CN109192940A - A kind of poly modified Mxene composite material and preparation method of titanium dioxide/graphene - Google Patents
A kind of poly modified Mxene composite material and preparation method of titanium dioxide/graphene Download PDFInfo
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- CN109192940A CN109192940A CN201810912946.3A CN201810912946A CN109192940A CN 109192940 A CN109192940 A CN 109192940A CN 201810912946 A CN201810912946 A CN 201810912946A CN 109192940 A CN109192940 A CN 109192940A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- 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
A kind of poly modified Mxene composite material of titanium dioxide/graphene, is made of following methods: (1) Mxene presoma being added in HF acid solution, heating stirring, etching；(2) material after etching is centrifuged, is washed, ultrasound is dry, obtains Mxene material；(3) Mxene material is added to the water, ultrasonic disperse, adds surface charge modifying dose, stirring；(4) Nano titanium dioxide, graphene oxide are separately added into water, ultrasonic disperse, obtain titanium dioxide, graphene oxide dispersion respectively；(5) titanium dioxide, graphene oxide dispersion are added sequentially in Mxene dispersion liquid, are stirred, filtered, it is dry；(6) in an inert atmosphere, it is heat-treated.Nano titanium dioxide part, which is interspersed in Mxene interlayer, improves the longitudinal direction Mxene electric conductivity, and partial adsorbates improve its surface conductivity in Mxene material surface；Graphene coated improves Mxene surface conductivity on the surface Mxene；The lithium ion battery specific capacity assembled is high, high rate performance, good cycling stability.
Description
Technical field
The present invention relates to a kind of composite material and preparation methods, and in particular to a kind of lithium ion battery negative material dioxy
Change the poly modified Mxene composite material and preparation method of titanium/graphene.
Background technique
Lithium ion battery is excellent because having high-energy density, high power density, environmental-friendly, long service life and security performance
More the advantages that, it has also become ideal energy storage device.
From after grapheme two-dimension material appearance, hot topic that two-dimensional material becomes as scientific research.Two-dimensional material has spy
Different layer structure, mechanics, optics, electrochemistry,.Excellent performance is illustrated in informatics.Currently, two-dimensional material exists
It is furtherd investigate in the fields such as catalyst, energy storage device, sensor and biomaterial.
Graphene is the Typical Representative of two-dimensional material.In addition to this, the hair of novel two-dimensional material Mxene a kind of in recent years
Now new member is added to for two-dimensional material family.In numerous two-dimensional materials, Mxene is due to the cheap, electronics with raw material
Excellent electric conductivity, stable structure, good cycling stability, and without precious metal are a kind of ideal supercapacitor and lithium from
Sub- cell negative electrode material.But due to intrinsic Mxene material surface and longitudinal poorly conductive, limit to a certain extent its
The application of energy storage field.
CN107633954A discloses a kind of graphene/Mxene combination electrode material and its application, although gained graphite
Alkene/Mxene composite material effectively raises Mxene material conductivity, but gained graphene/Mxene composite material is to Mxene
Material longitudinal direction electric conductivity is not modified raising.
CN107170587A discloses a kind of sulfur doping Mxene material and the preparation method and application thereof, although it is former to pass through sulphur
Son effectively increases its electric conductivity and chemical property to the material doped modification of Mxene, but its specific discharge capacity is relatively relatively low.
CN104496461 discloses a kind of based on Ti2The preparation method of the battery electrode material of CMxene, although by inserting
After layer removing, Mxene material interlamellar spacing expands.But Mxene material interlamellar spacing obtained by the preparation method comparatively still compared with
It is small, it can not be embedded in other materials inside it to improve Mxene material longitudinal direction electric conductivity.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of specific capacity
Height, high rate performance, good cycling stability are suitable for the poly modified Mxene composite wood of titanium dioxide/graphene of industrialized production
Material and preparation method thereof.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of titanium dioxide/graphene is poly modified
Mxene composite material, is made of following methods:
(1) Mxene presoma is added in HF acid solution, heating stirring, etching removes Al layers；
(2) the Mxene presoma after step (1) etching is centrifuged, is washed, ultrasonic disperse, it is dry, obtain Mxene material；
(3) Mxene material obtained by step (2) is added to the water, ultrasonic disperse, adds surface charge modifying dose, stirring obtains table
The positively charged Mxene dispersion liquid in face；
(4) Nano titanium dioxide, graphene oxide are added to the water respectively, ultrasonic disperse, respectively obtain titanium dioxide dispersion
Liquid, graphene oxide dispersion；
(5) that titanium oxide dispersion, graphene oxide dispersion be successively added to surface obtained by step (3) is positively charged
It in Mxene dispersion liquid, stirs, filters, it is dry, obtain black powder；
(6) black powder obtained by step (5) is placed in inert atmosphere, is heat-treated polynary to get titanium dioxide/graphene
Modified Mxene composite material.
