CN108258222A - A kind of MXene/ lithium sulfides/carbon composite anode material and preparation method thereof - Google Patents
A kind of MXene/ lithium sulfides/carbon composite anode material and preparation method thereof Download PDFInfo
- Publication number
- CN108258222A CN108258222A CN201810046164.6A CN201810046164A CN108258222A CN 108258222 A CN108258222 A CN 108258222A CN 201810046164 A CN201810046164 A CN 201810046164A CN 108258222 A CN108258222 A CN 108258222A
- Authority
- CN
- China
- Prior art keywords
- carbon
- lithium
- mxene
- anode material
- preparation
- 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.)
- Granted
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
- H01M4/366—Composites as layered products
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
-
- 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
- H01M4/625—Carbon or graphite
-
- 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 present invention relates to a kind of MXene/ lithium sulfides/carbon composite anode material and preparation method thereof, the method includes：（1）MAX phases powder is subjected to acid etching, is filtered, washed, dries, obtains the MXene nano materials with porous structure；（2）It by lithium sulfate wiring solution-forming, is mixed in proportion with Carbon materials or carbon matrix precursor, carbon/lithium sulfate or carbon matrix precursor/lithium sulfate composite material is made；（3）The heating stepses under protective atmosphere（2）In carbon/lithium sulfate or carbon matrix precursor/lithium sulfate composite material, above-mentioned composite material is reduced into lithium sulfide/carbon material by way of thermal reduction；（4）By step（1）In have porous structure MXene nano materials and step（3）In the mixing of lithium sulfide/carbon, ball milling is to get MXene/ lithium sulfides/carbon composite anode material.Compared with prior art, the advantages that the MXene/ lithium sulfides/carbon composite anode material electric conductivity height of the invention prepared, specific capacity height, good cycle, good rate capability, simple preparation process.
Description
Technical field
The invention belongs to lithium-sulfur cell technical field more particularly to a kind of MXene/ lithium sulfides/carbon composite anode material and
Preparation method.
Background technology
Lithium-sulfur cell becomes people's research since its energy density is high, environmentally friendly, electrode material is cheap
Hot spot.The positive electrode of lithium-sulfur cell is generally divided into two kinds of elemental sulfur class and lithium sulfide class.Elemental sulfur class positive electrode is inexpensive easily
, preparation process it is simple, but larger volume expansion is had in charge and discharge process, the structure of material is destroyed, so as to influence electricity
The chemical property in pond.It is first to charge with discharging again, therefore avoid material caused by volume expansion for lithium sulfide class material
Expect structural damage, better chemical property can be obtained.But lithium sulfide is to water and its sensitivity so for preparing to preserve and wait
Journey is much limited, and causes lithium sulfide expensive, constrains the development of lithium sulfide anode.
The poorly conductive of lithium sulfide, thus with the Material claddings of some good conductivities be also lithium sulfide research direction it
One.Patent CN106299261A discloses a kind of lithium sulfide/carbon composite nano-material, restores lithium sulfate using carbon and synthesizes vulcanization
The nanocomposite of lithium/carbon, applied in the equipment such as lithium-sulfur cell.But the electric conductivity of the lithium sulfide synthesized in this way and
Specific capacity is limited.
MXene is a kind of novel transition metal carbon (nitrogen) compound two dimensional crystal, has the structure similar with graphene, chemistry
Formula is Mn+1Xn, wherein n=1,2 or 3, M be early stage transition metal element, X is carbon or nitrogen, this kind of material can lead to
Hydrofluoric acid dissociation laminate ceramic MAX (A is major element) is crossed to obtain, at present, MXene answering in the positive electrode of battery
With also more rare, patent 201610951729.6 discloses two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound and nano-sulfur particles are compound
Material and its preparation and application, the composite material is by two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheets and nano-sulfur
Grain is formed, be nano-sulfur particles growth in situ on two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound MXene nanometer sheets surface, be expressed as S@
MXene.By individual layer or the stable suspension of two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) the compound MXene nanometer sheets of few layer its with thio sulphur
Sour sodium or sodium polysulfide solution mixing make the nano-sulfur homoepitaxial that reaction generates in two dimension using formic acid as reducing agent
MXene nanometer sheets surface, it is neutralized, washing, centrifugation obtains two-dimentional magnesium-yttrium-transition metal carbon (nitrogen) compound and nano-sulfur particles are compound
Material, as lithium-sulphur cell positive electrode.But the invention only with the surface areas of MXene nanometer sheets it is big the characteristics of fix quilt
The sulfur granules of reduction.
In summary, MXene has the novel of property as a kind of, and the application in cell positive material also has
It waits to further expand, therefore, it is necessary to a kind of new lithium sulfur battery anode material and preparation method thereof be developed, to further improve
The problem of discharge capacity existing for lithium sulfur battery anode material is low, specific capacity is small.
Invention content
It is for the above-mentioned prior art the problem of, compound the present invention intends to provide a kind of MXene/ lithium sulfides/carbon
Positive electrode and preparation method thereof, compared with prior art, MXene/ lithium sulfides/carbon composite anode material prepared by the present invention are led
The advantages that electrical height, specific capacity height, good cycle, good rate capability, simple preparation process.
