CN102354748A - Anode material for lithium ion battery and preparation method thereof - Google Patents

Anode material for lithium ion battery and preparation method thereof Download PDF

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CN102354748A
CN102354748A CN201110293967XA CN201110293967A CN102354748A CN 102354748 A CN102354748 A CN 102354748A CN 201110293967X A CN201110293967X A CN 201110293967XA CN 201110293967 A CN201110293967 A CN 201110293967A CN 102354748 A CN102354748 A CN 102354748A
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preparation
lithium
ion battery
lithium ion
lithium titanate
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郑军伟
赵晓梅
周群
桓佳君
李亚斌
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Suzhou University
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Suzhou University
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Abstract

The invention discloses a preparation method of an anode material for a lithium ion battery, which comprises the following steps of: mixing titanium dioxide with lithium carbonate to be ball-milled evenly, carrying out heat preservation for 10-180 minutes at the temperature of 750-850 DEG C and cooling to obtain lithium titanate; and mixing the lithium titanate with a solid-state nitrogen source compound to be calcined with the protection of protective gas, and obtaining the anode material for the lithium ion battery after reaction. In the step of preparing the lithium titanate, the time for heat preservation of raw materials at high temperature is greatly shortened, the aggregation of material particles caused by long-time ignition is avoided, the particle size of the lithium titanate is greatly reduced, and the modification area of TiN after the lithium titanate is nitrided is increased, so that the conductivity performance of the prepared anode material for the lithium ion battery is improved. In addition, due to the reduction of the particle size of the lithium titanate, the migration distance of lithium ions in a charge-discharge process of the lithium ion battery is reduced, and thus the large current charge-discharge performance of the anode material for the lithium ion battery is improved.

Description

A kind of lithium ion battery cathode material and its preparation method
Technical field
The present invention relates to technical field of lithium ion, more particularly, relate to a kind of lithium ion battery cathode material and its preparation method.
Background technology
In recent years, along with highlighting of the problems such as exhausted day by day and global warming of resource, the life style of green low-carbon has received to be advocated.Wherein, to come part to replace the internal-combustion engines vehicle of consumption of fossil fuels be one of main method that solves energy crisis and ecological deterioration to development electric motor car and hybrid electric vehicle.Driving power is to influence the critical component that electric motor car is promoted the use of, and nowadays widely used driving power comprises lead-acid battery, ni-mh/NI-G, lithium ion battery etc.Advantages such as in various driving powers, lithium ion battery is owing to have the energy density height, and cyclicity is good, and self-discharge rate is low, long service life and environmental pressure are little have obtained extensive studies.
At present; Lithium ion battery mainly with material with carbon element as negative material; But; Because the embedding lithium current potential of material with carbon element and the current potential of lithium metal are very approaching; When large current charge, be easy at negative terminal surface constrained dendritic growth lithium; Thereby the potential safety hazard of bringing makes safety problem become the development bottleneck of the electronic vehicle vehicles of influence.And the carbon negative pole is prone to form solid electrolyte interface film (SEI film) on its surface in the first charge-discharge process, and battery performance is descended, and is difficult to satisfy the requirement of lithium ion battery high current charge-discharge.
Spinel lithium titanate (Li 4Ti 5O 12) with the potential difference of lithium electrode be 1.5V, in battery charge and discharge process, be difficult for forming dendrite lithium, security performance is good, and in charge and discharge process, Li +Embedding take off Li 4Ti 5O 12Material structure does not almost have influence, thereby makes Li 4Ti 5O 12Has good cycle performance.In addition, Li 4Ti 5O 12Have also that discharging voltage balance, embedding lithium current potential are high, enclosed pasture efficient is high, can in the electrolytical burning voltage of most liquid interval, use and with characteristics such as electrolyte formation SEI film, compare Li with the cathode of lithium material with the carbon negative pole 4Ti 5O 12Have better chemical property and fail safe.Therefore, Li 4Ti 5O 12It is a kind of cell negative electrode material that has application prospect.