Preferably, in step (1), the mass fraction of HF acid solution used is 25 ~ 65%；The Mxene presoma and HF acid
Mass ratio is 1: 25 ~ 65.The concentration of the HF acid solution is too low or excessively high, is all difficult to obtain the Mxene of complete layer structure.
Preferably, in step (1), etch period is 4 ~ 10 h, more preferable 6 ~ 10h.The etch period is too long or too short
It will lead to Mxene presoma over etching or etching be insufficient.
Preferably, in step (1), the heating stirring speed be 200 ~ 600 turns/min, more preferable 300 ~ 400 turns/
min；The heating stirring temperature is 40 ~ 100 DEG C, more preferable 80 ~ 90 DEG C；The time of the heating stirring is 4 ~ 10h, more preferably
6~10h.The etching temperature it is too low or it is excessively high will lead to Mxene presoma etch insufficient or structural damage.
Preferably, in step (2), the centrifugal rotational speed is 3000 ~ 12000 turns/min；The washing, which refers to, uses deionization
Water and ethanol washing, more preferably cross washing respectively, washing times >=10 time；The power of the ultrasonic disperse is 200 ~ 400 W,
Ultrasonic time is 0.5 ~ 2 h；The drying temperature is 60 ~ 100 DEG C, and the time is 6 ~ 12 h.
Preferably, in step (3), the quality of the water is 400~800 times of Mxene mass；The function of the ultrasonic disperse
Rate is 200~400 W, and the time is 0.5~2 h；Described surface charge modifying dose and Mxene of mass ratio is 5~15 times；It is described
Mixing speed is 200~400 turns/min, and the time is 1~4 h.
Preferably, in step (3), the charged surface modifying agent is ammonium hydroxide, ammonium hydrogen carbonate or cetyl trimethyl bromine
Change one or more of ammonium.Surface charge modifying dose in water, can ionize out ammonia root cation, it is negatively charged to be adsorbed on surface
The Mxene material surface of lotus obtains the positively charged Mxene in surface, is more advantageous to absorption titanium dioxide, graphene oxide.If
Surface charge modifying dose of dosage is too small, then cannot sufficiently to negative electrical charge Mxene carry out it is charge-modified, if surface charge modifying dose with
Amount is excessive, will cause the waste of surface charge modifying dose of resource.
Preferably, in step (4), the mass ratio of the Nano titanium dioxide, graphene oxide and Mxene is 5~
10:100.The quality of the water is titanium dioxide, 500 ~ 1500 times of graphene oxide quality；The ultrasonic disperse frequency is
200~400 W, time are 0.5~2 h.
Preferably, in step (5), the titanium oxide dispersion, graphene oxide dispersion addition sequence are followed successively by two
Titanium oxide dispersion liquid, graphene oxide dispersion；The mixing speed is 200 ~ 400 turns/min, and the time is 6 ~ 12 h；It is described dry
Dry temperature is 60~100 DEG C, and the time is 6 ~ 12 h.
Preferably, in step (6), the heat treatment temperature is 300 ~ 600 DEG C, and the time is 6 ~ 12 h；The inert atmosphere
For argon gas, argon/one or more of hydrogen gaseous mixture or nitrogen.
Beneficial effects of the present invention are as follows:
(1) the present invention gained poly modified Mxene composite material of titanium dioxide/graphene, titanium dioxide are embedded in/are adsorbed on
Mxene interlamellar spacing and surface, graphene coated effectively improve Mxene material longitudinal direction and surface conductance on the surface Mxene
Property, improve its chemical property；
(2) lithium that the present invention gained poly modified Mxene of composite cathode material of lithium ion battery titanium dioxide/graphene is assembled
Ion battery specific capacity with higher, excellent cycle performance and reversible capacity.
