CN106025200B - A kind of preparation method and applications of N doping MXene cell negative electrode material - Google Patents
A kind of preparation method and applications of N doping MXene cell negative electrode material Download PDFInfo
- Publication number
- CN106025200B CN106025200B CN201610347054.4A CN201610347054A CN106025200B CN 106025200 B CN106025200 B CN 106025200B CN 201610347054 A CN201610347054 A CN 201610347054A CN 106025200 B CN106025200 B CN 106025200B
- Authority
- CN
- China
- Prior art keywords
- mxene
- doping
- negative electrode
- alc
- cell negative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of preparation method of N doping MXene cell negative electrode material and its applications in lithium ion battery and sodium-ion battery.Preparation method includes the preparation of MXene material and carries out two steps of N doping to MXene material, wherein the invention discloses the solvent-thermal method, heat treating process, plasma processing and the microwave irradiation vapor phase methods that carry out N doping to MXene material.The N doping MXene material that the present invention is prepared by a variety of methods has good conductive property, stable circulation performance, high rate performance and higher specific surface area, large-scale development and application suitable for lithium ion battery or sodium-ion battery.
Description
Technical field
The invention belongs to battery technology field, in particular to the preparation method of a kind of MXene cell negative electrode material and its answer
With.
Background technique
With the high speed development of modern society, traditional energy is increasingly depleted, and finding new clean energy resource becomes more urgent.
Lithium ion battery is since with high energy density, power density, operating voltage is high, self-discharge rate is low, memory-less effect, circulation
Service life is long, the unique advantages such as pollution-free, rapidly develops into a kind of most important and state-of-the-art secondary cell.
The lithium ion battery negative material being commercialized at present mostly uses greatly that cheap, thermal stability is good, environmental-friendly
Graphitized carbon material, but since the intercalation potential of graphite is relatively low, it is easy to cause the decomposition of electrolyte and the precipitation of dendrite lithium,
Cause a series of safety problem.It is, thus, sought for higher than carbon material intercalation potential, cheap and easy to get, safe and reliable is new
Negative electrode material.
On the other hand, the reserves of sodium element are that extremely abundant (metallic element is number four in the earth's crust, and Zhan is always stored up in the earth's crust
The 2.64% of amount), and it is cheap, it is in same main group with elemental lithium, chemical property is similar, and electrode potential is also relatively.
Therefore, sodium-ion battery starts new round research boom.Currently, the sodium-ion battery for seeking high capacity and excellent cycling performance is negative
Pole material becomes the new hot spot of battery research field.
Since the radius ratio lithium ion of sodium ion is big, the graphitic carbon negative electrode material of business application is reached in lithium ion battery
Free deintercalation due to its interlamellar spacing smaller (0.335 nm) without being able to satisfy sodium ion can not be applied in sodium-ion battery.
And disordering, the biggish hard Carbon materials of interlamellar spacing be then more suitable as anode material of lithium-ion battery, store up sodium mechanism master
If being carried out by way of assembling deintercalation of the sodium ion between lamella and in micropore in hard carbon, specific capacity highest
It can achieve 300mAh/g.But cyclical stability is still poor, is not able to satisfy the needs of practical 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 are early stage transition metal element, and X is carbon or/and nitrogen.This kind of materials can pass through hydrogen
Fluoric acid dissociation laminate ceramic MAX phase obtain, have good electric conductivity, low ion diffusional resistance, low open-circuit voltage and
High memory capacity, meanwhile, it is capable to well by battery behavior in conjunction with fake capacitance behavior, so that capacity is further increased, it is non-
Often it is suitable as lithium ion battery or anode material of lithium-ion battery.After N doping, C atom in part is by N atom in MXene
Replace, surface has a large amount of defect, further increases its specific capacity, high rate performance, stable circulation performance etc..
Summary of the invention
To make up for the shortcomings of the above existing technologies, technical problem to be solved by the invention is to provide N doping MXene
The preparation method of material and its application in lithium ion battery and sodium-ion battery.
The present invention provides a kind of preparation methods of N doping MXene cell negative electrode material material, comprising the following steps:
The preparation of MXene material: hydrofluoric acid solution is added with the matched proportion density of 0.02 ~ 0.2g/ml in MAX phase by step 1
In, certain time is stirred at room temperature, removes the A atomic layer in MAX phase, takes lower layer's solid, be washed with deionized and be centrifuged,
It is 5 ~ 7 to pH value;60 ~ 120oC is dried in vacuo 8 ~ 48h;Powder after drying is placed in heat-treatment furnace, H is passed through2/ Ar mixing
Gas, 400 ~ 800oC is heat-treated 1 ~ 4h;The MXene material is made;
Step 2 carries out N doping to MXene material made from step 1;
Wherein, the MXene material is a kind of transition metal carbide or carbonitride two dimensional crystal, chemical formula are
Mn+1Xn, n=1,2 or 3, M is early stage transition metal element, and X is carbon or/and nitrogen.It is M that the MAX, which is a kind of chemical formula,n+ 1AXnTernary layered compound, wherein M, X, n are identical as M, X, n in MXene material, A be third, the 4th major element.
Further, the MAX phase is Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC;The MXene material that step 1 is prepared
Expect that corresponding is respectively Ti3C2, Ti2C, V2C or Nb2C。
Further, present invention employs a variety of methods carries out N doping to MXene material made from step 1, wherein side
Method one is solvent-thermal method, specifically: MXene powder made from the step 1 and reproducibility nitrogen-containing solvent are placed in reaction kettle
Hydro-thermal reaction is carried out, high-temperature process is carried out later and obtains the N doping MXene material;Wherein reproducibility nitrogen-containing solvent are as follows: with
The mixed solvent that urea is nitrogen source, acetoxime is reducing agent.
