CN109786705A - A kind of lithium titanate anode material and its preparation method and application with multistage carbon coating network structure - Google Patents

A kind of lithium titanate anode material and its preparation method and application with multistage carbon coating network structure Download PDF

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CN109786705A
CN109786705A CN201910042451.4A CN201910042451A CN109786705A CN 109786705 A CN109786705 A CN 109786705A CN 201910042451 A CN201910042451 A CN 201910042451A CN 109786705 A CN109786705 A CN 109786705A
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carbon
lithium titanate
lithium
network structure
preparation
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张军峰
侯士峰
徐继正
台利芝
刘梦瑶
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Yucheng Baer New Material Co Ltd
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Yucheng Baer New Material Co Ltd
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention relates to a kind of lithium titanate anode materials and its preparation method and application with multistage carbon coating network structure, by TiO2The internal carbon doping in situ in the doping realization lithium titanate raw material presoma of novel conductive carbon material is carried out in preparation process, then is synthesized by external secondary packet carbon with the external lithium titanate anode material with conventional carbon-coated multistage carbon coating network structure of internal new carbon doping.The present invention has the lithium titanate anode material of multistage carbon coating network structure, it can be achieved that fast charging and discharging under big multiplying power and giving full play to the capacity of active material inside material particles, is suitable for electrode material of secondary lithium ion battery.

Description

A kind of lithium titanate anode material and its preparation side with multistage carbon coating network structure Method and application
Technical field
The present invention relates to a kind of lithium titanate anode materials and preparation method thereof with multistage carbon coating network structure, can answer For lithium ion secondary battery, belong to lithium titanate anode material synthesis technical field.
Background technique
Li4Ti5O12As lithium ion battery negative material, in charge and discharge, the insertion and abjection of lithium ion are to material structure Have little effect, referred to as zero strain material, and can in the range of subzero 50 DEG C to 75 DEG C normal use, therefore be to answer One of preferred material for power battery.But since lithium titanate material is a kind of semiconductor material, lithium ion and electronics are led Electrically it is poor, cause made of lithium ion battery high power charging-discharging when polarization phenomena than more serious, lithium titanate inside particles hold Amount is difficult to play, and high rate performance is not good enough.
In order to improve lithium titanate electron conduction and lithium ion transport, generally use nanosizing, metal ion mixing and The methods of carbon coating.The most commonly used is carbon coating, the electric conductivity and lithium ion transport of material can be improved, but can also encounter Because of carbon coating, unevenly or caused by carbon material poorly conductive material particle size homogeneity difference and conductive network structure are incomplete Problem, to influence the high rate charge-discharge performance of material entirety;
Doping or cladding novel conductive agent carbon material, utilize the three-dimensional conductive network of the formation such as graphene, carbon nanotube, Ke Yiti Electrical contact and electron conduction between high particle and between particle and collector, while new carbon specific surface with higher Product.Electrolyte can be adsorbed and store, the transmission for lithium ion and electronics provides channel, reaches and improves multiplying power property and cyclicity Energy.As Chinese patent application (publication number CN101630732A) discloses a kind of carbon nanotube loaded nanoscale metatitanic acid lithium composite Carbon nano tube dispersion liquid and titanium source, lithium source and doped chemical are mixed together uniformly by preparation method for material, this method, heat drying system Lithium titanate predecessor is obtained, sintering obtains the material of carbon nanotube composite lithium titanate under inert gas;Chinese patent (publication number CN102376937A a kind of preparation method of nano lithium titanate/graphene is disclosed in), this method is using the micron prepared Grade lithium titanate and graphene mixing and ball milling, improve the multiplying power and cycle performance of material.Above-mentioned patent is only in lithium titanate material Coated with carbon nanotube or graphene etc., and still lack effective conductive network structure inside material particles, in big multiplying power Under charge and discharge, lithium ion and electronics are difficult to quickly be transferred to inside particles, cannot give full play to material capacity.
Summary of the invention
Aiming at the above shortcomings existing in the prior art, an object of the present invention is to provide a kind of with multistage carbon coating The lithium titanate anode material of network structure is, it can be achieved that fast charging and discharging under big multiplying power and give full play to activity inside material particles The capacity of substance.
Meanwhile another object of the present invention also resides in and provides a kind of preparation method of above-mentioned lithium titanate anode material, passes through In TiO2The doping that novel conductive carbon material is carried out in preparation process realizes that the internal carbon in situ in lithium titanate raw material presoma is mixed It is miscellaneous then external with conventional carbon-coated multistage conductive carbon with the doping of internal new carbon by the synthesis of external secondary packet carbon The lithium titanate anode material of network.
Again, the use the present invention also provides above-mentioned lithium titanate anode material as electrode material of secondary lithium ion battery On the way.
In order to achieve the above-mentioned object of the invention, technical solution of the present invention is as follows:
A kind of preparation method of lithium titanate anode material with multistage carbon coating network structure, step packet are provided in the present invention It includes:
(1) butyl titanate, dehydrated alcohol, novel conductive carbon material and auxiliary additive are uniformly mixed, obtain ethyl alcohol dispersion Liquid;
(2) it is vigorously stirred down, preferably speed of agitator 500-1000 rpm, the preferred deionization of water is added into step (1) dispersion liquid Water obtains suspension emulsion;
(3) suspension emulsion of step (2) is heated, carries out hydro-thermal reaction;
(4) step (3) reaction system vacuum filter such as uses vacuum pump using circulatory water, and the sediment being obtained by filtration is washed with dehydrated alcohol It washs and (preferably washs three times, use the dehydrated alcohol isometric with step (3) reaction solution every time), then dry, preferably 60 DEG C true Dry 12 h of sky form the TiO 2 precursor that nanoscale adulterates novel conductive carbon material in situ;
(5) lithium salts and the TiO 2 precursor of step (4) are mixed, ball milling mixes (such as wet ball grinding) after solvent is added, so After dry, briquetting, carry out first time calcination processing, obtain first time calcined product;
(6) first time calcined product is crushed into such as preferred 200 mesh mesh screen of mistake, is then mixed with organic carbon source, solvent, ball milling mixes (such as wet ball grinding), is then dried, briquetting, then carries out second of calcination processing, obtains second of calcined product;
(7) second of calcined product is pulverized and sieved, obtains the lithium titanate anode material with multistage carbon coating network structure.