Detailed description of the invention
Fig. 1 is that 1 gained composite cathode material of lithium ion battery titanium dioxide/graphene of the embodiment of the present invention is poly modified
The XRD diagram of Mxene；
Fig. 2 is the 1 poly modified Mxene of gained composite cathode material of lithium ion battery titanium dioxide/graphene of the embodiment of the present invention
SEM figure；
Fig. 3 is the 1 poly modified Mxene of gained composite cathode material of lithium ion battery titanium dioxide/graphene of the embodiment of the present invention
The discharge-rate performance chart of assembled lithium ion battery；
Fig. 4 is the 1 poly modified Mxene of gained composite cathode material of lithium ion battery titanium dioxide/graphene of the embodiment of the present invention
The discharge cycle performance figure of assembled lithium ion battery；
Fig. 5 is the 1 poly modified Mxene of gained composite cathode material of lithium ion battery titanium dioxide/graphene of the embodiment of the present invention
The impedance spectra of assembled lithium ion battery.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Graphene oxide used in the embodiment of the present invention is purchased from middle section's epoch nanometer；Usedization of the embodiment of the present invention
Reagent is learned to obtain by routine business approach unless otherwise specified.
Embodiment 1
(1) 30 gHF sour (mass fraction 40%) are added in polytetrafluoroethyltank tank, 1.0 gMxene forerunners is added thereto
Body stirs 6 h, performs etching to Mxene presoma at 400 turns/min, 90 DEG C of constant temperature；
(2) Mxene obtained by step (1) is added to the water, is centrifuged under 10000 turns/min, by precipitating deionized water and anhydrous
Ethyl alcohol is distinguished cross washing 10 times, under 400 W, is ultrasonically treated 1 h, and at 80 DEG C, dry 10 h obtain Mxene material；
(3) Mxene material obtained by 0.1 g step (2) is added in 60 mL deionized waters, at 400 W, carries out ultrasonic disperse 1
0.8 g ammonium hydrogen carbonate is added in h, under 400 turns/min, stirs 2 h, obtains surface charge modifying Mxene material dispersion liquid；
(4) 0.005 g Nano titanium dioxide and graphene oxide are added in 5 mL deionized waters respectively, under 400 W, are surpassed
Sound disperses 2 h, obtains titanium oxide dispersion, graphene oxide dispersion respectively；
(5) titanium oxide dispersion obtained by step (4), graphene oxide dispersion are successively added to surface obtained by step (3)
In charge-modified Mxene dispersion liquid, under 400 turns/min, 8 h are stirred, are filtered, washing, at 80 DEG C, dry 10 h,
Obtain black powder；
(6) by black powder obtained by step (5) in argon/hydrogen gaseous mixture (volume fraction of hydrogen is 5%) inert atmosphere, in 400
At DEG C, 10 h of heat treatment are carried out, the poly modified Mxene composite cathode material of lithium ion battery of titanium dioxide/graphene is obtained.
Change as shown in Figure 1, composite cathode material of lithium ion battery titanium dioxide/graphene is polynary obtained by the embodiment of the present invention
Property Mxene XRD diffraction maximum and standard card (PDF#52-0875,71-1166) unanimously, illustrate gained titanium dioxide, graphene
Poly modified Mxene is pure phase.
Change as shown in Fig. 2, composite cathode material of lithium ion battery titanium dioxide/graphene is polynary obtained by the embodiment of the present invention
Property Mxene SEM figure, titanium dioxide uniformly adsorbs/is embedded in the surface Mxene and layer, and graphene coated is on its surface.
Battery assembly: the poly modified Mxene composite wood of titanium dioxide/graphene obtained by 0.08 g the present embodiment is weighed respectively
Material is used as negative electrode material, and 0.01 g acetylene black (SP) is added and makees conductive agent and 0.01 g PVDF(HSV-900) make binder, it fills
1.5 mL NMP dispersion mixings are added after dividing grinding, cathode pole piece is made in slurry on the copper foil of 20 μ m-thicks after sizing mixing uniformly,
With lithium metal to be positive in anaerobism glove box, using more empty polypropylene as diaphragm, 1mol/L LiPF6Ethylene carbonate and carbonic acid
Dimethyl ester and the mixed solution of dimethyl carbonate (volume ratio=1:1:1) are electrolyte assembled battery, are assembled into 2025 button
Battery；In the case where voltage range is 0.01~3 V, the constant current charge-discharge performance of the lithium ion battery assembled is tested.