The method two for the N doping that the present invention uses is N2Heat treating process, specifically: by MXene made from the step 1
Material is placed in heat-treatment furnace, is passed through H2/N2Mixed gas, 600 ~ 1200oC is heat-treated 2 ~ 8h, and N doping MXene material is made
Material.
The method three for the N doping that the present invention uses is NH3Heat treating process, the NH3Heat treating process are as follows: by the step 1
MXene material obtained is placed in heat-treatment furnace, is passed through NH with the flow velocity of 1:13/ Ar and H2/ Ar mixed gas, 400 ~
1000oC is heat-treated 1 ~ 6h, and the N doping MXene material is made.
The method four for the N doping that the present invention uses for plasma processing, specifically: will be made from the step 1
MXene material is dispensed into chitosan, and the mass ratio of the MXene material and chitosan is 1 ~ 6:1, which is applied to
On glass-carbon electrode, the N of upper state is placed it in2In plasma gas stream, when gas stream touches the surface MXene, make part carbon
Atom is replaced by nitrogen-atoms, and the N doping MXene material is made;Wherein it is placed in the N of upper state2Place in plasma gas stream
The reason time is 1 ~ 3min, nitrogen content 0.08wt.% ~ 1.3wt.% of N doping MXene material.
The method five for the N doping that the present invention uses for microwave irradiation vapor phase method, specifically: will be made from the step 1
MXene material is scattered in unsaturated carbonate ammonium salt solution, and stirring 12 ~ 36h of dipping obtains MXene intercalation compound filter cake after filtering,
By gained MXene intercalation compound filter cake 35 ~ 70oThen C vacuum drying will fill the MXene intercalation compound after drying
Container be placed in micro-wave oven, under full power irradiate 1 ~ 3min, be made N doping MXene material.
The present invention also provides the N doping MXene cell negative electrode materials as made from method made above.And it uses and is somebody's turn to do
Battery cathode uses, and is fabricated to lithium ion battery or sodium-ion battery, the present invention provides using N doping MXene as battery cathode
The method that material makes lithium ion battery or sodium-ion battery.
N doping MXene cell negative electrode material prepared by the present invention have good electric conductivity, low ion diffusional resistance,
Low open-circuit voltage and high memory capacity, meanwhile, it is capable to well by battery behavior in conjunction with fake capacitance behavior, thus further
Capacity is improved, lithium ion battery and anode material of lithium-ion battery are highly suitable as.It is mixed in preparation method of the present invention by nitrogen
It is miscellaneous, make the surface MXene that there is a large amount of defect, capacity further increases, compared to the MXene material for not carrying out N doping, specific volume
Amount, which increases, can reach 45%.
Detailed description of the invention
Fig. 1 is the MXene material Ti in application examples 1 undoped with nitrogen3C2It is sodium-ion battery made from negative electrode material in electric current
Cyclic voltammetry curve when density 0.5A/g, 0.01~3V of voltage range.
Fig. 2 is N doping MXene material N-Ti in application examples 13C2It is close in electric current for sodium-ion battery made from negative electrode material
Spend cyclic voltammetry curve when 0.5A/g, 0.01~3V of voltage range.
Fig. 3 is the MXene material Ti in application examples 2 undoped with nitrogen3C2It is lithium ion battery made from negative electrode material in electric current
Cyclic voltammetry curve when density 0.5A/g, 0.01~3V of voltage range.
Fig. 4 is N doping MXene material N-Ti in application examples 23C2It is close in electric current for sodium-ion battery made from negative electrode material
Spend cyclic voltammetry curve when 0.5A/g, 0.01~3V of voltage range.
Fig. 5 is the MXene material Ti in application examples 3 undoped with nitrogen3C2It is sodium-ion battery made from negative electrode material in electric current
Cyclic voltammetry curve when density 0.5A/g, 0.01~3V of voltage range.
Fig. 6 is N doping MXene material N-Ti in application examples 33C2It is close in electric current for sodium-ion battery made from negative electrode material
Spend cyclic voltammetry curve when 0.5A/g, 0.01~3V of voltage range.
Fig. 7 is the MXene material Ti in application examples 4 undoped with nitrogen3C2It is lithium ion battery made from negative electrode material in electric current
Cyclic voltammetry curve when density 0.5A/g, 0.01~3V of voltage range.
Fig. 8 is N doping MXene material N-Ti in application examples 43C2It is close in electric current for sodium-ion battery made from negative electrode material
Spend cyclic voltammetry curve when 0.5A/g, 0.01~3V of voltage range.
Specific embodiment
Present invention will be further explained by specific examples below, it should be understood, however, that, these embodiments are only
For specifically describing use in more detail, but should not be understood as present invention is limited in any form.
This part carries out general description to the material and test method that arrive used in present invention experiment.Although being
It realizes many materials used in the object of the invention and operating method is it is known in the art that still the present invention still uses up herein
It may detailed description.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and behaviour
It is well known in the art as method.
Embodiment 1
N doping MXene material, specific steps are prepared using solvent-thermal method in the present embodiment are as follows:
1) it prepares MXene material: MAX phase being added in hydrofluoric acid solution with the matched proportion density of 0.02 ~ 0.2g/ml, in room
Temperature is lower to stir certain time, removes A atomic layer;Lower layer's solid is taken, be washed with deionized and is centrifuged, until pH value is 5 ~ 7;60
~120oC is dried in vacuo 8 ~ 48h;Powder after drying is placed in heat-treatment furnace, H is passed through2/ Ar gaseous mixture, 400 ~ 800oC heat
Handle 1 ~ 4h;The MXene material is made.
