CN106025200A - Preparation method and application of nitrogen-doped MXene battery anode material - Google Patents

Preparation method and application of nitrogen-doped MXene battery anode material Download PDF

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CN106025200A
CN106025200A CN201610347054.4A CN201610347054A CN106025200A CN 106025200 A CN106025200 A CN 106025200A CN 201610347054 A CN201610347054 A CN 201610347054A CN 106025200 A CN106025200 A CN 106025200A
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mxene
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CN106025200B (en
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姜银珠
郝梦倩
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Zhejiang University ZJU
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention discloses a preparation method of a nitrogen-doped MXene battery anode material and application thereof in a lithium ion battery and a sodium ion battery. The preparation method of the nitrogen-doped MXene battery anode material comprises two steps of preparation of an MXene material and nitrogen doping on the MXene material, wherein the invention discloses a solvothermal method, a thermal treatment method, a plasma treatment method and a microwave irradiation gas phase method which are used for carrying out the nitrogen doping on the MXene material. According to the preparation method of the nitrogen-doped MXene battery anode material, disclosed by the invention, the nitrogen-doped MXene battery anode material prepared through multiple methods has good conductivity, good cyclic stability, good rate capability and higher specific surface area, and is suitable for large-scale development and application of the lithium ion battery or the sodium ion battery.

Description

A kind of N doping MXene The preparation method and applications of cell negative electrode material
Technical field
The invention belongs to cell art, particularly to the preparation method and applications of a kind of MXene cell negative electrode material.
Background technology
Along with the high speed development of modern society, traditional energy is the most exhausted, finds new clean energy resource and becomes the most urgent.Lithium ion battery due to have high energy density, power density, running voltage is high, self-discharge rate is low, memory-less effect, have extended cycle life, the unique advantage such as pollution-free, develop into a kind of most important and state-of-the-art secondary cell rapidly.
The lithium ion battery negative material of commercialization at present uses low price, Heat stability is good, eco-friendly graphitized carbon material mostly, but owing to the intercalation potential ratio of graphite is relatively low, it is easily caused the decomposition of electrolyte and the precipitation of dendrite lithium, causes a series of safety problem.It is, thus, sought for the new negative material higher, cheap and easy to get, more safe and reliable than material with carbon element intercalation potential.
On the other hand, in the earth's crust, the reserves of sodium element are (in the earth's crust, metallic element are number four, and accounts for the 2.64% of gross reserves) extremely enriched, and cheap, are in same main group with elemental lithium, and chemical property is similar, and electrode potential is the most relatively.Therefore, sodium-ion battery starts new round research boom.At present, the anode material of lithium-ion battery seeking high power capacity and excellent cycling performance becomes the focus that battery research field is new.
Owing to the radius ratio lithium ion of sodium ion is big, reach in lithium ion battery the graphitic carbon negative electrode material of business application due to its interlamellar spacing less by (0.335 Nm) the free deintercalation of sodium ion can not be met, it is impossible to be applied in sodium-ion battery.Disordering, hard carbon class material that interlamellar spacing is bigger be then more suitable as anode material of lithium-ion battery, its storage sodium mechanism mainly by the deintercalation between lamella of sodium ion and is carried out by the way of gathering in micropore in hard carbon, and specific capacity is the highest can reach 300mAh/g.But, cyclical stability is the most poor, it is impossible to meet the needs of reality application.
MXene is a kind of novel transition metal carbide two dimensional crystal, has the structure similar with Graphene.Chemical formula is Mn+1Xn, wherein n=1,2 or 3, M is in early days transition metal, and X is carbon or/and nitrogen element.This class material can be obtained by Fluohydric acid. laminate ceramic MAX phase of dissociating, there is good electric conductivity, low ion diffusional resistance, low open-circuit voltage and high memory capacity, simultaneously, well battery behavior can be combined with fake capacitance behavior, thus improve capacity further, be highly suitable as lithium ion battery or anode material of lithium-ion battery.After N doping, in MXene, part C atom is replaced by atom N, and surface has substantial amounts of defect so that it is specific capacity, high rate performance, stable circulation performance etc. improve further.
Summary of the invention
In order to make up above-mentioned the deficiencies in the prior art, the technical problem to be solved is to provide preparation method and its application in lithium ion battery and sodium-ion battery of N doping MXene material.