It describes according to the present invention, in some embodiments, in step (1), the butyl titanate, novel conductive Carbon material, dehydrated alcohol, auxiliary additive volume ratio be (10-20): (10-50): (100-500): (5-50).
Preferably, it is a kind of or several to be selected from graphene oxide, carbon nanotube and Ketjen black etc. for the novel conductive carbon material The mixing of kind, in some embodiment of the invention, the graphene oxide and carbon nanotube preferably use its alcohol dispersion liquid, point Scattered concentration is preferably 1-5 mg/mL;Ketjen black is preferably Ketjen black powder, the preferred 20-50 nm of granularity.
It is further preferred that the novel conductive carbon material is graphene oxide and/or carbon nanotube, most preferably aoxidize The mixing of graphene and carbon nanotube;Wherein, the preferred lamellar spacing of the graphene oxide is 1-20 nm, and lamella diameter is 2- 10 μm, wherein the preferred caliber of carbon nanotube is 5-30 nm, and pipe range is 10-50 μm.The novel conductive that the present invention uses Carbon material has excellent electric conductivity and lithium ion transport, is widely used as the conductive additive of various new composite material, Improve the chemical property of material.Wherein graphene is the two-dimentional carbon material with layer structure, has excellent electric conductivity, With huge specific surface area, the substrate of particle growth can be used as, realize and the flexibility of particle is coated;Carbon nanotube is a kind of tool The one-dimensional carbon material of linear structure has unique middle control structure, while also with excellent electric conductivity and biggish comparing table Area, mutually winding can form the three-dimensional net structure of nanoscale;Ketjen black is a kind of carbon materials with ultra-high conductivity Material has unique branched form, can form more conductive path.
In the present invention, the novel conductive carbon material is more preferably the mixing of graphene oxide and carbon nanotube, Graphene oxide and carbon nanotube mass are 1:(0.2-5 than preferred scope).Graphene oxide is lamellar structure, while being had soft Toughness can adhere to nanoparticle, realization electronics and Li ion in the quick transmission of two-dimensional surface in front, but exist and be difficult to construct The deficiency of the three-dimensional net structure of nanoscale;Carbon nanotube is one-dimensional linear structure, and fully dispersed carbon nanotube can be realized Cross-linked network on three-dimensional space realizes three-dimensional conductive network structure, but the caliber of carbon nanotube is smaller, cannot be as graphene one Sample, which is realized in face, to be transmitted, and therefore, the multimeshed network of electric conductivity and ion transporting can be achieved in the compounding of the two, more efficiently in fact Existing high power charging-discharging.
Preferably, the auxiliary additive is one or more of acetic acid, nitric acid and polyethylene glycol;Further preferably The polyethylene glycol for being 400 or more for glacial acetic acid, concentrated nitric acid (preferably such as the concentrated nitric acid of 68wt% or so concentration) and molecular weight One or more of mixing.
Preferably, step (1) of the present invention is mixed in closed container in some specific examples, and when mixing preferably adopts With magnetic agitation, the further preferred 200-800 rpm of revolving speed makes system mixing be uniformly dispersed.
It describes according to the present invention, in some embodiments, in step (2), the water (such as deionized water) is added Amount and the volume ratio of butyl titanate are (10-20): (100-500);The additional amount of deionized water is preferably butyl titanate body Long-pending 5-50 times is most preferably identical as dehydrated alcohol volume in step (1).
It describes according to the present invention, in some embodiments, in step (3), the hydro-thermal reaction, temperature 60- 180 DEG C, preferably 100-150 DEG C, time are 2-36 h, preferably 6-16 h.
It describes according to the present invention, in some embodiments, the nanoscale that step (4) is formed adulterates novel lead in situ The TiO 2 precursor of electrical carbon material, wherein carbon doping mass ratio is 1-5 wt%.The novel conductive carbon material of doping is embedded in Between titanium dioxide precursor particle, form three-dimensional netted conductive carbon structure, be conducive to lithium ion and electronics in inside particles and Interparticle transmission simultaneously because the presence of carbon material, prevents the hard aggregation between nanoparticle, therefore can be improved material and lead Electrically, reduce internal resistance, for it is subsequent prepare electrode material when, can further promote material internal particle capacity play, promoted electricity Tankage and high rate performance.
It describes according to the present invention, in some embodiments, in step (5), the lithium salts and titanium dioxide forerunner The molar ratio of body is (4-4.4): 5, with the mole of Ti element in the mole of Li element in lithium salts and TiO 2 precursor Meter.
Preferably, the lithium salts is lithium hydroxide or lithium carbonate.
Preferably, the solvent is the mixing of one or more of deionized water, dehydrated alcohol, acetone, the solvent Dosage is preferably used for 2-5 times of ball milling solid powder quality.
