CN109546093A - Redox graphene and four oxidations three are modified titanium carbide lithium ion battery negative material and preparation method thereof suddenly - Google Patents
Redox graphene and four oxidations three are modified titanium carbide lithium ion battery negative material and preparation method thereof suddenly Download PDFInfo
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- H01M4/00—Electrodes
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- 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
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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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Abstract
The present invention discloses redox graphene and four oxidations three modified titanium carbide lithium ion battery negative material and preparation method thereof suddenly, uses carbon titanium aluminide, manganese dioxide, graphene oxide for raw material, the MnO controlled in preparation process2The concentration of suspension, experiment with GO solution are made by Hummers method.The present invention prepares rGO and Mn using hydro-thermal method and oxidation-reduction method3O4Modified Ti3C2Tx, overcome Ti3C2TxThe disadvantage of negative electrode material chemical property difference.The present invention provides the lithium ion battery negative material with excellent chemical property with a kind of simple process, low-cost method of modifying.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, more particularly to a kind of redox graphene
(rGO) and four aoxidize three violent (Mn3O4) modified titanium carbide (Ti3C2Tx) material and preparation method thereof.
Background technique
The energy is the principal element for influencing social development, while being also the basis of socio-economic development.Energy industry is both
The basic industry of national economy, and be technology-intensive industries.Therefore, energy science and technology innovation is in entire State Scientific and Technological Innovation System
In occupy highly important status.Lithium ion battery have many advantages, such as energy density is high, have extended cycle life with memory-less effect and
It is considered as optimal energy-storage travelling wave tube.This also makes heat of the research of lithium ion battery electrode material as current investigation of materials
Point.The critical material of lithium ion battery first is that negative electrode material, but many problems of negative electrode material limit lithium ion battery
Further apply.Therefore, the raising of negative electrode material performance is very necessary.
Since the acquisition Nobel Prize in 2010, graphene is with its unique two-dimensional structure and excellent electricity, mechanics
Performance and the research hotspot for becoming material and related fields, and the research boom to two-dimensional material has been started in the world.It is other
Two-dimensional material such as hexagonal boron nitride, metal oxide etc. also results in the very big concern of researcher.Nearest two-dimensional material increases again
A new family MXene is added, it is by ternary layered carbonitride MAX phase (general formula Mn+1AXn, M is early stage transition gold
Belong to, A is III, IV major element, and X is carbon or nitrogen, n=1,2,3) by the selective corrosions such as hydrofluoric acid go out it is A layers therein after must
Class two-dimensional transition metal carbon (nitrogen) compound arrived.Due to itself and the similitude in graphene-structured, commonly known as
"MXene".As a kind of two-dimensional material, MXene show its in the potential using value in electrochemical energy storage field, especially when
Due to unique two-dimensional structure and good electric conductivity when it is as lithium ion battery negative material, and show preferable
Chemical property.Ti3C2Tx(wherein T is to be formed by functional group on surface in preparation process, such as hydroxyl (- OH), fluorine-based (- F)
Deng) it is a kind of typical MXene material, the presence of the functional groups such as-F formed in etching process and-OH will increase lithium ion
Diffusional resistance, reduce memory capacity (Ti3C2F2(130mAh/g)、Ti3C2(OH)2(67mAh/g)), work as Ti3C2TxApplied to lithium
Ion battery cathode material, battery performance are severely impacted.
