CN107910528A - A kind of lithium titanate composite material and preparation method thereof, negative plate and lithium ion battery - Google Patents

A kind of lithium titanate composite material and preparation method thereof, negative plate and lithium ion battery Download PDF

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Publication number
CN107910528A
CN107910528A CN201711145359.8A CN201711145359A CN107910528A CN 107910528 A CN107910528 A CN 107910528A CN 201711145359 A CN201711145359 A CN 201711145359A CN 107910528 A CN107910528 A CN 107910528A
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lithium titanate
lithium
composite material
ruthenium
solution
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CN107910528B (en
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赵微
詹世英
马美品
李海军
蔡惠群
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Luoyang Gree Titanium New Energy Co ltd
Shijiazhuang Zhongbo Automobile Co ltd
Gree Altairnano New Energy Inc
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Yinlong New Energy Co Ltd
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Priority to PCT/CN2018/113370 priority patent/WO2019096012A1/en
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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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention is on a kind of lithium titanate composite material and preparation method thereof, negative plate and lithium ion battery, is related to battery technology field.The technical solution mainly used for：A kind of preparation method of lithium titanate composite material, includes the following steps：1) ruthenic oxide/titanium dioxide compound is prepared；2) using ruthenic oxide/titanium dioxide compound, lithium source as raw material, lithium titanate composite material is prepared.A kind of lithium titanate composite material is prepared by the above method.A kind of negative plate includes above-mentioned lithium titanate composite material；A kind of lithium ion battery includes above-mentioned negative plate.Present invention is mainly used for a kind of lithium titanate composite material to conduct electricity very well of offer, and during negative active core-shell material of the lithium titanate composite material for lithium ion battery, the high rate performance of lithium ion battery can be improved.

Description

A kind of lithium titanate composite material and preparation method thereof, negative plate and lithium ion battery
Technical field
The present invention relates to a kind of battery technology field, more particularly to a kind of lithium titanate composite material and preparation method thereof, Negative plate and lithium ion battery.
Background technology
With petering out for the fossil fuels such as coal, oil, natural gas, mankind nowadays are faced with the unprecedented energy Crisis, while reasonable utilization and saving non-renewable resources, finds and exploitation regenerative resource is imperative.However, Lead-acid battery, nickel-cadmium cell, nickel during the regenerative resources such as development and utilization solar energy, wind energy and geothermal energy necessarily The energy storage device that hydrogen battery and lithium ion battery etc. can be recycled.In many chemical energy storage batteries, lithium ion battery because Its high workload current potential, high-energy-density, long circulation life, the features such as self discharge is small, use temperature range is wide, memory-less effect and Get most of the attention.
At present, the negative material of lithium ion battery uses various embedding lithium carbon materials mostly.But due to the potential of carbon resistance rod Potential with lithium metal is very close to when over-charging of battery, the easy precipitating metal lithium in carbon resistance rod surface, can form dendrite and cause short Road, easily triggers thermal runaway when temperature is excessive.Spinelle Li4Ti5O12It is 1.55V relative to the electrode potential of lithium metal, reaction has Very flat charge and discharge platform, is had a safety feature；And Li4Ti5O12It is a kind of " zero strain " insertion material, in discharge and recharge During there is extremely stable structure and excellent cycle performance.Although Li4Ti5O12Theoretical specific capacity there was only 175mA H/g, but since its reversible lithium ion deinsertion ratio is close to 100%, therefore its actual specific capacity is generally kept in 150-160mAh/ g.But Li4Ti5O12The electric conductivity of material is poor, and larger polarization is also easy to produce during high power charging-discharging, constrains it Application in lithium ion battery.
For lithium titanate (Li4Ti5O12) disadvantages mentioned above existing for material, the prior art are mainly more had using following two The means of effect are modified lithium titanate material：Firstth, modification by ion-doping, the Doped ions studied at present mainly have Mg2+、 Al3+、Sn4+、W4+、Ni4+、V5+With F- etc.；The conduction of lithium titanate material can not only be effectively improved by introducing a small amount of metallic element Property, it can also reduce under redox reaction voltage or caused low potential and extra voltage platform occur；It is but existing Technology mainly carries out ion doping using solid phase method；It is low for equipment requirements and traditional solid phase method is although easy to operate, but its The product grain of synthesis is uneven, crystalline form is irregular, particle size distribution range is wide and synthesis cycle is grown, it is difficult to realizes lithium titanate material Efficient utilization.Secondth, charcoal cladding/composite modified, it mainly using graphene, acetylene black, multi-walled carbon nanotube etc. is used as charcoal Source coats lithium titanate or for composite with lithium titanate, to improve the electronic conductivity of lithium titanate material；However, by material The scattering problems of carbon source such as the limitation of compatibility and preparation, mixing plant between material, graphene and itself and lithium titanate material Composite effect it is still bad so that the battery capacity and high rate performance of prepared electrode are undesirable.
The content of the invention
In view of this, the present invention provides a kind of lithium titanate composite material and preparation method thereof, negative plate and lithium ion battery, Main purpose is to provide a kind of lithium titanate composite material to conduct electricity very well, and the lithium titanate composite material is used for lithium-ion electric During the negative active core-shell material in pond, the high rate performance of lithium ion battery can be improved.