Preferably, the first time calcination temperature is 200-450 DEG C, and soaking time is 1-12 h, heating rate 2-11 ℃/min.It is preferably calcined in tube furnace in some examples of the present invention, further preferably in inert atmosphere such as nitrogen when calcining It is carried out under gas or argon gas.
Preferably, before undefined structure lithium titanate of the first time calcined product for internal doping novel conductive carbon material Body, partial size 50-500 nm.
Preferably, Ball-milling Time described in step (5) and step (6) is 1-12 h, rotational speed of ball-mill in some embodiments For 200-500 rpm.It is preferred that wet ball grinding, specifically can be used following operating procedure, proportionally weighs lithium salts and titanium dioxide Presoma, mixing postposition enter in ball grinder, add solvent and zirconium ball, carry out wet ball grinding.
Preferably, briquetting operations described in step (5) and step (6) in some embodiments, the pressed powder used Machine pressure is 10-30 Mpa(gauge pressure), the time is 1-10 min, preferably pressurization 3-10 min;The preferably thin bulk of briquetting shape is thin Block thickness 0.5-3 cm.
Describe according to the present invention, in some embodiments, in step (6), the first time calcined product with have The mass ratio of machine carbon source is (10-50): 1.
Preferably, the organic carbon source is at least one of glucose, sucrose or starch etc.;
Preferably, the solvent is one or more of deionized water, dehydrated alcohol, acetone, and dosage is preferably used for ball 2-5 times for grinding solid powder quality.
Preferably, second of calcination temperature is 500-850 DEG C, and soaking time is 1-12 h, heating rate 2-11 ℃/min.Second calcining is preferably calcined in tube furnace, and when calcining further preferably carries out under an inert atmosphere.Institute The lithium titanate material that second of calcined product structure is internal doping novel conductive carbon material outer layer packet carbon is stated, because inside is adulterated Carbon material and the nanosizing for realizing titanium source, so as to be sufficiently mixed under small scale with lithium source, required calcination temperature is lower than The calcination temperature of pure phase lithium titanate solid phase method, while the oxygen-containing official in high-temperature burning process in the new carbons such as graphene oxide The redox graphene etc. for being reduced to that there is high electrical conductivity can be rolled into a ball, to form conductive network structure in inside.
It describes according to the present invention, in some embodiments, the mistake sieve mesh number in step (7) is 150-400 mesh.
A kind of lithium titanate anode material with multistage carbon coating network structure, the lithium titanate anode are also provided in the present invention Material can be prepared by any of the above-described preparation method.
The lithium titanate anode material with multistage carbon coating network structure of the present invention, structure include internal go back The three-dimensional conductive network structure that the novel conductives carbon material such as former graphene oxide and carbon nanotube is constructed, may be implemented lithium ion and Electronics gives full play to material internal capacity in the quick transmission of material internal.Rather than the method for the present invention preparation, without inside The lithium titanate material for the complete crystal structure that carbon is mixed with, because its material intrinsic conductivity is poor, complete crystal structure lacks Lithium ion transport channel causes lithium ion and electronics to be difficult to that material appearance cannot be played completely in material internal freely quickly transmission Amount.External carbon coating is carried out in second of calcination process simultaneously, organic carbon source is coated on lithium titanate particle surface, by lithium titanate Crystal grain be limited in clad, it is suppressed that crystal grain excessively grow up, while obtained after high-temperature calcination surface layer cladding it is amorphous Carbon has porous structure and good electric conductivity, is conducive to electronics and ion is transferred into the inside of lithium titanate material, thus shape At with inside and outside multistage conductive carbon network structure.For the high power charging-discharging and internal capacity of lithium titanate material Performance has to improve significantly.
The lithium titanate anode material with multistage carbon coating network structure of the present invention, partial size are 0.1-2 μm, just Grade particle size is 10-100 nm;Wherein carbon accounting 2-7 wt%, to have the lithium titanate of multistage carbon coating network structure Negative electrode material gross mass meter.Heretofore described primary particle refers to the precipitate particles that step (4) most initially forms;It is described Lithium titanate anode material with multistage carbon coating network structure is final product, is grown up by the reunion or fusion of primary particle It is formed.
Further provided in the present invention the above-mentioned lithium titanate anode material with multistage carbon coating network structure lithium from Application in sub- secondary cell.
Lithium titanate anode material of the invention can be used for preparing lithium ion cell electrode, and preparation method is art technology Well known to personnel, such as it is prepared into lithium titanate anode material, binder (such as PVDF) and conductive agent (such as conductive black) for raw material Electrode.Then battery further is assembled into (such as with electrolyte, diaphragm (such as microporous polypropylene membrane) using lithium piece as to electrode Button cell).
By the above-mentioned battery standing comprising lithium titanate anode material of the present invention for a period of time as carried out electric performance test after 6h, Its first discharge specific capacity range is 160-168 mAh/g such as 164.5 mAh/g, and tap density is that range is 1.05-1.35 g/ cm3Such as 1.21 g/cm3, test condition is as follows: test constant current charge-discharge current density is 10 C, and test charging/discharging voltage range is 1.0 V-2.5 V。
Technical solution of the present invention compared with the existing technology, the beneficial effect is that:
The present invention is adulterated by carrying out a carbon of novel conductive carbon material in TiO 2 precursor preparation process first, suppression Growing up for titanium material particle has been made, while having realized novel conductive carbon material and lithium titanate precursor raw material on nanoscale Uniformly mixing, realizes the doping of inside particles, to realize inside crystalline product in precursor particle growth process The channel for being conducive to lithium ion and electron-transport is avoided because of the lower intrinsic conductivity of lithium titanate raw material and poor lithium ion Transmittability realizes that the capacity of lithium titanate inside particles active matter gives full play to.Again by secondary carbon coating, make lithium titanate material Partial size maintains sub-micron, while three-dimensional conductive network structure, lithium ion are all formd between solid particle and inside particle Transmission path shortens, and no matter in micro-scale or macro-scale material all has excellent electric conductivity, is a kind of to have multistage The lithium titanate material of carbon coating network.This method process stabilizing, carbon coating are uniform, have multistage carbon coating network structure, conductive Property is good, and lot stability is good, excellent electrochemical performance.
