitride) MXene nanosheet suspension, ultrasonically mixing the two suspensions uniformly, and then carrying out vacuum filtration to obtain a flexible composite film of the two-dimensional transition metal carbon (nitride) and the nano silicon particles or freeze drying to obtain composite powder of the two-dimensional transition metal carbon (nitride) and the nano silicon particles.
Preferably, the concentration of the two-dimensional transition group metal carbon (nitride) nanosheet suspension is 0.2-1.5 mg/mL; the concentration of the nano silicon particle suspension is 0.2-3 mg/mL.
The two-dimensional transition metal carbon (nitride) MXene nanosheet suspension is prepared according to the following method, but is not limited to the following method: dissolving LiF in hydrochloric acid, slowly adding powder of a ternary layered carbon nitride compound such as MAX into the solution, magnetically stirring for 6-72h at 30-55 ℃, washing and centrifuging a reaction product by using ethanol until the pH value of supernatant is 6.2-6.8, adding a dried solid sample into deionized water, ultrasonically stripping for 1-2h under the protection of flowing argon, and centrifuging for 0.5-2h at the rotating speed of 3000-4000r.p.m to obtain a stable suspension of few-layer or single-layer transition metal carbon (nitride) MXene nanosheets, wherein the concentration of the suspension is 0.2-1.5 mg/mL.
The silicon nanoparticle suspension is prepared by the following method, but is not limited to the following method: adding the silicon nano-particles into ethanol, and carrying out ultrasonic treatment for 1-2h under the protection of flowing argon and at the frequency of 40-100kHz and the power of 50-200W to obtain a stable silicon nano-particle suspension.
Preferably, the ultrasonic frequency when the two suspensions are uniformly mixed is 40-100kHz, the ultrasonic power is 50-200W, and the ultrasonic time is 0.5-1 h; the freeze drying is carried out for 2 to 5 hours at the temperature of between 30 ℃ below zero and 50 ℃ below zero, and then the mixture is dried for 12 to 36 hours under vacuum at the temperature of between 50 ℃ below zero and 70 ℃ below zero; the vacuum filtration is carried out for 6-12h under the conditions that the air extraction rate is 4-6L/s and the vacuum degree is 0.03-0.06 Pa; and then the film is naturally dried in the air at room temperature and peeled off to obtain the flexible composite film.
The invention also provides application of the two-dimensional transition group metal carbide (nitride) and nano silicon particle composite material in a lithium ion battery cathode material.
The concrete application is as follows: stirring the two-dimensional transition metal carbide (nitride) and nano-silicon particle composite powder, the binder and the acetylene black obtained by freeze drying into electrode slurry according to the mass percentage of 60-80%, 10-30% and 10-30% respectively, coating the electrode slurry on a copper foil, controlling the thickness to be 20-200 mu m, and assembling the button lithium ion battery as a negative electrode after vacuum drying (generally 12-24 h); or the flexible composite film of the two-dimensional transition metal carbide (nitride) and the nano silicon particles obtained by vacuum filtration is directly used as a negative electrode for assembling the button lithium ion battery. And no conductive agent or adhesive is required to be added.
Has the advantages that:
1. the invention adopts nano silicon particle suspension and two-dimensional transition metal carbon (nitride) MXene nanosheet suspension to be uniformly mixed, and then the mixture is subjected to vacuum filtration to obtain a flexible composite film which is directly prepared into an electrode assembly battery or is subjected to freeze drying to obtain composite powder, a binder and acetylene black, and the composite powder, the binder and the acetylene black are stirred into slurry to prepare the electrode assembly battery. The prepared two-dimensional transition group metal carbide (nitride) and nano silicon particle composite material has the advantages of uniform dispersion and composition of nano silicon particles and two-dimensional transition group metal carbide (nitride) MXene nanosheets, large contact area and simple preparation process.
