CN109336170A - A kind of preparation method of Li4Ti5O12 negative electrode material - Google Patents

A kind of preparation method of Li4Ti5O12 negative electrode material Download PDF

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CN109336170A
CN109336170A CN201811237536.XA CN201811237536A CN109336170A CN 109336170 A CN109336170 A CN 109336170A CN 201811237536 A CN201811237536 A CN 201811237536A CN 109336170 A CN109336170 A CN 109336170A
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preparation
negative electrode
electrode material
temperature
ball
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陈建设
祝喆
刘奎仁
李斌川
韩庆
王飞
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Northeastern University China
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 invention belongs to technical field of energy material more particularly to a kind of Li4Ti5O12The preparation method of negative electrode material.Firstly, titanium source, lithium source and organic matter are mixed, Li is prepared using low-temperature combustion method4Ti5O12Presoma；Then, using high-temperature machinery force chemistry by the Li4Ti5O12Precursor preparation is at Li4Ti5O12Powder.This method simple process, easy to operate, less energy consumption, reaction process is easy to control, and is suitble to industrialized production, is obtained Li4Ti5O12Powder diameter is about 200nm.

Description

A kind of Li4Ti5O12The preparation method of negative electrode material
Technical field
The invention belongs to technical field of energy material more particularly to a kind of Li4Ti5O12The preparation method of negative electrode material.
Background technique
With getting worse for environmental pollution and energy shortage, the development and application of clean energy resource is extremely urgent, therewith phase The use of the energy storage technology answered especially electrochmical power source is also in urgent need to be improved.Lithium ion battery is because its is small in size, quality is small, energy is close Degree is big, good cycling stability, self discharge are small, memory-less effect and advantages of environment protection, in national economy and daily life Play increasingly important role.
Traditional lithium ion battery uses the carbon-based materials such as graphite as negative electrode material, and there are security risks, i.e., in fast charge The intercalation potential of Shi Shimo is too low, close to 0V (vs.Li/Li+), Li dendrite easily is formed in electrode surface, porous septum is exposed and makes At internal short-circuit.And Li4Ti5O12Material has " zero strain " effect and very flat charge and discharge platform during removal lithium embedded (about 1.55Vvs.Li/Li+), therefore, there is very high cyclical stability and safety.But Li4Ti5O12Ionic conductivity , the Li that numerous researchers by ion doping and surface modification treatment improved lower with respect to graphite with electronic conductivity4Ti5O12 Electron conduction；Li is improved by designing the nano particle of different shape4Ti5O12Ionic conductivity.
Currently, Li4Ti5O12Preparation method mainly have high temperature solid-state method, sol-gel method and hydro-thermal ion synthetic method. But material made from high temperature solid-state method generally has agglomeration, and particle diameter distribution is uneven, particle is larger, leads to the internal resistance of cell It is larger with polarizing；Sol-gel method preparation process is more complicated, and technical process is difficult to control, and raw materials used is organic matter, is led It causes preparation cost higher, is unfavorable for being mass produced；Reaction condition is changeable during the reaction for hydro-thermal ion synthetic method, not easily-controllable System, reaction can release big calorimetric in the closed confined space, and there are security risks, be not suitable for industrialized production.
Summary of the invention
(1) technical problems to be solved
For existing technical problem, the present invention provides a kind of Li4Ti5O12The preparation method of negative electrode material, the party Method simple process, easy to operate, less energy consumption, reaction process is easy to control, and is suitble to industrialized production.
(2) technical solution
In order to achieve the above object, a kind of Li of the present invention4Ti5O12The preparation method of negative electrode material:
Prepare Li4Ti5O12The step of presoma: it using titanium source, lithium source and organic matter as raw material, is prepared using low-temperature combustion method Li4Ti5O12Presoma；
The step of preparing powder: use high-temperature machinery force chemistry by the Li4Ti5O12Precursor preparation is at Li4Ti5O12 Powder.
Further, the Li4Ti5O12The preparation of presoma, includes the following steps:
S1, titanium source is dispersed in water, is mixed after heating for dissolving with concentrated ammonia liquor, obtain white precipitate；
S2, it precipitates, is obtained containing TiO described in dilute nitric acid dissolution2+Nitrate solution；
S3, contain TiO for described2+Nitrate solution mixed with organic matter, lithium source, it is rear be added ammonium hydroxide obtain mixing it is molten Liquid；
S4, the mixed solution is heated, carries out self-propagating combustion after forming gel, obtains low-temperature combustion synthesis Li4Ti5O12Presoma.
