CN104577092B - A kind of composite Nano lithium titanate material and preparation method thereof - Google Patents

A kind of composite Nano lithium titanate material and preparation method thereof Download PDF

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CN104577092B
CN104577092B CN201410854770.2A CN201410854770A CN104577092B CN 104577092 B CN104577092 B CN 104577092B CN 201410854770 A CN201410854770 A CN 201410854770A CN 104577092 B CN104577092 B CN 104577092B
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preparation
lithium titanate
lithium
parts
nanometer wire
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CN104577092A (en
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时浩
梅佳
黄友元
孔东亮
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BTR New Material Group Co Ltd
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Shenzhen BTR New Energy Materials Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of composite Nano lithium titanate material and preparation method thereof, wherein, this composite Nano lithium titanate material includes nanoscale lithium titanate particulate and graphene, and the nanoscale lithium titanate particulate is nanometer thread-like flecks, and the chemical composition of the nanoscale lithium titanate particulate is Li4Ti5O12, the graphene dispersion is between nanoscale lithium titanate particulate.This composite Nano lithium titanate material has higher electrical conductivity；After being prepared into half-cell by this composite Nano lithium titanate material, test shows that its specific discharge capacity is more than 160mAh/g；When this composite Nano lithium titanate material is applied into the fields such as lithium battery, ultracapacitor, there is the characteristics of function admirables such as circulation, multiplying power.

Description

A kind of composite Nano lithium titanate material and preparation method thereof
Technical field
The present invention relates to a kind of composite, more particularly to a kind of composite Nano lithium titanate material, the invention further relates to one The preparation method of kind composite Nano lithium titanate material, belongs to novel energy resource material technology field.
Background technology
Lithium battery is a kind of battery system of high-energy-density, and it includes electrolyte, barrier film and electrode material.Wherein electrode Material is most important for the performance of lithium battery.Traditional lithium battery is used as negative pole using graphite type material.In recent years, lithium titanate material Material has obtained the concern of people.Lithium titanate material has the advantages that " zero strain ", platform stable so that it is in electrokinetic cell Using having obtained extensive concern.
As novel anode material, it is also obvious that being exactly poorly conductive the shortcomings that lithium titanate, its high rate performance is caused to be paid no attention to Think.Mainly improve its electric conductivity by means such as doping, pattern controls (including nanosizing) at present.Publication No. CN102468485A patent discloses a kind of preparation method of lithium titanate composite material, and it includes graphene and nanoscale metatitanic acid Lithium particulate.Nanoscale lithium titanate microparticle outer surface has carbon coating layer, and graphene is distributed in outside carbon coating layer, nanoscale lithium titanate Particulate chemistry composition is Li4Ti5-XMXO12, and 0.001≤X ＜ 5, M are transition metal.This invention lithium titanate composite material, By the carbon coating layer of nanoscale lithium titanate microparticle surfaces, in lithium titanate lattice in doping metals M and lithium titanate composite material Doped graphene, the electric conductivity of lithium titanate composite material is substantially increased, significantly improve composite charge-discharge magnification.
Publication No. CN101486488A patent discloses a kind of preparation method of nano spinelle lithium titanate.It is with two Titanium oxide, metatitanic acid or titanate are synthesis under normal pressure 6-48 hours at 6-15mol/L alkali lye and 90-130 DEG C with concentration, so Reaction product is washed or pickling afterwards, and ion exchange 10min-3 is carried out under normal pressure with the aqueous solution containing lithium ion My god, filtering, filter cake, which is calcined, produces the nano spinelle lithium titanate.Invention product is brilliant for wire or the graininess point of nanoscale Stone lithium titanate.
In the prior art, the control sent and realize doping and pattern to lithium titanate material is not gone out from raw material also.
The content of the invention
First technical problem to be solved by this invention is to provide a kind of high compound of electrical conductivity for the state of the art to receive Rice lithium titanate material.
Second technical problem to be solved by this invention is to provide a kind of simple to operate, environment amenable composite Nano The preparation method of lithium titanate material.
Technical scheme is used by the present invention solves above-mentioned first technical problem：A kind of composite Nano lithium titanate material Material, including nanoscale lithium titanate particulate and graphene, the nanoscale lithium titanate particulate are nanometer thread-like flecks, the nanoscale The chemical composition of lithium titanate particulate is Li4Ti5O12, the graphene dispersion is between nanoscale lithium titanate particulate.
Wherein, the number of plies≤10 of the graphene.