Yet, Li 4Ti 5O 12Electronic structure be that the 3d unoccupied orbital of Ti has the 2eV band-gap energy, makes Li 4Ti 5O 12Intrinsic conductivity lower, only be 10 -9S/cm, therefore, in order to make Li 4Ti 5O 12In the high current charge-discharge battery material, obtain better application, need Li 4Ti 5O 12Modify or modification.In the prior art, mainly be to Li 4Ti 5O 12Material surface carries out carbon to be modified, though improved material conductivity, has reduced tap density.Another kind method is through at Li 4Ti 5O 12Finishing TiN film improve the electric conductivity of material.According to Li 4Ti 5O 12Material characteristics, Li 4Ti 5O 12In Ti and N be combined into TiN with metallic conduction performance, N can combine closely at Li through chemical bond 4Ti 5O 12The surface is improved the electric conductivity of material, thereby is improved its large current density electrical property under the prerequisite that does not reduce tap density.Concrete, Snyder M Q (referring to: Journal of Power Sources, 2007,165 (1): 379-385) reported through atomic layer deposition method (ALD) at Li 4Ti 5O 12Surface deposition one deck TiN makes Li 4Ti 5O 12Electric conductivity be improved, still, this method complicated operation, cost are high, condition is difficult to control.Kyu-Sung Park (referring to: J.Am.Chem.Soc., 2008,130 (45): 14930-14931) reported with the ammonia decomposition method at Li 4Ti 5O 12Surface preparation TiN film, the ammonia that this method is used has corrosivity and danger, and when large-scale production, is difficult to the control material cladding uniformity.
The Li that the lithium ion battery negative material of above-mentioned report all prepares more than 10 hours with roasting under the high temperature 4Ti 5O 12Material is a raw material, because Li 4Ti 5O 12Particle is very easily reunited, and long-time roasting meeting causes Li 4Ti 5O 12Particle is excessive, thereby makes the finishing of preparation that the Li of TiN arranged 4Ti 5O 12The electric conductivity and the high rate during charging-discharging of negative material are relatively poor.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of lithium ion battery cathode material and its preparation method, and the lithium ion battery negative material of this method preparation has excellent conducting performance and high rate during charging-discharging.
In order to solve above technical problem, the present invention provides a kind of preparation method of lithium ion battery negative material, may further comprise the steps:
Step a) is mixed titanium dioxide and lithium carbonate, and ball milling evenly back is incubated 10～180 minutes down at 750～850 ℃, obtains lithium titanate after the cooling;
Step b) is mixed said lithium titanate with the solid nitrogen source compound, calcining under the protective gas protection obtains lithium ion battery negative material after the reaction then.
Preferably, the holding temperature of said step a) is 800 ℃.
Preferably, the temperature retention time of said step a) is 20～120 minutes.
Preferably, the temperature retention time of said step a) is 30～60 minutes.
Preferably, said solid nitrogen source compound is one or more in urea, biuret, cyanamide, cyanamid dimerization, melamine, ammelide and the ammeline.
Preferably, said titanium dioxide and lithium carbonate are mixed is specially:
Is 1 by titanium with the mol ratio of lithium: titanium dioxide and lithium carbonate are mixed in (0.8～1).
Preferably, the weight ratio of said solid nitrogen source compound and said lithium titanate is (2.5～20): 100.
Preferably, calcination condition described in the step b) is: the speed with 5～10 ℃/min is warming up to 800 ℃, calcines 30 minutes.
Preferably, said protective gas is nitrogen, helium or argon gas.
Accordingly, the present invention also provides a kind of lithium ion battery negative material of above-mentioned preparation method's preparation.
The invention provides a kind of preparation method of lithium ion battery negative material, may further comprise the steps: titanium dioxide and lithium carbonate are mixed, and ball milling is even, is incubated 10～180 minutes down at 750～850 ℃, obtains lithium titanate after the cooling; Said lithium titanate is mixed with the solid nitrogen source compound, and calcining under the protective gas protection obtains lithium ion battery negative material after the reaction then.In the step of preparation lithium titanate; Because the present invention has shortened raw material temperature retention time at high temperature greatly; Stoped the gathering of the material particle that long-time calcination causes; The particle diameter of lithium titanate is reduced greatly; Improve the modification area of lithium titanate TiN behind nitrogen treatment, thereby improved the electric conductivity of the lithium ion battery negative material of preparation.And, because reducing of lithium titanate particle diameter the migration distance of lithium ion in the lithium ion battery charge and discharge process, thereby improved the high rate during charging-discharging of lithium ion battery negative material.