Further, the titanium source is titanyl sulfate, titanium sulfate, titanium tetrachloride or butyl titanate；
The organic matter is citric acid, urea, triethanolamine or glycine；
The lithium source is lithium nitrate, lithium acetate or lithium carbonate.
Further, lithium source in the step S3, the titanium source in the step S1, the organic matter in the step S3 Molar concentration rate is 0.82~0.86:1:1~2.
Further, in the step S1, the temperature of heating is 60~70 DEG C, titanium source and the mixed solution of concentrated ammonia liquor For neutrality.
Further, in the step S3, the pH value of mixed solution is greater than 5.
Further, in the step S4, the temperature of heating is 60~80 DEG C, the temperature of self-propagating combustion is 550~ 600℃。
Further, the preparation Li4Ti5O12The step of powder be 700~800 DEG C at a temperature of, by Li4Ti5O12Before It drives body and carries out ball-milling treatment, obtain Li4Ti5O12Powder.
Further, the ball material mass ratio of the ball-milling treatment is 15~25:1.
Further, the time of the ball-milling treatment is 5~7h, and the revolving speed of the ball-milling treatment is 45~55r/min.
Self- propagating: using a kind of technology of chemical reaction self-heat generation synthetic material, be otherwise known as conbustion synthesis (Combustion Synthesis).Its fundamental is: 1, using chemical heat release, complete (or part) does not need outer Heat source；2, the product of required composition and structure is obtained by the automatic holding reaction that fast automatic wave burns；3, by changing heat Release and transmission speed come the speed of control process, temperature, conversion ratio and product composition and structure.
(3) beneficial effect
The beneficial effects of the present invention are:
1, method provided by the invention first prepares Li with low-temperature combustion method4Ti5O12Then presoma uses high-temperature machinery Force chemistry prepares Li4Ti5O12Negative electrode material, this method simple process, easy to operate, less energy consumption are suitable for industrialized production.
2, in method provided by the invention, low-temperature combustion method self-designed L i4Ti5O12Presoma can control Li4Ti5O12Size And pattern, and cost of material is cheap, can reduce preparation nanometer Li4Ti5O12Cost.
3, method provided by the invention, compared to conventional high temperature solid phase method easily 12~long-time high-temperature calcination for 24 hours, this Invention can prepare a nanometer Li within the relatively short time4Ti5O12Material shortens the production cycle, saving is prepared into This, is more suitable for industrialized production and application.
4, method provided by the invention, without using high energy ball mill, only can successfully be made compared with the slow-speed of revolution (50r/min) Standby nanometer Li out4Ti5O12Material.
5, calcining and ball milling are carried out simultaneously in same high temperature furnace, reduce operating procedure by method provided by the invention, The production time is saved, new method is provided for large-scale industrial production.
Detailed description of the invention
Fig. 1 is the reacting flow chart in the embodiment of the present invention 1；
Fig. 2 is Li in the embodiment of the present invention 14Ti5O12The SEM of presoma schemes；
Fig. 3 is Li in the embodiment of the present invention 14Ti5O12The SEM of powder schemes；
Fig. 4 is Li in the embodiment of the present invention 14Ti5O12The granularity graph of powder.
Specific embodiment
In order to preferably explain the present invention, in order to understand, with reference to the accompanying drawing, by specific embodiment, to this hair It is bright to be described in detail.
Present embodiment proposes a kind of Li4Ti5O12The preparation method of negative electrode material prepares Li4Ti5O12The step of presoma: Using titanium source, lithium source and organic matter as raw material, Li is prepared using low-temperature combustion method4Ti5O12Presoma；The step of preparing powder: it adopts With high-temperature machinery force chemistry by the Li4Ti5O12Precursor preparation is at Li4Ti5O12Powder.
Specifically comprise the following steps:
S1, it takes titanium source to be dispersed in water, dissolves by heating, dropwise addition concentrated ammonia liquor adjusting solution to neutrality, and generate white precipitate Ti(OH)4·nH2O.Wherein, titanium source is chosen as titanyl sulfate, titanium sulfate, titanium tetrachloride or butyl titanate, preferably sulfuric acid oxygen Titanium, heating temperature are 60~70 DEG C.
S2, make that the precipitating is washed with deionized, filter and retain filter cake (precipitating), wash through deionized water to washing SO is free of in liquid4 2-Until ion, with the dilute nitric acid dissolution precipitating, TiO (NO is obtained3)2Solution.
Wherein, with the BaCl of 0.5mol/L2Solution examines in cleaning solution whether contain SO4 2-Ion.
S3, organic matter and lithium source be dissolved in deionized water respectively, be stirring evenly and then adding into TiO (NO3)2Solution obtains Mixed solution.