To reach above-mentioned purpose, present invention generally provides following technical solution：
On the one hand, the embodiment of the present invention provides a kind of preparation method of lithium titanate composite material, it is characterised in that including Following steps：
1) ruthenic oxide/titanium dioxide compound is prepared；
2) using ruthenic oxide/titanium dioxide compound, lithium source as raw material, lithium titanate composite material is prepared.
The object of the invention to solve the technical problems can be also applied to the following technical measures to achieve further.
Preferably, the step 2) includes：
21) react ruthenic oxide/titanium dioxide compound and lithium source, obtain mixing the lithium titanate compound of ruthenium；
22) make the lithium titanate compound absorption ruthenium ion for mixing ruthenium, obtain lithium titanate composite material.
Preferably, the step 2) includes：Ruthenic oxide/titanium dioxide compound and lithium source are reacted, obtains lithium titanate Composite material.
Preferably, the step 1), including：
11) surfactant modified ruthenic oxide is utilized；
12) ruthenic oxide after modification is mixed with solvent, dispersion liquid is made；
13) make the dispersion liquid, buffer solution, the mixing of tetra-n-butyl titanate solution, be made and contain ruthenic oxide/titanium dioxide The mixture of compound.
Preferably, the step 11) is specially：
Powder ruthenium dioxide is dispersed in surfactant solution；
The ruthenic oxide after modification is isolated from solution；
Wherein, the size of the powder ruthenium dioxide is 10-15nm.
Preferably, the surfactant solution selects polyvinylpyrrolidonesolution solution；Wherein, the ruthenic oxide and institute The mass ratio for stating polyvinylpyrrolidone is 1：(5-300)；The mass fraction of the polyvinylpyrrolidonesolution solution is 10-40g/ L。
Preferably, in the step 12)：
The solvent includes absolute ethyl alcohol and water；Wherein, the ruthenic oxide after the modification, absolute ethyl alcohol, the quality of water Than for：(2-50)：(5-20)：1.
Preferably, the step 13) is specially：
Buffer solution is first first added into the dispersion liquid, adds tetra-n-butyl titanate solution, is stirred, is uniformly mixed.
Preferably, in the step 13)：The volume ratio of the buffer solution and the dispersion liquid is 1：(400-800)；Titanium The volume ratio of sour four N-butyl solution and the dispersion liquid is 1：(40-90)；
Wherein, the buffer solution selects tetramethyl ammonium hydroxide solution, and the volume of the tetramethyl ammonium hydroxide solution Fraction is 5-15%；And/or the tetra-n-butyl titanate solution selects tetra-n-butyl titanate ethanol solution, and the metatitanic acid four is just The volume fraction of butyl acetate solution is 1-20%.
Preferably, the step 21) is specially：Using sol-gal process, make ruthenic oxide/titanium dioxide compound and lithium Source is reacted, and obtains mixing the lithium titanate compound of ruthenium.
Preferably, when the step 1) includes step 13), the step 21) is specially：
Lithium source is added dropwise into the mixture containing ruthenic oxide/titanium dioxide compound, after continuously stirring setting time, obtains To wet gel；
Xerogel is obtained after carrying out burin-in process, drying and processing successively to the wet gel；Wherein, the xerogel is to mix The lithium titanate composite material of ruthenium.
Preferably, the lithium source selects lithium acetate ethanol solution；Wherein, the concentration of the lithium acetate ethanol solution is 0.4- 1mol/L；The molar ratio of lithium acetate in the lithium acetate ethanol solution and the tetra-n-butyl titanate in tetra-n-butyl titanate solution For (0.8-0.9)：1.
Preferably, it is to the condition of wet gel progress burin-in process：25-50 DEG C of aging temperature, ageing time 3-5 Hour；And/or
To the wet gel carry out drying and processing condition be：50-100 DEG C of drying temperature, drying time are small for 10-30 When.
Preferably, the step 22), including：
The lithium titanate compound for mixing ruthenium is reacted with ruthenium salting liquid, precipitated；
After carrying out calcination processing to the precipitation, lithium titanate composite material is obtained.
Preferably, the ruthenium salting liquid selects the nitric acid ruthenium solution that concentration is 0.5-2g/L；And in the nitric acid ruthenium solution The mass ratio of nitric acid ruthenium and the lithium titanate compound for mixing ruthenium is 1：(20-100)；And/or it is described mix ruthenium lithium titanate it is compound Thing is reacted with ruthenium salting liquid in ultrasonic-microwave hybrid reaction system；And the condition of ultrasonic-microwave reaction is：Power is 50- 100W, reaction temperature are 500-1000 DEG C, when the reaction time is 6-12 small.
Preferably, before the step of making the lithium titanate compound for mixing ruthenium be reacted with ruthenium salting liquid, further including to mix The step of lithium titanate compound grind into powder of ruthenium；And/or
It is to the condition calcined that precipitates：Calcining heat is 500-1000 DEG C, calcination time 6-12h.