Transition metal oxide has attracted because of a series of its excellent properties and has much ground as lithium ion battery negative material
The interest for the person of studying carefully.Mn3O4There is price relative to the oxide of the metals such as Co, Cu, Ni as one kind of transition metal oxide
Cheaply, advantages of environment protection.Mn3O4Theoretical specific capacity be up to 896mAh/g, but Mn3O4Conductivity it is small, in charge and discharge
Volume expansion is big in the process, limits its further applying in lithium ion battery negative material.In order to increase Mn3O4Electricity
Conductance and its volume expansion of inhibition, adding conductive agent in the material is that one kind selects well.There is researcher to utilize one-step method
Carbon coating Mn is made3O4The chemical property of nanocomposite is very outstanding, under the current density of 0.04A/g, specific volume for the first time
Amount is up to 1246mAh/g [Wang C, Yin L, Xiang D, et al.ACS Applied Materials and
Interfaces,2012,4(3):1636-1642]；Furthermore with the compound one-dimensional Mn of two-dimensional graphene3O4Nano wire obtains one kind
Folding flexible compound nano material, under the current density of 0.1A/g, specific capacity is up to 1271mAh/g [Wang J for the first time
G,Jin D D,Zhou R,et al.ACS Nano,2016,10(6):6227-6234].In addition to this, there is researcher's utilization
Newest two dimension MXene material Ti3C2TxThe transition metal oxide SnO of compound high capacity2, obtain a kind of new composite wood
Material, the specific capacity under the current density of 0.1A/g are 1030mAh/g [Wang F, Wang Z J, Zhu J F, et
al.Journal of Materials Science,2017,52(7):3556-3565]。
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of redox graphene and four oxidations three are violent
Modified titanium carbide lithium ion battery negative material and preparation method thereof prepares rGO (reduction using hydro-thermal method and oxidation-reduction method
Graphene oxide) and Mn3O4Modified Ti3C2TxLithium ion battery negative material, to improve Ti3C2TxChemical property.This hair
It is bright to use a kind of simple process, low-cost method, a kind of negative electrode of lithium ion battery with excellent chemical property is provided
Material.
Technical purpose of the invention is achieved by following technical proposals:
A kind of redox graphene and four oxidations three modified titanium carbide lithium ion battery negative materials and its preparation side suddenly
Method carries out as steps described below:
Step 1, by Ti3AlC2Powder is distributed in the hydrofluoric acid aqueous solution of 30-70wt% of mass percent and is handled,
Sediment obtains black powder, as Ti after drying3C2TxPowder；
In step 1, in hydrofluoric acid aqueous solution, the mass percent of hydrofluoric acid is 50-60wt%.
In step 1, selection 20-25 degrees Celsius of room temperature lower stewing process 20-24 hours.
In step 1, sediment distilled water is centrifugated 5 times, until pH value of solution reaches 4-5, then will precipitating
Object is put into vacuum oven, 10-12 hours dry at 60-80 DEG C, obtains black powder.
In step 1, it selects Ti3AlC2Powder 300-350 mesh of sieving.
Step 2, the Ti prepared by step 13C2TxPowder be placed in it is in the aqueous suspension of manganese dioxide and evenly dispersed, then
Graphene oxide aqueous dispersion is added and is uniformly dispersed, obtains black suspension；
In step 2, dispersed using mechanical or ultrasound, the time dispersed is at least 30min, preferably 1-
1.5 hour.
In step 2, in the suspension of manganese dioxide, manganese dioxide concentration is 0.01-0.2 mol/L, preferably
0.05-0.2 mol/L.
In step 2, graphene oxide (GO) aqueous dispersion is made by Hummers method, and the concentration of graphene oxide is
1-10 mg/mls, preferably 5-10 mg/mls.
In step 2, the aqueous suspension of manganese dioxide and graphene oxide aqueous dispersion are isometric ratio.
Step 3, black suspension step 2 obtained is placed in reaction kettle after sealing, from room temperature in air atmosphere
20-25 degrees Celsius are warming up to 160-200 degrees Celsius with 1-5 degrees Celsius per minute of speed and keep the temperature 6-20 hours, natural
It is after being cooled to room temperature, sediment filtration washing is dry, black powder is obtained, as redox graphene and four oxidations three is violent
Modified titanium carbide lithium ion battery negative material；
In step 3, reaction kettle is the reaction kettle of polytetrafluoroethylliner liner.
In step 3,180-200 are warming up to from 20-25 degrees Celsius of room temperature with 1-5 degrees Celsius per minute of speed to take the photograph
Family name's degree simultaneously keeps the temperature 12-16 hours, cooled to room temperature.
In step 3, sediment in reaction kettle being washed with distilled water 3-5 times, sediment is put into drying box, and 80-
It is 10-12 hours dry at 90 DEG C, 300-350 meshes are regrind and crossed, rGO and Mn are obtained3O4Modified Ti3C2TxMaterial.