Wherein, lithium source, titanium source, organic matter molar concentration rate be 0.82~0.86:1:1~2.
Organic matter is chosen as citric acid, urea, triethanolamine or glycine, preferably citric acid.Have in aqueous solution The citric acid of stronger complexation of metal ions ability is as incendiary agent, by the complexing of citric acid, by the hydrate monomer of titanium The three-dimensional network shape oligomer with certain space construction is connected into, it is these oligomeric shapes, not of uniform size, but be evenly distributed In aqueous solution, the colloidal sol of stable homogeneous is formed.
Lithium source is chosen as lithium nitrate, lithium acetate or lithium carbonate, preferably lithium nitrate.
S4, concentrated ammonia liquor is added into mixed solution, mixed solution is adjusted to pH value greater than 5.
S5, it is stirred evaporation at a temperature of mixed solution is placed in 60~80 DEG C, after gel to be formed, gel is moved into In corundum crucible, being placed in 550~600 DEG C preheated of Muffle furnace makes its self-propagating combustion, obtains Li4Ti5O12Forerunner Body.
S6, the Li that will be obtained4Ti5O12Presoma is put into stainless steel jar mill with 15~25:1 of ball material mass ratio, sealing. Ball grinder is put into high temperature energy ball grinder burner hearth, starts ball mill, is persistently rotated with the revolving speed of 45~55r/min, simultaneously Burner hearth is warming up to 700~800 DEG C, and keeps the temperature 5~7h.
S7, closing ball mill wait for that burner hearth is cooled to room temperature, and take out ball grinder, obtain even-grained nanometer Li4Ti5O12Powder End.
In the present embodiment, low-temperature combustion method is using nitrate as oxidant, and organic matter occurs as reducing agent Strong redox reaction, combustion generated gas generate that particle is tiny, Li of large specific surface area4Ti5O12Precursor powder. Wherein, Li4Ti5O12Presoma is spherical morphology, uniform particle sizes, about 100nm.
Pass through self-designed L i4Ti5O12Presoma can control Li4Ti5O12Size and shape, and without using high revolving speed ball Two steps of conventional high-energy ball milling and heating are merged, greatly reduce reaction duration, consolidated by universal high temperature by grinding machine The 12 of phase method~be greatly reduced for 24 hours to 5~7h, it is receiving for 200nm that average grain diameter can be successfully prepared under low-down revolving speed Rice Li4Ti5O12Powder.
In the present embodiment, Mechanosensitive channels make powder particle lattice dot matrix aligning section in Process During High Energy Ball Milling Divide and lose periodically and formed lattice defect, distortion of lattice occurs, powder particle is generated stress and answered by intense plastic strain Become, generate a large amount of lattice defects, particle is decrystallized, material surface chemical bond rupture and generate unsaturated bond, free ion and electricity Son makes to increase in crystal, reduces temperature needed for generating reaction product.The equilibrium constant and reaction rate of substance reaction are normal Number significantly increases, and improves the diffusion coefficient of solid phase reaction, reduces reaction activity, so that lithium ion be made to be easier to diffuse into In titanium dioxide lattice, lithium titanium oxygen compound is formed.Stress, strain, the generation of defect and a large amount of nanometer crystal boundaries, phase boundary, make powder Last activity greatly improves.
In the reaction process of high-temperature machinery force chemistry, reaction pressure is constant, and the mechanical force of ball milling keeps powder further thin Change and disperse more uniform, in addition, ball milling appropriate has refined crystal grain, increased specific surface area, so as to improve power Condition makes just to will do it to obtain more complete reaction under the higher temperature long period originally, in lower temperature and short period Inside also it can be realized.Simultaneously as the presence of ball milling, reduces the generation of agglomeration.
Li is prepared with other4Ti5O12Ball milling operation high energy ball mill can only be carried out used in the method for powder to compare, In the present embodiment, the high temperature energy ball grinder (patent No.: CN200610047810) used, by calcining and ball milling same It is carried out simultaneously in high temperature furnace, reduces operating procedure, save the production time, new side is provided for large-scale industrial production Method.
Now in conjunction with Figure of description and specific embodiment, the present invention is further described:
Embodiment 1
As shown in Figure 1, being the reacting flow chart of the present embodiment, include the following steps:
S1, the TiOSO for taking 40g4Solid adds water to dissolve by heating, dropwise addition concentrated ammonia liquor adjusting solution to pH=7, and generates white It precipitates Ti (OH)4·nH2O。
Wherein, heating temperature is 60 DEG C.