On the other hand, the embodiment of the present invention provides a kind of lithium titanate composite material, wherein, the lithium titanate composite material It is prepared by the preparation method of the lithium titanate composite material described in any of the above-described.
On the other hand, the embodiment of the present invention provides a kind of negative plate, wherein, the negative plate includes carbon described above Silicon composite.
On the other hand, the embodiment of the present invention provides a kind of lithium battery, wherein, the lithium battery includes described above bear Pole piece.
Compared with prior art, lithium titanate composite material of the invention and preparation method thereof, negative plate and lithium ion battery At least there is following beneficial effect：
On the one hand, the embodiment of the present invention provides a kind of preparation method of lithium titanate composite material, main to include preparing two Ruthenium-oxide/titanium dioxide compound and using ruthenic oxide/titanium dioxide compound, lithium source as raw material, prepares and internal mixes ruthenium Lithium titanate composite material；Since the lithium titanate composite material that this method is prepared mixes ruthenium, so as to improve lithium titanate composite material Electric conductivity, and improve the high rate performance of battery.
Further, the preparation method of lithium titanate composite material provided in an embodiment of the present invention internal mixes ruthenium preparing After lithium titanate compound, ruthenium ion is also introduced outside lithium titanate compound, further improves the conduction of lithium titanate composite material Property, and improve the high rate performance of battery.
Further, the preparation method of lithium titanate composite material provided in an embodiment of the present invention is preparing ruthenic oxide/bis- During titanium oxide compound, ruthenic oxide first is modified with PVP, can so promote cladding of the titanium dioxide to ruthenic oxide.Also, When tetra-n-butyl titanate hydrolyzes, buffer solution is added so that ruthenic oxide/titanium dioxide compound particle is uniform, and uses colloidal sol Gel method prepares lithium titanate composite material, finally so that lithium titanate composite material particle size is more homogeneous, can obtain higher The utilization of effect.
On the other hand, the embodiment of the present invention also provides a kind of lithium titanate composite material prepared by the above method, and the titanium Sour lithium composite material is applied on negative plate and lithium ion battery, the final high rate performance for improving battery.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention, And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate attached drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is a kind of preparation flow figure of the preparation method for lithium titanate composite material that the embodiment of the present invention provides；
Fig. 2 is the XRD diagram of lithium titanate composite material obtained by the embodiment of the present invention 1 and embodiment 2；
Fig. 3 is lithium titanate composite material 1C charging and discharging curves obtained by the embodiment of the present invention 1；
Fig. 4 is lithium titanate composite material 2C charging and discharging curves obtained by the embodiment of the present invention 1；
Fig. 5 is the multiplying power discharging property of lithium titanate composite material obtained by the embodiment of the present invention and pure phase lithium titanate material Comparison diagram.
Embodiment
Further to illustrate the present invention to reach the technological means and effect that predetermined goal of the invention is taken, below in conjunction with Attached drawing and preferred embodiment, to embodiment, structure, feature and its effect according to the present patent application, describe in detail such as Afterwards.In the following description, what different " embodiment " or " embodiment " referred to is not necessarily the same embodiment.It is in addition, one or more Special characteristic, structure or feature in a embodiment can be combined by any suitable form.
On the one hand, the embodiment of the present invention provides a kind of preparation method of lithium titanate composite material, as shown in Figure 1, the preparation Method includes the following steps：
First, ruthenic oxide/titanium dioxide compound is prepared.Specifically, which mainly includes：
11) surfactant modified ruthenic oxide is utilized.
Powder ruthenium dioxide is dispersed in surfactant solution；Fully after reaction, after isolating modification from solution Ruthenic oxide.The size of powder ruthenium dioxide is 10-15nm.
It is preferred that surfactant solution selects polyvinylpyrrolidonesolution solution (PVP solution)；Wherein, ruthenic oxide with The mass ratio of polyvinylpyrrolidone is 1：(5-300)；The mass fraction of polyvinylpyrrolidonesolution solution is 10-40g/L.
The step is specific as follows：Nanometer powder ruthenic oxide is dispersed in PVP (polyvinylpyrrolidone) solution, fully Reaction；The ruthenic oxide precipitation that the PVP of generation is modified is isolated.
Here, the purpose that the step carries out ruthenic oxide using surfactant surface modification is to promote step 13) cladding of titanium dioxide in ruthenic oxide.
12) ruthenic oxide after modification is mixed with solvent, dispersion liquid is made.
In this step, solvent includes absolute ethyl alcohol and water.Wherein, the matter of the ruthenic oxide after modification, absolute ethyl alcohol, water Measuring ratio is：(2-50)：(5-20)：1.
The step is specially：The ruthenic oxide precipitation that the PVP that step 11) is isolated is modified is added in absolute ethyl alcohol, And water is added, it is uniformly dispersed, obtains dispersion liquid.
13) make dispersion liquid, buffer solution, the mixing of tetra-n-butyl titanate solution, be made compound containing ruthenic oxide/titanium dioxide The mixture of thing.