In the technical solution of the present invention, carbon titanium aluminide Ti used3AlC2Powder is commercial product, and graphite oxide is used in experiment
Alkene (GO) solution is made by Hummers method, the manganese dioxide (MnO controlled in preparation process2) suspension concentration be 0.01-
0.2 mol/L, the dosage of GO solution is 10 milliliters (1-10 mg/ml), using hydro-thermal method and oxidation-reduction method system
It is standby, manganese dioxide (MnO2) mangano-manganic oxide (Mn is reduced under high-temperature and high-pressure conditions caused by water heating kettle3O4), specifically
Reaction equation it is as follows: Exist simultaneously
High-temperature and high-pressure conditions caused by water heating kettle, which are lauched the hydrogen ion decomposited, has reproducibility, so that graphene oxide (GO) is gone back
Original is at redox graphene (rGO).With Ti3C2TxSpecific capacity for the lithium ion battery of cathode is relatively low, this is to influence its electricity
The key factor of chemical property, by the conductive material of compound some high capacity, while using some highly conductive carbon materials come
The capacity for optimizing material contact conduction mode, reducing diffusional resistance and inhibition high-capacity material of the lithium ion in active material
Decaying, to improve lithium ion battery negative material Ti3C2TxChemical property.The present invention uses the rGO and height of high conductivity
The Mn of capacity3O4Modified Ti3C2Tx, Mn3O4High capacity can increase Ti3C2TxLithium ion embedding capacity, rGO not only can be with
Inhibit Mn3O4Capacity attenuation in charge and discharge process, and reduce diffusional resistance of the lithium ion in active material, increase
The contact area of active material and electrolyte, also by Ti3C2TxIntermittent two-dimensional layered structure bridging is at complete three-dimensional network
Structure to form continuous conductive network, and reduces Charge-transfer resistance R in battery with superior conductivityctWith
Warburg impedance Ws, so as to improve the chemical property of battery.
The present invention prepares rGO and Mn using hydro-thermal method and oxidation-reduction method3O4Modified Ti3C2TxNegative electrode of lithium ion battery material
Material.RGO not only can effectively solve Mn3O4During charge and discharge cycles the problem of capacity attenuation, also by Ti3C2TxLayer with layer it
Between bridge the diffusion rate for improving lithium ion together, form unique three-dimensional net structure, constitute three-dimensional conductive net
Network improves the electric conductivity of material.This method not only increases the contact area of active material and electrolyte, also improve lithium from
Son reduces Charge-transfer resistance R in battery in the transmittability of material internalctWith Warburg impedance Ws, to improve
Ti3C2TxThe chemical property of negative electrode material.
The present invention has prepared rGO and Mn using hydro-thermal method and oxidation-reduction method3O4Modified Ti3C2TxMaterial is had
There is the lithium ion battery negative material of excellent chemical property.Preparation process of the present invention is simple, and material electrochemical performance is excellent, fits
Close industrialized production.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 2,5 Yu comparative example.
Fig. 2 is the first charge-discharge curve of the embodiment of the present invention 1,2,3 and comparative example under 0.05A/g current density
Figure.
Fig. 3 is that the charge and discharge cycles of the embodiment of the present invention 2,3,4,5 and comparative example under 0.5A/g current density are bent
Line chart.
Fig. 4 is the AC impedance spectroscopy of the embodiment of the present invention 2,5 Yu comparative example.
Specific embodiment
The present invention is described further combined with specific embodiments below.
Comparative example, with Ti3C2TxPowder is lithium ion battery negative material
By 1 gram of Ti3AlC2Powder crosses 325 meshes, then by Ti3AlC2Powder is distributed to the hydrogen that mass percent is 50%
In aqueous fluorine acid solution, 24 hours are stood under 20-25 degrees Celsius of room temperature, sediment distilled water is centrifugated 5 times, Zhi Daorong
Until liquid pH=5.Then sediment is put into vacuum oven, it is 12 hours dry at 80 DEG C, black powder is obtained, i.e.,
Ti3C2TxPowder.With Ti3C2TxPowder remembers control sample as lithium ion battery negative material.The powder is formed and tied
Structure test is assembled into button cell using conventional method, then carries out electrochemical property test.