The invention provides the preparation method of a kind of N doping MXene cell negative electrode material material, comprise the following steps:
Step one, the preparation of MXene material: MAX phase is added in hydrofluoric acid solution with the matched proportion density of 0.02 ~ 0.2g/ml, is stirred at room temperature certain time, remove the A atomic layer in MAX phase, take off a layer solid, be washed with deionized and be centrifuged, be 5 ~ 7 to pH value；60 ~ 120oC is vacuum dried 8 ~ 48h；Dried powder body is placed in heat-treatment furnace, is passed through H2/ Ar gaseous mixture, 400 ~ 800oC heat treatment 1 ~ 4h；Prepare described MXene material；
Step 2, the MXene material preparing step one carries out N doping；
Wherein, described MXene material is a kind of transition metal carbide or carbonitride two dimensional crystal, and its chemical formula is Mn+1Xn, n=1,2 or 3, M is in early days transition metal, and X is carbon or/and nitrogen element.Described MAX is M for a kind of chemical formulan+1AXnTernary layered compound, wherein M, X, n are identical with M, X, the n in MXene material, and A is the three, the 4th major elements.
Further, described MAX phase is Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC；What MXene material that step one is prepared was corresponding is respectively Ti3C2, Ti2C, V2C or Nb2C。
Further, present invention employs multiple method and the MXene material that step one is prepared is carried out N doping, wherein method one is solvent-thermal method, particularly as follows: the MXene powder body and the reproducibility nitrogen-containing solvent that described step one are prepared are placed in reactor and carry out hydro-thermal reaction, carry out high-temperature process afterwards and obtain described N doping MXene material；Wherein reproducibility nitrogen-containing solvent is: with carbamide for mixed solvent as reducing agent of nitrogen source, acetone oxime.
The method two of the N doping that the present invention uses is N2Heat treating process, particularly as follows: be placed in heat-treatment furnace by the MXene material that described step one prepares, is passed through H2/N2Mixed gas, 600 ~ 1200oC heat treatment 2 ~ 8h, prepares N doping MXene material.
The method three of the N doping that the present invention uses is NH3Heat treating process, described NH3Heat treating process is: is placed in heat-treatment furnace by the MXene material that described step one prepares, is passed through NH with the flow velocity of 1:13/ Ar and H2/ Ar mixed gas, 400 ~ 1000oC heat treatment 1 ~ 6h, prepares described N doping MXene material.
The method four of the N doping that the present invention uses is plasma processing, particularly as follows: the MXene material that described step one prepares is dispensed in chitosan, described MXene material is 1 ~ 6:1 with the mass ratio of chitosan, is applied on glass-carbon electrode by this dispersion liquid, is placed on the N of upper state2In plasma gas stream, when gas stream touches MXene surface, make part carbon atom be replaced by nitrogen-atoms, prepare described N doping MXene material；Wherein it is placed in the N of upper state2The process time in plasma gas stream is 1 ~ 3min, the nitrogen content 0.08wt.% ~ 1.3wt.% of N doping MXene material.
The method five of the N doping that the present invention uses is microwave exposure vapor phase method, particularly as follows: the MXene material that described step one prepares is scattered in unsaturated carbonate ammonium salt solution, stirring dipping 12 ~ 36h, obtains MXene intercalation compound filter cake, by gained MXene intercalation compound filter cake 35 ~ 70 after filtrationoC is vacuum dried, and is then placed in microwave oven by the container filling dried MXene intercalation compound, irradiation 1 ~ 3min under full power, prepares N doping MXene material.
Present invention also offers the N doping MXene cell negative electrode material prepared by method made above.And use this battery cathode to use, it is fabricated to lithium ion battery or sodium-ion battery, the invention provides and make lithium ion battery or the method for sodium-ion battery with N doping MXene for cell negative electrode material.
N doping MXene cell negative electrode material prepared by the present invention has good electric conductivity, low ion diffusional resistance, low open-circuit voltage and high memory capacity, simultaneously, well battery behavior can be combined with fake capacitance behavior, thus improve capacity further, it is highly suitable as lithium ion battery and anode material of lithium-ion battery.By N doping in preparation method of the present invention, making MXene surface have substantial amounts of defect, capacity improves further, compares the MXene material not carrying out N doping, and specific capacity increases can reach 45%.
Accompanying drawing explanation
Fig. 1 is the MXene material Ti of undoped p nitrogen in application examples 13C2The sodium-ion battery cyclic voltammetry curve when electric current density 0.5A/g, voltage range 0.01～3V prepared for negative material.