Wherein, MAX phase is respectively Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC;The MXene material prepared respectively corresponds
For Ti3C2, Ti2C, V2C or Nb2C。
2) carry out N doping: using MXene made from step 1) as raw material, urea is nitrogen source, with the ratio of the amount of substance for 0.2
~ 0.6 is added in deionized water, while it is reducing agent, H that 5 ~ 40mmol/L acetoxime (DMKO), which is added,2/ Ar gaseous mixture is protection
Gas, 120 ~ 200oUnder C, 2 ~ 8h of hydro-thermal;Lower layer's solid is taken, be centrifuged and is washed, 60 ~ 120oC is dried in vacuo 8 ~ 48h;It will dry
Powder afterwards is placed in tube furnace, is passed through H2/ Ar mixed gas, 400 ~ 800oC is heat-treated 4 ~ 12h, and N doping MXene is made
Material.
Embodiment 2
N is used in the present embodiment2Heat treating process prepares N doping Mxene material, specific steps are as follows:
1) prepare MXene material: identical as 1 step 1) of embodiment, it is M that wherein MAX phase, which is chemical formula,n+1AXnTernary layers
Shape compound, wherein MAX phase is respectively Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC;The MXene material prepared respectively corresponds
For Ti3C2, Ti2C, V2C or Nb2C。
2) it carries out N doping: MXene powder made from step 1) being placed in tube furnace, H is passed through2/N2Gaseous mixture, 600
~1200oC is heat-treated 2 ~ 8h, and N doping MXene material is made.
Embodiment 3
NH is used in the present embodiment3Heat treating process prepares N doping Mxene material, specific steps are as follows:
1) prepare MXene material: identical as 1 step 1) of embodiment, wherein MAX phase is respectively Ti3AlC2, Ti2AlC,
V2AlC or Nb2AlC;The MXene material prepared respectively corresponds as Ti3C2, Ti2C, V2C or Nb2C。
2) it carries out N doping: MXene powder made from step 1) being placed in tube furnace, is each led into the flow velocity of 1:1
NH3/ Ar and H2/ Ar gaseous mixture, 400 ~ 1000oC is heat-treated 1 ~ 6h, and N doping MXene is made.
Embodiment 4
N doping Mxene material, specific steps are prepared using plasma processing in the present embodiment are as follows:
1) prepare MXene material: identical as 1 step 1) of embodiment, wherein MAX phase is respectively Ti3AlC2, Ti2AlC,
V2AlC or Nb2AlC;The MXene material prepared respectively corresponds as Ti3C2, Ti2C, V2C or Nb2C。
2) it carries out N doping: MXene powder made from step 1) is dispensed into the chitosan (quality of MXene and chitosan
Than placing it in the N of 99.75 Pa then the dispersion liquid to be applied on glass-carbon electrode in 1 ~ 6:1)2In plasma chamber,
When being 1 ~ 3min between when treated, nitrogen content can be adjusted to 1.3wt.% by 0.08%wt..
Embodiment 5
N doping MXene material, specific steps are prepared using microwave irradiation vapor phase method in the present embodiment are as follows:
1) prepare MXene material: identical as 1 step 1) of embodiment, wherein MAX phase is respectively Ti3AlC2, Ti2AlC,
V2AlC or Nb2AlC;The MXene material prepared respectively corresponds as Ti3C2, Ti2C, V2C or Nb2C。
2) it carries out N doping: unsaturated carbonate being dispersed with the proportion of 0.8 ~ 1.5g/mL by MXene powder made from step 1)
In ammonium salt solution, stirring 12 ~ 36h of dipping, filtering obtains MXene intercalation compound filter cake after filtering;By the filter cake 35 ~ 70oC
Vacuum drying.MXene intercalation compound after vacuum drying is contained in glass container, is placed in micro-wave oven, under full power
1min is irradiated, N doping MXene material is made.
Application examples 1
The application example uses made from above-described embodiment that N doping MXene material is cell negative electrode material, using coating method
Battery cathode is made, is then mounted to sodium-ion battery and is tested.Specific step is as follows:
The preparation of step 1) cathode: it is sub- that 10ml dimethyl is added in 0.3g N doping MXene material made from above-described embodiment
In sulfone (DMSO), 18h is stirred at room temperature;N doping MXene dimethyl sulfoxide suspension after stirring is placed in a centrifuge, 800
R/min centrifugation, takes lower layer's solid;Solid is added in 300ml deionized water after being centrifuged, and it is suspended that ultrasound obtains N doping MXene
Liquid;N doping MXene suspension is centrifuged in 400 r/min, takes supernatant liquor;Supernatant liquor is centrifuged in 800r/min, is taken
Lower layer's solid, in 120oC is dried in vacuo for 24 hours;According to the ratio of mass ratio 8:1:1, by after drying N doping MXene powder,
Kynoar binder and conductive agent Ketjen black are uniformly mixed, and suitable NMP(N- methyl pyrrolidone is added) solution is super
Sound dispersion is mixing uniformly to form slurry coated in the electrode slice that diameter is 15mm on copper foil, is cut into after dry, in vacuum condition
Under it is 10 hours dry in 120 DEG C;It is made using N doping MXene material as the battery cathode sheet of negative electrode material.
The installation of step 2 battery and test: in the glove box of argon atmosphere, using electrode slice obtained above as cathode, with
Metallic sodium piece is used as to electrode, the NaPF of 1M6(EC:DEC=1:1) solution is diaphragm with Celgard 2300 as electrolyte,
It is assembled into 2025 button sodium-ion batteries.Battery charging and discharging experiment is filled on new prestige (Neware) battery test system using constant current
Discharge mode carries out, and voltage tester scope is that 0.01~3V is tested.If Fig. 2 is that the application example is obtained using above-described embodiment
N doping MXene material N-Ti3C2The circulation volt of sodium-ion battery in current density 0.5A/g, 0.01~3V of voltage range
Pacify curve.In order to compare, using the preparation of duplicate electrode and battery installation method, using the MXene for not carrying out N doping
Material Ti3C2, sodium-ion battery is made, under same test condition, its cyclic voltammetry curve of survey is as shown in Figure 1.From two figures
As can be seen that compared to Ti3C2, N-Ti3C2Specific capacity for the sodium-ion battery of negative electrode material increases 17%.