Description of drawings
Fig. 1 is the Li of the embodiment of the invention 1 preparation 4Ti 5O 12The XRD diffracting spectrum of/TiN negative material;
Fig. 2 is the Li of the embodiment of the invention 1 preparation 4Ti 5O 12The scanning electron microscopy sheet of/TiN negative material;
Fig. 3 is the Li of the embodiment of the invention 1 preparation 4Ti 5O 12The Raman spectrum of/TiN negative material;
Fig. 4 is the Li of the embodiment of the invention 1 preparation 4Ti 5O 12/ TiN negative material and lithium sheet are formed the specific discharge capacity curve of button cell under different multiplying;
Fig. 5 is the Li of the embodiment of the invention 1 and 2 preparations 4Ti 5O 12The XRD diffracting spectrum of/TiN negative material;
Fig. 6 is the Li of the embodiment of the invention 1 preparation 4Ti 5O 12The Li of/TiN and comparative example 1 preparation 4Ti 5O 12Form specific discharge capacity and the cycle period curve of button cell under 3.0C as positive electrode and lithium sheet respectively;
Fig. 7 is the AC impedance spectrogram of the embodiment of the invention 1 and the lithium ion battery negative material of comparative example 1～2 preparation.
Embodiment
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The invention discloses a kind of preparation method of lithium ion battery negative material, may further comprise the steps:
Step a) is mixed titanium dioxide and lithium carbonate, and ball milling evenly back is incubated 10～180 minutes down at 750～850 ℃, obtains lithium titanate after the cooling;
Step b) is mixed said lithium titanate with the solid nitrogen source compound, calcining under the protective gas protection obtains lithium ion battery negative material after the reaction then.
In above-mentioned preparation method, the present invention at first prepares lithium titanate, then with the lithium titanate nitrogen treatment, thereby obtains the lithium titanate of finishing TiN, i.e. lithium ion battery negative material.
In said step a), the present invention is the titanium source compound with titanium dioxide, is Li source compound with the lithium carbonate, through this titanium dioxide and lithium carbonate at high temperature are incubated, obtains lithium titanate after the reaction.Said titanium dioxide and lithium carbonate are mixed is specially, and be 1 by titanium with the mol ratio of lithium: titanium dioxide and lithium carbonate are mixed in (0.8～1), and preferably, the mol ratio of said titanium and lithium is 1: 0.8～1.In order to make titanium dioxide and lithium carbonate can realize sufficient mixing, preferably adopt ball mill that titanium dioxide and lithium carbonate ball milling is even, this ball mill preferably adopts planetary ball mill; In mechanical milling process, preferably that mixed material ball milling in decentralized medium of titanium dioxide and lithium carbonate is even, said decentralized medium is preferably acetone or alcohol etc.; After ball milling was even, preferably the product that ball milling is obtained was at room temperature dry, and the ball milling time is preferably 2～5 hours, more preferably 3 hours.
In the process of lithium titanate, holding temperature is the key factor of the lithium titanate of influence preparation, and temperature is too high, will cause the lithium carbonate mass loss, and temperature is crossed to hang down and then is unfavorable for the reaction between titanium dioxide and the lithium carbonate, is unfavorable for the formation of lithium titanate.The holding temperature that the present invention adopts is preferably 780～820 ℃, most preferably is 800 ℃.Under this temperature, titania powder behind ball milling and lithium carbonate powder fully react, and form the lithium titanate particle.The present invention preferably directly places mixed material behind the ball milling of said titanium dioxide and lithium carbonate under 750～850 ℃ the high temperature and is incubated calcination, need not to adopt the temperature programming process.