The step is specially：After buffer solution is added to dispersion liquid, tetra-n-butyl titanate solution is added, is stirred, mixing Uniformly.
It is preferred that the volume ratio of buffer solution and dispersion liquid is 1：(400-800)；Tetra-n-butyl titanate solution and described scattered The volume ratio of liquid is 1：(40-90)；
Wherein, the buffer solution selects tetramethyl ammonium hydroxide solution, and the volume of the tetramethyl ammonium hydroxide solution Fraction is 5-15%, is preferably 10%.Tetra-n-butyl titanate solution selects tetra-n-butyl titanate ethanol solution, and four positive fourth of metatitanic acid The volume fraction of ester solution is 1-20%.
In this step, the purpose for adding buffer solution is as follows：Meeting after being mixed due to tetra-n-butyl titanate solution with dispersion liquid Hydrolyze, and hydrolyze acutely, so, by adding buffer solution, to relax the speed of hydrolysis, ultimately form the two of size uniform Ruthenium-oxide/titanium dioxide compound particle.
2nd, using ruthenic oxide/titanium dioxide compound, lithium source as two kinds of raw materials therein, metatitanic acid lithium composite is prepared Material.
The step mainly includes following two schemes：
The first scheme：Make ruthenic oxide/titanium dioxide compound, lithium source reaction, directly prepare metatitanic acid lithium composite Material.
This kind of scheme is that the lithium titanate composite material finally obtained only mixes ruthenium in inside.
Second scheme includes the following steps：
21) react ruthenic oxide/titanium dioxide compound and lithium source, obtain mixing ruthenium lithium titanate compound (equivalent to The final products of the first scheme).
22) make the lithium titanate compound absorption ruthenium ion for mixing ruthenium, obtain lithium titanate composite material.
Second scheme, is on the basis of obtaining inside and mixing the lithium titanate compound of ruthenium, is mixing ruthenium lithium titanate material Outside introduces ruthenium ion, obtains the inside and outside lithium titanate composite material for mixing ruthenium.
It is preferred that step 21) is specially：Using sol-gal process, make ruthenic oxide/titanium dioxide compound and lithium source anti- Answer, obtain mixing the lithium titanate compound of ruthenium.It is preferred that when step 1) includes step 13), the step 21) is specially：Xiang Han Have in the mixture of ruthenic oxide/titanium dioxide compound and lithium source is added dropwise, after continuously stirring setting time, obtain wet gel；It is right Wet gel obtains xerogel after carrying out burin-in process, drying and processing successively；Wherein, xerogel is the metatitanic acid lithium composite for mixing ruthenium Material.It is preferred that the preferred lithium acetate ethanol solution of lithium source in the embodiment of the present invention (in addition can also select Lithium carbonate solution, grass Sour lithium solution).Wherein, the concentration of the lithium acetate ethanol solution is 0.4-1mol/L；Lithium acetate in lithium acetate ethanol solution Molar ratio with the tetra-n-butyl titanate in tetra-n-butyl titanate solution is (0.8-0.9)：1.It is preferred that wet gel is carried out old Changing the condition handled is：25-50 DEG C of aging temperature, when ageing time is 3-5 small.It is preferred that wet gel carries out drying and processing Condition is：50-100 DEG C of drying temperature, when drying time is 10-30 small.Wherein, the preparation process of the first scheme can refer to step It is rapid 21).
Step 21) is specially：In the dispersion liquid of step 13), buffer solution, tetra-n-butyl titanate solution after mixing, to Wherein be added dropwise lithium acetate ethanol solution, continuously stir 2 it is small when after, obtain wet gel.Wet gel is put into one section of aging in baking oven After time, then drying and processing is carried out, obtain xerogel.
Step 22), specifically includes：
221) lithium titanate compound (xerogel) for mixing ruthenium is reacted with ruthenium salting liquid, precipitated.
It is preferred that ruthenium salting liquid selects the nitric acid ruthenium solution that concentration is 0.5-2g/L；And in nitric acid ruthenium solution nitric acid ruthenium with The mass ratio for mixing the lithium titanate compound of ruthenium is 1：(20-100).
It is preferred that the lithium titanate compound for mixing ruthenium is reacted with ruthenium salting liquid in ultrasonic-microwave hybrid reaction system； And the condition of ultrasonic-microwave reaction is：Power is 50-100W, and reaction temperature is 500-1000 DEG C, when the reaction time is 6-12 small.
It is preferred that before the step of making the lithium titanate compound for mixing ruthenium be reacted with ruthenium salting liquid, ruthenium will be mixed by further including The step of lithium titanate compound grind into powder.
222) after carrying out calcination processing to precipitation, lithium titanate composite material is obtained.
It is preferred that the condition calcined to precipitation is：In atmosphere, calcining heat is 500-1000 DEG C, calcination time For 6-12h.Due to having water, ethanol in precipitation that 221) step obtains, step 222) calcining be mainly used for removing ethanol, Water, and improve the crystallinity of lithium titanate composite material.
On the other hand, the embodiment of the present invention also provides a kind of lithium titanate composite material, wherein, lithium titanate composite material is by upper The preparation method for the lithium titanate composite material stated is prepared.