2. The two-dimensional transition metal carbide (nitride) and nano silicon particle composite material is used as a lithium ion battery cathode, and the two-dimensional transition metal carbide (nitride) MXene with unique two-dimensional morphology, excellent conductivity and large specific surface area is compounded with silicon, so that the defect of silicon conductivity can be improved, the volume change in the processes of lithium intercalation and lithium deintercalation can be effectively relieved and absorbed, and the cycle stability of the battery and the utilization rate of silicon active substances can be obviously improved.
3. The invention directly uses the two-dimensional transition group metal carbide (nitride) and nano silicon particle flexible composite film as the lithium ion battery cathode, can avoid the introduction of a binder and a conductive agent, further reduces the internal resistance of the battery, has simple process and is easy to be compatible with the existing lithium ion battery production process and equipment.
Drawings
FIG. 1 shows a two-dimensional transition metal carbide Ti prepared in example 1 of the present invention3C2TxAnd a two-dimensional transition metal carbide Ti with a silicon content of 65 wt.%3C2TxXRD pattern of the composite material with nano silicon particles.
FIG. 2 is a two-dimensional transition metal carbide Ti with a silicon content of 65 wt.% prepared in example 1 of the present invention3C2TxAnd optical electron microscope images of the nano silicon particle composite material.
FIG. 3 is a scanning electron micrograph of a two-dimensional transition group metal carbide and nano-silicon particle composite prepared in example 1 and example 2; wherein (a) is the two-dimensional transition metal carbide Ti prepared in example 1 having a silicon content of 65 wt.%3C2TxScanning electron microscope images of the nano silicon particle composite material; (b) is the two-dimensional transition metal carbide Ti with a silicon content of 65 wt.% prepared in example 23C2TxAnd scanning electron microscope images of the nano silicon particle composite material.
FIG. 4 is a two-dimensional transition metal carbonitride Ti of 65 wt.% silicon prepared in example 4 of the present invention3CNTxAnd scanning electron microscope images of the nano silicon particle composite material.
FIG. 5 shows that the negative electrode of the composite material prepared in example 1 of the present invention is used as a lithium ion battery cathode at 100mA g-1Charge and discharge curves at current density.
FIG. 6 shows that the composite materials prepared in examples 1 and 4 of the present invention have a negative electrode area of 100mAg for lithium ion batteries -1100 cycles of stability tests at current density.
Detailed Description
The technical scheme of the invention is clearly and completely described by combining the specific embodiment. It should be noted that the following description is only a preferred example of the present invention and is not intended to limit the present invention, and those skilled in the art can make various modifications and changes. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1
(1) Two-dimensional transition metal carbide Ti3C2TxPreparation of nanosheet suspension: 10mL of dilute HCl with the concentration of 6M and 0.666g of LiF are added into a plastic bottle, and 1g of ternary layered carbide Ti which is sieved by a 400-mesh sieve is slowly added under magnetic stirring3AlC2Powder is magnetically stirred for 12 hours at the temperature of 30 ℃ and the rotating speed of 250r.p.m, after the reaction is finished, the product is washed by ethanol and centrifuged until the pH value of supernatant is 6.2, the precipitate is dried at room temperature, 0.1g of the dried precipitate is added into 50mL of deionized water, ultrasonic stripping is carried out for 0.5 hour under the protection of flowing argon and the frequency of 40kHz and the power of 100W, and then the precipitate is centrifuged for 1 hour at the rotating speed of 3500r.p.m to obtain few-layer or single-layer two-dimensional transition group metal carbide Ti3C2TxA stable suspension of nanoplatelets at a concentration of 0.4 mg/mL.