But; Because the lithium titanate particle is very easily reunited; Long-time roasting meeting causes lithium titanate particle accumulation phenomenon serious; Thereby make the lithium titanate particle of preparation excessive; Therefore, in step a), the temperature retention time that the present invention adopts is preferably 20～120 minutes; More preferably 30～60 minutes, most preferably be 30 minutes.In addition, for the cooling step after the insulation, the present invention preferably adopts the method for cooling at room temperature, need not in certain insulation environment, and the cooling rate cooling with slower helps industrialization and produces continuously.Compared with prior art, the present invention has shortened temperature retention time greatly, has avoided the gathering of lithium titanate particle effectively, has increased the specific area of the lithium titanate of preparation.After the lithium titanate particle carried out nitrogenize, all formed the TiN modification at each lithium titanate particle surface, N combines closely on the lithium titanate surface through chemical bond, has improved the modification area of TiN, has improved the electric conductivity of the lithium ion battery negative material of preparation greatly.And, because reducing of lithium titanate particle diameter the migration distance of lithium ion in the charge and discharge process, thereby improved the high rate during charging-discharging of lithium ion battery negative material.
After preparing lithium titanate; Said lithium titanate is mixed with the solid nitrogen source compound, and the solid nitrogen source compound that the present invention adopts is preferably one or more in urea, biuret, cyanamide, cyanamid dimerization, melamine, ammelide and the ammeline.Because that urea has is cheap, safety is easy to get, and the catabolite when different temperatures is respectively biuret, cyanamide or poly cyanamide, therefore, the solid nitrogen source compound that the present invention adopts is preferably urea.The weight ratio of said solid nitrogen source compound and said lithium titanate is preferably (2.5～20): 100, more preferably (2.5～10): 100, most preferably be 6: 100.Said lithium titanate is mixed with the solid nitrogen source compound is specially: lithium titanate is mixed with the solid nitrogen source compound, and ball milling is even in decentralized medium, and said decentralized medium is preferably acetone or alcohol.To lithium titanate and solid nitrogen source compound ball milling evenly after, preferably with its 20～120 ℃ dry down, said baking temperature is preferably 50～120 ℃.In step b), said protective gas is preferably nitrogen, helium or argon gas, avoids and gas reactions such as airborne oxygen.
In the process that the mixture of lithium titanate and solid nitrogen source compound is calcined; N in Ti in the lithium titanate and the solid nitrogen source compound is combined into the TiN with metallic conduction performance; N combines closely on the lithium titanate material surface through chemical bond; Under the prerequisite that does not reduce tap density, improve the electric conductivity of lithium titanate, improved the large current density electrical property of lithium titanate.Calcining heat is to influence the key factor that lithium ion battery negative material forms, and calcining heat is too high, and the lithium ion battery negative material mass loss that will cause preparing is serious, and can not form the lithium titanate of finishing titanium nitride, i.e. Li 4Ti 5O 12/ TiN; Temperature is low excessively, will be unfavorable for the reaction of lithium titanate and solid nitrogen source compound.Calcination condition described in the step b) is: the speed with 5～10 ℃/min is warming up to 800 ℃, calcines 30 minutes.
In sum, the present invention significantly reduced in the reaction time of preparation during lithium titanate, had stoped the gathering of the material particle that long-time calcination causes, the particle diameter of lithium titanate is reduced greatly.Reducing of this lithium titanate particle diameter on the one hand, after to the lithium titanate nitrogen treatment, improved the modification area of TiN, thereby improved the electric conductivity of the lithium ion battery negative material of preparation; On the other hand, because reducing of lithium titanate particle diameter the migration distance of lithium ion in the charge and discharge process, thereby improved the high rate during charging-discharging of lithium ion battery negative material.In addition, the present invention has reduced raw material in the following reaction time of hot conditions, has saved the energy, is beneficial to suitability for industrialized production.