An object of the present invention is to provide a kind of MXene/ lithium sulfides/carbon composite anode material.
The second object of the present invention is to provide a kind of preparation method of MXene/ lithium sulfides/carbon composite anode material.
The third object of the present invention is to provide answering for above-mentioned MXene/ lithium sulfides/carbon composite anode material and preparation method thereof
With.
For achieving the above object, the invention discloses following technical proposals：
First, the invention discloses a kind of MXene/ lithium sulfides/carbon composite anode material, the positive electrode is by MXene
Material, lithium sulfide, carbon composition, wherein, carbon coating on the surface of lithium sulfide, carbon/lithium sulfide be attached to MXene materials intercalation it
Between.
Secondly, the invention discloses a kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, specifically, institute
Preparation method is stated to include the following steps：
(1) MAX phases powder is subjected to acid etching, is filtered, washed, dries, obtain the MXene nanometer materials with porous structure
Material；
(2) by lithium sulfate wiring solution-forming, mixed in proportion with Carbon materials or carbon matrix precursor, be made carbon/lithium sulfate or
Carbon matrix precursor/lithium sulfate composite material；
(3) carbon/lithium sulfate under protective atmosphere in heating stepses (2) or carbon matrix precursor/lithium sulfate composite material lead to
Above-mentioned composite material is reduced into lithium sulfide/carbon material by the mode for crossing thermal reduction；
(4) the MXene nano materials for having porous structure in step (1) are mixed with lithium sulfide/carbon in step (3),
Ball milling is to get MXene/ lithium sulfides/carbon composite anode material.
In step (1), the MAX phase materials have the characteristics that cation-intercalated and surface modification, molecular formula Mb+ 1NaXb, wherein, M is selected from the mixture of one or more of following elements：Ti、Zr、Nb、Cr、Mo、V、Ta；N is selected from down
The mixture of one or more of column element：Li、Na、K、Mg、Al、Si；X be C or/and N, b=1,2 or 3；0≤a≤
1.5。
Preferably, in step (1), the MAX powder includes：Ti3AlC2、Ti2AlC、Ta4AlC3、TiNbAlC、
(V0.5Cr0.5)3AlC2、V2AlC、Nb2AlC、Nb4AlC3、Ti3AlCN、Ti3SiC2、Ti2SiC、Ta4SiC3、TiNbSiC、
(V0.5Cr0.5)3SiC2、V2SiC、Nb2SiC、Nb4SiC3、Ti3SiCN etc..
It is further preferred that the MAX powder is Ti3AlC2、Ti2AlC、Ta4AlC3、V2AlC。
In step (1), the condition of the acid etching is：The hydrofluoric acid that mass concentration is 1%-50% is used to be reacted at 0-90 DEG C
0.5-48 hours.
In step (2), the carbon material includes：In carbon black, graphite, graphene, carbon nanotube, carbon fiber, porous carbon
One or more kinds of mixtures.
In step (2), the carbon matrix precursor includes：In pitch, carbohydrate, polyethylene, phenolic resin, gelatin, polyurethane
One or more kinds of mixtures.
In step (2), the mass ratio of the lithium sulfate and carbon material is 1:(2-10).
In step (2), the mass ratio of the lithium sulfate and carbon matrix precursor is 1:(3-20).
In step (3), the inert atmosphere includes the mixing of one or more of nitrogen, argon gas, helium, neon
Object.
In step (3), the heating temperature is 300-1500 DEG C, time 1-3h.
In step (4), the mass ratio of the MXene nano materials and lithium sulfide/carbon is 1:(1-10).
In step (4), the Ball-milling Time is 0.5-20h.
Finally, the invention discloses the preparation method and applications of above-mentioned MXene/ lithium sulfides/carbon composite anode material, institutes
It states to apply and include：For in lithium-sulfur cell, electric vehicle or energy storage material.
It should be noted that in the MAX phase materials that the present invention uses, M atoms are accumulated for six side's solid matters, and X atoms are filled in
MX layers are formed in the octahedral voids that above-mentioned six sides close-packed configuration is formed, cationic N is unordered to be inserted between MX laminates, forms uniqueness
Intercalation configuration, this structure can be provided in charge and discharge process ion transmission channel, after MAX phase materials are by acid etching,
Form the porous MXene nano materials with unique intercalation configuration, intercalation configuration and it is porous can be in battery charging and discharging
Smooth channel is provided simultaneously for the insertion of electronics and removing in the process, can avoid the problem that cell expansion well, meanwhile,
Due to this intercalation configuration and it is porous itself have the function of it is extraordinary accommodate electronics, lithium-sulfur cell can be further improved
The specific capacity and cycle performance of anode.
Compared with prior art, the present invention achieves following advantageous effect：
(1) the MXene/ lithium sulfides/carbon composite anode material good conductivity of the invention prepared, specific capacity height, cycle performance
Well, the advantages that good rate capability, simple preparation process.