(2) Two-dimensional transition metal carbide Ti3C2TxPreparing a nano silicon particle composite material: 30mg of nano-silicon particles (average size50nm) was dispersed in 15mL of an ethanol solution and sonicated at a frequency of 40kHz and a power of 100W for 1h, followed by mixing with 40mL of Ti3C2TxMixing the nanosheet suspension, performing ultrasonic treatment for 30min, performing vacuum filtration on the uniformly mixed suspension for 9h under the conditions that the air extraction rate is 4L/s and the vacuum degree is 0.04Pa, naturally drying in air at room temperature, and peeling to obtain a two-dimensional transition metal carbide Ti with the silicon content of 65 wt%3C2TxWith the flexible composite film of nano-silicon particles (fig. 1), the XRD pattern of the composite material of the following example is substantially identical to that of example 1.
(3) And (3) electrochemical performance testing: a two-dimensional transition metal carbide Ti with a silicon content of 65 wt%3C2TxThe flexible composite film with the nano silicon particles (the thickness is 18 μm, and the figure 2 and the figure 3(a)) is subjected to sheet knocking to be used as a negative electrode; a lithium sheet is taken as a positive electrode, a Celgard diaphragm is adopted, and LiPF with the concentration of 1mol/L is selected as electrolyte6And assembling the solution (wherein the solvent is Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1: 1) into the button lithium ion battery. At 100mA g-1Constant current charging and discharging are carried out under the current density, and the first discharge capacity is 4462mAh g-1(FIG. 5), the discharge capacity after 100 cycles was 1453mAh g-1(FIG. 6).
Example 2
(1) Two-dimensional transition metal carbide Ti3C2TxPreparation of nanosheet suspension: 10mL of dilute HCl with the concentration of 6M and 0.666g of LiF are added into a plastic bottle, and 1g of ternary layered carbide Ti which is sieved by a 600-mesh sieve is slowly added under magnetic stirring3AlC2Powder is magnetically stirred for 24 hours at the temperature of 35 ℃ and the rotating speed of 250 r.p.m.m.the product is washed and centrifuged by ethanol after the reaction is finished until the pH value of supernatant is 6.2, 0.2g of the dried precipitate is added into 100mL of deionized water at room temperature, ultrasonic stripping is carried out for 1 hour under the protection of flowing argon and the frequency of 40kHz and the power of 100W, and then the mixture is centrifuged for 1 hour at the rotating speed of 3500 r.p.m.to obtain few-layer or single-layer two-dimensional transition group metal carbide Ti3C2TxA stable suspension of nanoplatelets at a concentration of 0.6 mg/mL.
(2) Two-dimensional transition metal carbide Ti3C2TxPreparing a nano silicon particle composite material: dispersing 60mg of nano silicon particles (average size of 50nm) in 40mL of ethanol solution, performing ultrasonic treatment at frequency of 40kHz and power of 100W for 1h, and mixing with 50mL of Ti3C2TxMixing the nanosheet suspension liquid and performing ultrasonic treatment for 30min, pouring the uniformly mixed suspension liquid into a stainless steel disc, pre-freezing for 2h at-50 ℃, then putting the suspension liquid into a freeze dryer, and performing freeze drying for 24h at-50 ℃ and under the pressure of 10Pa to obtain a two-dimensional transition metal carbide Ti with the silicon content of 65 wt%3C2TxAnd compounding the powder with nano silicon particles.