On the other hand, the embodiment of the present invention also provides a kind of negative plate, wherein, negative plate includes above-mentioned carbon silicon composite wood Material.
On the other hand, the embodiment of the present invention also provides a kind of lithium battery, wherein, lithium battery includes above-mentioned negative plate.
Further illustrated below by EXPERIMENTAL EXAMPLE.
Embodiment 1
The present embodiment prepares a kind of lithium titanate composite material, comprises the following steps that：
1) 0.02g nanometer titanium dioxide ruthenium powders are distributed in the PVP solution of 20g/L of 100ml, stirring reaction 10h will After the powder ruthenium dioxide of the lurid PVP modifications of generation is separated, it is added in the absolute ethyl alcohol of 100ml, adds The deionized water of 10ml, after ultrasonic disperse 5min, obtains dispersion liquid.
2) TMAH solution that 200ul volume fractions are 10% is added drop-wise in dispersion liquid, then adds 200ml volumes thereto Fraction is the ethanol solution of 5% tetra-n-butyl titanate, stirs 15min, is uniformly mixed, obtains containing ruthenic oxide/titanium dioxide The mixture of titanium compound.
3) the lithium acetate ethanol solution of the 0.4mol/L of 80ml is added dropwise into mixture obtained by step 2), is obtained after stirring 2h Yellow gum.Yellow gum is placed in 3h in 35 DEG C of baking ovens and obtains white gels.White gels are placed in 80 DEG C of baking ovens dry 20h obtains xerogel.Wherein, xerogel is the lithium titanate compound for mixing ruthenium.
4) after xerogel is clayed into power, it is added in the 0.5g/L nitric acid ruthenium solutions of 100ml, is placed in ultrasonic-microwave mixing 1h is reacted at 50W, 60 DEG C in reaction system, precipitation is separated and is placed in calcining at 800 DEG C of air atmosphere in tube furnace 8h, obtains lithium titanate composite material.
The lithium titanate composite material of the preparation of 1.2g embodiments 1 is weighed, adds a certain amount of conductive agent, binding agent and N- methyl Powder after ball milling, using planetary ball mill ball milling 3h, is painted the film of 152um thickness, through true by pyrrole network alkanone on aluminium foil The disk of a diameter of 12mm is cut into after sky is dry, pole piece quality is accurately weighed after drying and calculates activity substance content.Select gold It is to electrode and reference electrode to belong to lithium piece, and membrane selects microporous polypropylene membrane, and electrolyte is the EC (ethylene carbonate) of 1mol/L With organic mixed solution (VEC of DEC (diethyl carbonate)：VDEC=1：1) button cell, is assembled in vacuum glove box, is adopted Sealed with buckle battery mouth sealer, obtain button cell.
Embodiment 2
The present embodiment prepares a kind of lithium titanate composite material, comprises the following steps that：
1) 0.01g nanometer titanium dioxide ruthenium powders are distributed in the PVP solution of 20g/L of 100ml, stirring reaction 10h will After the powder ruthenium dioxide of the lurid PVP modifications of generation is separated, it is added in the absolute ethyl alcohol of 100ml, adds The deionized water of 15ml, after ultrasonic disperse 5min, obtains dispersion liquid.
2) TMAH solution that 180ul volume fractions are 10% is added drop-wise in dispersion liquid, then adds 120ml volumes thereto Fraction is the ethanol solution of 10% tetra-n-butyl titanate, stirs 15min, is uniformly mixed, obtains containing ruthenic oxide/titanium dioxide The mixture of titanium compound.
3) the lithium acetate ethanol solution of the 0.5mol/L of 80ml is added dropwise into mixture obtained by step 2), is obtained after stirring 2h Yellow gum.Yellow gum is placed in 3h in 40 DEG C of baking ovens and obtains white gels.White gels are placed in 90 DEG C of baking ovens dry 20h obtains xerogel.Wherein, xerogel is the lithium titanate compound for mixing ruthenium.
4) after xerogel is clayed into power, it is added in the 1g/L nitric acid ruthenium solutions of 100ml, it is anti-is placed in ultrasonic-microwave mixing Answer in system and react 1h at 50W, 70 DEG C, precipitation is separated and is placed in calcining at 800 DEG C of air atmosphere in tube furnace 10h, obtains lithium titanate composite material.
The lithium titanate composite material of the preparation of 1.2g embodiments 2 is weighed, adds a certain amount of conductive agent, binding agent and N- methyl Powder after ball milling, using planetary ball mill ball milling 3h, is painted the film of 152um thickness, through true by pyrrole network alkanone on aluminium foil The disk of a diameter of 12mm is cut into after sky is dry, pole piece quality is accurately weighed after drying and calculates activity substance content.Select gold It is to electrode and reference electrode to belong to lithium piece, and membrane selects microporous polypropylene membrane, and electrolyte is the EC (ethylene carbonate) of 1mol/L With organic mixed solution (VEC of DEC (diethyl carbonate)：VDEC=1：1) button cell, is assembled in vacuum glove box, is adopted Sealed with buckle battery mouth sealer, obtain button cell.