(2) MXene/ lithium sulfides/carbon composite anode material prepared by the present invention, MXene contain certain capacity, therefore energy
Enough further improve the capacity of MXene/ lithium sulfides/carbon composite anode material prepared by the present invention.
Description of the drawings
The accompanying drawings which form a part of this application are used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation do not form the improper restriction to the application for explaining the application.
Fig. 1 is the Ti corroded in embodiment 13C2The SEM figures of sample.
Fig. 2 is Ti in embodiment 13C2The charging and discharging curve figure of the composite positive pole of/lithium sulfide/carbon.
Fig. 3 is Ti in embodiment 13C2Cycle figure under the composite positive pole 0.5C multiplying powers of/lithium sulfide/carbon.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.It is unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
As described in background, MXene is as a kind of new material with property, in cell positive material
In application need to be further expanded, therefore, the present invention propose a kind of MXene/ lithium sulfides/carbon composite anode material and its
Preparation method is further illustrated the present invention in conjunction with embodiment.
Embodiment 1：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) 5gTi is weighed3AlC2, the HF solution of mass fraction 10% is added in, reacts 10h at 30 DEG C, filtering drying obtains
Ti3C2。
(2) it is soluble in water that 6.4g lithium sulfates are weighed, 12.8g carbon blacks is added in and is uniformly mixed under agitation, be subsequently dried,
Obtain carbon black/lithium sulfate composite material.
(3) carbon black in step (2)/lithium sulfate composite material is added as in tube furnace under the protection of high-purity argon gas
Heat keeps the temperature 2 hours to 800 DEG C, obtains lithium sulfide/carbon material.
(4) Ti in step (1)3C2With lithium sulfide/carbon material in mass ratio 1 in step (3)：1 mixing, ball milling 1h, i.e.,
Obtain Ti3C2The composite positive pole of/lithium sulfide/carbon.
The Ti obtained to the present embodiment3C2The composite positive pole of/lithium sulfide/carbon carries out structure observation and cycle performance is surveyed
Examination, as a result as shown in Figs. 1-3；Wherein：
Fig. 1 is the Ti corroded in the present embodiment3C2The SEM figures of sample, it can be seen from the figure that Ti3C2Have
The distinctive intercalation configuration of MXene materials, this structure can provide the channel of ion transmission in charge and discharge process, improve lithium sulphur
The specific capacity of the anode of battery improves the cycle performance of lithium sulfur battery anode material.
Fig. 2 is Ti in the present embodiment3C2The charging and discharging curve figure of the composite positive pole of/lithium sulfide/carbon.It can be with from figure
Find out, since second week, curve is the charging and discharging curve of typical lithium-sulfur cell.
Fig. 3 is Ti in embodiment 13C2Cycle figure of the composite positive pole of/lithium sulfide/carbon under 0.5C multiplying powers.From figure
As can be seen that after cycle 60 weeks, capacity residue 510mAh/g, capacity retention ratio 80%
Embodiment 2：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) 5gTi is weighed2AlC adds in the HF solution of mass fraction 1%, reacts 0.5h at 90 DEG C, filtering drying obtains
Ti2C。
(2) it is soluble in water that 6.4g lithium sulfates are weighed, 64g graphite is added in and is uniformly mixed under agitation, be subsequently dried, obtain
To graphite/lithium sulfate composite material.
(3) graphite in step (2)/lithium sulfate composite material is added as in tube furnace under the protection of high pure nitrogen
Heat keeps the temperature 3 hours to 300 DEG C, obtains lithium sulfide/carbon material.
(4) Ti in step (1)2C and lithium sulfide/carbon material in mass ratio 1 in step (3)：3 mixing, ball milling 0.5h,
Up to Ti2The composite positive pole of C/ lithium sulfides/carbon.
Embodiment 3：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) 5gTi is weighed3AlC2, the HF solution of mass fraction 50% is added in, reacts 48h at 0 DEG C, filtering drying obtains
Ti3C2。
(2) it is soluble in water that 6.4g lithium sulfates are weighed, 32g graphenes is added in and is uniformly mixed under agitation, be subsequently dried,
Obtain graphene/lithium sulfate composite material.
(3) by the graphene in step (2)/lithium sulfate composite material as in tube furnace, under the protection of high pure nitrogen
It is heated to 1500 DEG C and keeps the temperature 1 hour, obtain lithium sulfide/carbon material.
(4) Ti in step (1)3C2With lithium sulfide/carbon material in mass ratio 1 in step (3)：10 mixing, ball milling 2h,
Up to Ti3C2The composite positive pole of/lithium sulfide/carbon.
Embodiment 4：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) 5gTi is weighed2AlC adds in the HF solution of mass fraction 5%, reacts 20h at 50 DEG C, filtering drying obtains
Ti2C。
(2) it is soluble in water that 5g lithium sulfates are weighed, 15g pitches is added in and is uniformly mixed under agitation, be subsequently dried, obtain
Pitch/lithium sulfate composite material.
(3) pitch in step (2)/lithium sulfate composite material is added as in tube furnace under the protection of high-purity helium
Heat keeps the temperature 1.5 hours to 500 DEG C, obtains lithium sulfide/carbon material.