Detailed description of the invention
Fig. 1 is the lithium titanate XRD diagram of packet carbon outside internal doping redox graphene in embodiment 1;
Fig. 2 is TiO 2 precursor primary nanoparticle (i.e. primary particle) SEM that graphene oxide is adulterated in embodiment 1 Figure;
Fig. 3 is the lithium titanate SEM figure of packet carbon outside internal doping redox graphene in embodiment 1;
Fig. 4 is the lithium titanate SEM figure of packet carbon outside internal doped carbon nanometer pipe in embodiment 2;
Fig. 5 is the lithium titanate SEM figure of packet carbon outside internal doping Ketjen black in embodiment 3;
Fig. 6 is that the lithium titanate SEM of internal doping graphene oxide and carbon nanotube mixture outside packet carbon schemes in embodiment 4;
Fig. 7 is the lithium titanate SEM figure of packet carbon outside internal non-impurity-doped in comparative example 1;
Fig. 8 is that graphene oxide undopes the metatitanic acid adulterated inside titanium dioxide but together with external packet carbon in comparative example 2 Lithium SEM figure;
Fig. 9 is the lithium titanate SEM figure that internal-external is all made of organic carbon source packet carbon in comparative example 3.
Specific embodiment
Technical solution of the present invention is described in detail with comparative example combined with specific embodiments below.
Embodiment and comparative example primary raw material source:
From Shandong Li Te Nanosolutions GmbH, lamellar spacing is 1-20 nm for graphene oxide buying, and lamella diameter is 2-10 μm;
From Shandong great Zhan nano material Co., Ltd, caliber is 5-30 nm for carbon nanotube buying, and pipe range is 10-50 μm;
The certainly Japanese lion king of Ketjen black buying, granularity 20-50 nm;
Other raw materials are common commercially available industrial raw material unless otherwise noted.
Two, product test: lithium electric test equipment is new prestige battery test system, is surveyed using button cell CR2032 Examination.
Embodiment 1
17 ml butyl titanates are weighed, 30 ml concentration are 5 mg/ml graphene oxide dispersions, are added to the anhydrous second of 250 ml In alcohol, 10 ml glacial acetic acid are added, it is uniform to be placed in magnetic agitation in closed container, obtains alcohol dispersion liquid.
250 ml deionized waters are slowly added dropwise, water is added to be vigorously stirred in the process, revolving speed 500-1000 rpm forms grey black Suspension emulsion.
Lotion is transferred in the reaction kettle that volume is 1 L, in an oven 150 DEG C of 6 h of hydro-thermal reaction.
Using vacuum pump using circulatory water vacuum filter, the sediment being obtained by filtration is collected, dehydrated alcohol washs 3 times, adds every time The isometric dehydrated alcohol of upper step reaction solution, 60 DEG C of 12 h of vacuum drying form nanoscale doping novel conductive carbon material in situ Titanium dioxide predecessor, wherein carbon doping ratio be 4wt%.
The presoma smashes it through 200 mesh mesh screens, and 1.2 g, mono- hydronium(ion) lithia, with rubbing for Li element and Ti element The molar ratio of that meter, a hydronium(ion) lithia and TiO 2 precursor is 4.3:5.Be placed in ball milling and mix, add 25 ml without Water-ethanol, 4 h of ball milling, 300 rpm of rotational speed of ball-mill, tabletting after drying, the powder compressing machine pressure used is 20 Mpa(table Pressure), the time is 5 min, and thin bulk, thin piece of 0.8 cm of thickness is placed in tube furnace, carries out first time calcination processing, every according to 5 DEG C The heating rate of minute is warming up to 200 DEG C under Ar gas atmosphere, keeps the temperature 3 h.
200 mesh mesh screens are smashed it through, are mixed with 0.25 g sucrose, the mass ratio of first time calcined product and sucrose is 100: 3.2, add 25 ml dehydrated alcohol ball milling, 6 h, 300 rpm of rotational speed of ball-mill, tabletting after drying is placed in tube furnace, is forged for the second time Burning processing is warming up to 800 DEG C according to 2 DEG C of rates per minute under Ar gas atmosphere, keeps the temperature 3 h.
Ground 200 mesh mesh screen obtains carbon-coated lithium titanate anode material outside internal doping redox graphene, Partial size is 200-500 nm, and Primary particle size is 10-50 nm, wherein 4.2 wt% of carbon accounting.
The lithium titanate of the present embodiment synthesis has preferable crystal structure as shown in Figure 1.Fig. 2 is before Nano titanium dioxide The SEM that body particle forms the primary nanoparticle (hydro-thermal reaction 30 minutes) at initial stage is driven, because of the graphene oxide of bigger serface Presence, TiO 2 particles can be nucleation point with surface of graphene oxide and internal pore structure, thus in final product Doped with the TiO 2 particles of graphene oxide inside middle formation, realize with lithium source through ball mill crushing abundant mixed under small scale It closes, lithium ion in conjunction with titanium source, is formed lithium titanate precursor particle, forged using packet carbon by the pore structure of graphene oxide It burns, forms the particle of about 300 relatively uniform nm of its partial size after pulverizing and sieving, particle surface and inside realize graphene Doping and external carbon coating, as shown in Figure 3.