Wherein, a diameter of 100nm~2000nm of the nanoscale lithium titanate particulate, such as 200nm, 500nm, 1000nm, 1200nm, 1500nm, 1800nm, specific surface area are 10~100m2/ g, such as 20m2/g、50m2/g、60m2/g、 80m2/g。
Technical scheme is used by the present invention solves above-mentioned second technical problem：A kind of composite Nano lithium titanate material Preparation method, comprise the following steps：
(1) nanometer wire titanium dioxide fine particles are prepared；
(2) in parts by weight, by 100 parts of nanometer wire titanium dioxide fine particles, 37~115 parts (such as 40 parts, 60 Part, 70 parts, 80 parts, 90 parts, 100 parts, 105 parts, 110 parts) lithium source mixing, grind, calcine, crush, cross mesh sieve, be made and compound receive Rice lithium titanate material.
In step (1), the nanometer wire titanium dioxide fine particles are prepared using the method for electrostatic spinning.
Wherein, when preparing nanometer wire titanium dioxide fine particles using electrostatic spinning, the composition solution used is including as follows The component of parts by weight：
Wherein, the solvent is pure water, methanol, ethanol, DMF (DMF), tetrahydrofuran, N- methyl pyrroles It is more than one or both of pyrrolidone；
Preferably, the titanium source is butyl titanate or alkyl titanate；
Preferably, the viscosity modifier is fine polyvinyl alcohol, polyethylene glycol, polypropylene, polyacrylamide, polyvinyl It is more than one or both of pyrrolidones.
In step (1), the preparation of the nanometer wire titanium dioxide fine particles comprises the following steps：
Titanium source is dissolved in solvent by (1a) by proportioning, and viscosity modifier and graphene are sequentially added by proportioning, is stirred, and is made Composition solution for electrostatic spinning；
(1b) uses electrostatic spinning apparatus, and the composition solution is made into nanometer wire titanic oxide material；
The nanometer wire titanic oxide material is placed in calciner by (1c), in inert gas, 500~900 Calcine 1~10 hour, cool down at DEG C, smash, cross mesh sieve, nanometer wire titanium dioxide fine particles are made.
Wherein, the operating procedure of step (1b) is：The composition solution is added to the syringe of electrostatic spinning apparatus In, the syringe is disposed vertically and lower section is placed with aluminium foil, in 10~40kV, such as 20kV, 23kV, 25kV, 30kV, 33kV High direct voltage under, nanometer wire titanic oxide material is made on aluminium foil；
Preferably, in step (1b), the external diameter of the syringe needle of the syringe is 1.2mm, internal diameter 0.79mm；
Preferably, in step (1b), the distance between the syringe needle of the aluminium foil and syringe is 10~30cm, such as 12cm, 15cm、20cm、22cm、27cm；
Preferably, in step (1c), the calciner is tunnel cave；
Preferably, in step (1c), the inert gas is nitrogen；
Preferably, in step (1c), in the calciner, with 1~10 DEG C/min, for example, 2 DEG C/min, 3 DEG C/min, 5 DEG C/min, 7 DEG C/min heating rate be warming up to 500~900 DEG C, such as 600 DEG C, 650 DEG C, 700 DEG C, 800 DEG C, 830 DEG C；
Preferably, in step (1c), crushed using mechanical crusher or jet mill；
Preferably, in step (1c), the mesh of the mesh number of the mesh sieve >=200.
In step (2), the lithium source is one or both of lithium carbonate, lithium hydroxide, lithium dihydrogen phosphate or lithium acetate More than；
Preferably, in step (2), in parts by weight, the lithium source be 3.7~36.6 parts, such as 4 parts, 10 parts, 17 Part, 20 parts, 28 parts, 33 parts of lithium carbonate and 41.6~4.2 parts, such as 40 parts, 31 parts, 22 parts, 15 parts, 9 parts, 5 parts of hydrogen-oxygen Change the mixture of lithium；
Preferably, in step (2), when the nanometer wire titanium dioxide fine particles, lithium source are mixed, planetary type ball-milling is used Machine ball milling mixing 5~24 hours, such as 6 hours, 10 hours, 12 hours, 15 hours, 20 hours；
Preferably, in step (2), the calcining refers in tunnel cave, in a nitrogen atmosphere, with 1~10 DEG C/min, example As 2 DEG C/min, 5 DEG C/min, 7 DEG C/min, 8 DEG C/min heating rate are warming up to 600~900 DEG C, for example, 650 DEG C, 700 DEG C, 720 DEG C, 780 DEG C, 800 DEG C, 850 DEG C, be incubated 10~48 hours, for example, 15 hours, 20 hours, 23 hours, 27 hours, it is 30 small When, 36 hours, 40 hours；
Preferably, in step (2), the mesh of the mesh number of the mesh sieve >=200.