Embodiment 3
The present embodiment prepares a kind of lithium titanate composite material, comprises the following steps that：
1) 0.01g nanometer titanium dioxide ruthenium powders are distributed in the PVP solution of 25g/L of 100ml, stirring reaction 10h will After the powder ruthenium dioxide of the lurid PVP modifications of generation is separated, it is added in the absolute ethyl alcohol of 100ml, adds The deionized water of 20ml, after ultrasonic disperse 5min, obtains dispersion liquid.
2) TMAH solution that 200ul volume fractions are 10% is added drop-wise in dispersion liquid, then adds 150ml volumes thereto Fraction is the ethanol solution of 5% tetra-n-butyl titanate, stirs 15min, is uniformly mixed, obtains containing ruthenic oxide/titanium dioxide The mixture of titanium compound.
3) the lithium acetate ethanol solution of the 0.5mol/L of 50ml is added dropwise into mixture obtained by step 2), is obtained after stirring 2h Yellow gum.Yellow gum is placed in 3h in 45 DEG C of baking ovens and obtains white gels.White gels are placed in 70 DEG C of baking ovens dry 15h obtains xerogel.Wherein, xerogel is the lithium titanate compound for mixing ruthenium.
4) after xerogel is clayed into power, it is added in the 0.8g/L nitric acid ruthenium solutions of 100ml, is placed in ultrasonic-microwave mixing 2h is reacted at 50W, 60 DEG C in reaction system, precipitation is separated and is placed in calcining at 900 DEG C of air atmosphere in tube furnace 10h, obtains lithium titanate composite material.
The lithium titanate composite material of the preparation of 1.2g embodiments 3 is weighed, adds a certain amount of conductive agent, binding agent and N- methyl Powder after ball milling, using planetary ball mill ball milling 3h, is painted the film of 152um thickness, through true by pyrrole network alkanone on aluminium foil The disk of a diameter of 12mm is cut into after sky is dry, pole piece quality is accurately weighed after drying and calculates activity substance content.Select gold It is to electrode and reference electrode to belong to lithium piece, and membrane selects microporous polypropylene membrane, and electrolyte is the EC (ethylene carbonate) of 1mol/L With organic mixed solution (VEC of DEC (diethyl carbonate)：VDEC=1：1) button cell, is assembled in vacuum glove box, is adopted Sealed with buckle battery mouth sealer, obtain button cell.
Embodiment 4
The present embodiment prepares a kind of lithium titanate composite material, comprises the following steps that：
1) 0.01g nanometer titanium dioxide ruthenium powders are distributed in the PVP solution of 30g/L of 100ml, stirring reaction 10h will After the powder ruthenium dioxide of the lurid PVP modifications of generation is separated, it is added in the absolute ethyl alcohol of 100ml, adds The deionized water of 5ml, after ultrasonic disperse 5min, obtains dispersion liquid.
2) TMAH solution that 230ul volume fractions are 10% is added drop-wise in dispersion liquid, then adds 200ml volumes thereto Fraction is the ethanol solution of 5% tetra-n-butyl titanate, stirs 15min, is uniformly mixed, obtains containing ruthenic oxide/titanium dioxide The mixture of titanium compound.
3) the lithium acetate ethanol solution of the 0.7mol/L of 45ml is added dropwise into mixture obtained by step 2), is obtained after stirring 2h Yellow gum.Yellow gum is placed in 4h in 40 DEG C of baking ovens and obtains white gels.White gels are placed in 80 DEG C of baking ovens dry 25h obtains xerogel.Wherein, xerogel is the lithium titanate compound for mixing ruthenium.
4) after xerogel is clayed into power, it is added in the 0.9g/L nitric acid ruthenium solutions of 100ml, is placed in ultrasonic-microwave mixing 1h is reacted at 60W, 80 DEG C in reaction system, precipitation is separated and is placed in calcining at 800 DEG C of air atmosphere in tube furnace 8h, obtains lithium titanate composite material.
The lithium titanate composite material of the preparation of 1.2g embodiments 4 is weighed, adds a certain amount of conductive agent, binding agent and N- methyl Powder after ball milling, using planetary ball mill ball milling 3h, is painted the film of 152um thickness, through true by pyrrole network alkanone on aluminium foil The disk of a diameter of 12mm is cut into after sky is dry, pole piece quality is accurately weighed after drying and calculates activity substance content.Select gold It is to electrode and reference electrode to belong to lithium piece, and membrane selects microporous polypropylene membrane, and electrolyte is the EC (ethylene carbonate) of 1mol/L With organic mixed solution (VEC of DEC (diethyl carbonate)：VDEC=1：1) button cell, is assembled in vacuum glove box, is adopted Sealed with buckle battery mouth sealer, obtain button cell.
Embodiment 5
The present embodiment prepares a kind of lithium titanate composite material, comprises the following steps that：
1) 0.02g nanometer titanium dioxide ruthenium powders are distributed in the PVP solution of 30g/L of 100ml, stirring reaction 10h will After the powder ruthenium dioxide of the lurid PVP modifications of generation is separated, it is added in the absolute ethyl alcohol of 100ml, adds The deionized water of 15ml, after ultrasonic disperse 5min, obtains dispersion liquid.