S2, make that the precipitating is washed with deionized, filter and retain filter cake (precipitating), wash through deionized water to washing SO is free of in liquid4 2-Until ion, with the dilute nitric acid dissolution precipitating, TiO (NO is obtained3)2Solution.
Wherein, with the BaCl of 0.5mol/L2Solution examines in cleaning solution whether contain SO4 2-Ion.
S3, respectively by the C of 48g6H8O7With the LiNO of 14.13g3It is dissolved in deionized water, is stirring evenly and then adding into TiO (NO3)2Solution obtains mixed solution.
S4, concentrated ammonia liquor is added into mixed solution, mixed solution is adjusted to pH=6.
S5, it is stirred evaporation at a temperature of mixed solution is placed in 60 DEG C, after gel to be formed, gel is moved into corundum In crucible, being placed in 550 DEG C preheated of Muffle furnace makes its self-propagating combustion, obtains Li4Ti5O12Presoma.
S6, the Li that will be obtained4Ti5O12Presoma is put into stainless steel jar mill with ball material mass ratio 15:1, sealing.By ball Grinding jar is put into high temperature energy ball grinder burner hearth, is started ball mill, is persistently rotated with the revolving speed of 50r/min, while by burner hearth liter Temperature keeps the temperature 7h to 700 DEG C.
S7, closing ball mill wait for that burner hearth is cooled to room temperature, and take out ball grinder, obtain even-grained nanometer Li4Ti5O12Powder End.
As shown in Fig. 2, for Li in this implementation4Ti5O12The SEM of presoma schemes, it can be seen that low-temperature combustion synthesis Li4Ti5O12Presoma, pattern are spherical, uniform particle sizes, about 100nm.
It as shown in Figure 3,4, is final Li in the present embodiment4Ti5O12The SEM of powder schemes and granularity graph, it can be seen that Li4Ti5O12The partial size of powder is between 0.1~1 μm, and meso-position radius is about 200nm, and even size distribution, pattern is spherical.
Embodiment 2
S1, the TiOSO for taking 40g4Solid adds water to dissolve by heating, dropwise addition concentrated ammonia liquor adjusting solution to pH=7, and generates white It precipitates Ti (OH)4·nH2O。
Wherein, heating temperature is 65 DEG C.
S2, make that the precipitating is washed with deionized, filter and retain filter cake (precipitating), wash through deionized water to washing SO is free of in liquid4 2-Until ion, with the dilute nitric acid dissolution precipitating, TiO (NO is obtained3)2Solution.
Wherein, with the BaCl of 0.5mol/L2Solution examines in cleaning solution whether contain SO4 2-Ion.
S3, respectively by the C of 72g6H8O7With the LiNO of 14.48g3It is dissolved in deionized water, is stirring evenly and then adding into TiO (NO3)2Solution obtains mixed solution.
S4, concentrated ammonia liquor is added into mixed solution, mixed solution is adjusted to pH=7.
S5, it is stirred evaporation at a temperature of mixed solution is placed in 70 DEG C, after gel to be formed, gel is moved into corundum In crucible, being placed in 580 DEG C preheated of Muffle furnace makes its self-propagating combustion, obtains Li4Ti5O12Presoma.
S6, the Li that will be obtained4Ti5O12Presoma is put into stainless steel jar mill with ball material mass ratio 20:1, sealing.By ball Grinding jar is put into high temperature energy ball grinder burner hearth, is started ball mill, is persistently rotated with the revolving speed of 50r/min, while by burner hearth liter Temperature keeps the temperature 6h to 750 DEG C.
S7, closing ball mill wait for that burner hearth is cooled to room temperature, and take out ball grinder, obtain even-grained nanometer Li4Ti5O12Powder End.
Embodiment 3
S1, the TiOSO for taking 40g4Solid adds water to dissolve by heating, dropwise addition concentrated ammonia liquor adjusting solution to pH=7, and generates white It precipitates Ti (OH)4·nH2O。
Wherein, heating temperature is 70 DEG C.
S2, make that the precipitating is washed with deionized, filter and retain filter cake (precipitating), wash through deionized water to washing SO is free of in liquid4 2-Until ion, with the dilute nitric acid dissolution precipitating, TiO (NO is obtained3)2Solution.
Wherein, with the BaCl of 0.5mol/L2Solution examines in cleaning solution whether contain SO4 2-Ion.
S3, respectively by the C of 96g6H8O7With the LiNO of 14.82g3It is dissolved in deionized water, is stirring evenly and then adding into TiO (NO3)2Solution obtains mixed solution.
S4, concentrated ammonia liquor is added into mixed solution, mixed solution is adjusted to pH=8.