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just to further specifying the features and advantages of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
Embodiment 1
Li 4Ti 5O 12The preparation of material: in Li: the Ti mol ratio is that 0.8: 1 ratio takes by weighing Li 2CO 3With Detitanium-ore-type TiO 2, acetone is solvent, with 300 rev/mins rotating speeds ball milling 3 hours in planetary ball mill, the gained mixed material places 800 ℃ Muffle furnace calcination to take out in 30 minutes after drying under the room temperature, be cooled to after the room temperature Li 4Ti 5O 12
Li 4Ti 5O 12The preparation of/TiN negative material: account for above-mentioned gained Li by urea 4Ti 5O 12Weight ratio be 6% to add urea; Acetone is solvent; With 300 rev/mins rotating speeds ball milling 3 hours in planetary ball mill; The gained mixed material is after drying under the room temperature; Place tube furnace; Speed with 10 ℃/minute under argon atmospher is warming up to 800 ℃, and keeps being cooled to room temperature after 30 minutes, gets Li 4Ti 5O 12/ TiN negative material.
Material property characterizes:
Through the crystal structure of XRD diffractometer analysis of material, can know that from Fig. 1 the crystal structure before and after TiN modifies is spinel-type Li 4Ti 5O 12, i.e. the modification of TiN does not change Li 4Ti 5O 12The main crystal structure of material.Fig. 2 is the Li of present embodiment preparation 4Ti 5O 12The scanning electron microscopy sheet of/TiN can be known Li from figure 4Ti 5O 12/ TiN material particle size is about 500nm.Fig. 3 is the Li of present embodiment preparation 4Ti 5O 12The Raman spectrum of/TiN, as can be seen from the figure, at 152cm -1One sharp-pointed absworption peak is arranged, be illustrated in Li 4Ti 5O 12Truly have TiN to exist in the material.
Electrochemical property test:
With prepared negative material Li 4Ti 5O 12/ TiN and Super P and PVDF (N-methyl pyrrolidone solution) mix by mass ratio at 8: 1: 1, coat uniformly on the aluminium foil with rubbing method, are placed in the vacuum drying chamber 120 ℃ of dryings then 12 hours, in glove box with EC/DEC=1: 1LiPF 6Being electrolyte, is the imbibition film with the glass fiber filter paper, and the PP film is a barrier film, and lithium metal is that battery cathode is assembled into 2016 button cells.
Battery to preparation is tested, and when charge-discharge magnification is consistent, gets specific discharge capacity and the recurrence relation curve under the different multiplying.Can find out like Fig. 4, by the Li of present embodiment preparation 4Ti 5O 12The battery that/TiN negative material makes is respectively 174.5mAh/g, 161.6mAh/g, 158.7mAh/g, 142mAh/g, 115.1mAh/g, 74.2mAh/g and 174.3mAh/g at 0.1C, 0.5C, 1C, 5C, 10C, 20C and the specific discharge capacity that returns 0.1C once more.
Embodiment 2
Li 4Ti 5O 12The preparation of material is identical with embodiment 1 method, and calcination is 10 minutes in 800 ℃ of Muffle furnaces.
Li 4Ti 5O 12The preparation of/TiN negative material is identical with embodiment 1.
To the XRD test result of the negative material of present embodiment preparation as shown in Figure 5, visible by figure, mixed material is at 800 ℃ of calcinations existing a large amount of product Li after 10 minutes 4Ti 5O 12Generate, but still have more TiO 2Unreacted.
Li 4Ti 5O 12The preparation of/TiN negative material is identical with embodiment 1 with electro-chemical test.
Electrochemical property test method to the negative material of present embodiment preparation is identical with embodiment 1.Li by the present embodiment preparation 4Ti 5O 12The battery that/TiN negative material makes discharges and recharges under the 3C multiplying power discharging and recharging 5 all after dates under the 0.2C multiplying power, and specific discharge capacity first is 165.8mAh/g, is 141.1mAh/g at the specific discharge capacity of circulation 200 all after dates, and capability retention is 85.1%.
Embodiment 3
Li 4Ti 5O 12Material preparation is identical with embodiment 1, and calcination is 1 hour in 800 ℃ of Muffle furnaces.
Li 4Ti 5O 12Be dispersant with the absolute ethyl alcohol in the preparation of/TiN negative material, other preparation is identical with embodiment 1 with electro-chemical test.