From fig. 1, it can be seen that there is Ti in X-ray diffraction curve in #03C2Tx(002) crystal face characteristic peak；It can from Fig. 2
The first discharge specific capacity for knowing #0 under 0.05A/g current density is 404.6mAh/g, and initial charge specific capacity is 275.1mAh/g,
The coulombic efficiency of first charge-discharge is 67.8%.Fig. 3 shows that the capacity under 0.5A/g current density after #0 circulation 50 times is
116.2mAh/g, capacity retention ratio 60.4%.From test result it can be seen that no CNT and Fe2O3Compound Ti3C2TxIt is negative
The capacity of the lithium ion battery of pole is very low, and cycle performance is not high.
1-Mn of embodiment3O4Modified Ti3C2TxThe sample 1 of lithium ion battery negative material
By 1 gram of Ti3AlC2Powder crosses 325 meshes, then by Ti3AlC2Powder is distributed to the hydrogen fluorine that the number of quality hundred is 50%
In acid liquid, 24 hours are stood under 20-25 degrees Celsius of room temperature, sediment distilled water is centrifugated 5 times, until pH value of solution
Until=5.Then sediment is put into vacuum oven, it is 12 hours dry at 80 DEG C, obtain black powder.By 0.021
Gram MnO2It is put into 20 milliliters of distilled water with gained black powder, stirs 1.5 hours, sonic oscillation 30 minutes, obtain at room temperature
Black suspension.Black suspension is put into the reaction kettle of polytetrafluoroethylliner liner, reaction kettle is then put into baking oven, 180
DEG C heat preservation 12 hours.After natural cooling, sediment in reaction kettle is washed with distilled water 3 times.Sediment is put into drying box,
It is 12 hours dry at 90 DEG C, 325 meshes are ground and crossed later, finally obtain the Mn of 0.01 mol/L3O4Modified Ti3C2TxLithium
Ion battery cathode material is denoted as sample 1, wherein 0.01 mol/L refers to the addition manganese dioxide (MnO in distilled water2) after,
In suspension, concentration of the manganese dioxide in suspension is 0.01mol/L, similarly hereinafter.
Using sample 1 as lithium ion battery negative material, button cell is assembled into using conventional method, battery is carried out
Charge-discharge property test under 0.05A/g current density, Fig. 2 show that its chemical property does not almost have compared with control sample
There is improvement.
2-Mn of embodiment3O4Modified Ti3C2TxThe sample 2 of lithium ion battery negative material
By 1 gram of Ti3AlC2Powder crosses 325 meshes, then by Ti3AlC2Powder is distributed to the hydrogen fluorine that mass fraction is 50%
In acid solution, 24 hours are stood at room temperature, sediment distilled water is centrifugated 5 times, until pH value of solution=5.Then
Sediment is put into vacuum oven, it is 12 hours dry at 80 DEG C, obtain black powder.By 0.105 gram of MnO2And gained
Black powder is put into 20 milliliters of distilled water, is stirred 1.5 hours at room temperature, sonic oscillation 30 minutes, is obtained black suspension.It will
Black suspension is put into the reaction kettle of polytetrafluoroethylliner liner, and reaction kettle is then put into baking oven, and 180 DEG C keep the temperature 12 hours.
After natural cooling, sediment in reaction kettle is washed with distilled water 3 times.Sediment is put into drying box, it is dry at 90 DEG C
12 hours, 325 meshes were ground and crossed later, finally obtain the Mn of 0.05 mol/L3O4Modified Ti3C2TxNegative electrode of lithium ion battery
Material is denoted as sample 2.
Fig. 1 is the stereoscan photograph of 2 microstructure of sample, is found in Ti3C2TxUniform Mn is attached on layer3O4?