As shown in figure 3, under 0.1 C multiplying power (mA of 1 C=300 h/g), the lithium ion battery assembled discharges ratio for the first time
Capacity reaches 749.4 mAh/g, and under 0.2 C, 0.5 C, 1 C, 2 C, 5 C multiplying powers, first discharge specific capacity is respectively
318.8 mAh/g,270.0 mAh/g,239.7 mAh/g,212.6 mAh/g,150.9 mAh/g；At big times of 10 C and 15 C
Under rate, first discharge specific capacity respectively reaches 117.5 mAh/g and 101.3 mAh/g, later under the multiplying power of 0.1 C, puts
Electric specific capacity still can reach 286 mAh/g, illustrate that the poly modified Mxene composite material of titanium dioxide/graphene of preparation has
Excellent reversible capacity.
As shown in figure 4, the lithium ion battery first discharge specific capacity assembled can reach 739.7 under 0.1 C multiplying power
MAh/g, after 100 circulations, specific discharge capacity is still 300 mAh/g.Illustrate that lithium ion battery obtained by the embodiment of the present invention is negative
The lithium ion battery that the pole poly modified Mxene of composite material titanium dioxide/graphene is assembled has excellent cycle performance.
As shown in figure 5, the lithium ion battery assembled has lesser internal resistance, illustrate lithium ion obtained by the embodiment of the present invention
The poly modified Mxene electric conductivity of battery cathode composite material titanium dioxide/graphene is greatly improved.
From the foregoing, it will be observed that the poly modified Mxene composite material of titanium dioxide/graphene obtained by the embodiment of the present invention was assembled
Lithium ion battery has higher specific discharge capacity and good high rate performance and cycle performance, the introducing of titanium dioxide and graphene
Effectively raise the electric conductivity of Mxene material.
Embodiment 2
(1) 30 gHF sour (mass fraction 25%) are added in polytetrafluoroethyltank tank, 1.0 gMxene forerunners is added thereto
Body stirs 10 h, performs etching to Mxene presoma at 300 turns/min, 85 DEG C of constant temperature；
(2) Mxene obtained by step (1) is added to the water, is centrifuged under 5000 turns/min, by precipitating deionized water and anhydrous second
Alcohol is distinguished cross washing 10 times, under 400 W, is ultrasonically treated 1 h, and at 80 DEG C, dry 10 h obtain Mxene material；
(3) Mxene material obtained by 0.1 g step (2) is added in 60 mL deionized waters, at 400 W, carries out ultrasonic disperse 1
1.5 g ammonium hydroxide are added in h, under 400 turns/min, stir 1 h, obtain surface charge modifying Mxene material dispersion liquid；
(4) 0.01 g Nano titanium dioxide and graphene oxide are added in 5 mL deionized waters respectively, under 400 W, are surpassed
Sound disperses 2 h, obtains titanium oxide dispersion, graphene oxide dispersion respectively；
(5) titanium oxide dispersion obtained by step (4), graphene oxide dispersion are added to surface charge obtained by step (3)
In modified Mxene dispersion liquid, under 400 turns/min, 8 h are stirred, are filtered, washing, at 80 DEG C, dry 12 h are obtained black
Color powder；
(6) black powder obtained by step (5) is placed in argon gas, at 600 DEG C, carries out 6 h of heat treatment, obtain titanium dioxide/stone
The black poly modified Mxene composite cathode material of lithium ion battery of alkene.
Through detecting, composite cathode material of lithium ion battery titanium dioxide/graphene obtained by the embodiment of the present invention is poly modified
The position of characteristic peak on XRD Mxene is consistent with standard card, illustrates that the gained poly modified Mxene of titanium dioxide/graphene is
Pure phase.
Through detecting, composite cathode material of lithium ion battery titanium dioxide, graphene obtained by the embodiment of the present invention are poly modified
Mxene, titanium dioxide are uniformly adsorbed/are embedded in the surface Mxene and layer, and graphene coated is on its surface.