(3) And (3) electrochemical performance testing: a two-dimensional transition metal carbide Ti with a silicon content of 65 wt%3C2TxMixing and stirring the nano silicon particle composite powder, acetylene black and polyvinylidene fluoride according to the mass ratio of 8:1:1 to prepare slurry, uniformly coating the slurry on a copper foil current collector (the thickness is 50 mu m) by using a coating machine, drying the slurry in vacuum for 24 hours, then knocking the sheet to be used as a negative electrode, using a lithium sheet as a positive electrode, adopting a Celgard diaphragm, and adopting LiPF (lithium ion plasma) with the concentration of 1mol/L as electrolyte6And assembling the solution (wherein the solvent is Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1: 1) into the button lithium ion battery. At 100mA g-1Constant current charging and discharging are carried out under the current density, and the first discharge capacity is 3786mAh g-1Discharge capacity after 100 cycles of 1652mAh g-1。
Example 3
(1) Two-dimensional transition metal carbide Ti3C2TxPreparation of nanosheet suspension: 10mL of dilute HCl with the concentration of 6M and 0.666g of LiF are added into a plastic bottle, and 1g of ternary layered carbide Ti which is sieved by a 600-mesh sieve is slowly added under magnetic stirring3AlC2Powder is magnetically stirred for 36 hours at 40 ℃ and the rotating speed of 300r.p.m, after the reaction is finished, the product is washed by ethanol and centrifuged until the pH value of supernatant is 6.2, the precipitate is dried at room temperature, 0.4g of the precipitate is added into 100mL of deionized water, under the protection of flowing argon, ultrasonic stripping is carried out for 1 hour under the frequency of 40kHz and the power of 100W, and then the precipitate is centrifuged for 1 hour at the rotating speed of 3000r.p.m to obtain few-layer or single-layer two-dimensional transition group metal carbideTi3C2TxA stable suspension of nanoplatelets at a concentration of 1.1 mg/mL.
(2) Two-dimensional transition metal carbide Ti3C2TxPreparing a nano silicon particle composite material: dispersing 20mg of nano silicon particles (average size 50nm) in 30mL of ethanol solution, performing ultrasonic treatment at frequency of 40kHz and power of 100W for 1h, and mixing with 42mL of Ti3C2TxMixing the nanosheet suspension, performing ultrasonic treatment for 30min, performing vacuum filtration on the uniformly mixed suspension for 12h under the conditions of air extraction rate of 4L/s and vacuum degree of 0.04Pa, naturally drying in air at room temperature, and peeling to obtain a two-dimensional transition metal carbide Ti with silicon content of 30 wt%3C2TxAnd the nano silicon particles are flexibly compounded with the film.
(3) And (3) electrochemical performance testing: a flexible composite film (with the thickness of 12 mu m) with the silicon content of 30 wt.% is subjected to sheet knocking to serve as a negative electrode, a lithium sheet is taken as a positive electrode, a Celgard diaphragm is adopted, and LiPF with the concentration of 1mol/L is adopted as electrolyte6And assembling the solution (wherein the solvent is Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1: 1) into the button lithium ion battery. At 100mA g-1Constant current charge and discharge are carried out under the current density, and the first discharge capacity is 2560mAh g-1And the discharge capacity after 100 cycles is 879mAh g-1。
Example 4
(1) Two-dimensional transition metal carbonitride Ti3CNTxPreparation of nanosheet suspension: 10mL of diluted 6M HCl and a certain amount of LiF are added into a plastic bottle, and 1g of ternary layered carbonitride Ti which is sieved by a 400-mesh sieve is slowly added under magnetic stirring3AlCN powder, magnetically stirring the AlCN powder at the temperature of 30 ℃ and the rotating speed of 250r.p.m for 6 hours, washing and centrifuging a product by using ethanol after the reaction is finished until the pH value of supernatant is 6.5, drying a precipitate at room temperature, adding 0.1g of the dried precipitate into 50mL of deionized water, ultrasonically stripping the precipitate for 0.5 hour at the frequency of 80kHz and the power of 100W under the protection of flowing argon, and centrifuging the precipitate for 0.5 hour at the rotating speed of 3000r.p.m to obtain a few-layer or single-layer two-dimensional transition metal carbonitride Ti-N-nitride3CNTxA stable suspension of nanoplatelets at a concentration of 0.8 mg/mL.
(2) Two-dimensional transition metal carbonitride Ti3CNTxPreparing a nano silicon particle composite material: dispersing 30mg of nano silicon particles (average size of 50nm) in 10mL of ethanol solution, performing ultrasonic treatment at frequency of 80kHz and power of 100W for 0.5h, and mixing with 60mL of Ti3CNTxMixing the nanosheet suspension, performing ultrasonic treatment for 30min, performing vacuum filtration on the uniformly mixed suspension for 12h under the conditions that the air extraction rate is 4L/s and the vacuum degree is 0.04Pa, naturally drying the uniformly mixed suspension in air at room temperature, and peeling the naturally dried suspension to obtain the two-dimensional transition metal carbonitride Ti with the silicon content of 65 wt%3CNTxAnd the nano silicon particles are flexibly compounded with the film.