Grain.Using sample 2 as lithium ion battery negative material, button cell is assembled into using conventional method to sample 2, to battery into
Row first charge-discharge, charge and discharge cycles and ac impedance measurement.As can be seen from Figure 2, head of the sample 2 under 0.05A/g current density
Secondary specific discharge capacity is 594.3mAh/g, and charge specific capacity 300.1mAh/g has been respectively increased 47% compared with control sample
With 9%, the coulombic efficiency for the first time of sample 2 is 50%.Fig. 3 shows the appearance under 0.5A/g current density after the circulation of sample 2 50 times
Amount is 173.4mAh/g, and capacity retention ratio is only 62.1%, this is because Mn3O4Volume can occur during charge and discharge cycles
Variation, so as to cause the rapid decay of capacity.As can be seen from Figure 4, the AC impedance curve of sample 2 is in high frequency region and intermediate frequency zone
Half circular diameter is respectively less than control sample, low frequency range straight incline angle also greater than control sample, so Mn3O4It reduces multiple
The contact resistance of condensation material and electrolyte improves lithium ion in the transmittability of material internal.
3-Mn of embodiment3O4Modified Ti3C2TxThe sample 3 of lithium ion battery negative material
By 1 gram of Ti3AlC2Powder crosses 325 meshes, then by Ti3AlC2Powder is distributed to the hydrogen fluorine that mass fraction is 50%
In acid solution, 24 hours are stood at room temperature, sediment distilled water is centrifugated 5 times, until pH value of solution=5.Then
Sediment is put into vacuum oven, it is 12 hours dry at 80 DEG C, obtain black powder.By 0.42 gram of MnO2It is black with gained
Color powder is put into 20 milliliters of distilled water, is stirred 1.5 hours at room temperature, sonic oscillation 30 minutes, is obtained black suspension.It will be black
Color suspension is put into the reaction kettle of polytetrafluoroethylliner liner, and reaction kettle is then put into baking oven, and 180 DEG C keep the temperature 12 hours.From
So after cooling, sediment in reaction kettle is washed with distilled water 3 times.Sediment is put into drying box, dry 12 at 90 DEG C
Hour, 325 meshes are ground and crossed later, finally obtain the Mn of 0.2 mol/L3O4Modified Ti3C2TxNegative electrode of lithium ion battery material
Material, is denoted as sample 3.
Using sample 3 as lithium ion battery negative material, button cell is assembled into using conventional method to sample 3, it is right
Battery carries out first charge-discharge test.As can be seen from Figure 2, first discharge specific capacity of the sample 3 under 0.05A/g current density is
133% and 53% has been respectively increased in 942.9mAh/g, charge specific capacity 421.8mAh/g compared with control sample, sample 3
Coulombic efficiency is 44.7% for the first time, this is because excessive Mn3O4So that the rapidly increase of embedding lithium irreversible for the first time.Fig. 3 shows
Capacity after sample 3 recycles 50 times under 0.5A/g current density is 145.6mAh/g, and capacity retention ratio is only 47.4%, this is
Due to Mn3O4Volume change can occur, during charge and discharge cycles so as to cause the rapid decay of capacity.
4-Mn of embodiment3O4Modified Ti3C2TxThe sample 4 of lithium ion battery negative material
By 1 gram of Ti3AlC2Powder crosses 325 meshes, then by Ti3AlC2Powder is distributed to the hydrogen fluorine that mass fraction is 50%
In acid solution, 24 hours are stood at room temperature, sediment distilled water is centrifugated 5 times, until pH value of solution=5.Then
Sediment is put into vacuum oven, it is 12 hours dry at 80 DEG C, obtain black powder.By 0.42 gram of MnO2It is black with gained
Color powder is put into 10 milliliters of distilled water, at room temperature stirring 1.5 hours, and sonic oscillation 30 minutes, then by 10 milliliters of GO solution
It is slowly dropped into wherein, stirs 1 hour at room temperature, continue sonic oscillation 30 minutes, obtain black suspension.Black suspension is put
Enter in the reaction kettle of polytetrafluoroethylliner liner, reaction kettle is then put into baking oven, 180 DEG C keep the temperature 12 hours.It, will after natural cooling
Sediment is washed with distilled water 3 times in reaction kettle.Sediment is put into drying box, 12 hours dry at 90 DEG C, Zhi Houyan
325 meshes are ground and crossed, the Mn of 0.2 mol/L is finally obtained3O4With the modified Ti of rGO3C2TxLithium ion battery negative material is denoted as
Sample 4.