Gained lithium titanate anode material prepares electrode as follows: lithium titanate material, binder, conductive agent are in mass ratio It is prepared into electrode for the ratio of 90:5:5, using lithium piece as to electrode, electrolyte is done with 1M-LiPF6 EC/EMC solution, poly- third Alkene microporous barrier is diaphragm, is assembled into CR2032 button cell.And stand 6 hours.Battery after standing is placed on new prestige battery testing Electric performance test is carried out on instrument, constant current charge-discharge experiment is carried out with the current density of 10 C, test charging/discharging voltage range is 1.0 V - 2.5 V.The lithium titanate material that the present embodiment obtains, first discharge specific capacity are 164.5 mAh/g, tap density For 1.21 g/cm3
Embodiment 2
17 ml butyl titanates are weighed, 50 ml carbon nano tube dispersion liquids are added in 250 ml dehydrated alcohols, add 10 ml Glacial acetic acid, it is uniform to be placed in magnetic agitation in closed container, obtains dispersion liquid.
250 ml deionized waters are slowly added dropwise, water is added to be vigorously stirred in the process, revolving speed 500-1000 rpm forms grey black Suspension emulsion.
Lotion is transferred in the reaction kettle that volume is 1L, in an oven 180 DEG C of 2 h of hydro-thermal reaction.
Using vacuum pump using circulatory water vacuum filter, the sediment being obtained by filtration is collected, dehydrated alcohol washs 3 times, adds every time The isometric dehydrated alcohol of upper step reaction solution, 60 DEG C of 12 h of vacuum drying form nanoscale doping novel conductive carbon material in situ Titanium dioxide predecessor, wherein carbon doping ratio be 3.4wt%.
The presoma smashes it through 200 mesh mesh screens, and 1.2 g, mono- hydronium(ion) lithia, with rubbing for Li element and Ti element The molar ratio of that meter, a hydronium(ion) lithia and TiO 2 precursor is 4.3:5.It is placed in ball milling and mixes, add 20 ml third 4 h of ketone ball milling, 300 rpm of rotational speed of ball-mill, tabletting after drying, the powder compressing machine pressure used is 20Mpa(gauge pressure), the time For 5min, thin bulk, thin piece of 1.1 cm of thickness is placed in tube furnace, first time calcination processing is carried out, according to 5 DEG C of liters per minute Warm rate is warming up to 300 DEG C in a nitrogen atmosphere, keeps the temperature 2 h.
200 mesh mesh screens are smashed it through, are mixed with 0.2 g starch, the mass ratio of first time calcined product and starch is 100: 2.5, add 20 ml acetone ball milling, 6 h, 300 rpm of rotational speed of ball-mill, tabletting after drying is placed in tube furnace, carries out at second of calcining Reason is warming up to 750 DEG C according to 3 DEG C of rates per minute in a nitrogen atmosphere, keeps the temperature 6 h.
Ground 200 mesh mesh screen obtains carbon-coated lithium titanate anode material, such as Fig. 4 outside internal doped carbon nanometer pipe Shown, product complete crystal form, partial size 200-500 nm, nanotube is distributed in grain surface, and is partially submerged into intra-die, shape At conductive network structure, Primary particle size 20-60nm, wherein carbon accounting 4.4wt%.
Gained lithium titanate anode material prepares electrode as follows: lithium titanate material, binder, conductive agent are in mass ratio It is prepared into electrode for the ratio of 90:5:5, using lithium piece as to electrode, electrolyte is done with 1M-LiPF6 EC/EMC solution, poly- third Alkene microporous barrier is diaphragm, is assembled into CR2032 button cell.And stand 6 hours.Battery after standing is placed on new prestige battery testing Electric performance test is carried out on instrument, constant current charge-discharge experiment is carried out with the current density of 10 C, test charging/discharging voltage range is 1.0 V - 2.5 V.The lithium titanate material that the present embodiment obtains, first discharge specific capacity are 163.7 mAh/g, tap density For 1.28 g/cm3
Embodiment 3
20 ml butyl titanates are weighed, 0.17 g Ketjen black is added in 300 ml dehydrated alcohols, and 10 ml nitric acid of addition are (dense Spend 68 wt%), it is uniform to be placed in magnetic agitation in closed container, obtains dispersion liquid.
300 ml deionized waters are slowly added dropwise, water is added to be vigorously stirred in the process, revolving speed 500-1000 rpm forms grey black Suspension emulsion.
Lotion is transferred in the reaction kettle that volume is 1L, in an oven 150 DEG C of 6 h of hydro-thermal reaction.
Using vacuum pump using circulatory water vacuum filter, the sediment being obtained by filtration is collected, dehydrated alcohol washs 3 times, adds every time The isometric dehydrated alcohol of upper step reaction solution, 60 DEG C of 12 h of vacuum drying form nanoscale doping novel conductive carbon material in situ Titanium dioxide predecessor, wherein carbon doping ratio be 3.0wt%.
The presoma crushed 200 mesh mesh screens, and 1.3 g, mono- hydronium(ion) lithia, with mole of Li element and Ti element The molar ratio of meter, a hydronium(ion) lithia and TiO 2 precursor is 4.4:5.Be placed in ball milling and mix, add 30 ml go from Sub- 6 h of water for ball milling, 500 rpm of rotational speed of ball-mill, tabletting after drying, the powder compressing machine pressure used is 15Mpa(gauge pressure), when Between be 8min, thin bulk, thin piece of thickness 0.9cm is placed in tube furnace, carries out first time calcination processing, per minute according to 3 DEG C Heating rate is warming up to 280 DEG C under Ar gas atmosphere, keeps the temperature 3 h.