Fig. 2 is N doping MXene material N-Ti in application examples 13C2The sodium-ion battery cyclic voltammetry curve when electric current density 0.5A/g, voltage range 0.01～3V prepared for negative material.
Fig. 3 is the MXene material Ti of undoped p nitrogen in application examples 23C2The lithium ion battery cyclic voltammetry curve when electric current density 0.5A/g, voltage range 0.01～3V prepared for negative material.
Fig. 4 is N doping MXene material N-Ti in application examples 23C2The sodium-ion battery cyclic voltammetry curve when electric current density 0.5A/g, voltage range 0.01～3V prepared for negative material.
Fig. 5 is the MXene material Ti of undoped p nitrogen in application examples 33C2The sodium-ion battery cyclic voltammetry curve when electric current density 0.5A/g, voltage range 0.01～3V prepared for negative material.
Fig. 6 is N doping MXene material N-Ti in application examples 33C2The sodium-ion battery cyclic voltammetry curve when electric current density 0.5A/g, voltage range 0.01～3V prepared for negative material.
Fig. 7 is the MXene material Ti of undoped p nitrogen in application examples 43C2The lithium ion battery cyclic voltammetry curve when electric current density 0.5A/g, voltage range 0.01～3V prepared for negative material.
Fig. 8 is N doping MXene material N-Ti in application examples 43C2The sodium-ion battery cyclic voltammetry curve when electric current density 0.5A/g, voltage range 0.01～3V prepared for negative material.
Detailed description of the invention
The present invention is further illustrated below by specific embodiment, it should be understood, however, that, these embodiments are only used for specifically describing in more detail use, and are not to be construed as limiting in any form the present invention.
This part to the present invention test used in material and test method carry out general description.Although by realize many materials that the object of the invention used and operational approach is to it is known in the art that but the present invention still describes in detail as far as possible at this.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and operational approach are well known in the art.
Embodiment 1
The present embodiment uses solvent-thermal method prepare N doping MXene material, concretely comprises the following steps:
1) MXene material is prepared: MAX phase added in hydrofluoric acid solution with the matched proportion density of 0.02 ~ 0.2g/ml, be stirred at room temperature certain time, remove A atomic layer；Take off a layer solid, be washed with deionized and be centrifuged, be 5 ~ 7 to pH value；60 ~ 120oC is vacuum dried 8 ~ 48h；Dried powder body is placed in heat-treatment furnace, is passed through H2/ Ar gaseous mixture, 400 ~ 800oC heat treatment 1 ~ 4h；Prepare described MXene material.
Wherein, MAX phase is respectively Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC；The MXene material prepared corresponds to Ti respectively3C2, Ti2C, V2C or Nb2C。
2) carrying out N doping: the MXene prepared with step 1) is as raw material, and carbamide is nitrogen source, be 0.2 ~ 0.6 to add in deionized water with the ratio of the amount of material, being simultaneously introduced 5 ~ 40mmol/L acetone oxime (DMKO) is reducing agent, H2/ Ar gaseous mixture is protection gas, 120 ~ 200oUnder C, hydro-thermal 2 ~ 8h；Take off a layer solid, be centrifuged and wash, 60 ~ 120oC is vacuum dried 8 ~ 48h；Dried powder body is placed in tube furnace, is passed through H2/ Ar mixed gas, 400 ~ 800oC heat treatment 4 ~ 12h, prepares N doping MXene material.
Embodiment 2
The present embodiment uses N2Heat treating process prepares N doping Mxene material, concretely comprises the following steps:
1) prepare MXene material: identical with embodiment 1 step 1), wherein MAX phase be chemical formula be Mn+1AXnTernary layered compound, wherein MAX phase be respectively Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC；The MXene material prepared corresponds to Ti respectively3C2, Ti2C, V2C or Nb2C。
2) N doping is carried out: be placed in tube furnace by the MXene powder body that step 1) prepares, be passed through H2/N2Gaseous mixture, 600 ~ 1200oC heat treatment 2 ~ 8h, prepares N doping MXene material.
Embodiment 3
The present embodiment uses NH3Heat treating process prepares N doping Mxene material, concretely comprises the following steps:
1) preparing MXene material: identical with embodiment 1 step 1), wherein MAX phase is respectively Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC；The MXene material prepared corresponds to Ti respectively3C2, Ti2C, V2C or Nb2C。
2) N doping is carried out: be placed in tube furnace by the MXene powder body that step 1) prepares, each lead into NH with the flow velocity of 1:13/ Ar and H2/ Ar gaseous mixture, 400 ~ 1000oC heat treatment 1 ~ 6h, prepares N doping MXene.