2) TMAH solution that 150ul volume fractions are 10% is added drop-wise in dispersion liquid, then adds 150ml volumes thereto Fraction is the ethanol solution of 12% tetra-n-butyl titanate, stirs 15min, is uniformly mixed, obtains containing ruthenic oxide/titanium dioxide The mixture of titanium compound.
3) the lithium acetate ethanol solution of the 1mol/L of 60ml is added dropwise into mixture obtained by step 2), Huang is obtained after stirring 2h Coloring agent body.Yellow gum is placed in 5h in 35 DEG C of baking ovens and obtains white gels.White gels are placed in 90 DEG C of baking ovens dry 25h Obtain xerogel.Wherein, xerogel is the lithium titanate compound for mixing ruthenium.
4) after xerogel is clayed into power, it is added in the 2g/L nitric acid ruthenium solutions of 100ml, it is anti-is placed in ultrasonic-microwave mixing Answer in system and react 2h at 60W, 80 DEG C, precipitation is separated and is placed in calcining 9h at 100 DEG C of air atmosphere in tube furnace, Obtain lithium titanate composite material.
The lithium titanate composite material of the preparation of 1.2g embodiments 5 is weighed, adds a certain amount of conductive agent, binding agent and N- methyl Powder after ball milling, using planetary ball mill ball milling 3h, is painted the film of 152um thickness, through true by pyrrole network alkanone on aluminium foil The disk of a diameter of 12mm is cut into after sky is dry, pole piece quality is accurately weighed after drying and calculates activity substance content.Select gold It is to electrode and reference electrode to belong to lithium piece, and membrane selects microporous polypropylene membrane, and electrolyte is the EC (ethylene carbonate) of 1mol/L With organic mixed solution (VEC of DEC (diethyl carbonate)：VDEC=1：1) button cell, is assembled in vacuum glove box, is adopted Sealed with buckle battery mouth sealer, obtain button cell.
Comparative example
1.2g pure phase lithium titanate composite materials are weighed, add a certain amount of conductive agent, binding agent and N- methyl pyrrole network alkanones, Using planetary ball mill ball milling 3h, the powder after ball milling is painted to the film of 152um thickness on aluminium foil, is cut after vacuum dried Into the disk of a diameter of 12mm, pole piece quality is accurately weighed after drying and calculates activity substance content.It is pair to select metal lithium sheet Electrode and reference electrode, membrane select microporous polypropylene membrane, and electrolyte is the EC (ethylene carbonate) and DEC (carbonic acid of 1mol/L Diethylester) organic mixed solution (VEC：VDEC=1：1) button cell, is assembled in vacuum glove box, using button cell Sealing machine is sealed, and obtains button cell.
It is tested for the property below：
X-ray diffraction test (XRD tests) is carried out to lithium titanate composite material prepared by embodiment 1, test collection of illustrative plates refers to Shown in Fig. 2.
The diffraction maximum of metal Ru is not seen from the XRD spectrum of Fig. 2, the reason is that metatitanic acid lithium composite prepared by embodiment 1 The amount of ruthenium is considerably less in material.
Wherein, the 1C charging and discharging curves of the button cell prepared by embodiment 1 are as shown in Figure 3.Button prepared by embodiment 1 The 2C charge and discharge cycles curves of formula battery are as shown in Figure 4.Lithium titanate material and pure phase lithium titanate material prepared by embodiment 1 Multiplying power discharging property contrasts, as shown in Figure 5.The lithium titanate composite material that it can be seen from Fig. 3 to Fig. 5 prepared by embodiment 2 is led Electrically, battery high rate performance is good.
The above described is only a preferred embodiment of the present invention, not make limitation in any form to the present invention, according to Any simple modification, equivalent change and modification made according to the technical spirit of the present invention to above example, still falls within this hair In the range of bright technical solution.

Claims (19)

1. a kind of preparation method of lithium titanate composite material, it is characterised in that include the following steps：
1) ruthenic oxide/titanium dioxide compound is prepared；
2) using ruthenic oxide/titanium dioxide compound, lithium source as raw material, lithium titanate composite material is prepared.
2. the preparation method of lithium titanate composite material according to claim 1, it is characterised in that the step 2) includes：
21) react ruthenic oxide/titanium dioxide compound and lithium source, obtain mixing the lithium titanate compound of ruthenium；
22) make the lithium titanate compound absorption ruthenium ion for mixing ruthenium, obtain lithium titanate composite material.
3. the preparation method of lithium titanate composite material according to claim 1, it is characterised in that the step 2) includes：
Ruthenic oxide/titanium dioxide compound and lithium source are reacted, obtains lithium titanate composite material.
4. according to the preparation method of claim 1-3 any one of them lithium titanate composite materials, it is characterised in that the step 1), including：
11) surfactant modified ruthenic oxide is utilized；
12) ruthenic oxide after modification is mixed with solvent, dispersion liquid is made；
13) make the dispersion liquid, buffer solution, the mixing of tetra-n-butyl titanate solution, be made compound containing ruthenic oxide/titanium dioxide The mixture of thing.