Application examples 2
The application example uses made from above-described embodiment that N doping MXene material is cell negative electrode material, using coating method
Battery cathode is made, is then mounted to lithium ion battery and is tested.As application examples 1, difference is specific steps
When carrying out battery installation, using metal lithium sheet as to electrode, the LiPF of 1M6(EC:DEC=1:1) solution is as electrolyte.Test
As a result if Fig. 4 is that the application example uses N doping MXene material N-Ti made from above-described embodiment3C2In current density 0.5A/g,
The cyclic voltammetry curve of lithium ion battery when 0.01~3V of voltage range.For the purposes of comparison, using not carrying out N doping
MXene material Ti3C2, lithium ion battery is made, under same test condition, its cyclic voltammetry curve of survey is as shown in Figure 3.From
In two figures as can be seen that compared to Ti3C2, N-Ti3C2Specific capacity for the lithium ion battery of negative electrode material increases 29%.
Application examples 3
The application example uses made from above-described embodiment that N doping MXene material is cell negative electrode material, using suction method
Battery cathode is made, is then mounted to sodium-ion battery and is tested.Specific step is as follows:
0.3g N doping MXene is added in 10ml dimethyl sulfoxide (DMSO), 18h is stirred at room temperature;By the nitrogen after stirring
Doping MXene dimethyl sulfoxide suspension is placed in a centrifuge, and 800 r/min centrifugation takes lower layer's solid;Solid after centrifugation is added
Enter in 300ml deionized water, ultrasound obtains N doping MXene suspension;By N doping MXene suspension 400 r/min from
The heart, taking supernatant liquor N-MXene is precursor liquid, is filtered to polycarbonate leaching film, 20 ~ 80oC is dried in vacuo 5 ~ 15min, stripping
It is 8 ~ 24 hours dry in 40 ~ 80 DEG C under vacuum conditions from film is obtained, it is made using N doping MXene material as negative electrode material
Battery cathode sheet.Subsequent installation battery is as application examples 1.For the purposes of comparison, while testing not carry out N doping
MXene be negative electrode material sodium-ion battery.
Fig. 5 and Fig. 6 is respectively the application example preparation with Ti3C2And N-Ti3C2For negative electrode material sodium-ion battery in electricity
Cyclic voltammetry curve when current density 0.5A/g, 0.01~3V of voltage range, it can be seen from the figure that compared to Ti3C2, N-
Ti3C230.3% is increased for the battery specific capacity of negative electrode material.
Application examples 4
The application example uses made from above-described embodiment that N doping MXene material is cell negative electrode material, using suction method
Battery cathode is made, is then mounted to lithium ion battery and is tested.As application examples 3, difference is specific steps
When carrying out battery installation, using metal lithium sheet as to electrode, the LiPF of 1M6(EC:DEC=1:1) solution is as electrolyte.Equally
In order to compare, while the MXene not carry out N doping is tested as the sodium-ion battery of negative electrode material.
Fig. 7 and Fig. 8 is respectively the Ti of the application example preparation3C2And N-Ti3C2For negative electrode material lithium ion battery in electric current
Cyclic voltammetry curve when density 0.5A/g, 0.01~3V of voltage range, it can be seen from the figure that compared to Ti3C2, N-Ti3C2
45% is increased for the battery specific capacity of negative electrode material.
In above application examples, when making battery cathode, N doping MXene battery cathode prepared by the present invention can also be used
Material and other materials are mixed to form on collector, and battery cathode is made, as N-MXene is mixed or N-MXene with graphene
It is mixed with carbon nanotube (CNTs).
Claims (8)
1. a kind of preparation method of N doping MXene cell negative electrode material, it is characterised in that the following steps are included:
The preparation of the MXene material: hydrofluoric acid solution is added with the matched proportion density of 0.02~0.2g/ml in MAX phase by step 1
In, certain time is stirred at room temperature, removes the A atomic layer in MAX phase, takes lower layer's solid, be washed with deionized and be centrifuged,
It is 5~7 to pH value;In 60~120 DEG C of 8~48h of vacuum drying;Powder after drying is placed in heat-treatment furnace, H is passed through2/Ar
Gaseous mixture, in 400~800 DEG C of 1~4h of heat treatment;The MXene material is made;
Step 2 carries out N doping to the MXene material, the N doping MXene cell negative electrode material is made;
Wherein, the MXene material is a kind of transition metal carbide two dimensional crystal, chemical formula Mn+1Xn, n=1,2 or 3, M
For early stage transition metal element, X is carbon;
Wherein, it is M that the MAX, which is a kind of chemical formula,n+1AXnTernary layered compound, wherein in M, X, n and MXene material
M, X, n are identical, and A is third or the 4th major element;
The MAX phase is Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC;The MXene material that step 1 is prepared is corresponding to be respectively
Ti3C2, Ti2C, V2C or Nb2C;
The method that step 2 carries out N doping to the MXene material is solvent-thermal method, the solvent-thermal method are as follows: by the step
MXene powder made from one and reproducibility nitrogen-containing solvent, which are placed in reaction kettle, carries out hydro-thermal reaction, later in 400~800 DEG C of heat
Processing obtains the N doping MXene cell negative electrode material;
The wherein reproducibility nitrogen-containing solvent are as follows: by nitrogen source, acetoxime of urea be the mixed solvent of reducing agent.