Compared with prior art, the advantage of the invention is that：Nanoscale lithium titanate in this composite Nano lithium titanate material Particulate is the particulate of nanometer wire, and its chemical composition is Li4Ti5O12, and graphene dispersion in nanoscale lithium titanate particulate it Between.Composite Nano lithium titanate material based on said structure has higher electrical conductivity, and its electrical conductivity reaches as high as 10-2S/cm； After being prepared into half-cell by this composite Nano lithium titanate material, test shows that its specific discharge capacity is more than 160mAh/g；This is multiple Nano lithium titanate materials application is closed when the fields such as lithium battery, ultracapacitor, there is the spy of the function admirables such as circulation, multiplying power Point.
In addition, this composite Nano lithium titanate material is first micro- using the method preparation nanometer wire titanium dioxide of electrostatic spinning Grain, then prepares nanowire shape lithium titanate composite material using it as raw material, and its is simple to operate, and environmentally friendly, from And alleviate the environmental pressure in New Energy Industry.
Brief description of the drawings
When Fig. 1 is that the embodiment of the present invention 1 prepares nanometer wire titanium dioxide fine particles, electrostatic spinning process schematic diagram.
Embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
Embodiment 1
The composite Nano lithium titanate material of the present embodiment, including nanoscale lithium titanate particulate and graphene, wherein, nanoscale Lithium titanate particulate is nanometer thread-like flecks, and its chemical composition is Li4Ti5O12, and to be then scattered in nanoscale lithium titanate micro- for graphene Between grain.
Wherein, a diameter of 100nm~2000nm of nanoscale lithium titanate particulate, specific surface area are 10~100m2/g；In order to So that the composite Nano lithium titanate material of the present embodiment has preferably electric conductivity, the number of plies of graphene is less than 10.
The preparation method of the composite Nano lithium titanate material of the present embodiment comprises the following steps：
(1) nanometer wire titanium dioxide fine particles are prepared；
The step can meet to prepare nanometer wire simultaneously when preparing nanometer wire titanium dioxide fine particles using any The method of titanium dioxide precursor used in composite titanic acid lithium material, as the preferable mode of the present embodiment, using Static Spinning The method of silk prepares a nanometer wire composite titanium dioxide particulate, and its process includes the system of the composition solution for electrostatic spinning It is standby, composition solution is formed by nanometer wire, collecting process by electrostatic spinning process and burnt till, pulverizing process, finally give It is adapted to the precursor for preparing nanometer wire composite lithium titanate material.
This process specifically includes following operating procedure：
(1a) is counted in parts by weight, and 10 parts of titanium sources are dissolved in 100 parts of solvents, and high-speed stirred 1~10 hour is until dissolving Completely, 1 portion of viscosity modifier is added, high-speed stirred 1~10 hour is to adjust the viscosity of solution to being applied to gluing for electrostatic spinning Degree, 0.1 part of graphene is added, high-speed stirred 1~10 hour, the composition solution for electrostatic spinning is made；
In this step, solvent is pure water, methanol, ethanol, DMF, tetrahydrofuran, N- crassitudes It is more than one or both of ketone；Viscosity modifier is the various macromolecule organics dissolved in above-mentioned solvent, preferably poly- Vinyl alcohol, polyethylene glycol, polypropylene are fine, more than one or both of polyacrylamide, PVP, work Be in order to the viscosity of regulation composition solution be suitable for carry out electrostatic spinning；Titanium source is to dissolve in organic, the nothing of above-mentioned solvent Machine titanium source, including butyl titanate, various metatitanic acid alkyl fat, the present embodiment specifically select butyl titanate.
(1b) uses electrostatic spinning apparatus, and composition solution is made into nanometer wire titanic oxide material；
The electrostatic spinning apparatus of this step is carried out using syringe, and syringe needle is truncated 12#Stainless steel syringe needle, external diameter For 1.2mm, internal diameter 0.79mm, collection device uses aluminium foil.But the present embodiment not limited to this device, it can also use other industries General device for spinning.Composition solution is added in syringe, is disposed vertically, places aluminium foil immediately below it, aluminium foil with The distance between syringe needle is 10-30cm, such as 20cm.Apply 10-40kV, such as 20kV, 30kV high direct voltage at syringe needle, With the progress of electrostatic spinning, a nanometer wire titanic oxide material will be obtained on aluminium foil.