(3) And (3) electrochemical performance testing: two-dimensional transition metal carbonitride Ti with silicon content of 65 wt%3CNTxKnocking with flexible composite film (thickness of 10 μm, figure 4) of nanometer silicon particles to obtain negative electrode, lithium plate as positive electrode, Celgard diaphragm, and electrolyte solution of LiPF with concentration of 1mol/L6And assembling the solution (wherein the solvent is Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1: 1) into the button lithium ion battery. At 100mA g-1Constant current charging and discharging are carried out under the current density, and the first discharge capacity is 3527mAh g-1Discharge capacity after 100 cycles of 475mAh g-1(FIG. 6).
Example 5
(1) Two-dimensional transition metal carbonitride Ti3CNTxPreparation of nanosheet suspension: 10mL of dilute 6M HCl and 0.662g LiF were added to a plastic bottle, and 1g of 600 mesh sieve of ternary layered carbonitride Ti was slowly added under magnetic stirring3AlCN powder, magnetically stirring the AlCN powder at the temperature of 35 ℃ and the rotating speed of 250r.p.m for 12 hours, washing and centrifuging a product by using ethanol after the reaction is finished until the pH value of supernatant is 6.6, drying a precipitate at room temperature, adding 0.2g of the dried precipitate into 150mL of deionized water, ultrasonically stripping the precipitate for 1 hour at the frequency of 40kHz and the power of 200W under the protection of flowing argon, and centrifuging the precipitate for 1 hour at the rotating speed of 3000r.p.m to obtain few-layer or single-layer two-dimensional transition group metal carbonitride Ti-nitride3CNTxA stable suspension of nanoplatelets at a concentration of 1.2 mg/mL.
(2)Two-dimensional transition metal carbonitride Ti3CNTxPreparing a nano silicon particle composite material: dispersing 30mg of nano silicon particles (average size of 20nm) in 30mL of ethanol solution, performing ultrasonic treatment at frequency of 40kHz and power of 200W for 1h, and mixing with 40mL of Ti3CNTxMixing the nanosheet suspension, performing ultrasonic treatment for 30min, pouring the uniformly mixed suspension into a stainless steel disc, pre-freezing for 3h at-40 ℃, then putting the suspension into a freeze dryer, and performing freeze drying for 24h at-50 ℃ and under the pressure of 10Pa to obtain a two-dimensional transition metal carbonitride Ti carbonitride with the silicon content of 65 wt%3CNTxAnd compounding the powder with nano silicon particles.
(3) And (3) electrochemical performance testing: two-dimensional transition metal carbonitride Ti with silicon content of 65 wt%3CNTxMixing and stirring the nano silicon particle composite powder, acetylene black and polyvinylidene fluoride according to the mass ratio of 6:2:2 to prepare slurry, uniformly coating the slurry on a copper foil current collector (the thickness is 150 mu m) by using a coating machine, carrying out vacuum drying for 24h, then knocking the sheet to be used as a negative electrode, using a lithium sheet as a positive electrode, adopting a Celgard diaphragm, and adopting LiPF (lithium ion plasma) with the concentration of 1mol/L as electrolyte6And assembling the solution (wherein the solvent is Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1: 1) into the button lithium ion battery. At 100mA g-1Constant current charging and discharging are carried out under the current density, and the first discharge capacity is 3036mAh g-1And the discharge capacity after 100 cycles was 552mAh g-1。
Example 6
(1) Two-dimensional transition metal carbonitride Ti3CNTxPreparation of nanosheet suspension: 10mL of dilute 6M HCl and 0.662g LiF were added to a plastic bottle, and 1g of 600 mesh sieve of ternary layered carbonitride Ti was slowly added under magnetic stirring3AlCN powder, magnetically stirring the mixture for 18 hours at the temperature of 35 ℃ and the rotating speed of 300r.p.m, washing and centrifuging a product by using ethanol after the reaction is finished until the pH value of supernatant is 6.6, drying a precipitate at room temperature, adding 0.4g of the dried precipitate into 150mL of deionized water, ultrasonically stripping the precipitate for 1 hour at the frequency of 80kHz and the power of 150W under the protection of flowing argon, and centrifuging the precipitate for 1 hour at the rotating speed of 3000r.p.m to obtain a few-layer or single-layer two-dimensional transition group metal carbonitride Ti carbonitride3CNTxA stable suspension of nanoplatelets at a concentration of 1.5 mg/mL.