200 mesh mesh screens are smashed it through, are mixed with 0.25 g sucrose, the mass ratio of first time calcined product and sucrose is 100: 3.2, add 30 ml deionized water ball milling, 4 h, 500 rpm of rotational speed of ball-mill, tabletting after drying is placed in tube furnace, is forged for the second time Burning processing is warming up to 700 DEG C according to 5 DEG C of rates per minute under Ar gas atmosphere, keeps the temperature 9 h.
Ground 200 mesh mesh screen obtains carbon-coated lithium titanate anode material outside internal doping Ketjen black, such as Fig. 5 institute Show.Crystal grain 500-800 nm, particle size uniformity is good, and Primary particle size is 20-50 nm, wherein carbon accounting 5.1wt%.
Gained lithium titanate anode material prepares electrode as follows: lithium titanate material, binder, conductive agent are in mass ratio It is prepared into electrode for the ratio of 90:5:5, using lithium piece as to electrode, electrolyte is done with 1M-LiPF6 EC/EMC solution, poly- third Alkene microporous barrier is diaphragm, is assembled into CR2032 button cell.And stand 6 hours.Battery after standing is placed on new prestige battery testing Electric performance test is carried out on instrument, constant current charge-discharge experiment is carried out with the current density of 10 C, test charging/discharging voltage range is 1.0 V - 2.5 V.The lithium titanate material that the present embodiment obtains, first discharge specific capacity are 161.4 mAh/g, tap density For 1.33 g/cm3
Embodiment 4
20 ml butyl titanates are weighed, 2 ml concentration are 5 mg/ml graphene oxide dispersions, 30 ml concentration, 1 mg/ml carbon Nanotube dispersion liquid is added in 300 ml dehydrated alcohols, adds 10 ml glacial acetic acid, (molecular weight is 0.1 g polyethylene glycol 800) it, is placed in closed container that magnetic agitation is uniform, obtains dispersion liquid.
280 ml deionized waters are slowly added dropwise, water is added to be vigorously stirred in the process, revolving speed 500-1000 rpm forms grey black Suspension emulsion.
Lotion is transferred in the reaction kettle that volume is 1L, in an oven 160 DEG C of 5 h of hydro-thermal reaction.
Using vacuum pump using circulatory water vacuum filter, the sediment being obtained by filtration is collected, dehydrated alcohol washs 3 times, adds every time The isometric dehydrated alcohol of upper step reaction solution, 60 DEG C of 12 h of vacuum drying form nanoscale doping novel conductive carbon material in situ Titanium dioxide predecessor, wherein carbon doping ratio be 2.8wt%.
The presoma smashes it through 200 mesh mesh screens, and 1.15 g, mono- hydronium(ion) lithia, with rubbing for Li element and Ti element The molar ratio of that meter, a hydronium(ion) lithia and TiO 2 precursor is 4.2:5.Be placed in ball milling and mix, add 30 ml without Water-ethanol, 4 h of ball milling, 500 rpm of rotational speed of ball-mill, tabletting after drying, the powder compressing machine pressure used is 20Mpa(table Pressure), time 8min, thin bulk, thin piece of 0.8 cm of thickness is placed in tube furnace, carries out first time calcination processing, every according to 5 DEG C The heating rate of minute is warming up to 300 DEG C in a nitrogen atmosphere, keeps the temperature 3 h.
200 mesh mesh screens are smashed it through, are mixed with 0.21 g glucose, the mass ratio of first time calcined product and glucose is 100:2.9 adds 4 h of 30ml dehydrated alcohol ball milling, 400 rpm of rotational speed of ball-mill, and tabletting after drying is placed in tube furnace, carries out second Secondary calcination processing is warming up to 720 DEG C according to 3 DEG C of rates per minute in a nitrogen atmosphere, keeps the temperature 8 h.
Ground 200 mesh mesh screen obtains internal doped graphene and the carbon-coated lithium titanate anode material of carbon nanotube outer Material, as shown in Figure 6.Partial size 300-600 nm, partial size is regular, good evenness, and carbon nanotube equal distribution is uniform, Primary particle size For 20-50nm, wherein carbon accounting 3.9wt%.
Gained lithium titanate anode material prepares electrode as follows: lithium titanate material, binder, conductive agent are in mass ratio It is prepared into electrode for the ratio of 90:5:5, using lithium piece as to electrode, electrolyte is done with 1M-LiPF6 EC/EMC solution, poly- third Alkene microporous barrier is diaphragm, is assembled into CR2032 button cell.And stand 6 hours.Battery after standing is placed on new prestige battery testing Electric performance test is carried out on instrument, constant current charge-discharge experiment is carried out with the current density of 10 C, test charging/discharging voltage range is 1.0 V - 2.5 V.The lithium titanate material that the present embodiment obtains, first discharge specific capacity are 164.8 mAh/g, tap density For 1.27 g/cm3
Comparative example 1
Doping without novel conductive carbon material: weighing 17 ml butyl titanates, is added in 250 ml dehydrated alcohols, adds Add 10 ml glacial acetic acid, it is uniform to be placed in magnetic agitation in closed container, and 250 ml deionized waters are slowly added dropwise, and adds acute during water Strong stirring forms white emulsion, lotion is transferred in the reaction kettle that volume is 1 L, in an oven 150 DEG C of 12 h of reaction.It receives The sediment formed in collection reaction kettle, ethanol washing 3 times, vacuum drying forms titanium dioxide predecessor.After the presoma crushes 200 mesh mesh screens are crossed, are placed in ball milling with 1.2 g, mono- hydronium(ion) lithia, 40 ml dehydrated alcohol ball milling, 4 h, rotational speed of ball-mill are added 300 rpm, pressed powder after drying, are placed in tube furnace, according to 5 DEG C of rates per minute, are warming up to 300 under Ar gas atmosphere DEG C, keep the temperature 2 h.200 mesh mesh screens are crossed after product grinding, is placed in ball milling and mixes with 0.5 g sucrose, add 40 ml dehydrated alcohol balls 3 h, 300 rpm of rotational speed of ball-mill are ground, dry tabletting is placed in tube furnace, according to 5 DEG C of rates per minute, rises under Ar gas atmosphere Temperature keeps the temperature 3 h to 850 DEG C.Ground 200 mesh mesh screen obtains the carbon-coated lithium titanate anode material of only outer layer, such as Fig. 7 institute Show, particle size is inhomogenous, and external carbon coating is uneven, and there are particle aggregations and crystal structure defects.