2. a kind of preparation method of N doping MXene cell negative electrode material, it is characterised in that the following steps are included:
The preparation of the MXene material: hydrofluoric acid solution is added with the matched proportion density of 0.02~0.2g/ml in MAX phase by step 1
In, certain time is stirred at room temperature, removes the A atomic layer in MAX phase, takes lower layer's solid, be washed with deionized and be centrifuged,
It is 5~7 to pH value;In 60~120 DEG C of 8~48h of vacuum drying;Powder after drying is placed in heat-treatment furnace, H is passed through2/Ar
Gaseous mixture, in 400~800 DEG C of 1~4h of heat treatment;The MXene material is made;
Step 2 carries out N doping to the MXene material, the N doping MXene cell negative electrode material is made;
Wherein, the MXene material is a kind of transition metal carbide two dimensional crystal, chemical formula Mn+1Xn, n=1,2 or 3, M
For early stage transition metal element, X is carbon;
Wherein, it is M that the MAX, which is a kind of chemical formula,n+1AXnTernary layered compound, wherein in M, X, n and MXene material
M, X, n are identical, and A is third or the 4th major element;
The MAX phase is Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC;The corresponding difference of MXene material that step 1 is prepared
For Ti3C2, Ti2C, V2C or Nb2C;
The method that wherein step 2 carries out N doping to the MXene material is N2 Heat treating process, the N2 Heat treating process are as follows: will
MXene material made from the step 1 is placed in heat-treatment furnace, is passed through H2 /N2 Mixed gas, at 600~1200 DEG C of heat
2~8h is managed, the N doping MXene cell negative electrode material is made.
3. a kind of preparation method of N doping MXene cell negative electrode material, it is characterised in that the following steps are included:
The preparation of the MXene material: hydrofluoric acid solution is added with the matched proportion density of 0.02~0.2g/ml in MAX phase by step 1
In, certain time is stirred at room temperature, removes the A atomic layer in MAX phase, takes lower layer's solid, be washed with deionized and be centrifuged,
It is 5~7 to pH value;In 60~120 DEG C of 8~48h of vacuum drying;Powder after drying is placed in heat-treatment furnace, H is passed through2/Ar
Gaseous mixture, in 400~800 DEG C of 1~4h of heat treatment;The MXene material is made;
Step 2 carries out N doping to the MXene material, the N doping MXene cell negative electrode material is made;
Wherein, the MXene material is a kind of transition metal carbide two dimensional crystal, chemical formula Mn+1Xn, n=1,2 or 3, M
For early stage transition metal element, X is carbon;
Wherein, it is M that the MAX, which is a kind of chemical formula,n+1AXnTernary layered compound, wherein in M, X, n and MXene material
M, X, n are identical, and A is third or the 4th major element;
The MAX phase is Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC;The MXene material that step 1 is prepared is corresponding to be respectively
Ti3C2, Ti2C, V2C or Nb2C;
The method that wherein step 2 carries out N doping to the MXene material is NH3Heat treating process, the NH3Heat treating process are as follows:
MXene material made from the step 1 is placed in heat-treatment furnace, NH is passed through with the flow velocity of 1:13/ Ar and H2/ Ar gaseous mixture
The N doping MXene cell negative electrode material is made in 400~1000 DEG C of 1~6h of heat treatment in body.
4. a kind of preparation method of N doping MXene cell negative electrode material, it is characterised in that the following steps are included:
The preparation of the MXene material: hydrofluoric acid solution is added with the matched proportion density of 0.02~0.2g/ml in MAX phase by step 1
In, certain time is stirred at room temperature, removes the A atomic layer in MAX phase, takes lower layer's solid, be washed with deionized and be centrifuged,
It is 5~7 to pH value;In 60~120 DEG C of 8~48h of vacuum drying;Powder after drying is placed in heat-treatment furnace, H is passed through2/Ar
Gaseous mixture, in 400~800 DEG C of 1~4h of heat treatment;The MXene material is made;
Step 2 carries out N doping to the MXene material, the N doping MXene cell negative electrode material is made;
Wherein, the MXene material is a kind of transition metal carbide two dimensional crystal, chemical formula Mn+1Xn, n=1,2 or 3, M
For early stage transition metal element, X is carbon;
Wherein, it is M that the MAX, which is a kind of chemical formula,n+1AXnTernary layered compound, wherein in M, X, n and MXene material
M, X, n are identical, and A is third or the 4th major element;
The MAX phase is Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC;The MXene material that step 1 is prepared is corresponding to be respectively
Ti3C2, Ti2C, V2C or Nb2C;
The method that wherein step 2 carries out N doping to the MXene material is plasma processing, the plasma processing
Are as follows: MXene material made from the step 1 is dispensed into chitosan, the mass ratio of the MXene material and chitosan is 1
The dispersion liquid is applied on glass-carbon electrode by~6:1, places it in the N of upper state2In plasma gas stream, the contact of gas stream
When to the surface MXene, replaces part carbon atom by nitrogen-atoms, the N doping MXene cell negative electrode material is made;Wherein set
In the N of upper state2The processing time in plasma gas stream is 1~3min, the nitrogen content of N doping MXene material
0.08wt.%~1.3wt.%.