Using sample 4 as lithium ion battery negative material, button cell is assembled into using conventional method to sample 4, it is right
Battery carries out first charge-discharge, charge and discharge cycles and ac impedance measurement.As can be seen from Figure 3, the sample 4 under 0.5A/g current density
Capacity after circulation 50 times is 157.1mAh/g, and capacity retention ratio is only 38.2%, although having, rGO is modified, Mn3O4Contain
It measures too many, rGO during charge and discharge cycles is caused not improve Mn3O4Capacity attenuation.
5-Mn of embodiment3O4With the modified Ti of rGO3C2TxThe sample 5 of lithium ion battery negative material
By 1 gram of Ti3AlC2Powder crosses 325 meshes, then by Ti3AlC2Powder is distributed to the hydrogen fluorine that mass fraction is 50%
In acid solution, 24 hours are stood at room temperature, sediment distilled water is centrifugated 5 times, until pH value of solution=5.Then
Sediment is put into vacuum oven, it is 12 hours dry at 80 DEG C, obtain black powder.By 0.105 gram of MnO2And gained
Black powder is put into 10 milliliters of distilled water, is stirred 1.5 hours at room temperature, sonic oscillation 30 minutes, then that 10 milliliters of GO are molten
Liquid is slowly dropped into wherein, is stirred 1 hour at room temperature, is continued sonic oscillation 30 minutes, is obtained black suspension.By black suspension
It is put into the reaction kettle of polytetrafluoroethylliner liner, reaction kettle is then put into baking oven, 180 DEG C keep the temperature 12 hours.After natural cooling,
Sediment in reaction kettle is washed with distilled water 3 times.Sediment is put into drying box, it is 12 hours dry at 90 DEG C, later
325 meshes are ground and crossed, the Mn of 0.05 mol/L is finally obtained3O4With the modified Ti of rGO3C2TxLithium ion battery negative material, note
For sample 5.
Fig. 1 is the stereoscan photograph of 5 microstructure of sample, is found in Ti3C2TxUniform Mn is not only attached on layer3O4
Particle, and there is also the rGO of sheet.Using sample 5 as lithium ion battery negative material, to sample 5 using conventional side
Method is assembled into button cell, carries out first charge-discharge, charge and discharge cycles and ac impedance measurement to battery.Fig. 3 shows
Under 0.5A/g current density sample 5 recycle 50 times after specific capacity be 207.1mAh/g, capacity retention ratio 74.1%, this be by
Mn is inhibited in rGO3O4Capacity attenuation during charge and discharge cycles.As can be seen from Figure 4, the AC impedance curve of sample 5 is in height
Half circular diameter of frequency area and intermediate frequency zone is respectively less than control sample and sample 2, low frequency range straight incline angle also greater than right
Than sample, so rGO and Mn3O4The contact resistance for reducing composite material and electrolyte improves lithium ion in material internal
Transmittability.
Test method of the invention is as follows: with Ti produced by the present invention3C2Tx、Mn3O4Modified Ti3C2TxAnd rGO and
Mn3O4Modified Ti3C2TxMaterial is as active material, and Super-P is conductive agent, and Kynoar (PVDF) is binder, by matter
Amount weighs above-mentioned three kinds of substances than 80:10:10.PVDF is dissolved in N-Methyl pyrrolidone (NMP) and stirs 1.5 hours formation glue
Then Super-P is added into gained colloid and stirs 2 hours, active material powder is added later and continues stirring 3 hours for body.