The battery that is made by the negative material of present embodiment preparation discharges and recharges under the 3C multiplying power discharging and recharging 5 all after dates under the 0.2C multiplying power; Specific discharge capacity first is 155.5mAh/g; Specific discharge capacity at circulation 200 all after dates is 153.9mAh/g, and capability retention is 98.9%.
Embodiment 4
Li 4Ti 5O 12Material preparation is identical with embodiment 1.
Li 4Ti 5O 12Just account for Li in the preparation of/TiN negative material by urea 4Ti 5O 12Weight ratio be that 3% amount adds urea, other preparation is identical with embodiment 1 with electro-chemical test.
The battery that is made by the negative material of present embodiment preparation discharges and recharges under the 3C multiplying power discharging and recharging 5 all after dates under the 0.2C multiplying power; Specific discharge capacity first is 166.6mAh/g; Specific discharge capacity at circulation 200 all after dates is 144.7mAh/g, and capability retention is 86.9%.
Comparative example 1
Li 4Ti 5O 12The preparation of material: in Li: the Ti mol ratio is that 0.8: 1 ratio takes by weighing Li 2CO 3With Detitanium-ore-type TiO 2Acetone is solvent, and with 300 rev/mins rotating speeds ball milling 3 hours in planetary ball mill, gained mixed material drying under room temperature is placed in the Muffle furnace; Be warming up to 800 ℃ and keep cooling to room temperature with the furnace after 12 hours with 10 ℃/minute speed again, take out Li 4Ti 5O 12
Fig. 6 is the Li of embodiment 1 preparation 4Ti 5O 12The Li of/TiN and comparative example 1 preparation 4Ti 5O 12Form specific discharge capacity and the cycle period curve of button cell under 3.0C as positive electrode and lithium sheet respectively.As can be seen from the figure, the negative material of embodiment 1 preparation discharges and recharges under the 3C multiplying power, and its initial discharge specific capacity is 164.4mAh/g, and the 600 all after date capability retentions that circulate are 90.3%.The negative material of comparative example 1 preparation at the specific discharge capacity that under the 0.2C multiplying power, discharged and recharged for 5 cycles and embodiment 1 much at one; But under the 3C multiplying power, discharge and recharge; Specific discharge capacity first only is 145.1mAh/g; Be lower than the negative material of embodiment 1 preparation; And the circulation 600 all after dates specific discharge capacity be 41.6mAh/g; Capability retention is 28.7%, also significantly is lower than the negative material of embodiment 1 preparation.
Comparative example 2
Li 4Ti 5O 12The material preparation process is identical with embodiment 1, just calcination 12 hours in 800 ℃ of Muffle furnaces.
Li 4Ti 5O 12The preparation of/TiN negative material is identical with embodiment 1 with electro-chemical test.
The battery that is made by the negative material of this comparative example preparation discharges and recharges under the 3C multiplying power discharging and recharging 5 all after dates under the 0.2C multiplying power; Specific discharge capacity first is 150.9mAh/g; Specific discharge capacity at circulation 200 all after dates is 134.4mAh/g, and capability retention is 89.1%.
Fig. 7 is the AC impedance spectrogram of the embodiment 1 and the lithium ion battery negative material of comparative example 1～2 preparation.As can be seen from the figure, the AC impedance of the lithium ion battery negative material of embodiment 1 preparation is minimum, thereby resistance is minimum, both at Li 4Ti 5O 12Use the urea nitrogenize when just forming, can reduce its internal resistance, improve the conductance of material.The AC impedance of the lithium ion battery negative material of comparative example 1 preparation is maximum, means the high rate during charging-discharging that is unfavorable for material.The AC impedance of the ion battery negative material of comparative example 2 preparations is greater than the lithium ion battery negative material of embodiment 1 preparation.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.

Claims (10)

1. the preparation method of a lithium ion battery negative material may further comprise the steps:
Step a) is mixed titanium dioxide and lithium carbonate, and ball milling evenly back is incubated 10～180 minutes down at 750～850 ℃, obtains lithium titanate after the cooling;
Step b) is mixed said lithium titanate with the solid nitrogen source compound, calcining under the protective gas protection obtains lithium ion battery negative material after the reaction then.