5. a kind of preparation method of N doping MXene cell negative electrode material, it is characterised in that the following steps are included:
The preparation of the MXene material: hydrofluoric acid solution is added with the matched proportion density of 0.02~0.2g/ml in MAX phase by step 1
In, certain time is stirred at room temperature, removes the A atomic layer in MAX phase, takes lower layer's solid, be washed with deionized and be centrifuged,
It is 5~7 to pH value;In 60~120 DEG C of 8~48h of vacuum drying;Powder after drying is placed in heat-treatment furnace, H is passed through2/Ar
Gaseous mixture, in 400~800 DEG C of 1~4h of heat treatment;The MXene material is made;
Step 2 carries out N doping to the MXene material, the N doping MXene cell negative electrode material is made;
Wherein, the MXene material is a kind of transition metal carbide two dimensional crystal, chemical formula Mn+1Xn, n=1,2 or 3, M
For early stage transition metal element, X is carbon;
Wherein, it is M that the MAX, which is a kind of chemical formula,n+1AXnTernary layered compound, wherein in M, X, n and MXene material
M, X, n are identical, and A is third or the 4th major element;
The MAX phase is Ti3AlC2, Ti2AlC, V2AlC or Nb2AlC;The MXene material that step 1 is prepared is corresponding to be respectively
Ti3C2, Ti2C, V2C or Nb2C;
The method that wherein step 2 carries out N doping to the MXene material is microwave irradiation vapor phase method, the microwave irradiation gas
Xiang Fa are as follows: disperse MXene material made from the step 1 in unsaturated carbonate ammonium salt solution, stirring 12~36h of dipping, filtering
After obtain MXene intercalation compound filter cake, by gained MXene intercalation compound filter cake 35~70 DEG C be dried in vacuo, then will
The container of MXene intercalation compound after filling drying is placed in micro-wave oven, and 1~3min is irradiated under full power, the nitrogen is made
Adulterate MXene cell negative electrode material.
6. N doping MXene cell negative electrode material made from a kind of preparation method of any one according to claim 1~5.
7. a kind of application of N doping MXene cell negative electrode material according to claim 6, it is characterised in that the nitrogen is mixed
Miscellaneous MXene cell negative electrode material is used as lithium ion battery negative material.
8. a kind of application of N doping MXene cell negative electrode material according to claim 6, it is characterised in that the nitrogen is mixed
Miscellaneous MXene cell negative electrode material is used as anode material of lithium-ion battery.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610347054.4A CN106025200B (en) | 2016-05-24 | 2016-05-24 | A kind of preparation method and applications of N doping MXene cell negative electrode material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610347054.4A CN106025200B (en) | 2016-05-24 | 2016-05-24 | A kind of preparation method and applications of N doping MXene cell negative electrode material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106025200A CN106025200A (en) | 2016-10-12 |
CN106025200B true CN106025200B (en) | 2019-07-30 |
Family
ID=57093557
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610347054.4A Active CN106025200B (en) | 2016-05-24 | 2016-05-24 | A kind of preparation method and applications of N doping MXene cell negative electrode material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106025200B (en) |
Families Citing this family (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106611653B (en) * | 2016-11-21 | 2018-06-12 | 南京邮电大学 | A kind of MOF composite materials and its preparation method and application |
CN106698430B (en) * | 2016-12-27 | 2018-11-02 | 陕西科技大学 | A kind of poly-dopamine is as transition zone titanium carbide growth in situ CNTs three-dimensional composite materials and preparation method thereof |
CN106784706B (en) * | 2016-12-27 | 2019-01-22 | 陕西科技大学 | A kind of carbon microspheres are as transition zone titanium carbide growth in situ CNTs three-dimensional composite material and preparation method thereof |
CN106744732A (en) * | 2017-01-11 | 2017-05-31 | 苏州大学 | The method of green syt two dimension transition metal carbide or nitride nano piece |
CN106892663B (en) * | 2017-01-20 | 2019-12-20 | 西南交通大学 | Lamellar nitride ceramic particles and preparation method thereof |
CN107161999A (en) * | 2017-05-18 | 2017-09-15 | 深圳大学 | One kind is based on Ti2The preparation method of CMXene battery electrode material |
CN107170587B (en) * | 2017-05-26 | 2019-10-25 | 中国石油大学(北京) | A kind of sulfur doping MXene material and the preparation method and application thereof |
CN107492641A (en) * | 2017-07-31 | 2017-12-19 | 安阳工学院 | A kind of titanium carbide four vulcanizes three titanium composite materials and preparation method thereof |
CN107777688B (en) * | 2017-10-13 | 2020-01-07 | 合肥工业大学 | Preparation method of sheet-like Mxene sheet material |
CN108091862B (en) * | 2017-12-15 | 2019-09-03 | 山东大学 | A kind of MXene- metallic composite and preparation method thereof |
CN108493502B (en) * | 2018-04-13 | 2021-05-11 | 深圳市得朗高科技有限公司 | Double-carbon and double-MXene pole ion high-performance battery |
CN108831760A (en) * | 2018-06-15 | 2018-11-16 | 武汉工程大学 | A kind of N doping MXene material and its preparation method and application |
CN109261181A (en) * | 2018-09-10 | 2019-01-25 | 浙江大学 | Utilize the Ti of isopropylamine intercalation and layering3C2Fabricated in situ TiO2@Ti3C2Method and product |
CN109261180A (en) * | 2018-09-10 | 2019-01-25 | 浙江大学 | Utilize the Ti of dimethyl sulfoxide intercalation and layering3C2Fabricated in situ TiO2@Ti3C2Method and product |