Battery assembly: with embodiment 1；In the case where voltage range is 0.01~3 V, to the perseverance electricity of the lithium ion battery assembled
Stream charge-discharge performance is tested.
Through detecting, (mA of 1 C=300 h/g), the lithium ion battery first discharge specific capacity assembled under 0.1 C multiplying power
Reach 682.6 mAh/g, under 0.2 C, 0.5 C, 1 C, 2 C, 5 C multiplying powers, first discharge specific capacity is respectively 285.5
mAh/g,228.0 mAh/g,195.9 mAh/g,178.2 mAh/g,141.6 mAh/g；At 10 C and the big multiplying power of 15 C,
First discharge specific capacity respectively reaches 106.5 mAh/g and 89.1 mAh/g, later under the multiplying power of 0.1 C, specific discharge capacity
It still can reach 278.9 mAh/g, it is excellent to illustrate that the poly modified Mxene composite material of titanium dioxide/graphene of preparation has
Reversible capacity.
Through detecting, under 0.1 C multiplying power, the lithium ion battery first discharge specific capacity assembled can reach 682.6 mAh/
G, after 100 circulations, specific discharge capacity is still 281.8 mAh/g.Illustrate negative electrode of lithium ion battery obtained by the embodiment of the present invention
The lithium ion battery that the poly modified Mxene of composite material titanium dioxide/graphene is assembled has excellent cycle performance.
It is detected, the lithium ion battery internal resistance assembled is that 31.4 Ω illustrate lithium ion battery obtained by the embodiment of the present invention
The poly modified Mxene electric conductivity of anode material titanium dioxide/graphene is greatly improved.
From the foregoing, it will be observed that the poly modified Mxene composite material of titanium dioxide/graphene obtained by the embodiment of the present invention was assembled
Lithium ion battery has higher specific discharge capacity and good high rate performance and cycle performance, the introducing of titanium dioxide and graphene
Effectively raise the electric conductivity of Mxene material.
Comparative example 1
(1) 30 gHF sour (mass fraction 40%) are added in polytetrafluoroethyltank tank, 1.0 gMxene forerunners is added thereto
Body at 90 DEG C of constant temperature, stirs 6 h, performs etching to Mxene presoma under 300 turns/min；
(2) Mxene obtained by step (1) is added to the water, is centrifuged under 10000 turns/min, by precipitating deionized water and anhydrous
Ethyl alcohol is distinguished cross washing 10 times, under 400 W, is ultrasonically treated 1 h, and at 80 DEG C, dry 10 h obtain Mxene material；
(3) Mxene material obtained by 0.1 g step (2) is added in 80 mL deionized waters, at 400 W, carries out ultrasonic disperse 2
0.8 g ammonium hydrogen carbonate is added in h, under 400 turns/min, stirs 2 h, obtains surface charge modifying Mxene material dispersion liquid；
(4) 0.005 g graphene oxide is added in 5 mL deionized waters, under 400 W, 2 h of ultrasonic disperse obtains graphite oxide
Alkene dispersion liquid；
(5) graphene oxide dispersion obtained by step (4) Mxene surface charge modifying obtained by step (3) is added to disperse
In liquid, under 400 turns/min, 8 h are stirred, are filtered, washing, at 80 DEG C, dry 8 h obtain black powder；
(6) black powder obtained by step (5) is placed in nitrogen, at 400 DEG C, carries out heat treatment 10h, it is modified to obtain graphene
Mxene composite cathode material of lithium ion battery.
Through detecting, the modified Mxene of composite cathode material of lithium ion battery graphene obtained by the embodiment of the present invention is special on XRD
The position for levying peak is consistent with standard card, illustrates that the modified Mxene of gained graphene is pure phase.
Through detecting, the modified Mxene of composite cathode material of lithium ion battery graphene obtained by the embodiment of the present invention, graphene packet
Overlay on its surface.
Battery assembly: with embodiment 1；In the case where voltage range is 0.01~3 V, to the perseverance electricity of the lithium ion battery assembled
Stream charge-discharge performance is tested.