Gained lithium titanate anode material prepares electrode as follows: lithium titanate material, binder, conductive agent are in mass ratio It is prepared into electrode for the ratio of 90:5:5, using lithium piece as to electrode, electrolyte is done with 1M-LiPF6 EC/EMC solution, poly- third Alkene microporous barrier is diaphragm, is assembled into CR2032 button cell.And stand 6 hours.Battery after standing is placed on new prestige battery testing Electric performance test is carried out on instrument, constant current charge-discharge experiment is carried out with the current density of 10 C, test charging/discharging voltage range is 1.0 V - 2.5 V.The lithium titanate material that the present embodiment obtains, first discharge specific capacity are 152.3 mAh/g, tap density For 1.39 g/cm3
Comparative example 2
Mono- hydronium(ion) lithia of 2.2 g titanium dioxide, 0.2 g graphene oxide and 1.2 g is weighed, is placed in ball milling and mixes, add 30 ml deionized waters, 6 h of ball milling, 300 rpm of rotational speed of ball-mill, it is dry after tabletting, be placed in tube furnace, it is per minute according to 5 DEG C Heating rate is warming up to 200 DEG C under nitrogen gas atmosphere, keeps the temperature 3 h.Minus 200 mesh mesh screen after grinding, it is mixed with 0.25 g sucrose It closes, adds 30 ml deionized water ball milling, 6 h, 300 rpm of rotational speed of ball-mill, tabletting after drying is placed in tube furnace, according to 2 DEG C every point The rate of clock is warming up to 800 DEG C in a nitrogen atmosphere, keeps the temperature 3 h.Ground 200 mesh mesh screen, obtains redox graphene With carbon-coated lithium titanate anode material, as shown in figure 8, grapheme material is added after TiO 2 particles are formed, Bu Nengyu It realizes nanoscale mixing, and in the product, the network structure that graphene is constructed cannot realize the ion of metatitanic acid lithium particle well And electronic conduction.
Gained lithium titanate anode material prepares electrode as follows: lithium titanate material, binder, conductive agent are in mass ratio It is prepared into electrode for the ratio of 90:5:5, using lithium piece as to electrode, electrolyte is done with 1M-LiPF6 EC/EMC solution, poly- third Alkene microporous barrier is diaphragm, is assembled into CR2032 button cell.And stand 6 hours.Battery after standing is placed on new prestige battery testing Electric performance test is carried out on instrument, constant current charge-discharge experiment is carried out with the current density of 10 C, test charging/discharging voltage range is 1.0 V - 2.5 V.The lithium titanate material that the present embodiment obtains, first discharge specific capacity are 155.7 mAh/g, tap density For 1.26 g/cm3
Comparative example 3
18 ml butyl titanates are weighed, 0.25 g glucose is added in 300 ml dehydrated alcohols, 13 ml glacial acetic acid are added, It is uniform to be placed in magnetic agitation in closed container, 260 ml deionized waters are slowly added dropwise, water is added to be vigorously stirred in the process, is formed greyish black Lotion is transferred in the reaction kettle that volume is 1 L, in an oven 170 DEG C of 4 h of reaction by color lotion.It collects and is formed in reaction kettle Sediment, ethanol washing 3 times, vacuum drying forms the titanium dioxide predecessor of internal doping conductive black.The precursor 200 mesh mesh screens and 1.25 g, mono- hydronium(ion) lithia are crossed after broken, are placed in ball milling and are mixed, add 25 ml acetone, 8 h of ball milling, ball milling 200 rpm of revolving speed, tabletting after drying, is placed in tube furnace, according to 5 DEG C of heating rates per minute, is warming up under Ar gas atmosphere 250 DEG C, keep the temperature 3 h.200 mesh mesh screens are crossed after grinding, are mixed with 0.22 g sucrose, are added 25 ml acetone ball milling, 4 h, rotational speed of ball-mill 300 rpm, tabletting after drying, are placed in tube furnace, according to 8 DEG C of rates per minute, are warming up to 800 DEG C under Ar gas atmosphere, Keep the temperature 6 h.Ground 200 mesh mesh screen obtains carbon-coated lithium titanate anode material outside internal doping conductive black, such as Fig. 9 Shown, after multilayer amorphous carbon cladding, although uniform particle diameter, lithium titanate crystal structure is unobvious, and electric conductivity compares graphene Or the doping such as carbon nanotube want poor, lithium ion and electronics lack the pore channel freely transmitted.