CN110105087B (en) * | 2018-10-10 | 2022-04-22 | 西南交通大学 | Ti3C2Method for regulating and controlling functional groups on surface of film |
CN109473606B (en) * | 2018-10-30 | 2021-12-28 | 肇庆市华师大光电产业研究院 | Self-supporting functional interlayer for lithium-sulfur battery and preparation method thereof |
CN109449405B (en) * | 2018-10-30 | 2020-10-20 | 肇庆市华师大光电产业研究院 | Sulfur-oxygen doped MXene-carbon nanotube composite material and application thereof in lithium-sulfur battery |
CN109434119B (en) * | 2018-11-08 | 2021-10-22 | 西安理工大学 | Preparation method of high-toughness MXene phase doped molybdenum alloy |
CN109553103B (en) * | 2018-12-14 | 2021-12-21 | 华南理工大学 | Two-dimensional self-crosslinking MXene film and preparation method thereof |
CN109888279B (en) * | 2019-01-15 | 2022-01-04 | 五邑大学 | Selenium-doped MXene material and preparation method and application thereof |
CN109786742B (en) * | 2019-01-15 | 2021-09-28 | 五邑大学 | Se-doped MXene battery negative electrode material and preparation method and application thereof |
CN109830659B (en) * | 2019-01-15 | 2022-01-04 | 五邑大学 | Te-doped MXene material and preparation method thereof |
CN109830661B (en) * | 2019-01-16 | 2022-01-04 | 五邑大学 | Selenium-doped MXene composite nano material and preparation method and application thereof |
CN109888203B (en) * | 2019-01-16 | 2022-01-04 | 五邑大学 | Tellurium-doped MXene composite material and preparation method and application thereof |
CN109888280B (en) * | 2019-01-23 | 2021-12-17 | 五邑大学 | Sulfur-doped MXene negative electrode material of potassium ion battery and preparation method thereof |
CN109911897A (en) * | 2019-03-01 | 2019-06-21 | 哈尔滨师范大学 | One-step synthesis method lacks layer Nb2The method and its application of C-material |
CN109755552B (en) * | 2019-03-15 | 2022-03-11 | 西南大学 | Carbon-encapsulated titanium oxynitride nanoparticle composite material and preparation method and application thereof |
CN109975382B (en) * | 2019-04-04 | 2021-06-22 | 北京工商大学 | Tyrosinase biosensor with phosphorus-doped MXene modified electrode and preparation method and application thereof |
CN110112419A (en) * | 2019-04-22 | 2019-08-09 | 天津大学 | It can the MXene aeroge cathode of lithium collector and preparation method thereof of high magnification fast charging and discharging, application |
CN110330020B (en) * | 2019-06-17 | 2023-01-06 | 昆明理工大学 | Method for efficiently removing MXene fluorine-containing functional groups by microwaves |
CN110354697A (en) * | 2019-06-24 | 2019-10-22 | 大连理工大学盘锦产业技术研究院 | A kind of mixed substrate membrane containing nano-grade molecular sieve and preparation method thereof based on MXene material |
CN110723737B (en) * | 2019-10-24 | 2021-01-26 | 郑州轻工业学院 | Wool ball type Ti3C2Preparation method and application of (MXene) nano material |
CN111029531B (en) * | 2020-01-02 | 2021-03-30 | 北京航空航天大学 | Monoatomic dispersed MXene material and application thereof to lithium battery negative electrode |
CN113113597B (en) * | 2020-01-13 | 2022-04-29 | 中国科学院宁波材料技术与工程研究所 | MAX phase material for lithium ion battery anode and preparation method thereof |
CN112072101A (en) * | 2020-08-14 | 2020-12-11 | 五邑大学 | Boron-doped MXene material and preparation method thereof |
CN112018354A (en) * | 2020-08-14 | 2020-12-01 | 五邑大学 | Array-shaped SnS2Preparation method of/MXene composite material |
CN111952568A (en) * | 2020-08-19 | 2020-11-17 | 山东大学 | Sandwich structure composite material and preparation method and application thereof |
CN112563338B (en) * | 2020-12-04 | 2022-04-19 | 广东工业大学 | Flexible self-powered photoelectric detector and preparation method and application thereof |
CN112695461B (en) * | 2020-12-14 | 2021-11-23 | 深圳市元鼎智能创新有限公司 | Preparation method of MXene material diaphragm applied to lithium ion battery |
CN114620728B (en) * | 2020-12-14 | 2023-10-03 | 北京航空航天大学 | Method and system for preparing two-dimensional material by gas phase method |
CN112968188B (en) * | 2021-02-03 | 2022-11-29 | 台州学院 | Nitrogen-doped MXene-supported Pd catalyst and preparation method and application thereof |
CN115050583A (en) * | 2021-03-09 | 2022-09-13 | 中国科学院大连化学物理研究所 | Three-dimensional nitrogen-doped MXene super capacitor electrode material and preparation method and application thereof |
CN113401905A (en) * | 2021-06-16 | 2021-09-17 | 哈尔滨师范大学 | High purity phase multilayer V2Preparation method and application of material C |
CN113690444A (en) * | 2021-08-26 | 2021-11-23 | 大连理工大学 | Li based on MXene and transition metal oxynitride composite structure2S-based battery positive electrode material and synthesis method thereof |
CN113984859B (en) * | 2021-09-28 | 2023-10-20 | 西安建筑科大工程技术有限公司 | Preparation method of nitrogen-doped MXene/MOF derivative composite material and formaldehyde sensor |
CN113937295B (en) * | 2021-10-15 | 2023-04-18 | 山东大学 | Self-assembled MXene/chitosan composite membrane and preparation method and application thereof |
CN114031077B (en) * | 2021-11-01 | 2023-10-24 | 上海交通大学 | Method for rapidly preparing two-dimensional nanomaterial MXene based on microwave irradiation |
CN114361570B (en) * | 2022-01-11 | 2023-09-01 | 山东大学 | Sodium battery and preparation method thereof |
CN114220961B (en) * | 2022-02-21 | 2022-07-19 | 浙江大学 | Composite nano material for sodium ion battery and preparation method thereof |
CN114512653B (en) * | 2022-02-22 | 2023-01-06 | 广东工业大学 | Preparation method of nitrogen-doped MXene-loaded molybdenum disulfide composite material, product and application of product |
CN114597362B (en) * | 2022-03-09 | 2023-12-29 | 吉林师范大学 | Lithium ion battery negative electrode material and preparation method thereof |
CN114907722B (en) * | 2022-04-21 | 2023-06-02 | 哈尔滨工程大学 | Nitrogen and sulfur doped Ti 3 C 2 T x Method for preparing MXene additive-free ink-jet printing ink |