Through detecting, (mA of 1 C=300 h/g), the lithium ion battery first discharge specific capacity assembled under 0.1 C multiplying power
Reach 495.1mAh/g, under 0.2 C, 0.5 C, 1 C, 2 C, 5 C multiplying powers, first discharge specific capacity is respectively 220.3
mAh/g,187.5 mAh/g,162.0 mAh/g,137.8 mAh/g,107.9 mAh/g；At 10 C and the big multiplying power of 15 C,
First discharge specific capacity respectively reaches 84.2 mAh/g and 81.5 mAh/g, and later under the multiplying power of 0.1 C, specific discharge capacity is still
It can reach 216.5 mAh/g, illustrate that the modified Mxene composite material of the graphene of preparation has excellent reversible capacity.
Through detecting, under 0.1 C multiplying power, the lithium ion battery first discharge specific capacity assembled can reach 495.1 mAh/
G, after 100 circulations, specific discharge capacity is still 201.3 mAh/g.
It is detected, the lithium ion battery internal resistance assembled is 68.9 Ω, and internal resistance is higher, and electric conductivity is slightly poor.
From the foregoing, it will be observed that the modified Mxene electric conductivity of composite cathode material of lithium ion battery graphene obtained by this comparative example fails
Adequately improved, it is relatively low in big multiplying power discharging specific capacity so as to cause prepared composite material.
Comparative example 2
(1) 30 gHF sour (mass fraction 40%) are added in polytetrafluoroethyltank tank, 1.0 gMxene forerunners is added thereto
Body at 90 DEG C of constant temperature, stirs 6 h, performs etching to Mxene presoma under 300 turns/min；
(2) Mxene obtained by step (1) is added to the water, is centrifuged under 10000 turns/min, by precipitating deionized water and anhydrous
Ethyl alcohol is distinguished cross washing 10 times, under 400 W, is ultrasonically treated 1 h, and at 80 DEG C, dry 10 h obtain Mxene material.
Through detecting, lithium ion battery negative material the Mxene position of characteristic peak and mark on XRD obtained by the embodiment of the present invention
Quasi- card is consistent, illustrates that gained Mxene is pure phase.
Through detecting, lithium ion battery negative material Mxene obtained by the embodiment of the present invention is multilayer chip structure, and interlamellar spacing is bright
It is aobvious.
Battery assembly: with embodiment 1；In the case where voltage range is 0.01~3 V, to the perseverance electricity of the lithium ion battery assembled
Stream charge-discharge performance is tested.
Through detecting, (mA of 1 C=300 h/g), the lithium ion battery first discharge specific capacity assembled under 0.1 C multiplying power
Reach 494.4mAh/g, under 0.2 C, 0.5 C, 1 C, 2 C, 5 C multiplying powers, first discharge specific capacity is respectively 109.9
mAh/g,80.1 mAh/g,61.0 mAh/g,43.7 mAh/g,12.5 mAh/g；At 10 C and the big multiplying power of 15 C, for the first time
Specific discharge capacity respectively reaches 12.5 mAh/g and 6.7 mAh/g, and later under the multiplying power of 0.1 C, specific discharge capacity is still reachable
To 96.5 mAh/g.
Through detecting, under 0.1 C multiplying power, the lithium ion battery first discharge specific capacity assembled can reach 494.4 mAh/
G, after 100 circulations, specific discharge capacity is still 91.3 mAh/g.
It is detected, the lithium ion battery internal resistance assembled is 123.6 Ω, and internal resistance is very high, and electric conductivity is poor.
From the foregoing, it will be observed that lithium ion battery negative material Mxene electric conductivity obtained by this comparative example is to be improved, prepared by
Mxene material is low in big multiplying power discharging specific capacity.
To sum up, the poly modified Mxene composite material of 1~2 gained titanium dioxide/graphene of the embodiment of the present invention is assembled
The battery that lithium ion battery is assembled relative to the modified Mxene and Mxene of graphene obtained by comparative example, electric discharge ratio with higher
Capacity and cycle performance show excellent chemical property under big multiplying power；It can be seen that 1~2 gained dioxy of the embodiment of the present invention
It is more stable during long circulating to change the lithium ion battery that is assembled of the poly modified Mxene composite material of titanium/graphene, this be by
In the introducing of titanium dioxide and graphene, the shortcomings that effectively improving longitudinal direction and the surface conductivity of Mxene material, improve
Material obtains specific discharge capacity, high rate performance and cycle performance.