Embodiment 4
The present embodiment uses plasma processing prepare N doping Mxene material, concretely comprises the following steps:
1) preparing MXene material: identical with embodiment 1 step 1), wherein MAX phase is respectively Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC；The MXene material prepared corresponds to Ti respectively3C2, Ti2C, V2C or Nb2C。
2) N doping is carried out: be dispensed into by the MXene powder body that step 1) prepares in chitosan (MXene is 1 ~ 6:1 with the mass ratio of chitosan), be then applied on glass-carbon electrode by this dispersion liquid, be placed on the N of 99.75 Pa2In plasma chamber, when treated between when being 1 ~ 3min, nitrogen content can be adjusted to 1.3wt.% by 0.08%wt..
Embodiment 5
The present embodiment uses microwave exposure vapor phase method prepare N doping MXene material, concretely comprises the following steps:
1) preparing MXene material: identical with embodiment 1 step 1), wherein MAX phase is respectively Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC；The MXene material prepared corresponds to Ti respectively3C2, Ti2C, V2C or Nb2C。
2) carry out N doping: be scattered in unsaturated carbonate ammonium salt solution with the proportioning of 0.8 ~ 1.5g/mL by the MXene powder body that step 1) prepares, stir dipping 12 ~ 36h, filter, after filtration, obtain MXene intercalation compound filter cake；By this filter cake 35 ~ 70oC is vacuum dried.MXene intercalation compound after vacuum drying is contained in glass container, is placed in microwave oven, irradiation 1min under full power, prepare N doping MXene material.
Application examples 1
Should use-case use above-described embodiment prepare N doping MXene material be cell negative electrode material, use coating method prepare battery cathode, be then mounted to sodium-ion battery and test.Specifically comprise the following steps that
Prepared by step 1) negative pole: the 0.3g N doping MXene material prepared by above-described embodiment adds in 10ml dimethyl sulfoxide (DMSO), and 18h is stirred at room temperature；Being placed in a centrifuge by N doping MXene dimethyl sulfoxide suspension after stirring, 800 r/min are centrifuged, and take off a layer solid；Will centrifugal after solid add in 300ml deionized water, ultrasonic obtain N doping MXene suspension；N doping MXene suspension is centrifuged at 400 r/min, takes the supernatant；The supernatant is centrifuged at 800r/min, takes off a layer solid, in 120oC is vacuum dried 24h；Ratio according to mass ratio 8:1:1, by dried N doping MXene powder, Kynoar binding agent and conductive agent Ketjen black mix homogeneously, add appropriate NMP(N-methyl pyrrolidone) solution ultrasonic disperse, it is mixing uniformly to form slurry to be coated on Copper Foil, it is cut into the electrode slice of a diameter of 15mm after drying, is dried 10 hours in 120 DEG C under vacuum；Prepare the battery cathode sheet with N doping MXene material as negative material.
Step 2) battery install and test: in the glove box of argon gas atmosphere, with above-mentioned prepared electrode slice as negative pole, using metallic sodium sheet as to electrode, the NaPF of 1M6(EC:DEC=1:1) solution is as electrolyte, with Celgard 2300 as barrier film, is assembled into 2025 button sodium-ion batteries.Battery charging and discharging experiment uses constant current charge-discharge pattern to carry out on new prestige (Neware) battery test system, and voltage tester scope is 0.01～3V to test.As Fig. 2 be should use-case use above-described embodiment prepare N doping MXene material N-Ti3C2In electric current density 0.5A/g, the cyclic voltammetry curve of sodium-ion battery during voltage range 0.01～3V.In order to contrast, use the preparation of duplicate electrode and battery installation method, use the MXene material Ti not carrying out N doping3C2, prepare sodium-ion battery, under same test condition, its cyclic voltammetry curve of survey is as shown in Figure 1.It can be seen that compared to Ti from two figures3C2, N-Ti3C2Specific capacity for the sodium-ion battery of negative material increases 17%.
Application examples 2
Should use-case use above-described embodiment prepare N doping MXene material be cell negative electrode material, use coating method prepare battery cathode, be then mounted to lithium ion battery and test.Concrete steps are the same with application examples 1, when its difference is that carrying out battery installs, using metal lithium sheet as to electrode, the LiPF of 1M6(EC:DEC=1:1) solution is as electrolyte.Test result such as Fig. 4 be should use-case use above-described embodiment prepare N doping MXene material N-Ti3C2In electric current density 0.5A/g, the cyclic voltammetry curve of lithium ion battery during voltage range 0.01～3V.Same in order to contrast, have employed the MXene material Ti not carrying out N doping3C2, prepare lithium ion battery, under same test condition, its cyclic voltammetry curve of survey is as shown in Figure 3.It can be seen that compared to Ti from two figures3C2, N-Ti3C2Specific capacity for the lithium ion battery of negative material increases 29%.
Application examples 3
Should use-case use above-described embodiment prepare N doping MXene material be cell negative electrode material, use suction method prepare battery cathode, be then mounted to sodium-ion battery and test.Specifically comprise the following steps that
0.3g N doping MXene is added in 10ml dimethyl sulfoxide (DMSO), 18h is stirred at room temperature；Being placed in a centrifuge by N doping MXene dimethyl sulfoxide suspension after stirring, 800 r/min are centrifuged, and take off a layer solid；Will centrifugal after solid add in 300ml deionized water, ultrasonic obtain N doping MXene suspension；Being centrifuged at 400 r/min by N doping MXene suspension, taking supernatant N-MXene is precursor liquid, on sucking filtration to polycarbonate leaching film, 20 ~ 80oC is vacuum dried 5 ~ 15min, peels off and obtains thin film, is dried 8 ~ 24 hours in 40 ~ 80 DEG C under vacuum, prepares the battery cathode sheet with N doping MXene material as negative material.Subsequent installation battery is as application examples 1.Same in order to contrast, test the sodium-ion battery with the MXene not carrying out N doping as negative material simultaneously.
Fig. 5 and Fig. 6 respectively should use-case prepare with Ti3C2And N-Ti3C2For the sodium-ion battery of negative material in electric current density 0.5A/g, cyclic voltammetry curve during voltage range 0.01～3V, it can be seen that compared to Ti3C2, N-Ti3C2Battery specific capacity for negative material increases 30.3%.
Application examples 4
Should use-case use above-described embodiment prepare N doping MXene material be cell negative electrode material, use suction method prepare battery cathode, be then mounted to lithium ion battery and test.Concrete steps are the same with application examples 3, when its difference is that carrying out battery installs, using metal lithium sheet as to electrode, the LiPF of 1M6(EC:DEC=1:1) solution is as electrolyte.Same in order to contrast, test the sodium-ion battery with the MXene not carrying out N doping as negative material simultaneously.
Fig. 7 and Fig. 8 respectively should the Ti for preparing of use-case3C2And N-Ti3C2For the lithium ion battery of negative material in electric current density 0.5A/g, cyclic voltammetry curve during voltage range 0.01～3V, it can be seen that compared to Ti3C2, N-Ti3C2Battery specific capacity for negative material increases 45%.
In above-mentioned application examples, when making battery cathode, it would however also be possible to employ N doping MXene cell negative electrode material prepared by the present invention and other materials are mixed to form on collector, prepare battery cathode, as N-MXene mixes with Graphene, or N-MXene mixes with CNT (CNTs).

Claims (10)

1. the preparation method of a N doping MXene cell negative electrode material, it is characterised in that comprise the following steps:
Step one, the preparation of described MXene material: MAX phase is added in hydrofluoric acid solution with the matched proportion density of 0.02 ~ 0.2g/ml, is stirred at room temperature certain time, remove the A atomic layer in MAX phase, take off a layer solid, be washed with deionized and be centrifuged, be 5 ~ 7 to pH value；60 ~ 120oC is vacuum dried 8 ~ 48h；Dried powder body is placed in heat-treatment furnace, is passed through H2/ Ar gaseous mixture, 400 ~ 800oC heat treatment 1 ~ 4h；Prepare described MXene material；
Step 2, carries out N doping to described MXene material, prepares described N doping MXene cell negative electrode material；
Wherein, described MXene material is a kind of transition metal carbide or carbonitride two dimensional crystal, and its chemical formula is Mn+1Xn, n=1,2 or 3, M is in early days transition metal, and X is carbon or/and nitrogen element；
Wherein, described MAX is M for a kind of chemical formulan+1AXnTernary layered compound, wherein M, X, n are identical with M, X, the n in MXene material, and A is the 3rd or the 4th major element.
The preparation method of a kind of N doping MXene cell negative electrode material the most according to claim 1, it is characterised in that described MAX phase is Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC；What MXene material that step one is prepared was corresponding is respectively Ti3C2, Ti2C, V2C or Nb2C。
The preparation method of a kind of N doping MXene cell negative electrode material the most according to claim 1, it is characterized in that, it is solvent-thermal method that step 2 carries out the method for N doping to described MXene material, described solvent-thermal method is: the MXene powder body and the reproducibility nitrogen-containing solvent that described step one are prepared are placed in reactor and carry out hydro-thermal reaction, carry out high-temperature process afterwards and obtain described N doping MXene cell negative electrode material；
Wherein said reproducibility nitrogen-containing solvent is: with carbamide for mixed solvent as reducing agent of nitrogen source, acetone oxime.
The preparation method of a kind of N doping MXene cell negative electrode material the most according to claim 1, it is characterised in that it is N that step 2 carries out the method for N doping to described MXene material2Heat treating process, described N2Heat treating process is: is placed in heat-treatment furnace by the MXene material that described step one prepares, is passed through H2/N2Mixed gas, 600 ~ 1200oC heat treatment 2 ~ 8h, prepares described N doping MXene cell negative electrode material.
The preparation method of a kind of N doping MXene cell negative electrode material the most according to claim 1, it is characterised in that it is NH that step 2 carries out the method for N doping to described MXene material3Heat treating process, described NH3Heat treating process is: is placed in heat-treatment furnace by the MXene material that described step one prepares, is passed through NH with the flow velocity of 1:13/ Ar and H2/ Ar mixed gas, 400 ~ 1000oC heat treatment 1 ~ 6h, prepares described N doping MXene cell negative electrode material.
The preparation method of a kind of N doping MXene cell negative electrode material the most according to claim 1, it is characterized in that, it is plasma processing that step 2 carries out the method for N doping to described MXene material, described plasma processing is: be dispensed in chitosan by the MXene material that described step one prepares, described MXene material is 1 ~ 6:1 with the mass ratio of chitosan, this dispersion liquid is applied on glass-carbon electrode, is placed on the N of upper state2In plasma gas stream, when gas stream touches MXene surface, make part carbon atom be replaced by nitrogen-atoms, prepare described N doping MXene cell negative electrode material；Wherein it is placed in the N of upper state2The process time in plasma gas stream is 1 ~ 3min, the nitrogen content 0.08wt.% ~ 1.3wt.% of N doping MXene material.
The preparation method of a kind of N doping MXene material the most according to claim 1, it is characterized in that, it is microwave exposure vapor phase method that step 2 carries out the method for N doping to described MXene material, described microwave exposure vapor phase method is: be scattered in unsaturated carbonate ammonium salt solution by the MXene material that described step one prepares, stirring dipping 12 ~ 36h, MXene intercalation compound filter cake is obtained, by gained MXene intercalation compound filter cake 35 ~ 70 after filtrationoC is vacuum dried, and is then placed in microwave oven by the container filling dried MXene intercalation compound, irradiation 1 ~ 3min under full power, prepares described N doping MXene cell negative electrode material.
8. the N doping MXene cell negative electrode material prepared according to claim 1～7 any one preparation method.
The application of a kind of N doping MXene cell negative electrode material the most according to claim 8, it is characterised in that described N doping MXene cell negative electrode material is used as lithium ion battery negative material.
The application of a kind of N doping MXene cell negative electrode material the most according to claim 8, it is characterised in that described N doping MXene cell negative electrode material is used as anode material of lithium-ion battery.
CN201610347054.4A 2016-05-24 2016-05-24 A kind of preparation method and applications of N doping MXene cell negative electrode material Active CN106025200B (en)

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CN115159451A (en) * 2022-08-04 2022-10-11 华北电力大学（保定） Preparation method of aluminum hydride/magnesium borohydride @ MXene composite hydrogen storage material
CN116282023A (en) * 2022-09-09 2023-06-23 深圳大学 Heteroatom doped MXene material and preparation method and application thereof
CN115818657A (en) * 2022-11-18 2023-03-21 仲恺农业工程学院 Preparation method of hybrid ion doped MBene composite material
CN115799519A (en) * 2023-02-08 2023-03-14 中国人民解放军国防科技大学 Modified lithium-rich layered oxide cathode material and preparation method and application thereof

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