CN114864858A (en) * | 2022-04-21 | 2022-08-05 | 山东大学 | Zinc battery metal cathode with interface protection layer and preparation method and application thereof |
CN115159451B (en) * | 2022-08-04 | 2023-04-07 | 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 |
CN115799519B (en) * | 2023-02-08 | 2023-06-06 | 中国人民解放军国防科技大学 | Modified lithium-rich layered oxide positive electrode material, and preparation method and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104016345A (en) * | 2014-06-03 | 2014-09-03 | 河海大学 | Method for preparing graphene-like two-dimensional laminar titanium carbide nanoplate |
CN104477895A (en) * | 2014-12-11 | 2015-04-01 | 百顺松涛(天津)动力电池科技发展有限公司 | Preparation method of nitrogen-doped graphene for cathode of lithium ion battery |
CN104882608A (en) * | 2015-05-06 | 2015-09-02 | 江南大学 | Preparation method of N-doped 3D graphene/graphite lithium ion battery negative material |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9193595B2 (en) * | 2011-06-21 | 2015-11-24 | Drexel University | Compositions comprising free-standing two-dimensional nanocrystals |
-
2016
- 2016-05-24 CN CN201610347054.4A patent/CN106025200B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104016345A (en) * | 2014-06-03 | 2014-09-03 | 河海大学 | Method for preparing graphene-like two-dimensional laminar titanium carbide nanoplate |
CN104477895A (en) * | 2014-12-11 | 2015-04-01 | 百顺松涛(天津)动力电池科技发展有限公司 | Preparation method of nitrogen-doped graphene for cathode of lithium ion battery |
CN104882608A (en) * | 2015-05-06 | 2015-09-02 | 江南大学 | Preparation method of N-doped 3D graphene/graphite lithium ion battery negative material |
Non-Patent Citations (4)
Title |
---|
"High-Performance Sodium Ion Batteries Based on a 3D Anode from Nitrogen-Doped Graphene Foams";Jiantie Xu等;《Advanced Materials》;20150216;第27卷;第2042-2048页 |
"Review on Recent Progress in Nitrogen-Doped Graphene: Synthesis, Characterization, and Its Potential Applications";Haibo Wang等;《ACS Catalysis》;20120316;第2卷;第781-794页 |
"Role of Surface Structure on Li-Ion Energy Storage Capacity of Two-Dimensional Transition-Metal Carbides";Yu Xie等;《J. Am. Chem. Soc.》;20140328;第136卷;第6385-6394页 |
"Ti3C2 MXene as a High Capacity Electrode Material for Metal (Li, Na,K, Ca) Ion Batteries";Dequan Er等;《ACS Applied materials & interfaces》;20140630;第6卷;第11173-11179页 |
Also Published As
Publication number | Publication date |
---|---|
CN106025200A (en) | 2016-10-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106025200B (en) | A kind of preparation method and applications of N doping MXene cell negative electrode material | |
CN110104630B (en) | Porous carbon composite material for battery diaphragm and preparation method and application thereof | |
CN105118972B (en) | Metal hydroxide coated carbon and sulfur lithium-sulfur battery positive electrode material, and preparation method and application thereof | |
CN107425185B (en) | Preparation method of carbon nanotube-loaded molybdenum carbide material and application of carbon nanotube-loaded molybdenum carbide material in lithium-sulfur battery positive electrode material | |
JP2021512463A (en) | Redox and ion adsorption electrodes and energy storage devices | |
CN107403911A (en) | Graphene/transition metal phosphide/C-base composte material, preparation method and lithium ion battery negative electrode | |
CN109698326B (en) | Organic tin phosphide/graphite oxide composite material for negative electrode of sodium-ion battery | |
Xu et al. | Nano-structured red phosphorus/porous carbon as a superior anode for lithium and sodium-ion batteries | |
CN108649190A (en) | Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite and its preparation method and application | |
CN105810914A (en) | Sulfur-doping porous carbon material of sodium ion battery and preparation method of sulfur-doping porous carbon material | |
CN109037554A (en) | A kind of Ni/C composite nano-fiber membrane applied to lithium-sulfur cell and preparation method thereof and lithium-sulfur cell | |
Zhang et al. | Hollow carbon nanocages toward long cycle lifespan lithium/sodium-ion half/full batteries | |
Jiang et al. | Flexible, nonflammable and Li-dendrite resistant Na2Ti3O7 nanobelt-based separators for advanced Li storage | |
CN106340633A (en) | Composite nano material for high performance lithium ion battery and preparation method thereof | |
CN108258241A (en) | A kind of cathode of lithium battery for inhibiting lithium dendrite growth using ZIF-8 porous carbon materials | |
CN108922788A (en) | A kind of PEDOT@Na3(VOPO4)2F composite material, preparation method and its application | |
CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
Luo et al. | In situ construction of efficient interface layer with lithiophilic nanoseeds toward dendrite‐free and low N/P ratio Li metal batteries | |
Xia et al. | Co3O4@ MWCNT modified separators for Li–S batteries with improved cycling performance | |
CN105118966A (en) | Sn-C composite material with high N content of lithium battery cathode and preparation method of Sn-C composite material | |
CN114597532A (en) | Method for directly regenerating failed lithium cobaltate positive electrode into high-voltage lithium cobaltate positive electrode and product | |
CN104600267B (en) | Graphene/titanium oxide composite manufacturing technique and its application process | |
CN110311111B (en) | N-doped CNT in-situ coated Co nanoparticle composite material and preparation and application thereof | |
CN111943259A (en) | Carbon-coated mesoporous dual-phase titanium dioxide and preparation method and energy storage application thereof | |
CN113937261B (en) | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery positive electrode plate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |