CN105762351A - Lithium titanate/M-graphene composite cathode material for lithium ion battery and preparation method of lithium titanate/M-graphene composite cathode material - Google Patents
Lithium titanate/M-graphene composite cathode material for lithium ion battery and preparation method of lithium titanate/M-graphene composite cathode material Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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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
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Abstract
The invention discloses a lithium titanate/M-graphene composite cathode material for a lithium ion battery and a preparation method of the lithium titanate/M-graphene composite cathode material. The lithium titanate/M-graphene composite cathode material is prepared by dually compounding graphene and metal particles. The preparation method comprises the following steps: preparing a pure-phase lithium titanate material by a hydrothermal method, then fully mixing the pure-phase lithium titanate material with graphene oxide and metal salt (or metal alkali), and performing reaction in a reaction kettle under the action of a proper amount of reducing agents to obtain the lithium titanate/M-graphene composite cathode material. According to the preparation method, the lithium titanate/M-graphene composite cathode material is prepared by reduction by a simple solvothermal method; the preparation method is easy to operate, low in requirement on conditions, low in cost and very suitable for industrial production; furthermore, the prepared lithium titanate/M-graphene composite cathode material is high in conductivity, high in specific capacity, high in high-rate discharging performance and excellent in circulating performance, and can be widely applied to various types of portable electronic equipment and electric automobiles.
Description
Technical field
The present invention relates to a kind of lithium ion battery negative material, be specifically related to lithium ion battery lithium titanate/M-Graphene
Composite negative pole material and preparation method thereof, is to prepare lithium titanate/M-Graphene with dual being combined of Graphene and metallic particles
Composite negative pole material.
Background technology
Lithium ion battery, as a new generation's secondary cell, has that operating voltage is high, energy density big, has extended cycle life, pacifies
Quan Xinggao, advantages of environment protection, be widely used in portable computer, mobile phone, digital camera, submarine, Aero-Space
In the electronic equipments such as field, and increasingly serious along with the exhaustion of the traditional energy such as oil, coal and environmental pollution, develop green
Look new forms of energy replace traditional energy to become more and more important, and present Ge great motor corporation is all falling over each other development new-energy automobile,
Using energy-storage battery as major impetus, and lithium ion battery becomes, because of its big advantage, the target that first they consider undoubtedly.
Negative material as the core of lithium ion battery, is always the emphasis studied of people, how to improve negative pole material
The chemical property of material becomes and improves performance of lithium ion battery and the key of actual application, development and the solution to new-energy automobile
Certainly energy crisis is significant.Since lithium ion battery is born, the relevant negative material of research mainly has following
Several: lithium metal, graphitized carbon material, amorphous carbon material, nitride, silica-base material, tin-based material, novel alloy, nanometer
Oxide and other material.Lithium battery uses lithium metal as negative pole in early days, although obtain the biggest capacity, but lithium is in charge and discharge
Electric process is easily formed dendrite, pierces through barrier film and cause internal short-circuit of battery, make battery have huge potential safety hazard.City now
The lithium ion battery commonly used on field is using material with carbon element as negative pole, although this material storage is big, with low cost, but this material
There is also specific capacity low, first charge-discharge efficiency is the highest, to shortcomings such as electrolyte are the lowest, meanwhile, in electrochemical reaction
During, solvent molecule can be brought into during the Lithium-ion embeding of partial salvation simultaneously, cause solvent to embed altogether, make graphite flake layer by
Gradually peeling off, eventually cause electrode breakages, cycle performance is deteriorated, and affects the life-span of battery.Spinel type lithium titanate Li4Ti5O12,
As a new generation's lithium ion battery negative material, Stability Analysis of Structures, in charge and discharge process, Volume Changes is the least, and only 0.3%, " zero
Strain " make it be difficult to be destroyed in cyclic process, thus there is cycle performance and security performance well；And, its work
Voltage stabilization, service life is long.But this material there is also conductance and ion diffusion rates is low, battery specific capacity is the highest, multiplying power
The shortcomings such as performance is bad.