5. the preparation method of lithium titanate composite material according to claim 4, it is characterised in that the step 11) is specific For：
Powder ruthenium dioxide is dispersed in surfactant solution；
The ruthenic oxide after modification is isolated from solution；
Wherein, the size of the powder ruthenium dioxide is 10-15nm.
6. the preparation method of lithium titanate composite material according to claim 5, it is characterised in that
The surfactant solution selects polyvinylpyrrolidonesolution solution；Wherein, the ruthenic oxide and the polyethylene pyrrole The mass ratio of pyrrolidone is 1：(5-300)；The mass fraction of the polyvinylpyrrolidonesolution solution is 10-40g/L.
7. the preparation method of lithium titanate composite material according to claim 4, it is characterised in that in the step 12)：
The solvent includes absolute ethyl alcohol and water；Wherein, the ruthenic oxide after the modification, absolute ethyl alcohol, the mass ratio of water are： (2-50)：(5-20)：1.
8. the preparation method of lithium titanate composite material according to claim 4, it is characterised in that the step 13) is specific For：
Buffer solution is first first added into the dispersion liquid, adds tetra-n-butyl titanate solution, is stirred, is uniformly mixed.
9. the preparation method of lithium titanate composite material according to claim 4, it is characterised in that in the step 13)： The volume ratio of the buffer solution and the dispersion liquid is 1：(400-800)；The tetra-n-butyl titanate solution and the dispersion liquid Volume ratio be 1：(40-90)；
Wherein, the buffer solution selects tetramethyl ammonium hydroxide solution, and the volume fraction of the tetramethyl ammonium hydroxide solution For 5-15%；And/or the tetra-n-butyl titanate solution selects tetra-n-butyl titanate ethanol solution, and the tetra-n-butyl titanate The volume fraction of solution is 1-20%.
10. according to claim 2, the preparation method of 4-9 any one of them lithium titanate composite materials, it is characterised in that described Step 21) is specially：Using sol-gal process, ruthenic oxide/titanium dioxide compound and lithium source are reacted, obtains mixing the titanium of ruthenium Sour lithium compound.
11. the preparation method of lithium titanate composite material according to claim 10, it is characterised in that when the step 1) is wrapped When including step 13), the step 21) is specially：
Lithium source is added dropwise into the mixture containing ruthenic oxide/titanium dioxide compound, after continuously stirring setting time, obtains wet Gel；
Xerogel is obtained after carrying out burin-in process, drying and processing successively to the wet gel；Wherein, the xerogel is to mix ruthenium Lithium titanate compound.
12. the preparation method of lithium titanate composite material according to claim 11, it is characterised in that the lithium source selects second Sour lithium ethanol solution；Wherein, the concentration of the lithium acetate ethanol solution is 0.4-1mol/L；In the lithium acetate ethanol solution The molar ratio of lithium acetate and the tetra-n-butyl titanate in tetra-n-butyl titanate solution is (0.8-0.9)：1.
13. the preparation method of lithium titanate composite material according to claim 11, it is characterised in that to the wet gel into The condition of row burin-in process is：25-50 DEG C of aging temperature, when ageing time is 3-5 small；And/or
To the wet gel carry out drying and processing condition be：50-100 DEG C of drying temperature, when drying time is 10-30 small.
14. the preparation method of lithium titanate composite material according to claim 2, it is characterised in that the step 22), bag Include：
The lithium titanate compound for mixing ruthenium is reacted with ruthenium salting liquid, precipitated；
After carrying out calcination processing to the precipitation, lithium titanate composite material is obtained.
15. the preparation method of lithium titanate composite material according to claim 14, it is characterised in that the ruthenium salting liquid choosing The nitric acid ruthenium solution for being 0.5-2g/L with concentration；And nitric acid ruthenium and the lithium titanate compound for mixing ruthenium in the nitric acid ruthenium solution Mass ratio be 1：(20-100)；And/or
The lithium titanate compound for mixing ruthenium is reacted with ruthenium salting liquid in ultrasonic-microwave hybrid reaction system；And ultrasound is micro- Ripple reaction condition be：Power is 50-100W, and reaction temperature is 500-1000 DEG C, when the reaction time is 6-12 small.
16. the preparation method of lithium titanate composite material according to claim 14, it is characterised in that make described to mix ruthenium Before the step of lithium titanate compound is reacted with ruthenium salting liquid, the step of the lithium titanate compound grind into powder of ruthenium will be mixed by further including Suddenly；And/or
It is to the condition calcined that precipitates：Calcining heat is 500-1000 DEG C, calcination time 6-12h.
17. a kind of lithium titanate composite material, it is characterised in that the lithium titanate composite material is by any one of claim 1-16 institutes The preparation method for the lithium titanate composite material stated is prepared.
18. a kind of negative plate, it is characterised in that the negative plate includes the carbon-silicon composite material described in claim 17.
19. a kind of lithium battery, it is characterised in that the lithium battery includes the negative plate described in claim 18.
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