(4) Ti in step (1)2C in step (3) with obtaining lithium sulfide/carbon material in mass ratio 1：5 mixing, ball milling
5h is to get Ti2The composite positive pole of C/ lithium sulfides/carbon.
Embodiment 5：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) 5gV is weighed2AlC adds in the HF solution of mass fraction 40%, reacts 45h at 10 DEG C, filtering drying obtains
V2C。
(2) it is soluble in water that 5g lithium sulfates are weighed, 15g polyethylene is added in and is uniformly mixed under agitation, be subsequently dried, obtain
To polyethylene/lithium sulfate composite material.
(3) by the polyethylene in step (2)/lithium sulfate composite material as in tube furnace, under the protection of high-purity helium
It is heated to 400 DEG C and keeps the temperature 2 hours, obtain lithium sulfide/carbon material.
(4) V in step (1)2C in step (3) with obtaining lithium sulfide/carbon material in mass ratio 1：8 mixing, ball milling
8h is to get V2The composite positive pole of C/ lithium sulfides/carbon.
Embodiment 6：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) 5gV is weighed2AlC adds in the HF solution of mass fraction 40%, reacts 40h at 70 DEG C, filtering drying obtains
V2C。
(2) it is soluble in water that 5g lithium sulfates are weighed, 75g phenolic resin is added in and is uniformly mixed under agitation, be subsequently dried,
Obtain phenolic resin/lithium sulfate composite material.
(3) by the phenolic resin in step (2)/lithium sulfate composite material as in tube furnace, in the protection of high-purity neon
Under be heated to 1200 DEG C keep the temperature 1 hour, obtain lithium sulfide/carbon material.
(4) V in step (1)2C in step (3) with obtaining lithium sulfide/carbon material in mass ratio 1：10 mixing, ball milling
13h is to get V2The composite positive pole of C/ lithium sulfides/carbon.
Embodiment 7：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) 5gTa is weighed4AlC3, the HF solution of mass fraction 40% is added in, reacts 3h at 80 DEG C, filtering drying obtains
Ta4C3。
(2) it is soluble in water that 5g lithium sulfates are weighed, 20g porous carbons is added in and is uniformly mixed under agitation, be subsequently dried, obtain
To porous carbon/lithium sulfate composite material.
(3) by the porous carbon in step (2)/lithium sulfate composite material as in tube furnace, under the protection of high pure nitrogen
It is heated to 1400 DEG C and keeps the temperature 1 hour, obtain lithium sulfide/carbon material.
(4) Ta in step (1)4C3With obtaining lithium sulfide/carbon material in mass ratio 1 in step (3)：3 mixing, ball milling
10h is to get Ta4C3The composite positive pole of/lithium sulfide/carbon.
Embodiment 8：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) 5gTa is weighed4AlC3, the HF solution of mass fraction 40% is added in, reacts 3h at 8 DEG C, filtering drying obtains
Ta4C3。
(2) it is soluble in water that 5g lithium sulfates are weighed, 100g glucose is added in and is uniformly mixed under agitation, be subsequently dried,
Obtain glucose/lithium sulfate composite material.
(3) by the glucose in step (2)/lithium sulfate composite material as in tube furnace, under the protection of high pure nitrogen
It is heated to 700 DEG C and keeps the temperature 2 hours, obtain lithium sulfide/carbon material.
(4) Ta in step (1)4C3With obtaining lithium sulfide/carbon material in mass ratio 1 in step (3)：6 mixing, ball milling
18h is to get Ta4C3The composite positive pole of/lithium sulfide/carbon.
Embodiment 9：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) 5gTi is weighed3AlC2, the HF solution of mass fraction 40% is added in, reacts 3h at 8 DEG C, filtering drying obtains
Ti3C2。
(2) it is soluble in water that 5g lithium sulfates are weighed, 40g polyurethane is added in and is uniformly mixed under agitation, be subsequently dried, obtain
To polyurethane/lithium sulfate composite material.
(3) by the polyurethane in step (2)/lithium sulfate composite material as in tube furnace, under the protection of high pure nitrogen
It is heated to 700 DEG C and keeps the temperature 2 hours, obtain lithium sulfide/carbon material.
(4) Ti in step (1)3C2With obtaining lithium sulfide/carbon material in mass ratio 1 in step (3)：6 mixing, ball milling
15h is to get Ti3C2The composite positive pole of/lithium sulfide/carbon.
Embodiment 10：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) 5gTi is weighed2AlC adds in the HF solution of mass fraction 40%, reacts 3h at 8 DEG C, filtering drying obtains
Ti2C。
(2) it is soluble in water that 5g lithium sulfates are weighed, 35g gelatin is added in and is uniformly mixed under agitation, be subsequently dried, obtain
Gelatin/lithium sulfate composite material.
(3) gelatin in step (2)/lithium sulfate composite material is added as in tube furnace under the protection of high pure nitrogen
Heat keeps the temperature 2 hours to 700 DEG C, obtains lithium sulfide/carbon material.
(4) Ti in step (1)2C in step (3) with obtaining lithium sulfide/carbon material in mass ratio 1：6 mixing, ball milling
20h is to get Ti2The composite positive pole of C/ lithium sulfides/carbon.
Comparative example 1：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) it is soluble in water that 6.4g lithium sulfates are weighed, 12.8g carbon blacks is added in and is uniformly mixed under agitation, be subsequently dried,
Obtain carbon black/lithium sulfate composite material.
(2) carbon black in step (1)/lithium sulfate composite material is added as in tube furnace under the protection of high-purity argon gas
Heat keeps the temperature 2 hours to 800 DEG C, obtains lithium sulfide/carbon material.
Lithium sulfide/carbon material is obtained to the present embodiment, cycle performance test is carried out under 0.5C multiplying powers, after cycle 60 weeks,
Capacity residue 310mAh/g, capacity retention ratio 54%.
Comparative example 2：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) it is soluble in water that 6.4g lithium sulfates are weighed, 64g graphite is added in and is uniformly mixed under agitation, be subsequently dried, obtain
To graphite/lithium sulfate composite material.
(2) graphite in step (1)/lithium sulfate composite material is added as in tube furnace under the protection of high pure nitrogen
Heat keeps the temperature 3 hours to 300 DEG C, obtains lithium sulfide/carbon material.
Lithium sulfide/carbon material is obtained to the present embodiment, cycle performance test is carried out under 0.5C multiplying powers, after cycle 60 weeks,
Capacity residue 322mAh/g, capacity retention ratio 57%.
Comparative example 3：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) it is soluble in water that 6.4g lithium sulfates are weighed, 32g graphenes is added in and is uniformly mixed under agitation, be subsequently dried,
Obtain graphene/lithium sulfate composite material.
(2) by the graphene in step (1)/lithium sulfate composite material as in tube furnace, under the protection of high pure nitrogen
It is heated to 1500 DEG C and keeps the temperature 1 hour, obtain lithium sulfide/carbon material.
Lithium sulfide/carbon material is obtained to the present embodiment, cycle performance test is carried out under 0.5C multiplying powers, after cycle 60 weeks,
Capacity residue 308mAh/g, capacity retention ratio 58%.
Comparative example 4：
A kind of preparation method of MXene/ lithium sulfides/carbon composite anode material, includes the following steps：
(1) it is soluble in water that 5g lithium sulfates are weighed, 15g pitches is added in and is uniformly mixed under agitation, be subsequently dried, obtain
Pitch/lithium sulfate composite material.
(2) pitch in step (1)/lithium sulfate composite material is added as in tube furnace under the protection of high-purity helium
Heat keeps the temperature 1.5 hours to 500 DEG C, obtains lithium sulfide/carbon material.
Lithium sulfide/carbon material is obtained to the present embodiment, cycle performance test is carried out under 0.5C multiplying powers, after cycle 60 weeks,
Capacity residue 316mAh/g, capacity retention ratio 56%.
The foregoing is merely the preferred embodiments of the application, are not limited to the application, for those skilled in the art
For member, the application can have various modifications and variations.All any modifications within spirit herein and principle, made,
Equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of MXene/ lithium sulfides/carbon composite anode material；It is characterized in that：The positive electrode is by MXene materials, vulcanization
Lithium, carbon composition；Wherein, carbon coating is on the surface of lithium sulfide, between carbon/lithium sulfide is attached between the intercalation of MXene materials.
2. the preparation method of MXene/ lithium sulfides/carbon composite anode material as described in claim 1；It is characterized in that：It is described
Preparation method includes the following steps：
(1) MAX phases powder is subjected to acid etching, is filtered, washed, dries, obtain the MXene nano materials with porous structure；
(2) it by lithium sulfate wiring solution-forming, is mixed in proportion with Carbon materials or carbon matrix precursor, before carbon/lithium sulfate or carbon is made
Drive body/lithium sulfate composite material；
(3) carbon/lithium sulfate under protective atmosphere in heating stepses (2) or carbon matrix precursor/lithium sulfate composite material, pass through heat
Above-mentioned composite material is reduced into lithium sulfide/carbon material by the mode of reduction；
(4) the MXene nano materials for having porous structure in step (1) are mixed with lithium sulfide/carbon in step (3), ball milling,
Up to MXene/ lithium sulfides/carbon composite anode material.
3. the preparation method of MXene/ lithium sulfides/carbon composite anode material as claimed in claim 2；It is characterized in that：It is described
MAX powder includes：Ti3AlC2、Ti2AlC、Ta4AlC3、TiNbAlC、(V0.5Cr0.5)3AlC2、V2AlC、Nb2AlC、Nb4AlC3、
Ti3AlCN、Ti3SiC2、Ti2SiC、Ta4SiC3、TiNbSiC、(V0.5Cr0.5)3SiC2、V2SiC、Nb2SiC、Nb4SiC3、
Ti3SiCN；Preferably, the MAX powder is Ti3AlC2、Ti2AlC、Ta4AlC3、V2AlC。
4. the preparation method of MXene/ lithium sulfides/carbon composite anode material as claimed in claim 2；It is characterized in that：It is described
The condition of acid etching is：Mass concentration is used to be reacted 0.5-48 hours at 0-90 DEG C for the hydrofluoric acid of 1%-50%.
5. the preparation method of MXene/ lithium sulfides/carbon composite anode material as claimed in claim 2；It is characterized in that：It is described
Carbon material includes：The mixture of one or more of carbon black, graphite, graphene, carbon nanotube, carbon fiber, porous carbon.
6. the preparation method of MXene/ lithium sulfides/carbon composite anode material as claimed in claim 2；It is characterized in that：It is described
Carbon matrix precursor includes：The mixture of one or more of pitch, carbohydrate, polyethylene, phenolic resin, gelatin, polyurethane.
7. the preparation method of MXene/ lithium sulfides/carbon composite anode material as claimed in claim 2；It is characterized in that：It is described
The mass ratio of lithium sulfate and carbon material is 1:(2-10)；The mass ratio of the lithium sulfate and carbon matrix precursor is 1:(3-20).
8. the preparation method of MXene/ lithium sulfides/carbon composite anode material as claimed in claim 2；It is characterized in that：It is described
Inert atmosphere includes the mixture of one or more of nitrogen, argon gas, helium, neon；The heating temperature is 300-
1500 DEG C, time 1-3h.
9. the preparation method of MXene/ lithium sulfides/carbon composite anode material as claimed in claim 2；It is characterized in that：It is described
The mass ratio of MXene nano materials and lithium sulfide/carbon is 1:(1-10)；The Ball-milling Time is：0.5-20h.
10. MXene/ lithium sulfides/carbon composite anode material as described in claim 1 and/or such as any one of claim 2-9 institutes
Application of the preparation method stated in lithium-sulfur cell, electric vehicle or energy storage material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810046164.6A CN108258222B (en) | 2018-01-17 | 2018-01-17 | MXene/lithium sulfide/carbon composite anode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810046164.6A CN108258222B (en) | 2018-01-17 | 2018-01-17 | MXene/lithium sulfide/carbon composite anode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108258222A true CN108258222A (en) | 2018-07-06 |
| CN108258222B CN108258222B (en) | 2020-04-14 |
Family
ID=62726531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810046164.6A Active CN108258222B (en) | 2018-01-17 | 2018-01-17 | MXene/lithium sulfide/carbon composite anode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108258222B (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301201A (en) * | 2018-09-19 | 2019-02-01 | 三峡大学 | The compound Ga of the double carbon structures of self-supporting2O3Negative electrode of lithium ion battery preparation method |
| CN109449404A (en) * | 2018-10-30 | 2019-03-08 | 肇庆市华师大光电产业研究院 | A kind of lithium sulfur battery anode material sulphur-nitrogen-doped carbon nano-fiber-MXene composite material and preparation method |
| CN109473646A (en) * | 2018-10-30 | 2019-03-15 | 肇庆市华师大光电产业研究院 | A kind of preparation method and application of sulphur-polypyrrole-two-dimensional layer carbonization titanium composite material |
| CN109535476A (en) * | 2018-11-27 | 2019-03-29 | 北京化工大学 | A kind of Mxene@chitosan@polyurethane foam three-dimensional composite material and its preparation method and application |
| CN109671576A (en) * | 2018-12-12 | 2019-04-23 | 福建翔丰华新能源材料有限公司 | Carbon nano tube-MXene composite three-dimensional porous carbon material and preparation method thereof |
| CN110416537A (en) * | 2019-08-02 | 2019-11-05 | 广东东岛新能源股份有限公司 | Lithium titanate composite anode material and preparation method thereof and lithium ion battery |
| CN110739429A (en) * | 2019-10-29 | 2020-01-31 | 肇庆市华师大光电产业研究院 | Preparation method of functional interlayer of lithium-sulfur battery |
| KR102085753B1 (en) * | 2018-11-23 | 2020-03-06 | 원광대학교 산학협력단 | Carbon fiber composite comprising unwoven carbon fabric coated with MAXene and oxidized carbon nanotube, method for manufacturing the same and use thereof |
| CN111180701A (en) * | 2020-01-06 | 2020-05-19 | 深圳大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111172672A (en) * | 2020-01-16 | 2020-05-19 | 太原师范学院 | MXenes/polyurethane thermal insulation material and preparation method thereof |
| EP3758109A1 (en) * | 2019-06-26 | 2020-12-30 | Chongqing University | Lithium-sulfur battery cathode material and preparation method thereof, lithium-sulfur battery cathode and preparation method thereof, and lithium-sulfur battery |
| CN112263974A (en) * | 2020-11-24 | 2021-01-26 | 山东大学 | Spray drying method for preparing Ti3C2Method for Tx/carbon black composite microsphere |
| CN112490426A (en) * | 2020-11-27 | 2021-03-12 | 青岛大学 | LiFePO4Preparation method of @ C/MXene composite material |
| CN113422112A (en) * | 2021-07-05 | 2021-09-21 | 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 |
| CN114203953A (en) * | 2021-11-25 | 2022-03-18 | 大连理工大学 | High-load lithium-rich anode based on MXene and micron lithium sulfide and application of high-load lithium-rich anode in quasi-solid-state non-negative lithium battery |
| CN114497499A (en) * | 2022-01-26 | 2022-05-13 | 中汽创智科技有限公司 | Lithium sulfide/carbon composite material with multilevel structure and preparation method and application thereof |
| CN114864901A (en) * | 2022-05-21 | 2022-08-05 | 复旦大学 | All-solid-state battery electrode material with double-carrier conduction and preparation method thereof |
| CN114899383A (en) * | 2022-06-06 | 2022-08-12 | 山东大学 | Preparation method of low-cost sodium battery positive electrode material |
| CN115000410A (en) * | 2022-07-07 | 2022-09-02 | 桂林理工大学 | Carbon nano tube-titanium carbide composite porous microsphere, preparation thereof and application thereof in lithium-sulfur battery |
| CN117558906A (en) * | 2024-01-11 | 2024-02-13 | 吉林大学 | Positive electrode material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2018
- 2018-01-17 CN CN201810046164.6A patent/CN108258222B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Title |
|---|
| D.H. WANG，ET AL.: ""Rational in-situ construction of three-dimensional reduced graphene oxide supported Li2S/C composite as enhanced cathode for rechargeable lithium-sulfur batteries"", 《JOURNAL OF POWER SOURCES》 * |
| ZHAN LIN，ET AL.: ""High-performance lithium/sulfur cells with a bi-functionally immobilized sulfur cathode"", 《NANO ENERGY》 * |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109301201A (en) * | 2018-09-19 | 2019-02-01 | 三峡大学 | The compound Ga of the double carbon structures of self-supporting2O3Negative electrode of lithium ion battery preparation method |
| CN109449404A (en) * | 2018-10-30 | 2019-03-08 | 肇庆市华师大光电产业研究院 | A kind of lithium sulfur battery anode material sulphur-nitrogen-doped carbon nano-fiber-MXene composite material and preparation method |
| CN109473646A (en) * | 2018-10-30 | 2019-03-15 | 肇庆市华师大光电产业研究院 | A kind of preparation method and application of sulphur-polypyrrole-two-dimensional layer carbonization titanium composite material |
| CN109473646B (en) * | 2018-10-30 | 2022-02-22 | 肇庆市华师大光电产业研究院 | Preparation method and application of sulfur-polypyrrole-two-dimensional layered titanium carbide composite material |
| KR102085753B1 (en) * | 2018-11-23 | 2020-03-06 | 원광대학교 산학협력단 | Carbon fiber composite comprising unwoven carbon fabric coated with MAXene and oxidized carbon nanotube, method for manufacturing the same and use thereof |
| CN109535476A (en) * | 2018-11-27 | 2019-03-29 | 北京化工大学 | A kind of Mxene@chitosan@polyurethane foam three-dimensional composite material and its preparation method and application |
| CN109671576B (en) * | 2018-12-12 | 2021-01-26 | 福建翔丰华新能源材料有限公司 | Carbon nano tube-MXene composite three-dimensional porous carbon material and preparation method thereof |
| CN109671576A (en) * | 2018-12-12 | 2019-04-23 | 福建翔丰华新能源材料有限公司 | Carbon nano tube-MXene composite three-dimensional porous carbon material and preparation method thereof |
| EP3758109A1 (en) * | 2019-06-26 | 2020-12-30 | Chongqing University | Lithium-sulfur battery cathode material and preparation method thereof, lithium-sulfur battery cathode and preparation method thereof, and lithium-sulfur battery |
| CN110416537B (en) * | 2019-08-02 | 2022-05-31 | 广东东岛新能源股份有限公司 | Lithium titanate composite negative electrode material, preparation method thereof and lithium ion battery |
| CN110416537A (en) * | 2019-08-02 | 2019-11-05 | 广东东岛新能源股份有限公司 | Lithium titanate composite anode material and preparation method thereof and lithium ion battery |
| CN110739429A (en) * | 2019-10-29 | 2020-01-31 | 肇庆市华师大光电产业研究院 | Preparation method of functional interlayer of lithium-sulfur battery |
| CN111180701A (en) * | 2020-01-06 | 2020-05-19 | 深圳大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111180701B (en) * | 2020-01-06 | 2022-07-05 | 深圳大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111172672A (en) * | 2020-01-16 | 2020-05-19 | 太原师范学院 | MXenes/polyurethane thermal insulation material and preparation method thereof |
| CN112263974A (en) * | 2020-11-24 | 2021-01-26 | 山东大学 | Spray drying method for preparing Ti3C2Method for Tx/carbon black composite microsphere |
| CN112490426A (en) * | 2020-11-27 | 2021-03-12 | 青岛大学 | LiFePO4Preparation method of @ C/MXene composite material |
| CN112490426B (en) * | 2020-11-27 | 2021-12-14 | 青岛大学 | LiFePO4Preparation method of @ C/MXene composite material |
| CN113422112A (en) * | 2021-07-05 | 2021-09-21 | 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 |
| CN114203953A (en) * | 2021-11-25 | 2022-03-18 | 大连理工大学 | High-load lithium-rich anode based on MXene and micron lithium sulfide and application of high-load lithium-rich anode in quasi-solid-state non-negative lithium battery |