Obtained slurry is coated in clean copper foil surface with adjustable spreader, the copper foil for being coated with slurry is placed in 60 in baking oven
It is DEG C dry 3 hours, then 12 hours dry at 90 DEG C.Copper foil after drying is micro- with a thickness of 20 in being depressed on double roller roll forming machine
Rice, it is spare then to go out about 12 millimeters of diameter of negative electrode tab from copper foil.All test batteries are all made of 2430 types in the present invention
Button cell.Battery is assembled in the glove box (relative humidity < 2%) of high-purity argon gas atmosphere.Used in assembling process
Diaphragm is 2400 microporous polypropylene membrane of Celgard, and electrolyte is 1mol/L LiPF6Ethylene carbonate (EC) and dimethyl carbon
Acid esters (DMC) mixed liquor (volume ratio of EC and DMC are 1:1).Use lithium piece (manufactured by the research of Beijing non-ferrous metal) for cathode
(in the assembling of lithium ion button half-cell, using lithium piece as cathode, negative electrode material prepared by the present invention is as anode).Assembling
The upper and lower cover and gasket of used in battery will in advance with alcohol washes it is clean after be dried.It is inhaled to remove all thing surfaces
All things are placed in glove box 4 hours or more by attached air and moisture before assembling battery.Battery specifically assembled
Journey are as follows: first negative electrode material disk is placed on tweezers in the glove box of relative humidity < 2% center of lower cover, be added suitable
Then electrolyte is sequentially placed into diaphragm, lithium piece, places it in central location, be finally putting into gasket compression, cover upper cover, assemble
At simulated battery.The simulated battery installed is put into battery special purpose copper mold, is tightened with spanner, battery is made to be isolated from the outside world
Sealing.Interface is sealed with sample sack, the simulated battery installed is removed glove box.
Battery is filled for the first time using high accuracy battery Performance Test System (new Weir Electronics Co., Ltd., Shenzhen)
Discharge performance, cycle performance etc. test (voltage: 0.001-3.0V).Charge and discharge system is as follows: (1) standing 5 minutes；(2) permanent electricity
Stream is discharged to 0.001V；(3) 2 minutes are stood；(4) constant current charge is to 3.0V.Use electrochemical workstation (Shanghai Chen Hua instrument
Co., Ltd) ac impedance measurement (frequency: 0.1-100000 hertz) is carried out to battery.Before test, to make the button newly assembled
Battery reaches stable state, needs to stand 12 hours and carries out electrochemical property test again.
Content record method carries out the adjustment of preparation technology parameter according to the present invention, and Mn of the present invention can be achieved3O4And rGO
Modified Ti3C2TxThe preparation of lithium ion battery negative material, and show the performance almost the same with embodiment.Above to this hair
It is bright to have done illustrative description, it should explanation, in the case where not departing from core of the invention, any simple deformation,
Modification or other skilled in the art can not spend the equivalent replacement of creative work to each fall within protection model of the invention
It encloses.
Claims (10)
1. a kind of redox graphene and four oxidations three are modified titanium carbide lithium ion battery negative material suddenly, which is characterized in that
It carries out as steps described below:
Step 1, by Ti3AlC2Powder is distributed in the hydrofluoric acid aqueous solution of 30-70wt% of mass percent and is handled, precipitating
Object obtains black powder, as Ti after drying3C2TxPowder；
Step 2, the Ti prepared by step 13C2TxPowder is placed in the aqueous suspension of manganese dioxide and evenly dispersed, adds
Graphene oxide aqueous dispersion is simultaneously uniformly dispersed, and obtains black suspension；In the suspension of manganese dioxide, manganese dioxide is dense
Degree is 0.01-0.2 mol/L, and graphene oxide aqueous dispersion is made by Hummers method, and the concentration of graphene oxide is 1-
10 mg/mls；
Step 3, black suspension step 2 obtained is placed in reaction kettle after sealing, from room temperature 20-25 in air atmosphere
Degree Celsius with 1-5 degrees Celsius per minute of speed be warming up to 160-200 degrees Celsius and keep the temperature 6-20 hours, naturally cool to
It is after room temperature, sediment filtration washing is dry, obtain black powder, as redox graphene and four three violent carbon modifieds of oxidation
Change titanium lithium ion battery negative material.
2. modified titanium carbide lithium ion battery is negative suddenly for a kind of redox graphene according to claim 1 and four oxidations three
Pole material, which is characterized in that in step 1, in hydrofluoric acid aqueous solution, the mass percent of hydrofluoric acid is 50-60wt%,
Selection 20-25 degrees Celsius of room temperature lower stewing process 20-24 hours.