Claims (8)
1. a kind of poly modified Mxene composite material of titanium dioxide/graphene, which is characterized in that be made of following methods:
(1) Mxene presoma is added in HF acid solution, heating stirring, etching removes Al layers；
(2) the Mxene presoma after step (1) etching is centrifuged, is washed, ultrasonic disperse, it is dry, obtain Mxene material；
(3) Mxene material obtained by step (2) is added to the water, ultrasonic disperse, adds surface charge modifying dose, stirring obtains table
The positively charged Mxene dispersion liquid in face；
(4) Nano titanium dioxide, graphene oxide are added to the water respectively, ultrasonic disperse, respectively obtain titanium dioxide dispersion
Liquid, graphene oxide dispersion；
(5) that titanium oxide dispersion, graphene oxide dispersion be successively added to surface obtained by step (3) is positively charged
It in Mxene dispersion liquid, stirs, filters, it is dry, obtain black powder；
(6) black powder obtained by step (5) is placed in inert atmosphere, is heat-treated polynary to get titanium dioxide/graphene
Modified Mxene composite material.
2. the poly modified Mxene composite material of titanium dioxide/graphene according to claim 1, it is characterised in that: step
(1) in, the mass fraction of the HF acid solution is 25 ~ 65%, and the Mxene presoma and HF acid mass ratio are 1:25 ~ 65；Institute
The speed for stating heating stirring is 200 ~ 600 turns/min, and the temperature of the heating stirring is 40 ~ 100 DEG C, the heating stirring
Time is 4 ~ 10h；The time of the etching is 4 ~ 10 h.
3. the poly modified Mxene composite material of titanium dioxide/graphene according to claim 1 or claim 2, it is characterised in that: step
Suddenly in (2), the revolving speed of the centrifugation is 3000 ~ 12000 turns/min；The washing refers to deionized water and ethanol washing, washes
Wash number >=10 time；The power of the ultrasonic disperse is 200 ~ 400 W, and the time of the ultrasonic disperse is 0.5 ~ 2 h；It is described dry
Dry temperature is 60 ~ 100 DEG C, and the time of the drying is 6 ~ 12 h.
4. the poly modified Mxene composite material of titanium dioxide/graphene described in one of -3 according to claim 1, it is characterised in that:
In step (3), the quality of the water is 400~800 times of Mxene quality of materials；The power of the ultrasonic disperse be 200~
400 W, the time of the ultrasonic disperse are 0.5~2 h；The mass ratio of described surface charge modifying dose and Mxene material is 5~
15 times；The speed of the stirring is 200~400 turns/min, and the time of the stirring is 1~4 h.
5. the poly modified Mxene composite material of titanium dioxide/graphene described in one of -4 according to claim 1, it is characterised in that:
In step (3), the charged surface modifying agent is one of ammonium hydroxide, ammonium hydrogen carbonate or cetyl trimethylammonium bromide or several
Kind.
6. the poly modified Mxene composite material of titanium dioxide/graphene described in one of -5 according to claim 1, it is characterised in that:
In step (4), the mass ratio of the Nano titanium dioxide, graphene oxide and Mxene is 5~10:100；The water
Quality is titanium dioxide, 500 ~ 1500 times of graphene oxide quality；The power of the ultrasonic disperse is 200~400 W, institute
The time for stating ultrasonic disperse is 0.5~2 h.
7. the poly modified Mxene composite material of titanium dioxide/graphene described in one of -6 according to claim 1, it is characterised in that:
In step (5), the titanium oxide dispersion, graphene oxide dispersion addition sequence are followed successively by titanium oxide dispersion, oxygen
Graphite alkene dispersion liquid；The speed of the stirring is 200 ~ 400 turns/min, and the time of the stirring is 6 ~ 12 h；The drying
Temperature be 60~100 DEG C, time of the drying is 6 ~ 12 h.
8. the poly modified Mxene composite material of titanium dioxide/graphene described in one of -7 according to claim 1, it is characterised in that:
In step (6), the temperature of the heat treatment is 300 ~ 600 DEG C, and the time of locating heat treatment is 6 ~ 12 h；The inert atmosphere
For argon gas, argon/one or more of hydrogen gaseous mixture or nitrogen.
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