S5, it is stirred evaporation at a temperature of mixed solution is placed in 80 DEG C, after gel to be formed, gel is moved into corundum In crucible, being placed in 600 DEG C preheated of Muffle furnace makes its self-propagating combustion, obtains Li4Ti5O12Presoma.
S6, the Li that will be obtained4Ti5O12Presoma is put into stainless steel jar mill with ball material mass ratio 25:1, sealing.By ball Grinding jar is put into high temperature energy ball grinder burner hearth, is started ball mill, is persistently rotated with the revolving speed of 50r/min, while by burner hearth liter Temperature keeps the temperature 5h to 800 DEG C.
S7, closing ball mill wait for that burner hearth is cooled to room temperature, and take out ball grinder, obtain even-grained nanometer Li4Ti5O12Powder End.
The technical principle of the invention is described above in combination with a specific embodiment, these descriptions are intended merely to explain of the invention Principle shall not be construed in any way as a limitation of the scope of protection of the invention.Based on explaining herein, those skilled in the art It can associate with other specific embodiments of the invention without creative labor, these modes fall within this hair Within bright protection scope.

Claims (10)

1. a kind of Li4Ti5O12The preparation method of negative electrode material, which is characterized in that
Prepare Li4Ti5O12The step of presoma: it using titanium source, lithium source and organic matter as raw material, is prepared using low-temperature combustion method Li4Ti5O12Presoma；
The step of preparing powder: use high-temperature machinery force chemistry by the Li4Ti5O12Precursor preparation is at Li4Ti5O12Powder.
2. Li according to claim 14Ti5O12The preparation method of negative electrode material, which is characterized in that the Li4Ti5O12Before The preparation for driving body, includes the following steps:
S1, titanium source is dispersed in water, is mixed after heating for dissolving with concentrated ammonia liquor, obtain white precipitate；
S2, it precipitates, is obtained containing TiO described in dilute nitric acid dissolution2+Nitrate solution；
S3, contain TiO for described2+Nitrate solution mixed with organic matter, lithium source, the rear ammonium hydroxide that is added obtains mixed solution；
S4, the mixed solution is heated, carries out self-propagating combustion after forming gel, obtains the Li of low-temperature combustion synthesis4Ti5O12 Presoma.
3. Li according to claim 24Ti5O12The preparation method of negative electrode material, which is characterized in that the titanium source is sulfuric acid Oxygen titanium, titanium sulfate, titanium tetrachloride or butyl titanate；
The organic matter is citric acid, urea, triethanolamine or glycine；
The lithium source is lithium nitrate, lithium acetate or lithium carbonate.
4. Li according to claim 24Ti5O12The preparation method of negative electrode material, which is characterized in that in the step S3 Lithium source, the titanium source in the step S1, the organic matter in the step S3 molar concentration rate be 0.82~0.86:1:1~2.
5. Li according to claim 24Ti5O12The preparation method of negative electrode material, which is characterized in that in the step S1, The temperature of heating is 60~70 DEG C, and titanium source and the mixed solution of concentrated ammonia liquor are neutrality.
6. Li according to claim 24Ti5O12The preparation method of negative electrode material, which is characterized in that in the step S3, The pH value of mixed solution is greater than 5.
7. Li according to claim 24Ti5O12The preparation method of negative electrode material, which is characterized in that in the step S4, The temperature of heating is 60~80 DEG C, and the temperature of self-propagating combustion is 550~600 DEG C.
8. Li according to claim 14Ti5O12The preparation method of negative electrode material, which is characterized in that the preparation Li4Ti5O12The step of powder be 700~800 DEG C at a temperature of, by Li4Ti5O12Presoma carries out ball-milling treatment, obtains Li4Ti5O12Powder.
9. Li according to claim 84Ti5O12The preparation method of negative electrode material, which is characterized in that the ball-milling treatment Ball material mass ratio is 15~25:1.
10. Li according to claim 84Ti5O12The preparation method of negative electrode material, which is characterized in that the ball-milling treatment Time is 5~7h, and the revolving speed of the ball-milling treatment is 45~55r/min.
CN201811237536.XA 2018-10-23 2018-10-23 A kind of preparation method of Li4Ti5O12 negative electrode material Pending CN109336170A (en)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
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
CN110255609A (en) * 2019-06-17 2019-09-20 昆明理工大学 A kind of method of liquid-phase combustion preparation pure phase sodium titanate

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN110255609A (en) * 2019-06-17 2019-09-20 昆明理工大学 A kind of method of liquid-phase combustion preparation pure phase sodium titanate
CN110255609B (en) * 2019-06-17 2022-01-04 昆明理工大学 Method for preparing pure-phase sodium titanate by liquid-phase combustion

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