The electrostatic spinning principle of this step is as shown in figure 1, in Fig. 1,1 is measuring pump, and 2 be syringe, and 3 be that composition is molten Liquid, 4 be high voltage power supply, and 5 be capillary, and 6 be taylor cone, and 7 be jet, and 8 be rotation or the receiving screen being fixedly mounted.
(1c) calcining, crush；
The general procedure that the equipment and process that this process uses are well known to those skilled in the art.The preferred work of the present embodiment Sequence is for example as follows：Nanometer wire titanic oxide material is placed in tunnel cave, under an inert atmosphere of nitrogen, 1~10 DEG C of heating rate/ Min, 1-10 hours are incubated at 500-900 DEG C, then furnace cooling；Disintegrating process then uses mechanical crusher or air-flowing type powder Broken machine is crushed, and crosses the mesh sieve of the mesh of mesh number >=200, and nanometer wire titanium dioxide fine particles are made.
(2) in parts by weight, by 100 parts of nanometer wire titanium dioxide fine particles, 23 parts of lithium hydroxides, 20 parts of carbonic acid Lithium, using planetary ball mill ball milling mixing 5~24 hours, such as 10h, 15h, 20h, need to only meet it is well mixed, In tunnel cave, with nitrogen inert atmosphere, 1~10 DEG C/min of heating rate, 10~48 hours being incubated at 600-900 DEG C；Powder It is broken, the mesh sieve of the mesh of mesh number >=200 is crossed, obtains the nanometer wire lithium titanate graphene composite material of the present embodiment.
In this step, nanometer wire titanium dioxide fine particles serve as titanium source, and 23 parts of lithium hydroxides, 20 parts of lithium carbonates serve as compound Lithium source.
After tested, the electrical conductivity of the composite Nano lithium titanate material of the present embodiment is 10-2S/cm, by the compound of the present embodiment After nano barium titanate lithium material is prepared into half-cell, test shows that its specific discharge capacity is 162mAh/g.
Embodiment 2
The present embodiment difference from Example 1 is：In this composite Nano lithium titanate material, the number of plies of graphene is 5 ~10 layers.
When preparing the composite Nano lithium titanate material of the present embodiment, in step (1a), titanium source is 20 parts, viscosity modifier For 6 parts, graphene is 0.6 part, titanium source and the selection reference embodiment 1 of the specific material of viscosity modifier；In step (2), lithium source The mixture of lithium hydroxide and 3.7 parts of lithium carbonate for 41.6 parts；Other operating procedures are with reference to embodiment 1.
After tested, the electrical conductivity of the composite Nano lithium titanate material of the present embodiment is 10-2S/cm, by the compound of the present embodiment After nano barium titanate lithium material is prepared into half-cell, test shows that its specific discharge capacity is 162mAh/g.
Embodiment 3
The present embodiment difference from Example 1 is：In this composite Nano lithium titanate material, the number of plies of graphene is 5 ~10 layers.
When preparing the composite Nano lithium titanate material of the present embodiment, in step (1a), titanium source is 30 parts, viscosity modifier For 10 parts, graphene is 1 part, titanium source and the selection reference embodiment 1 of the specific material of viscosity modifier；In step (2), lithium source is The mixture of 4.2 parts of lithium hydroxide and 36.6 parts of lithium carbonate；Other operating procedures are with reference to embodiment 1.
After tested, the electrical conductivity of the composite Nano lithium titanate material of the present embodiment is 10-2S/cm, by the compound of the present embodiment After nano barium titanate lithium material is prepared into half-cell, test shows that its specific discharge capacity is 163mAh/g.
Above content is only presently preferred embodiments of the present invention, for one of ordinary skill in the art, according to the present invention's Thought, there will be changes, this specification content should not be construed as to the present invention in specific embodiments and applications Limitation.