Graphene is to be stripped out from graphite material, the two-dimentional material of the only one layer of atomic thickness being made up of carbon atom
Material, is the thinnest the hardest, a kind of novel nano-material that electrical and thermal conductivity performance is the strongest having now been found that, has bigger ratio table
Area and good mechanical performance, be that a kind of preferably lithium titanate is material modified.The addition of Graphene not only increases negative pole material
The ability of material storage lithium, it is also possible to form conductive network and promote its electric conductivity, concurrently facilitate the diffusion path shortening lithium ion, make
The high rate charge-discharge performance of negative material has greatly improved.But due to the specific surface area that Graphene is huge, in reduction process
It is susceptible to aggregate stack definitely between middle graphene sheet layer, causes the specific surface area of composite and avtive spot to decline,
Affect the performance of chemical property.And the introducing of metallic nano-particle, the electric conductivity utilizing metal good is possible not only to further
The shortcoming improving lithium titanate material poorly conductive, the most nano level metallic is distributed in graphene film interlayer can also be stoped
The accumulation of graphene film interlayer and clustering phenomena, allow greater area of graphene sheet layer come out, thus receive more titanium
Acid lithium particle, and the introducing of metallic nano-particle can make up the graphene sheet layer shortcoming at vertical direction poorly conductive,
Between graphene sheet layer, structure plays a conductive transmission channels, increases electric conductivity, improves the actual application of lithium titanate material.
Summary of the invention
It is desirable to provide a kind of lithium ion battery lithium titanate/M-graphene composite negative pole, to be solved
Problem is that lithium titanate anode material electric conductivity is poor, and specific capacity is relatively low and the shortcoming such as high rate charge-discharge poor performance, utilizes graphite
Alkene and the dual chemical property improving material that is combined of metallic particles, provide simultaneously a kind of technical process simple, pollution-free,
The preparation method of lithium titanate/M (M=silver, the copper)-graphene composite negative pole consuming energy low.
The present invention solves technical problem and adopts the following technical scheme that
A kind of lithium ion battery lithium titanate/M-graphene composite negative pole, it is characterised in that:
Described composite negative pole material obtains at lithium titanate surface composite graphite alkene and metallic nano-particle, described composite negative pole
The chemical formula of material is Li4Ti5O12/ M-Graphene, is abbreviated as LTO/M-G, described metallic nano-particle M and represents, institute
The M stated is the one in silver nano-particle, nano-particle of copper.
The preparation method of composite negative pole material, it is characterised in that: described composite negative pole material be by the lithium titanate synthesized with
Graphene oxide, slaine or metal base mixing, prepare through reducing agent reduction, specifically includes following steps:
(1) graphite oxide is joined in solvent and carry out ultrasonic disperse 0.5-2h, make lamella scatter, obtain graphene oxide glue
Liquid solution, ultrasonic after the concentration of graphene oxide colloidal solution that obtains be 1.8-2.2g/L;
(2) pure phase lithium titanate is dissolved in absolute ethyl alcohol, obtains the emulsion of white, magnetic stirring apparatus quickly stirs, will
The graphene oxide colloidal solution that step (1) obtains is added thereto, after being sufficiently stirred for, then by slaine (or metal base) solution and
Appropriate reducing agent is added thereto, and the pH value of regulation system is alkalescence, continues quickly to stir 0.5-2h, the milkiness of described white
The concentration of liquid is 0.08-0.12g/mL；
(3) emulsion that step (2) obtains is moved in stainless steel autoclave, successive reaction 5-24h at 60 DEG C-150 DEG C, cold
But to being centrifuged after room temperature, wash, being dried, i.e. can get lithium titanate/M-graphene composite negative pole;
Described slaine is AgNO3, described metal base is the Cu (OH) of existing preparation2 。
The reducing agent of described slaine (metal base) solution can be glucose, formaldehyde, acetaldehyde, hydrazine hydrate；
The preparation method of described lithium ion battery lithium titanate/M-graphene composite negative pole, it is characterised in that: described
Graphite oxide is that the Hummer method improved is produced and obtained, and described pure phase lithium titanate is prepared by hydro-thermal method.
The preparation method of described lithium ion battery lithium titanate/M-graphene composite negative pole, it is characterised in that institute
Stating the 1%-5% that compound consumption is lithium titanate quality of Graphene, the consumption of described slaine (or metal base) is lithium titanate quality
2%-4%.
The preparation method of described lithium ion battery lithium titanate/M-graphene composite negative pole, it is characterised in that oxygen
The reducing agent of functionalized graphene can be one or more in hydrazine hydrate, sodium borohydride, absolute ethyl alcohol, ethylene glycol.
The preparation method of described lithium ion battery lithium titanate/M-graphene composite negative pole, it is characterised in that institute
The solvent stating graphite oxide can be one or more in deionized water, absolute ethyl alcohol, ethylene glycol.
The preparation method of described lithium ion battery lithium titanate/M-graphene composite negative pole, it is characterised in that institute
The hydro-thermal method stated is prepared pure phase lithium titanate and is comprised the following steps:
A. Li source compound is dissolved in deionized water, be configured to 1-4mol/L containing Li+Solution A, by molten for titanium source compound
In absolute ethyl alcohol, both volume ratios are 1:(1-5), form solution B, quickly under stirring, solution A is slowly added drop-wise to solution B
In, then proceed to stir 1-2h;
B. the white emulsion produced is transferred in polytetrafluoroethylene (PTFE) reactor, successive reaction 8-36h at 130-200 DEG C
After, it is centrifuged washing with deionized water or absolute ethyl alcohol, is then dried at 60-80 DEG C, obtains presoma；
C. the white powder obtained after described presoma being calcined 2-12h at 500-800 DEG C in air atmosphere is prepared
Pure phase lithium titanate;
Described titanium source compound is butyl titanate, tetraisopropyl titanate, TiO2One in-B；
Described Li source compound is the one in lithium hydroxide, lithium acetate, lithium carbonate, organolithium；
Mol ratio between Li in described lithium source and the Ti in titanium source is 4.3:5.
The preparation method of described lithium ion battery lithium titanate/M-graphene composite negative pole, it is characterised in that institute
The Hummer method of the improvement stated prepares graphite oxide, specifically includes following steps:
(1) potassium permanganate of 3-4 part graphite powder and 17-18 part mixed put in flask, by the concentrated sulfuric acid and SPA according to
Volume ratio be 9:1 ratio mixing after obtain mixed acid, a certain amount of mixed acid is joined in flask, quickly stirs, described
The mass volume ratio g/mL of graphite powder and mixed acid is 3:380-420；
(2) said mixture is continuously stirred 8-24h at 50-70 DEG C；
(3) again said mixture being cooled to room temperature, be poured slowly on the ice cube freezed in advance, this ice cube is by 400 parts of water
Form with the hydrogenperoxide steam generator that concentration is 30% of 8-10 part, stand a period of time until ice cube melts completely；
(4) it is dried to obtain graphite oxide after being respectively washed with water, watery hydrochloric acid, ethanol again.
Compared with prior art, beneficial effects of the present invention is embodied in:
1. the present invention uses the water heat transfer pure phase lithium titanate of gentleness, then by lithium titanate and graphite oxide, slaine (or gold
Belong to alkali), the solution such as NaOH and appropriate reducing agent be sufficiently mixed uniformly, be placed in reactor at 60-150 DEG C the most instead
Answer 5-24h, can not only be fully by graphene oxide with slaine (or metal base) is reduced to Graphene and metal is micro-in this condition
Grain, and be combined with this understanding and can also improve the adhesive force between lithium titanate and Graphene, make lithium titanate be dispersed in stone
Between ink alkene lamella, the existence of metallic simultaneously can stop again graphene sheet layer to occur to reunite and assemble in reduction process,
Make Graphene expose bigger specific surface area, it is provided that more storage lithium site, be conducive to improving the capacity of material and the most forthright
Energy.
2. the present invention uses Graphene and the dual cladding of metal particle, and the electric conductivity utilizing metallic particles good not only may be used
To improve the shortcoming of lithium titanate material poorly conductive further, and the introducing of metal particle can also make up graphene sheet layer and exist
The shortcoming of vertical direction poorly conductive, forms three-dimensional conductive network between the materials, increases electric conductivity, improve lithium titanate material
Chemical property.
Composite negative pole material the most of the present invention is combined has higher specific volume compared to pure phase lithium titanate or simple Graphene
Amount, more preferable high rate performance, be the most promising lithium ion battery negative material of one.
4. the present invention uses hydro-thermal method to prepare lithium titanate, can not only be more evenly distributed, lithium titanate that particle is more tiny
Particle, and the temperature and time of calcining can be reduced, greatly reduce energy consumption.
5. present invention process design is simple, the highest to equipment requirement, it is easy to accomplish industrialized production.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of graphite oxide, Graphene and the silver-graphene of embodiment 1 preparation.
Fig. 2 is lithium titanate and the lithium titanate/silver-graphene (AgNO of embodiment 2 preparation3Addition is the 3% of LTO weight)
X-ray diffraction spectrogram.
Fig. 3 is lithium titanate and the lithium titanate/silver-graphene (AgNO of embodiment 2 preparation3Addition is the 3% of LTO weight)
First charge-discharge curve under 0.2C.
Fig. 4 is the lithium titanate/silver-graphene (AgNO of embodiment 2 preparation3Addition is the 3% of LTO weight) in 1C multiplying power
Time cycle performance figure.
Fig. 5 is the lithium titanate/silver-graphene (AgNO of embodiment 2 preparation3Addition is the 3% of LTO weight) SEM figure.
Fig. 6 is lithium titanate/silver-graphene (hydrazine hydrate makees reducing agent) first charge-discharge under 0.2C of embodiment 3 preparation
Curve.
Fig. 7 is the lithium titanate/silver-graphene (AgNO of embodiment 4 preparation3Addition is the 1% of LTO weight) under 0.2C
First charge-discharge curve.
Fig. 8 is lithium titanate/copper-graphite alkene first charge-discharge curve under 0.2C of embodiment 6 preparation.
Detailed description of the invention
In order to further appreciate that present disclosure feature and beneficial effect, below by concrete example with reference
The present invention is made further details of elaboration, but does not limit protection scope of the present invention.
Embodiment 1:
In this example, graphite oxide, Graphene and silver-graphene prepare according to the following steps:
A, take 3g graphite powder and 18g potassium permanganate is put in flask and mixed, then add in flask by the dense sulphur of 360mL
The mixed acid that the SPA of acid and 40mL is obtained by mixing, is placed on after mixing on magnetic stirring apparatus and heats while stirring,
Successive reaction 12 hours at 50 DEG C, make graphite powder fully oxidized；After question response terminates, mixed solution is poured into freezing in advance
Frozen water in (this ice cube is made up of the hydrogenperoxide steam generator that mass fraction is 30% of 400ml water and about 8-10ml), stand
A period of time is until ice cube melts completely；Then, then it is respectively washed with deionized water, 0.1mol/L watery hydrochloric acid, absolute ethyl alcohol, dry
Just graphite oxide is obtained after dry.
B, the graphite oxide that 0.06g synthesizes is put in the absolute ethyl alcohol of 30mL, carry out one hour ultrasonic at normal temperatures
Process, make oxidized graphite flake layer separate, then the glucose solution prepared and silver nitrate solution are slowly added drop-wise to above-mentioned molten
In liquid, the quality of silver nitrate is also 0.06g, and the quality of the material of glucose is the twice of silver nitrate, and controlling solution is alkalescence,
Subsequently finely dispersed above-mentioned solution is transferred in polytetrafluoroethylene (PTFE) reactor, 120 DEG C of successive reactions 16 hours, make oxygen
Functionalized graphene and silver nitrate are the most fully reduced；After temperature naturally cools to room temperature, carry out washing be dried,
Finally give the Ag-G combination electrode material of black, as a comparison, we in the case of without silver nitrate individually with nothing
Water-ethanol is as solvent, and redox graphene in a kettle., as remaining operation all.
The X-ray diffraction spectrogram of graphite oxide, Graphene and silver-graphene that the present embodiment prepares is shown in Fig. 1.Figure a
For the XRD of graphite oxide, the interlamellar spacing being calculated this graphite oxide is 0.76nm, much larger than the interlayer of graphite (0.34nm)
Away from, this is owing to graphite is after Strong oxdiative, oxygen and the multiple bonding action of carbon atom so that between graphite flake layer and lamella
And the position such as layer edge introduces oxygen-containing functional group and other defect, thus interlamellar spacing becomes big；And utilize solvent-thermal method, with nothing
Water-ethanol is as reducing agent, and reduction has obtained Graphene, the diffraction maximum of (002) crystal face also by 10.8 ° move to right to about 25 ° (see
Figure b), can effectively reduce and produce Graphene by this explanation the method.Figure c is the thing phasor of the Ag-G obtained in the basic conditions,
Figure substantially can be seen that the diffraction maximum of (002) crystal face of Graphene, show the existence of Graphene, simultaneously comparison PDF card #
, there is (111), (200) of Ag, (220) diffraction maximum respectively at 38.29 °, 44.32 °, 64.46 ° in 04-0783, illustrates to add
AgNO3Graphene oxide through reduction after generate Graphene silver nano particle composite material, i.e. one step reduces oxygen simultaneously
Functionalized graphene and AgNO3To Graphene and Ag simple substance.But we have found that simultaneously and have also appeared in the XRD of Ag-G compound a little
Impurity peaks, through analyzing as silver oxide Ag2O, illustrates to also have in product a small amount of Ag+It is not completely reduced.
Embodiment 2:
In this example, lithium ion battery lithium titanate/silver-graphene composite negative pole material prepares according to the following steps:
A, weigh the LiOH.H of 0.043mol2O is dissolved in deionized water, and forming concentration is 2mol/L lithium hydroxide solution A, measures
The Ti(OC of 0.05mol4H9)4Pouring in absolute ethyl alcohol, both volume ratios are 1:1, are placed on magnetic stirring apparatus and quickly stir, shape
Become solution B；The solution A configured slowly is added drop-wise in solution B, then proceedes to stir 1-2h;The white milkiness that will produce
Liquid is transferred in polytetrafluoroethylene (PTFE) reactor, at 180 DEG C after successive reaction 24h, with deionized water or absolute ethyl alcohol carry out from
The heart washs, and is then dried at 60 DEG C, obtains presoma.Last calcining 8 hours at 700 DEG C, obtain white Li4Ti5O12?
Grain
B, first, takes in the absolute ethyl alcohol that the above-mentioned white LTO synthesized of 2g puts into 20mL, and quickly stirring makes material dispersion all
Even, then the GO(of the 2.0g/L configured first carried out one hour ultrasonically treated, makes oxidized graphite flake layer separate), glucose
Solution and silver nitrate solution are slowly added drop-wise in above-mentioned solution, GO and AgNO3Addition is the 3% of LTO weight, and glucose
Then according to the amount of material than for AgNO3: the consumption of glucose=1:2 adds, and controlling solution is alkalescence, subsequently by finely dispersed
Above-mentioned solution is transferred in polytetrafluoroethylene (PTFE) reactor, 120 DEG C of successive reactions 16 hours, treats that temperature naturally cools to room temperature
After carry out washing be dried, finally give the LTO/Ag-G combination electrode material of grey black.
Pure phase LTO, the X-ray diffraction spectrogram of LTO/Ag-G that the present embodiment prepares are shown in Fig. 2.Can be seen by figure
The diffraction maximum shape going out two kinds of samples is similar, all diffraction maximums all with spinelle Li4Ti5O12The mark of (JCPDS No.49-0207)
Quasi-collection of illustrative plates is consistent, belongs to cubic system Fd-3m space group, and diffraction maximum all compares sharply simultaneously, illustrates to utilize hydro-thermal method success
Purity and the highest lithium titanate material of degree of crystallinity are synthesized.Graphene, owing to becoming unformed shape so diffraction maximum is inconspicuous, does not has
The diffraction maximum being found silver is possibly due to the less reason of content, and the most also the addition of explanation Graphene and silver has no effect on titanium
The crystalline structure of acid lithium.
The sample LTO/Ag-G that the present embodiment prepares is made working electrode as active material, is 80 according to mass ratio:
The ratio of 10:10 weighs active material, acetylene black, Kynoar (PVDF), drips appropriate N-methyl pyrrole after mixing
Alkanone (NMP) to form slurry, even application is on aluminium foil subsequently, be placed in vacuum drying chamber in 120 DEG C be dried 12 hours,
It is washed into the circular electric pole piece positive pole as half-cell, using lithium sheet as to electrode, at the vacuum glove box of full argon gas with drift
In assemble, use Celgard2400 porous polyethylene barrier film and LiPF6/EC+DMC (EC and the DMC volume of 1.0mol/L
Than be 1:1) Xin Zhou nation electrolyte, voltage tester scope is 1.0-2.5V.Fig. 3 is LTO and Li4Ti5O12/ Ag-G is at 0.2C
Charging and discharging curve figure under multiplying power.LTO/Ag-G combination electrode is in the first discharge specific capacity of 0.2C multiplying power as can be seen from Figure
Reach 205.3mAh/g, far above specific capacity 165.7mAh/g of LTO, illustrated that LTO/Ag-G composite has higher appearance
Amount and storage lithium site.Fig. 4 is the LTO/Ag-G cycle performance figure when 1C multiplying power, as seen from Figure 4 through 40 circulations
Rear capacity is still maintained at 149.6mAh/g, illustrates that it has preferable cyclical stability.Fig. 5 is the LTO/ of embodiment 2 preparation
The SEM figure of Ag-G, the flaky texture in figure is Graphene.
The LTO/Ag-G that the present embodiment prepares not only has higher specific capacity and preferable cyclical stability, and
Its high rate performance is the most preferable.Wherein the discharge capacity first under 0.2C is that the discharge capacity first under 205.3mAh/g, 0.5C is
Discharge capacity first under 185.4mAh/g, 1C be the discharge capacity first under 179.3mAh/g, 2C be 155.7mAh/g, respectively
Higher than pure phase lithium titanate discharge capacity under each corresponding multiplying power (165.7mAh/g, 156.1mAh/g, 141.5mAh/g,
112.2mAh/g).
Embodiment 3:
In this example, lithium ion battery lithium titanate/silver-graphene composite negative pole material prepares according to the following steps:
A and embodiment 2 use identical method to prepare pure phase lithium titanate；
B, first, takes in the absolute ethyl alcohol that the above-mentioned white LTO synthesized of 2g puts into 20mL, and quickly stirring makes material dispersion all
Even, then the GO(of the 2.0g/L configured first carried out one hour ultrasonically treated, makes oxidized graphite flake layer separate), silver nitrate
Solution and hydrazine hydrate are slowly added drop-wise in above-mentioned solution, GO and AgNO3Addition is the 3% of LTO weight, and hydrazine hydrate is then pressed
According to the amount of material than for AgNO3: the consumption of hydrazine hydrate=1:2 adds, and subsequently finely dispersed above-mentioned solution is transferred to poly-four
In PVF reactor, 120 DEG C of successive reactions 16 hours, after temperature naturally cools to room temperature, carry out washing be dried,
Obtain the LTO/Ag-G combination electrode material of grey black eventually.
The composite negative pole material prepared by the present embodiment is assembled into battery, and concrete grammar is with embodiment 2, and hydrazine hydrate reduces
The LTO/Ag-G(AgNO that agent prepares3Addition is the 3% of LTO weight) composite first discharge specific capacity reaches
262.45mAh/g, but initial charge specific capacity only has 171.52 mAh/g, and coulombic efficiency only has 65.35% first；Second
Secondary charging and discharging capacity is respectively 167.92 mAh/g and 199.02 mAh/g, and coulombic efficiency is only 84.37%, less than grape
Sugar is as coulombic efficiency during reducing agent, and concrete data are shown in Fig. 6.
Embodiment 4:
In this example, lithium ion battery lithium titanate/silver-graphene composite negative pole material prepares according to the following steps:
A and embodiment 2 use identical method to prepare pure phase lithium titanate；
B, first, takes in the absolute ethyl alcohol that the above-mentioned white LTO synthesized of 2g puts into 20mL, and quickly stirring makes material dispersion all
Even, then the GO(of the 2.0g/L configured first carried out one hour ultrasonically treated, makes oxidized graphite flake layer separate), glucose
Solution and silver nitrate solution are slowly added drop-wise in above-mentioned solution, and GO addition is the 3% of LTO weight, AgNO3Addition is LTO weight
The 1% of amount, glucose then according to the amount ratio of material for AgNO3: the consumption of glucose=1:2 adds, and will be uniformly dispersed subsequently
Above-mentioned solution transfer in polytetrafluoroethylene (PTFE) reactor so that it is in the basic conditions in 120 DEG C of successive reactions 16 hours, treat
Temperature carries out washing and is dried after naturally cooling to room temperature, finally give the LTO/Ag-G combination electrode material of grey black.
The composite negative pole material prepared by the present embodiment is assembled into battery, and concrete grammar, with embodiment 2, records it at 0.2C
Under first discharge specific capacity be 187.97mAh/g, initial charge specific capacity is 166.27 mAh/g, and coulombic efficiency reaches first
To 88.46%.Platform difference between discharge and recharge is the least, only 0.042 mV, and charge and discharge platform is stable, and platform capacity is high, in detail
Data are shown in Fig. 7.
Embodiment 5:
In this example, lithium ion battery lithium titanate/silver-graphene composite negative pole material prepares according to the following steps:
A and embodiment 2 use identical method to prepare pure phase lithium titanate；
B, first, takes in the absolute ethyl alcohol that 2g white LTO puts into 20mL, and quickly stirring makes material be uniformly dispersed, then will configuration
The GO(of good 2.0g/L first carries out one hour ultrasonically treated, makes oxidized graphite flake layer separate), glucose solution, silver nitrate molten
Liquid is slowly added drop-wise in above-mentioned solution, GO and AgNO3Addition is the 3% of LTO weight, glucose is then according to material
Amount ratio is AgNO3: the consumption of glucose=1:2 adds, and transfers in polytetrafluoroethylene (PTFE) reactor by above-mentioned solution subsequently, 120
DEG C successive reaction 16 hours, carries out washing after temperature naturally cools to room temperature and is dried, finally give the LTO/Ag-of grey black
G combination electrode material.
The composite negative pole material prepared by the present embodiment is assembled into battery, and concrete grammar, with embodiment 2, records it at 0.2C
Under first discharge specific capacity be 205.69mAh/g, initial charge specific capacity is 166.60 mAh/g, and coulombic efficiency is first
80.99%, less than the coulombic efficiency under the conditions of alkalescence, meanwhile, platform is poor, and the polarization between platform is bigger.
Embodiment 6:
In this example, lithium ion battery lithium titanate/copper-graphite alkene composite negative pole material prepares according to the following steps:
A and embodiment 2 use identical method to prepare pure phase lithium titanate；
B, first, takes in the absolute ethyl alcohol that the above-mentioned white LTO synthesized of 2g puts into 20mL, and quickly stirring makes material dispersion all
Even, then the GO(of the 2.0g/L configured first carried out one hour ultrasonically treated, makes oxidized graphite flake layer separate), acetaldehyde molten
Liquid, brand-new Kocide SD solution are slowly added drop-wise in above-mentioned solution, GO and Cu(OH)2Addition is the 3% of LTO weight, second
The addition of aldehyde is Kocide SD according to the amount ratio of material: acetaldehyde=1:2 ratio addition.Subsequently by finely dispersed above-mentioned solution
Transfer in polytetrafluoroethylene (PTFE) reactor, 120 DEG C of successive reactions 16 hours, wash after temperature naturally cools to room temperature
Wash dry, finally give LTO/Cu-G composite negative pole material.
The composite negative pole material prepared by the present embodiment is assembled into battery, and concrete grammar, with embodiment 2, records it at 0.2C
Under first discharge specific capacity be 206.59mAh/g, initial charge specific capacity is 167.84 mAh/g, higher than pure phase lithium titanate
Specific capacity, and discharge platform is steady, polarizes less between platform, is a kind of well lithium ion battery material, concrete data are shown in figure
8。
Claims (8)
1. lithium ion battery lithium titanate/M-graphene composite negative pole, it is characterised in that: described composite negative pole material
Obtaining at lithium titanate surface composite graphite alkene and metallic nano-particle, the chemical formula of described composite negative pole material is
Li4Ti5O12/ M-Graphene, is abbreviated as LTO/M-G, described metallic nano-particle M and represents, described M is that silver nanoparticle is micro-
One in grain, nano-particle of copper.
2. the preparation method of lithium ion battery lithium titanate/M-graphene composite negative pole, it is characterised in that: described multiple
Closing negative material is to be mixed with graphene oxide, slaine or metal base by the lithium titanate synthesized, and is prepared into through reducing agent reduction
Arrive, specifically include following steps:
(1) graphite oxide is joined in solvent and carry out ultrasonic disperse 0.5-2h, make lamella scatter, obtain graphene oxide glue
Liquid solution, ultrasonic after the concentration of graphene oxide colloidal solution that obtains be 1.8-2.2g/L;
(2) pure phase lithium titanate is dissolved in absolute ethyl alcohol, obtains the emulsion of white, magnetic stirring apparatus quickly stirs, will
The graphene oxide colloidal solution that step (1) obtains is added thereto, after being sufficiently stirred for, then by slaine or metal base solution and suitable
The reducing agent of amount is added thereto, and the pH value of regulation system is alkalescence, continues quickly to stir 0.5-2h, the emulsion of described white
Concentration be 0.08-0.12g/mL；
(3) emulsion that step (2) obtains is moved in stainless steel autoclave, successive reaction 5-24h at 60 DEG C-150 DEG C, cold
But to being centrifuged after room temperature, wash, being dried, i.e. can get lithium titanate/M-graphene composite negative pole；
Described slaine is AgNO3, described metal base is the Cu (OH) of existing preparation2 ；
The reducing agent of described slaine or metal base can be glucose, formaldehyde, acetaldehyde, hydrazine hydrate.
The preparation method of lithium ion battery lithium titanate/M-graphene composite negative pole the most according to claim 2, its
It is characterised by: described graphite oxide is that the Hummer method improved is produced and obtained, and described pure phase lithium titanate is by hydro-thermal legal system
Standby and obtain.
The preparation method of lithium ion battery lithium titanate/M-graphene composite negative pole the most according to claim 2, its
Being characterised by, the 1%-5% that compound consumption is lithium titanate quality of described Graphene, the consumption of described slaine or metal base is titanium
The 2%-4% of acid lithium quality.
The preparation method of lithium ion battery lithium titanate/M-graphene composite negative pole the most according to claim 2, its
Being characterised by, the reducing agent of graphene oxide can be the one in hydrazine hydrate, sodium borohydride, absolute ethyl alcohol, ethylene glycol or several
Kind.
The preparation method of lithium ion battery lithium titanate/M-graphene composite negative pole the most according to claim 2, its
Being characterised by, the solvent of described graphite oxide can be one or more in deionized water, absolute ethyl alcohol, ethylene glycol.
The preparation method of lithium ion battery lithium titanate/M-graphene composite negative pole the most according to claim 2, its
Being characterised by, described hydro-thermal method is prepared pure phase lithium titanate and is comprised the following steps:
A. Li source compound is dissolved in deionized water, be configured to 1-4mol/L containing Li+Solution A, by molten for titanium source compound
In absolute ethyl alcohol, both volume ratios are 1:(1-5), form solution B, quickly under stirring, solution A is slowly added drop-wise to solution B
In, then proceed to stir 1-2h;
B. the white emulsion produced is transferred in polytetrafluoroethylene (PTFE) reactor, successive reaction 8-36h at 130-200 DEG C
After, it is centrifuged washing with deionized water or absolute ethyl alcohol, is then dried at 60-80 DEG C, obtains presoma；
C. the white powder obtained after described presoma being calcined 2-12h at 500-800 DEG C in air atmosphere is prepared
Pure phase lithium titanate;
Described titanium source compound is butyl titanate, tetraisopropyl titanate, TiO2One in-B；
Described Li source compound is the one in lithium hydroxide, lithium acetate, lithium carbonate, organolithium；
Mol ratio between Li in described lithium source and the Ti in titanium source is 4.3:5.
The preparation method of lithium ion battery lithium titanate/M-graphene composite negative pole the most according to claim 2, its
Being characterised by, the Hummer method of described improvement prepares graphite oxide, specifically includes following steps:
(1) potassium permanganate of 3-4 part graphite powder and 17-18 part mixed put in flask, by the concentrated sulfuric acid and SPA according to
Volume ratio be 9:1 ratio mixing after obtain mixed acid, a certain amount of mixed acid is joined in flask, quickly stirs, described
The mass volume ratio g/mL of graphite powder and mixed acid is 3:380-420；
(2) said mixture is continuously stirred 8-24h at 50-70 DEG C；
(3) again said mixture being cooled to room temperature, be poured slowly on the ice cube freezed in advance, this ice cube is by 400 parts of water
Form with the hydrogenperoxide steam generator that concentration is 30% of 8-10 part, stand a period of time until ice cube melts completely；
(4) it is dried to obtain graphite oxide after being respectively washed with water, watery hydrochloric acid, ethanol again.
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