(2) Two-dimensional transition metal carbonitride Ti3CNTxPreparing a nano silicon particle composite material: dispersing 20mg of nano silicon particles (average size of 80nm) in 15mL of ethanol solution, performing ultrasonic treatment at frequency of 80kHz and power of 150W for 1h, and mixing with 30mL of Ti3CNTxMixing the nanosheet suspension, performing ultrasonic treatment for 30min, performing vacuum filtration on the uniformly mixed suspension for 6h under the conditions of air extraction rate of 4L/s and vacuum degree of 0.04Pa, naturally drying in air at room temperature, and peeling to obtain a two-dimensional transition metal carbonitride Ti with silicon content of 30 wt%3CNTxAnd the nano silicon particles are flexibly compounded with the film.
(3) And (3) electrochemical performance testing: two-dimensional transition metal carbonitride Ti with silicon content of 30 wt%3CNTxTaking a flexible composite film (with the thickness of 25 mu m) with nano silicon particles as a negative electrode, taking a lithium sheet as a positive electrode, and adopting LiPF with the concentration of 1mol/L as electrolyte6And assembling the solution (wherein the solvent is Ethylene Carbonate (EC) and diethyl carbonate (DEC) according to the volume ratio of 1: 1) into the button lithium ion battery. At 100mA g-1Constant current charging and discharging are carried out under the current density, and the first discharge capacity is 2960mAh g-1And the discharge capacity after 100 cycles is 609mAh g-1。

Claims (6)

1. A two-dimensional transition group metal carbon and/or nitride and nano silicon particle composite material is characterized in that: the composite material is formed by uniformly dispersing and compounding two-dimensional transition group metal carbon and/or nitride nanosheets and nano silicon particles, and then a flexible composite film of the two-dimensional transition group metal carbon and/or nitride and the nano silicon particles is obtained through vacuum filtration or composite powder of the two-dimensional transition group metal carbon and/or nitride and the nano silicon particles is obtained through freeze drying; wherein the average size of the nano silicon particles is 10-100nm, and the percentage content of silicon in the total mass of the composite material is 20-85%; the thickness of the flexible composite film is 5-30 mu m.
2. The two-dimensional scroll of claim 1The composite material of the transition metal carbon and/or nitride and the nano silicon particles is characterized in that: the two-dimensional transition metal carbon and/or nitride is Ti3C2Tx、Ti3CNTx、Ti2CTx、(Ti0.5,Nb0.5)2CTx、(V0.5,Cr0.5)3C2Tx、Ta4C3Tx、V2CTx、Nb2CTx、Nb4C3Tx、(Nb0.8,Ti0.2)4C3Tx、(Nb0.8,Zr0.2)4C3Tx、Mo2TiC2Tx、Mo2Ti2C3Tx、Mo2CTx、Cr2TiC2Tx、Zr3C2TxOr Ti4N3Tx。
3. A method for preparing the two-dimensional transition group metal carbon and/or nitride and nano silicon particle composite material of claim 1, which comprises the following specific steps: adding the nano silicon particle suspension into the two-dimensional transition group metal carbon and/or nitride nanosheet suspension, ultrasonically mixing the two suspensions uniformly, and then carrying out vacuum filtration to obtain a flexible composite film of the two-dimensional transition group metal carbon and/or nitride and the nano silicon particles or freeze-drying to obtain composite powder of the two-dimensional transition group metal carbon and/or nitride and the nano silicon particles; wherein the concentration of the two-dimensional transition group metal carbon and/or nitride nanosheet suspension is 0.2-1.5 mg/mL; the concentration of the nano silicon particle suspension is 0.2-3 mg/mL; the freeze drying is carried out by pre-freezing for 2-5h at-30 to-50 ℃, and then drying for 12-36h under vacuum at-50 to-70 ℃.