2. preparation method according to claim 1 is characterized in that, the holding temperature of said step a) is 800 ℃.
3. preparation method according to claim 1 is characterized in that, the temperature retention time of said step a) is 20～120 minutes.
4. preparation method according to claim 3 is characterized in that, the temperature retention time of said step a) is 30～60 minutes.
5. preparation method according to claim 1 is characterized in that, said solid nitrogen source compound is one or more in urea, biuret, cyanamide, cyanamid dimerization, melamine, ammelide and the ammeline.
6. preparation method according to claim 1 is characterized in that, said titanium dioxide and lithium carbonate are mixed is specially:
Is 1 by titanium with the mol ratio of lithium: titanium dioxide and lithium carbonate are mixed in (0.8～1).
7. preparation method according to claim 1 is characterized in that, the weight ratio of said solid nitrogen source compound and said lithium titanate is (2.5～20): 100.
8. preparation method according to claim 1 is characterized in that, calcination condition described in the step b) is: the speed with 5～10 ℃/min is warming up to 800 ℃, calcines 30 minutes.
9. preparation method according to claim 1 is characterized in that, said protective gas is nitrogen, helium or argon gas.
10. the lithium ion battery negative material of any preparation method preparation of claim 1～9.
CN201110293967XA 2011-09-30 2011-09-30 Anode material for lithium ion battery and preparation method thereof Pending CN102354748A (en)

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CN103183509A (en) * 2013-04-17 2013-07-03 清华大学 Lithium titanate ceramic ball tritium propagation material and preparation method thereof
CN103337634A (en) * 2012-07-04 2013-10-02 淄博惠仁泽电子科技有限公司 Graphite cathode material coated with conductive titanium nitride network membrane on the surface and preparation method of the graphite cathode material
CN103985852A (en) * 2014-05-30 2014-08-13 合肥国轩高科动力能源股份公司 Preparation method for zirconium nitride-coated lithium titanate composite material
CN104169220A (en) * 2012-03-16 2014-11-26 帝化株式会社 Lithium titanate and production method and use for same
CN104269524A (en) * 2014-09-30 2015-01-07 李宏斌 Preparation and application of phosphate-cladded carbon-cladded nitrogenized rare-earth-doped Li4Ti5O12
CN105449187A (en) * 2015-12-20 2016-03-30 华南理工大学 Preparation method of high-performance co-doped lithium titanate electrode material
CN106058199A (en) * 2016-07-22 2016-10-26 天津巴莫科技股份有限公司 Cobalt titanium blue coated lithium titanate and preparation method thereof
CN106252623A (en) * 2016-08-26 2016-12-21 深圳博磊达新能源科技有限公司 A kind of carbon-nitrogen doped lithium titanate electrode material, preparation method and application
CN108470903A (en) * 2018-03-20 2018-08-31 上海电力学院 A kind of method of modifying of anode material of lithium-ion battery titanium dioxide
CN110021750A (en) * 2019-04-17 2019-07-16 东北大学 A kind of method of mechanical force assisted Solid-state synthesis lithium titanate anode material
CN110104677A (en) * 2019-04-01 2019-08-09 桂林电子科技大学 Composite titanic acid lithium material and the preparation method and application thereof
CN110817943A (en) * 2019-10-11 2020-02-21 攀钢集团攀枝花钢铁研究院有限公司 Lithium battery negative electrode material and solid-phase preparation method thereof

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CN104269524A (en) * 2014-09-30 2015-01-07 李宏斌 Preparation and application of phosphate-cladded carbon-cladded nitrogenized rare-earth-doped Li4Ti5O12
CN105449187A (en) * 2015-12-20 2016-03-30 华南理工大学 Preparation method of high-performance co-doped lithium titanate electrode material
CN106058199A (en) * 2016-07-22 2016-10-26 天津巴莫科技股份有限公司 Cobalt titanium blue coated lithium titanate and preparation method thereof
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