3. modified titanium carbide lithium ion battery is negative suddenly for a kind of redox graphene according to claim 1 and four oxidations three
Pole material, which is characterized in that in step 2, dispersed using mechanical or ultrasound, the time dispersed is at least
30min, preferably 1-1.5 hours.
4. modified titanium carbide lithium ion battery is negative suddenly for a kind of redox graphene according to claim 1 and four oxidations three
Pole material, which is characterized in that in step 2, in the suspension of manganese dioxide, manganese dioxide concentration be 0.05-0.2 moles/
It rises；Graphene oxide aqueous dispersion is made by Hummers method, and the concentration of graphene oxide is 5-10 mg/mls；Dioxy
The aqueous suspension and graphene oxide aqueous dispersion for changing manganese are isometric ratio.
5. modified titanium carbide lithium ion battery is negative suddenly for a kind of redox graphene according to claim 1 and four oxidations three
Pole material, which is characterized in that in step 3, be warming up to from 20-25 degrees Celsius of room temperature with 1-5 degrees Celsius per minute of speed
180-200 degrees Celsius and heat preservation 12-16 hours, cooled to room temperature.
6. a kind of redox graphene and four oxidations three are modified the preparation method of titanium carbide lithium ion battery negative material suddenly,
It is characterized in that, carries out as steps described below:
Step 1, by Ti3AlC2Powder is distributed in the hydrofluoric acid aqueous solution of 30-70wt% of mass percent and is handled, precipitating
Object obtains black powder, as Ti after drying3C2TxPowder；
Step 2, the Ti prepared by step 13C2TxPowder is placed in the aqueous suspension of manganese dioxide and evenly dispersed, adds
Graphene oxide aqueous dispersion is simultaneously uniformly dispersed, and obtains black suspension；In the suspension of manganese dioxide, manganese dioxide is dense
Degree is 0.01-0.2 mol/L, and graphene oxide aqueous dispersion is made by Hummers method, and the concentration of graphene oxide is 1-
10 mg/mls；
Step 3, black suspension step 2 obtained is placed in reaction kettle after sealing, from room temperature 20-25 in air atmosphere
Degree Celsius with 1-5 degrees Celsius per minute of speed be warming up to 160-200 degrees Celsius and keep the temperature 6-20 hours, naturally cool to
It is after room temperature, sediment filtration washing is dry, obtain black powder, as redox graphene and four three violent carbon modifieds of oxidation
Change titanium lithium ion battery negative material.
7. modified titanium carbide lithium ion battery is negative suddenly for a kind of redox graphene according to claim 6 and four oxidations three
The preparation method of pole material, which is characterized in that in step 1, in hydrofluoric acid aqueous solution, the mass percent of hydrofluoric acid is
50-60wt%, selection 20-25 degrees Celsius of room temperature lower stewing process 20-24 hours.
8. modified titanium carbide lithium ion battery is negative suddenly for a kind of redox graphene according to claim 6 and four oxidations three
The preparation method of pole material, which is characterized in that in step 2, dispersed using mechanical or ultrasound, the time dispersed
At least 30min, preferably 1-1.5 hours；In step 2, in the suspension of manganese dioxide, manganese dioxide concentration 0.05-
0.2 mol/L；Graphene oxide aqueous dispersion is made by Hummers method, and the concentration of graphene oxide is 5-10 milligrams/milli
It rises；The aqueous suspension and graphene oxide aqueous dispersion of manganese dioxide are isometric ratio.
9. modified titanium carbide lithium ion battery is negative suddenly for a kind of redox graphene according to claim 6 and four oxidations three
The preparation method of pole material, which is characterized in that in step 3, from 20-25 degrees Celsius of room temperature with 1-5 degrees Celsius per minute
Speed is warming up to 180-200 degrees Celsius and keeps the temperature 12-16 hours, cooled to room temperature.
10. redox graphene as described in claim 1 and four oxidations three are modified titanium carbide negative electrode of lithium ion battery material suddenly
Material is preparing the application in lithium ion battery material.
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Application publication date: 20190329 |