Claims (21)

  1. A kind of 1. preparation method of composite Nano lithium titanate material, it is characterised in that：It the described method comprises the following steps：
    (1) nanometer wire titanium dioxide fine particles are prepared, are comprised the following steps：
    Titanium source is dissolved in solvent by (1a) by proportioning, and viscosity modifier and graphene are sequentially added by proportioning, is stirred, is made for quiet The composition solution of Electrospun；
    (1b) uses electrostatic spinning apparatus, and the composition solution is made into nanometer wire titanic oxide material；
    The nanometer wire titanic oxide material is placed in calciner by (1c), in inert gas, at 500~900 DEG C Calcining 1~10 hour, cool down, smash, cross mesh sieve, nanometer wire titanium dioxide fine particles are made；
    (2) in parts by weight, 100 parts of nanometer wire titanium dioxide fine particles, 37~115 parts of lithium sources are mixed, grinding, forged Burn, crush, cross mesh sieve, composite Nano lithium titanate material is made；
    The composite Nano lithium titanate material includes nanoscale lithium titanate particulate and graphene, it is characterised in that：The nanoscale Lithium titanate particulate is nanometer thread-like flecks, and the chemical composition of the nanoscale lithium titanate particulate is Li4Ti5O12, the graphene It is scattered between nanoscale lithium titanate particulate.
  2. 2. preparation method according to claim 1, it is characterised in that：The number of plies≤10 of the graphene.
  3. 3. preparation method according to claim 1, it is characterised in that：The nanoscale lithium titanate particulate it is a diameter of 100nm~2000nm, specific surface area are 10~100m2/g。
  4. 4. preparation method according to claim 1, it is characterised in that：In step (1), the nanometer wire titanium dioxide is micro- Grain is prepared using the method for electrostatic spinning.
  5. 5. preparation method according to claim 4, it is characterised in that in step (1), prepared using the method for electrostatic spinning During nanometer wire titanium dioxide fine particles, the composition solution used includes the component of following parts by weight：
  6. 6. preparation method according to claim 5, it is characterised in that：The solvent is pure water, methanol, ethanol, N, N- bis- It is more than one or both of NMF, tetrahydrofuran, 1-METHYLPYRROLIDONE.
  7. 7. preparation method according to claim 5, it is characterised in that the titanium source is butyl titanate or alkyl titanate.
  8. 8. preparation method according to claim 5, it is characterised in that the viscosity modifier is polyvinyl alcohol, poly- second two Alcohol, polypropylene are fine, more than one or both of polyacrylamide, PVP.
  9. 9. preparation method according to claim 1, it is characterised in that the operating procedure of step (1b) is：By the combination Thing solution is added into the syringe of electrostatic spinning apparatus, and the syringe is disposed vertically and lower section is placed with aluminium foil, 10~ Under 40kV high direct voltage, nanometer wire titanic oxide material is made on aluminium foil.
  10. 10. preparation method according to claim 9, it is characterised in that in step (1b), outside the syringe needle of the syringe Footpath is 1.2mm, internal diameter 0.79mm.
  11. 11. preparation method according to claim 9, it is characterised in that in step (1b), the pin of the aluminium foil and syringe Distance between head is 10~30cm.
  12. 12. preparation method according to claim 1, it is characterised in that in step (1c), the calciner is tunnel Kiln.
  13. 13. preparation method according to claim 1, it is characterised in that in step (1c), the inert gas is nitrogen.
  14. 14. preparation method according to claim 1, it is characterised in that in step (1c), in the calciner, with 1 ~10 DEG C/min heating rate is warming up to 500~900 DEG C.
  15. 15. preparation method according to claim 1, it is characterised in that in step (1c), using mechanical crusher or gas Streaming pulverizer is crushed.
  16. 16. preparation method according to claim 1, it is characterised in that in step (1c), mesh number >=200 of the mesh sieve Mesh.
  17. 17. preparation method according to claim 1, it is characterised in that：In step (2), the lithium source is lithium carbonate, hydrogen-oxygen Change more than one or both of lithium, lithium dihydrogen phosphate or lithium acetate.
  18. 18. preparation method according to claim 1, it is characterised in that in step (2), in parts by weight, the lithium Source is the mixture of 3.7~36.6 parts of lithium carbonates and 41.6~4.2 parts of lithium hydroxides.
  19. 19. preparation method according to claim 1, it is characterised in that in step (2), by the nanometer wire titanium dioxide When titanium particulate, lithium source mixing, planetary ball mill ball milling mixing 5~24 hours is used.
  20. 20. preparation method according to claim 1, it is characterised in that in step (2), the calcining refers in tunnel cave In, in a nitrogen atmosphere, 600~900 DEG C are warming up to 1~10 DEG C/min heating rate, is incubated 10~48 hours.
  21. 21. preparation method according to claim 1, it is characterised in that in step (2), mesh number >=200 of the mesh sieve Mesh.
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