Gained lithium titanate anode material prepares electrode as follows: lithium titanate material, binder, conductive agent are in mass ratio It is prepared into electrode for the ratio of 90:5:5, using lithium piece as to electrode, electrolyte is done with 1M-LiPF6 EC/EMC solution, poly- third Alkene microporous barrier is diaphragm, is assembled into CR2032 button cell.And stand 6 hours.Battery after standing is placed on new prestige battery testing Electric performance test is carried out on instrument, constant current charge-discharge experiment is carried out with the current density of 10 C, test charging/discharging voltage range is 1.0 V - 2.5 V.The lithium titanate material that the present embodiment obtains, first discharge specific capacity are 154.5 mAh/g, tap density For 1.17 g/cm3

Claims (10)

1. a kind of preparation method of the lithium titanate anode material with multistage carbon coating network structure, which is characterized in that step packet It includes:
(1) butyl titanate, dehydrated alcohol, novel conductive carbon material and auxiliary additive are uniformly mixed, obtain ethyl alcohol dispersion Liquid;
(2) it is vigorously stirred down, preferably speed of agitator 500-1000 rpm, water, preferably deionization is added into step (1) dispersion liquid Water obtains suspension emulsion;
(3) suspension emulsion of step (2) is heated, carries out hydro-thermal reaction;
(4) by step (3) reaction system vacuum filter, the sediment being obtained by filtration is washed with dehydrated alcohol, dry, forms nanometer The TiO 2 precursor of grade doping novel conductive carbon material in situ;
(5) lithium salts and the TiO 2 precursor of step (4) mixing, ball milling mixes after solvent is added, it then dries, briquetting, First time calcination processing is carried out, first time calcined product is obtained;
(6) first time calcined product being crushed, is then mixed with organic carbon source, solvent, ball milling mixes, it then dries, briquetting, then Second of calcination processing is carried out, second of calcined product is obtained;
(7) second of calcined product is pulverized and sieved, obtains the lithium titanate anode material with multistage carbon coating network structure.
2. preparation method according to claim 1, it is characterised in that: in step (1), the butyl titanate novel is led Electrical carbon material, dehydrated alcohol, auxiliary additive volume ratio be (10-20): (10-50): (100-500): (5-50);And/or
Novel conductive carbon material mixing one or more of in graphene oxide, carbon nanotube and Ketjen black, it is described Graphene oxide and carbon nanotube preferably use its alcohol dispersion liquid, and dispersion concentration is preferably 1-5 mg/mL, the Ketjen black Preferably Ketjen black powder, granularity are preferably 20-50 nm;Preferably, the novel conductive carbon material be graphene oxide and/ Or carbon nanotube, the most preferably mixing of graphene oxide and carbon nanotube, graphene oxide and carbon nanotube mass are than preferred model It encloses for 1:(0.2-5);Wherein, the preferred lamellar spacing of the graphene oxide is 1-20 nm, and lamella diameter is 2-10 μm, In, the preferred caliber of carbon nanotube is 5-30 nm, and pipe range is 10-50 μm;And/or
The auxiliary additive is one or more of acetic acid, nitric acid and polyethylene glycol.
3. preparation method according to claim 1 or 2, it is characterised in that: deionized water described in step (2) and metatitanic acid four The volume ratio of butyl ester is (10-20): (100-500);And/or
Hydro-thermal reaction described in step (3), temperature are 60-180 DEG C, and preferably 100-150 DEG C, the time is 2-36 h, preferably 6-16h。
4. preparation method according to claim 1-3, it is characterised in that: lithium salts and dioxy described in step (5) The molar ratio for changing titanium precursors is (4-4.4): 5, with Ti element in the mole of Li element in lithium salts and TiO 2 precursor Molar amount;And/or
The lithium salts is lithium hydroxide or lithium carbonate;And/or
The solvent is one or more of deionized water, dehydrated alcohol, acetone;And/or
The calcination temperature is 200-450 DEG C, and soaking time is 1-12 h, and heating rate is 2-11 DEG C/min.
5. preparation method according to claim 1-4, it is characterised in that: described in step (5) and step (6) Ball-milling Time is 1-12 h, and rotational speed of ball-mill is 200-500 rpm;And/or
In step (5) and step (6), the briquetting operations, the powder compressing machine pressure used is 10-30 Mpa(gauge pressure), Time is 1-10min, preferably pressurization 3-10 min;The preferably thin bulk of briquetting shape, thin piece of thickness 0.5-3 cm.
6. preparation method according to claim 1-5, it is characterised in that: in step (6), the first time calcining The mass ratio of product and organic carbon source is (10-50): 1;And/or
The organic carbon source is at least one of glucose, sucrose or starch;And/or
The solvent is one or more of deionized water, dehydrated alcohol, acetone;And/or
Second of calcination temperature is 500-850 DEG C, and soaking time is 1-12 h, and heating rate is 2-11 DEG C/min.
7. preparation method according to claim 1-6, it is characterised in that: the sieving in step (7), sieve mesh number For 150-400 mesh.
8. a kind of lithium titanate anode material with multistage carbon coating network structure, it is characterised in that: by the claims 1-7 Any one the method is prepared.
9. the lithium titanate anode material with multistage carbon coating network structure according to claim 8, it is characterised in that: grain Diameter is 0.1-2 μm, and Primary particle size is 10-100 nm, wherein carbon accounting 2-7 wt%, to have multistage carbon coating net The lithium titanate anode material gross mass meter of network structure.
10. having multistage carbon coating network described in prepared by any one of claim 1-7 the method or claim 8 or 9 The application of the lithium titanate anode material of structure in a lithium ion secondary battery.
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Application publication date: 20190521