4. The method of claim 3, wherein: the ultrasonic frequency is 40-100kHz, the ultrasonic power is 50-200W, and the ultrasonic time is 0.5-1 h; the vacuum filtration is carried out for 6-12h under the conditions that the air extraction rate is 4-6L/s and the vacuum degree is 0.03-0.06 Pa.
5. Use of the two-dimensional transition group metal carbon and/or nitride and nano-silicon particle composite material of claim 1 in a lithium ion battery anode material.
6. The application of the composite material according to claim 5, wherein the composite powder of the two-dimensional transition metal carbon and/or nitride and the nano silicon particles, the binder and the acetylene black which are obtained by freeze drying are stirred into electrode slurry according to the mass percentage of 60-80%, 10-30% and 10-30% respectively, the electrode slurry is coated on a copper foil, the thickness is controlled to be 20-200 μm, and the electrode slurry is used as a negative electrode after vacuum drying to assemble a button type lithium ion battery; or the flexible composite film of the two-dimensional transition group metal carbon and/or nitride and the nano silicon particles obtained by vacuum filtration is directly used as a negative electrode for assembling the button lithium ion battery.
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CN108328616A (en) * 2018-04-20 2018-07-27 昆明理工大学 A kind of preparation method of three-dimensional MXene
CN109346681A (en) * 2018-08-17 2019-02-15 福建翔丰华新能源材料有限公司 A kind of nuclear shell structure nano silicon-MXene composite negative pole material and preparation method thereof
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CN112875706A (en) * 2021-01-05 2021-06-01 昆山宝创新能源科技有限公司 Self-supporting MXene/Si composite anode material and preparation method and application thereof
CN113422112B (en) * 2021-07-05 2023-04-11 大连理工大学 High-energy and high-safety all-solid-state secondary battery based on lithium sulfide anode and preparation method thereof
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105762360A (en) * 2016-04-01 2016-07-13 上海交通大学 Graphene-silicon-coated composite negative electrode material and preparing method and application thereof
CN106450205A (en) * 2016-11-02 2017-02-22 南京工业大学 Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof
CN106571244A (en) * 2016-11-02 2017-04-19 南京工业大学 Two-dimensional transition metal carbon (nitrogen) compound and two-dimensional transition metal sulfide nano-composite powder, and preparation and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105762360A (en) * 2016-04-01 2016-07-13 上海交通大学 Graphene-silicon-coated composite negative electrode material and preparing method and application thereof
CN106450205A (en) * 2016-11-02 2017-02-22 南京工业大学 Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof
CN106571244A (en) * 2016-11-02 2017-04-19 南京工业大学 Two-dimensional transition metal carbon (nitrogen) compound and two-dimensional transition metal sulfide nano-composite powder, and preparation and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Constraining Si Particles within Graphene Foam Monolith: Interfacial Modification for High-Performance Li + Storage and Flexible Integrated Configuration;Yue Ma等;《Adv. Funct. Mater.》;20160803;第26卷;第6797页摘要、第6805页左栏实验部分第1-3段 *
二维晶体Ti2CTx MXene的制备、剥离及其电化学性能;张天等;《人工晶体学报》;20160630;第45卷(第6期);第1515页引言部分 *

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