| CN114203953B (en) * | 2021-11-25 | 2023-11-21 | 大连理工大学 | High-load lithium-rich anode based on MXene and micron lithium sulfide and application of high-load lithium-rich anode in quasi-solid non-negative lithium battery |
| CN114497499A (en) * | 2022-01-26 | 2022-05-13 | 中汽创智科技有限公司 | Lithium sulfide/carbon composite material with multilevel structure and preparation method and application thereof |
| CN114497499B (en) * | 2022-01-26 | 2023-11-21 | 中汽创智科技有限公司 | Multi-stage structure lithium sulfide/carbon composite material and preparation method and application thereof |
| CN114864901A (en) * | 2022-05-21 | 2022-08-05 | 复旦大学 | All-solid-state battery electrode material with double-carrier conduction and preparation method thereof |
| CN114899383A (en) * | 2022-06-06 | 2022-08-12 | 山东大学 | Preparation method of low-cost sodium battery positive electrode material |
| CN115000410A (en) * | 2022-07-07 | 2022-09-02 | 桂林理工大学 | Carbon nano tube-titanium carbide composite porous microsphere, preparation thereof and application thereof in lithium-sulfur battery |
| CN115000410B (en) * | 2022-07-07 | 2023-12-26 | 桂林理工大学 | Positive electrode material of lithium-sulfur battery |
| CN117558906A (en) * | 2024-01-11 | 2024-02-13 | 吉林大学 | Positive electrode material and preparation method and application thereof |
| CN117558906B (en) * | 2024-01-11 | 2024-03-22 | 吉林大学 | Positive electrode material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108258222B (en) | 2020-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108258222A (en) | A kind of MXene/ lithium sulfides/carbon composite anode material and preparation method thereof | |
| Zheng et al. | Rational design of a tubular, interlayer expanded MoS 2–N/O doped carbon composite for excellent potassium-ion storage | |
| Bhattacharya et al. | Carambola-shaped SnO2 wrapped in carbon nanotube network for high volumetric capacity and improved rate and cycle stability of lithium ion battery | |
| Li et al. | Recent Advances of Two‐Dimensional (2 D) MXenes and Phosphorene for High‐Performance Rechargeable Batteries | |
| Wang et al. | Realizing high reversible capacity: 3D intertwined CNTs inherently conductive network for CuS as an anode for lithium ion batteries | |
| CN107579235B (en) | Preparation method of Mxene/S oxide compound applied to lithium-sulfur battery anode | |
| US10511016B2 (en) | Graphene-protected lead acid batteries | |
| CN105098185B (en) | Composite negative pole material and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery | |
| CN109273680B (en) | Porous silicon-carbon negative electrode material, preparation method thereof and lithium ion battery | |
| CN109921090B (en) | Lithium ion all-solid-state full battery and preparation method thereof | |
| Ou et al. | Exfoliated V5S8/graphite nanosheet with excellent electrochemical performance for enhanced lithium storage | |
| CN102447112B (en) | Silicon-carbon composite material, preparation method thereof and cathode material containing same as well as lithium ion battery | |
| KR101665104B1 (en) | The porous silicon based negative active material for a secondary battery and manufacturing method, and rechargeable lithium ion battery including the same | |
| CN106374087A (en) | Cathode material for long-circulation lithium-sulfur battery and preparation method thereof | |
| Wei et al. | Metal-organic framework derived binary-metal oxide/MXene composite as sulfur host for high-performance lithium-sulfur batteries | |
| WO2016202141A1 (en) | Tin/graphene oxide negative-electrode material for lithium batteries and preparation method therefor | |
| Tian et al. | Three-dimensional cross-linking composite of graphene, carbon nanotubes and Si nanoparticles for lithium ion battery anode | |
| Guo et al. | Silica template-assisted synthesis of SnO 2@ porous carbon composites as anode materials with excellent rate capability and cycling stability for lithium-ion batteries | |
| Tian et al. | The sandwiched buffer zone enables porous SnO2@ C micro-/nanospheres to toward high-performance lithium-ion battery anodes | |
| Wu et al. | Sn and SnO 2-graphene composites as anode materials for lithium-ion batteries | |
| CN112357956B (en) | Carbon/titanium dioxide coated tin oxide nanoparticle/carbon assembled mesoporous sphere material and preparation and application thereof | |
| Zhu et al. | Yolk-void-shell Si–C nano-particles with tunable void size for high-performance anode of lithium ion batteries | |
| Xue et al. | Controlled synthesis of alkalized Ti 3 C 2 MXene-supported β-FeOOH nanoparticles as anodes for lithium-ion batteries | |
| Xia et al. | Structure-designed synthesis of 3D MoS 2 anchored on ionic liquid modified rGO–CNTs inspired by a honeycomb for excellent lithium storage | |
| CN109301231A (en) | A kind of MoO3Compound carbon dots lithium ion battery anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |