CN110571428A - Pure-phase lithium titanate negative electrode material, preparation method thereof, negative electrode and battery - Google Patents

Pure-phase lithium titanate negative electrode material, preparation method thereof, negative electrode and battery Download PDF

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Publication number
CN110571428A
CN110571428A CN201910872209.XA CN201910872209A CN110571428A CN 110571428 A CN110571428 A CN 110571428A CN 201910872209 A CN201910872209 A CN 201910872209A CN 110571428 A CN110571428 A CN 110571428A
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negative electrode
electrode material
pure
lithium
lithium titanate
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何苗
邓晓千
冯叶锋
熊德平
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Guangdong University of Technology
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Guangdong University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—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
    • 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 the technical field of batteries, and particularly relates to a pure-phase lithium titanate negative electrode material, a preparation method thereof, a negative electrode and a battery. The invention provides a preparation method of a lithium titanate negative electrode material, which comprises the following steps: step 1, mixing a titanium source, a lithium source and a solvent to obtain a mixture; step 2, freezing the mixture to prepare an ice-cube-shaped solid mixture; step 3, carrying out vacuum drying treatment on the ice-cake-shaped solid mixture to obtain a dried substance; and 4, grinding the dried substance and then sintering to obtain the pure-phase lithium titanate negative electrode material. The pure-phase lithium titanate negative electrode material prepared by the method can effectively overcome the technical defects of low actual capacity and short cycle life in the charging and discharging process of the conventional lithium ion negative electrode material.

Description

Pure-phase lithium titanate negative electrode material, preparation method thereof, negative electrode and battery
Technical Field
the invention belongs to the technical field of electrochemistry, and particularly relates to a pure-phase lithium titanate negative electrode material, a preparation method thereof, a negative electrode and a battery.
Background
Today, the energy crisis is the focus of attention of many researchers, and people pay more and more attention to finding a novel energy storage device. And a large-scale energy storage technology is adopted, so that the development of renewable energy sources is facilitated, and the contradiction between power supply and demand is relieved. The battery energy storage is an important branch of an electric energy storage mode, and has the advantages of flexible configuration, high response speed, no limitation of external conditions such as geographic resources and the like, so that the battery energy storage is a mainstream energy storage mode. In battery energy storage, a lithium ion battery, as a typical representative of a novel energy source, has very obvious advantages, and becomes a secondary battery energy storage technology with the best comprehensive performance and the widest application at present by virtue of the advantages of high energy density, small self-discharge, high energy conversion efficiency, long cycle life and the like.
The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm and electrolyte, and the charge and discharge process of the lithium ion battery is realized by reversible cyclic intercalation and deintercalation of lithium ions between the positive electrode and the negative electrode. In a lithium ion battery, a negative electrode material is one of important factors influencing the capacity and the service life of the battery, and a passivation film is formed on the surface of carbon when the current commercialized carbon negative electrode material is charged and discharged for the first time, so that capacity loss is caused; carbon material intercalation potential and Li+The deposition potential is close, when the battery is overcharged, metal lithium may be precipitated on the surface of the carbon electrode to form Li dendrite to cause short circuit, and the carbon-based negative electrode material lithium ion battery has the problems of potential safety hazard and short cycle service life due to the influence of factors such as material pulverization during cycle use.
existing Li4Ti5O12the theoretical specific capacity of the Lithium Titanate (LTO) negative electrode material is 175mAh/g, the influence of lithium dendrite is avoided, the stable 1.55V platform potential is higher than the reduction potential of most electrolyte solvents, and an SEI film is not formed. However, the existing method for preparing the lithium titanate negative electrode material can cause the lithium titanate negative electrode material to generate agglomeration phenomena of different degrees, and the lithium titanate negative electrode material has small specific surface area, fast capacity attenuation and poor rate capability; meanwhile, the existing process for preparing lithium titanate cathode material is mostly a high-temperature solid-phase method, and the preparation method is used for preparing the lithium titanate cathode materialIt takes a long time.
Disclosure of Invention
In view of this, the application provides a pure-phase lithium titanate negative electrode material, a preparation method thereof, a negative electrode and a battery, which can effectively solve the technical defects of low actual capacity, short cycle life in the charge-discharge process, poor rate capability and long preparation time consumption of the existing lithium ion negative electrode material.
The invention provides a preparation method of a pure-phase lithium titanate negative electrode material, which comprises the following steps:
Step 1, mixing a titanium source, a lithium source and a solvent to obtain a mixture;
Step 2, freezing the mixture to prepare an ice-cube-shaped solid mixture;
Step 3, carrying out vacuum drying treatment on the ice-cake-shaped solid mixture to obtain a dried substance;
And 4, grinding the dried substance and then sintering to obtain the pure-phase lithium titanate negative electrode material.
Wherein, according to the chemical formula Li of lithium titanate4Ti5O12Stoichiometric ratio, the mass of the lithium source and the titanium source added respectively is weighed, and in order to enable the lithium source to react fully, the mass of the lithium source needs to be added 3-5 wt.% in excess after the stoichiometrically obtained mass of the addition.
Preferably, the titanium source and the solvent A are mixed to obtain a titanium source solution, and the lithium source and the solvent B are mixed to obtain a lithium source solution; the step 1 specifically comprises the following steps:
Firstly, mixing a titanium source with absolute ethyl alcohol, and then sequentially adding deionized water and nitric acid for mixing to obtain a clear and transparent titanium source solution;
Mixing a lithium source and water to obtain a lithium source solution;
Mixing the lithium source solution and the titanium source solution to obtain a mixture;
In the third step, the lithium source solution and the titanium source solution are mixed at the temperature of 80-100 ℃ to obtain a mixture.
specifically, in the first step, a titanium source is mixed with absolute ethyl alcohol to form a colorless and transparent solution 1, deionized water is added to form a milky white solution, nitric acid is added until the solution is completely clear and transparent to obtain a clear and transparent titanium source solution, and the mixing process is carried out at 80-90 ℃.
It is noted that, the application finds that the capacity and rate performance of the prepared pure-phase lithium titanate negative electrode material are better after nitric acid is added into a titanium source solution.
Preferably, the titanium source and the solvent can be mixed to obtain a titanium source solution, and the lithium source is directly mixed with the titanium source solution; the step 1 specifically comprises the following steps:
Step A, mixing a titanium source with absolute ethyl alcohol, and then adding deionized water and nitric acid for mixing to obtain a clear and transparent titanium source solution;
and step B, mixing the lithium source and the titanium source solution to obtain a mixture, wherein in the step B, the lithium source and the titanium source solution are mixed for 30-60 min at the temperature of 80-100 ℃ to obtain the mixture.
preferably, in step 1, the lithium source is selected from one or more of hydrated lithium hydroxide, lithium carbonate, lithium bromide and lithium nitrate; the molar concentration of the lithium source can be 0.5-2 mol/L.
More preferably, in step 1, the lithium source is selected from lithium carbonate or/and lithium nitrate.
Preferably, in step 1, the titanium source is selected from one or more of titanium dioxide P25, anatase titanium dioxide, butyl titanate, titanium isopropoxide or titanium tetrachloride.
preferably, in the step 1, the mixing temperature is 80-100 ℃, and the mixing time is 15-30 min.
Preferably, in the step 2, the freezing temperature of the freezing treatment is-10 ℃ to-75 ℃, and the freezing time of the freezing treatment is 12-24 h.
More preferably, in the step 2, the freezing temperature of the freezing treatment is-40 ℃ to-70 ℃, and the freezing time of the freezing treatment is 12-15 h.
Preferably, in the step 3, the drying temperature of the vacuum drying treatment is 10-40 ℃; the time of the vacuum drying treatment is 18-50 h.
More preferably, in the step 3, the drying temperature of the vacuum drying treatment is 10-25 ℃; the vacuum drying treatment time is 20-36 h.
Preferably, in the step 4, the temperature rise rate of the sintering is 3-5 ℃/min, the sintering temperature of the sintering is 800-850 ℃, and the sintering heat preservation time of the sintering is 12-15 h.
In step 4, the sintering atmosphere is air.
In step 4, the dried material is completely sintered in air at 800-850 ℃ to be maximally oxidized into the highest-priced titanium.
More preferably, in the step 4, the temperature rise rate of the sintering is 3-5 ℃/min, the sintering temperature of the sintering is 800 ℃, and the sintering heat preservation time of the sintering is 12-13 h.
Further, the application also provides a pure-phase lithium titanate negative electrode material, which comprises the pure-phase lithium titanate negative electrode material prepared by the preparation method.
Further, the application also provides a negative electrode, which comprises a negative electrode prepared from the pure-phase lithium titanate negative electrode material prepared by the preparation method.
The pure-phase lithium titanate negative electrode provided by the application can be prepared into a negative plate by a conventional method, for example, the pure-phase lithium titanate negative electrode material is weighed according to a certain mass proportion, acetylene black and an N-methylpyrrolidone solution of a binder PVDF are mixed (wherein the mass fraction of the pure-phase lithium titanate negative electrode material is more than 70%) and added into a small reagent bottle, and magnetic stirring is performed. And uniformly coating the obtained mixture slurry on a copper foil, drying in a vacuum drying oven, and taking out cut pieces to obtain the negative electrode.
further, the application also provides a sodium ion battery, which comprises a negative electrode made of the lithium titanate negative electrode material.
Furthermore, the invention also provides a lithium ion battery which comprises a negative electrode prepared from the negative electrode material prepared by the preparation method.
Further, the battery of the present invention is a battery produced by a conventional method, for example, the negative electrode sheet produced by using the negative electrode material of the present application as described above is used as a negative electrode, the positive electrode is a metal lithium sheet (counter electrode), the separator is polypropylene, and LiPF6for the electrolyte, the battery assembly was performed in a glove box filled with Ar to obtain a battery.
Wherein, pure phase lithium titanate negative electrode material: conductive agent: weighing and dropwise adding a prepared N-methyl pyrrolidone (NMP) solution of PVDF in a certain mass fraction at a ratio of 80:10: 10; then stirring for 8-24 h, and dropwise adding a small amount of NMP in the midway according to the viscosity of the slurry; after stirring uniformly, sucking the slurry by a dropper and dripping the slurry on a clean copper foil, and then uniformly coating the mixed slurry of the negative electrode material on the copper foil by using a scraper with the diameter of 20-50 mu m; placing the coated copper foil in a drying oven at 40-60 ℃ for 20-36 h, taking out, and cutting into pieces; weighing the cut pole pieces, and then drying the pole pieces in vacuum for 12-36 hours; 8. and assembling the button cell according to the cell assembling procedure, and then carrying out various performance tests. The vacuum drying condition is that the ultimate vacuum degree is 2.510-5Pa, the temperature is 40-60 ℃; the content of the pure-phase lithium titanate negative electrode material is 70-85 wt%, the content of the conductive agent is 10-20 wt%, and the content of the binder is 5-10 wt%. The anode material is selected from one or more of lithium cobaltate, lithium iron phosphate, lithium manganate and ternary anode materials, and the lithium metal sheet is adopted as an anode counter electrode material in the application. The conductive agent is selected from acetylene black or/and SuperP, and the conductive agent used in the application is acetylene black. The binder is oily binder polyvinylidene fluoride powder PVDF. The electrolyte is selected from electrolyte lithium salt and/or non-aqueous solvent, and the electrolyte used in the invention is 1M LiPF6EC：DMC(1:1)。
Referring to fig. 5, fig. 5 is a structural diagram of a lithium ion battery made of a pure-phase lithium titanate negative electrode material provided by the present invention. The battery is structurally characterized in that a positive electrode shell, a pure-phase lithium titanate negative electrode material (LTO), a diaphragm, a metal lithium sheet, a gasket, an elastic sheet and a negative electrode shell are arranged from bottom to top, wherein a proper amount of electrolyte is respectively dripped among the negative electrode material, the lithium sheet and the diaphragm.
Furthermore, the pure-phase lithium titanate negative electrode material can be prepared into a lithium ion battery and also can be prepared into a sodium ion battery.
This application utilizes the titanium source, three kinds of compositions of lithium source and solvent are freezing into cubic solid mixture of ice after directly mixing, structure through vacuum sublimation drying change lithium titanate, this application discovery is freezing earlier after the vacuum sublimation drying, the microstructure of pure phase lithium titanate negative electrode material is porous structure, do not discover to have the reunion phenomenon, porous structure has high porosity, low density and great specific surface area, can provide and store up the lithium position, and can provide the space for the volume expansion, reduce the negative effects that the volume expansion brought, thereby improve the capacity retention rate of negative electrode material lithium ion battery in charge-discharge process. The electrolyte is improved in moving speed to the electrode, a quick channel is provided for movement of lithium ions, and the structure of the pure-phase lithium titanate negative electrode material is stable due to the high stability of the porous structure, so that the specific capacity of the pure-phase lithium titanate negative electrode material is large, and the multiplying power is large. The preparation method mainly adopts a biochemical method of firstly freezing and then drying in vacuum, has simple process, does not need hydrothermal reaction or ball milling, does not need high-temperature solid phase operation or special equipment, has low preparation cost, is environment-friendly, and is suitable for large-scale industrial production. The preparation process disclosed by the application does not need to adopt a traditional high-temperature solid-phase method to prepare the pure-phase lithium titanate negative electrode material with the same quality, and the preparation time of the preparation process is shortened by 20-30% compared with that of the traditional high-temperature solid-phase method.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Fig. 1 is an XRD spectrum of a pure phase lithium titanate negative electrode material prepared in example 1 of the present invention;
Fig. 2 is an SEM image of a pure phase lithium titanate negative electrode material prepared in example 1 of the present invention;
fig. 3 is a long cycle performance and coulombic efficiency chart of a lithium ion battery made of the pure-phase lithium titanate negative electrode material prepared in example 1 of the present invention at 1C;
Fig. 4 is a graph of cycle performance and coulombic efficiency of a lithium ion battery made of the pure-phase lithium titanate negative electrode material prepared in example 1 of the present invention under different multiplying power;
Fig. 5 is a structural diagram of a lithium ion battery made of the pure-phase lithium titanate negative electrode material provided by the invention.
Detailed Description
The invention provides a preparation method of a pure-phase lithium titanate negative electrode material, a negative electrode and a battery, which can effectively overcome the technical defects of low actual capacity and short cycle life in the charging and discharging process of the conventional lithium ion negative electrode material.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials used in the following examples are all commercially available or self-made.
Example 1
The embodiment of the application provides a first preparation method of a pure-phase lithium titanate negative electrode material, which comprises the following steps:
1. According to Li4Ti5O1217.19g of n-butyl titanate is weighed according to the stoichiometric ratio, added into a 500mL beaker, 50mL of absolute ethyl alcohol is added into a water bath kettle at the temperature of 80 ℃, stirred fully to form a colorless and transparent n-butyl titanate solution, 50mL of deionized water is added into the n-butyl titanate solution, magnetic stirring is carried out fully to obtain a milky white solution, and HNO is dropped into the milky white solution3(the dosage of the nitric acid is until the milky solution becomes clear and transparent) until the solution is completely clear and transparent, so as to obtain a clear and transparent solution; wherein, the tetrabutyl titanate is hydrolyzed with the deionized water, so that the tetrabutyl titanate is firstly dissolved with the absolute ethyl alcohol;
According to Li4Ti5O12Weighing 2.87g (added in excess) of LiNO340mL of deionized water are added and stirred to prepare 1 mol/mL-l in lithium nitrate.
2. And (3) dropwise adding a lithium nitrate solution into the clear and transparent solution prepared in the step (1), stirring while dropwise adding in a water bath, and then continuously stirring for 30min at the temperature of 80 ℃ to obtain a mixture.
3. And (3) directly placing the mixture stirred in the step (2) in a freeze drying cold trap, freezing the mixture at the temperature of minus 70 ℃ into an ice-block-shaped solid mixture, taking out the mixture, placing the mixture above the cold trap, and carrying out vacuum drying for 36 hours at the drying temperature of 20 ℃ until the mixture is completely dried to obtain a dried substance.
4. And (3) taking out the dried substance obtained in the step (3), putting the dried substance into a corundum crucible, putting the corundum crucible into a muffle furnace, heating the corundum crucible to 800 ℃ in the air at the heating rate of 5 ℃/min, sintering, then preserving the heat for 12 hours, and finally naturally cooling to the room temperature to obtain the pure-phase lithium titanate negative electrode material.
5. And (3) weighing the pure-phase lithium titanate negative electrode material obtained in the step (4), mixing acetylene black and an NMP solution of a binder PVDF according to a mass ratio of 80:10:10, adding into a small reagent bottle, and magnetically stirring for 18 hours. And uniformly coating the obtained mixture slurry on a copper foil, drying in a vacuum drying oven at 60 ℃ for 12h, and taking out the cut pieces to obtain the negative plate. The pure-phase lithium titanate negative electrode material is a pure-phase LTO porous negative electrode material, the positive electrode is a metal lithium sheet (counter electrode), the diaphragm is polypropylene, and LiPF6for the electrolyte, the cell assembly was performed in a glove box filled with Ar gas, and then the assembled cell was subjected to electrochemical performance test.
the phase structure and microstructure of the pure-phase lithium titanate negative electrode material obtained in the embodiment are characterized and analyzed. As shown in fig. 1-2, fig. 1 is an XRD chart of the pure-phase lithium titanate negative electrode material provided in example 1 of the present application, and fig. 2 is an SEM chart of the pure-phase lithium titanate negative electrode material provided in example 1 of the present application. As known from XRD (X-ray diffraction) patterns, the diffraction peak of the pure-phase lithium titanate negative electrode material obtained in the embodiment has no impure phase and is pure Li4Ti5O12. In an SEM image of the pure-phase lithium titanate negative electrode material obtained in this example, it is found that after freeze vacuum sublimation drying, the microstructure thereof is a porous structure, and no agglomeration phenomenon is found.
Referring to fig. 3-4, fig. 3 is a long cycle performance and coulombic efficiency chart of a lithium ion battery made of the pure-phase lithium titanate negative electrode material prepared in example 1 of the present application at 1C; fig. 4 is a graph of cycle performance and coulombic efficiency of a lithium ion battery made of the pure-phase lithium titanate negative electrode material prepared in example 1 of the present application under different multiplying factors. Fig. 3 is a charge-discharge capacity and coulombic efficiency curve of a battery assembled by the pure-phase lithium titanate negative electrode material prepared in the embodiment under the same rate, the battery shows better cycle stability, and the specific capacity retention rate can reach 92.5% after 350 cycles under the rate of 1C. Fig. 4 shows that the pure-phase lithium titanate negative electrode material prepared by the method of the embodiment has good rate cycling performance, still has a large specific capacity under a rate of 2C, and the coulombic efficiency can reach 99.8% under different rates.
Compared with the conventional high-temperature solid-phase method, the time for preparing the pure-phase lithium titanate negative electrode material with the same quality is shortened by 20-30%, and the production efficiency is higher.
Example 2
embodiments of the present application provide a second pure-phase lithium titanate negative electrode material.
the same procedure as in example 1 was followed, except that: and 5, the mass ratio of the acetylene black to the binder PVDF of the pure-phase lithium titanate cathode material in the step 5 is 75:15: 10. The electrochemical performance of the assembled battery is tested at 25 ℃ and between 2.5 and 3.0V, and the result shows that the pure-phase lithium titanate negative electrode material has high specific capacity, stable circulation, excellent rate performance and excellent electrochemical performance. The specific capacity retention rate can reach 92.6 percent after 300 cycles under the multiplying power of 1C. And the specific capacity of 161mAh/g is still obtained under the 2C multiplying power, and the coulombic efficiency can reach 99.6 percent.
example 3
The embodiments of the present application provide a third pure phase lithium titanate negative electrode material.
The same procedure as in example 1 was followed, except that: the heating rate of the step 4 is 3 ℃/min, and the heat-preservation sintering time is 15 h. The electrochemical performance of the assembled battery is tested at 25 ℃ and between 2.5 and 3.0V, and the result shows that the pure-phase lithium titanate negative electrode material has high specific capacity, stable circulation, excellent rate performance and excellent electrochemical performance. The specific capacity retention rate can reach 92.3 percent after 300 cycles under the multiplying power of 1C. And the specific capacity of 162mAh/g is still obtained under the 2C multiplying power, and the coulombic efficiency can reach 99.7 percent.
Comparative example 1
The examples of the present application provide a first control product.
the same procedure as in example 1 was followed, except that: the sintering temperature in step 4 was 700 ℃ to obtain control 1. And carrying out electrochemical performance test on the assembled battery at 25 ℃ and between 2.5 and 3.0V. The results show that the control product 1 obtained by sintering at 700 ℃ has impurity phases, poor circulation stability and poorer rate capability than the product obtained in example 1. The specific capacity of the battery assembled by the comparison product 1 is low and is only 145 mAh/g. The specific capacity retention rate is only 72.3 percent after 300 cycles under the multiplying power of 1C; under a plurality of different multiplying powers, the specific capacity of only 45mAh/g is obtained under the 10C multiplying power.
Comparative example 2
The examples of the present application provide a second control product.
The same procedure as in example 1 was followed, except that: the sintering temperature in step 4 was 900 ℃ to obtain control product 2. And carrying out electrochemical performance test on the assembled battery at 25 ℃ and between 2.5 and 3.0V. The result shows that the control product 2 sintered at 900 ℃ has other lithium titanium oxide mixed phases, poor circulation stability and poorer rate capability than the control product of example 1. The specific capacity of the battery assembled by the comparison product 2 is low and is only 148 mAh/g. The specific capacity retention rate is only 72.9 percent after 300 cycles under the multiplying power of 1C; under a plurality of different multiplying factors, the specific capacity of 51mAh/g is only under 10C multiplying factor.
Comparative example 3
the examples of the present application provide a third control product.
The same procedure as in example 1 was followed, except that: the lithium source used in step 2 was hydrated lithium hydroxide to make control product 3. And carrying out electrochemical performance test on the assembled battery at 25 ℃ and between 2.5 and 3.0V. The results show that the control product 3 obtained by sintering under hydrated lithium hydroxide has other lithium titanium oxide hybrid phases, poor cycle stability and poorer rate performance than the control product obtained in example 1. The battery assembled by the comparison product 3 has low specific capacity, and is only 138 mAh/g. The specific capacity retention rate is only 71.3 percent after 300 cycles under the multiplying power of 1C; under a plurality of different multiplying powers, the specific capacity of only 45mAh/g is obtained under the 10C multiplying power. It can be seen from this comparative example that when hydrated lithium hydroxide is selected as the lithium source, the resulting battery negative electrode material has poor performance.
Comparative example 4
The examples of the present application provide a fourth control product.
The same procedure as in example 1 was followed, except that: step 1, preparing a solution without using nitric acid, namely:
1. Weighing 17.19 n-butyl titanate according to a stoichiometric ratio, adding the n-butyl titanate into a 500mL beaker, adding 50mL of absolute ethyl alcohol into a water bath kettle at the temperature of 80 ℃, fully stirring to form a colorless and transparent n-butyl titanate solution, adding 50mL of deionized water into the n-butyl titanate solution, and fully stirring by magnetic force to obtain a milky solution to obtain a solution;
Weighing 2.87g of LiNO according to the stoichiometric ratio340mL of deionized water was added thereto and stirred to prepare a 1mol/L lithium nitrate solution.
2. And (3) dropwise adding a lithium nitrate solution into the solution prepared in the step (1), stirring while dropwise adding in a water bath, and then continuously stirring for 30min to obtain a mixture.
3. And (3) directly placing the mixture stirred in the step (2) in a freeze drying cold trap, freezing the mixture at the temperature of minus 70 ℃ into an ice-block-shaped solid mixture, taking out the mixture, placing the mixture above the cold trap, and carrying out vacuum drying for 36 hours at the drying temperature of 20 ℃ until the mixture is completely dried to obtain a dried substance.
4. And (4) taking out the dried substance obtained in the step (3), putting the dried substance into a corundum crucible, putting the corundum crucible into a muffle furnace, heating the corundum crucible to 800 ℃ from room temperature at the heating rate of 5 ℃/min, sintering, then preserving heat for 12 hours, and finally naturally cooling to room temperature to obtain a control product 4. And carrying out electrochemical performance test on the assembled battery at 25 ℃ and between 2.5 and 3.0V. The result shows that the control product 4 obtained by sintering the n-butyl titanate solution prepared without nitric acid has other lithium titanium oxide mixed phases, poor circulation stability and poorer rate capability than that of the example 1. The specific capacity of the battery assembled by the comparison product 4 is low, and is only 156 mAh/g. The specific capacity retention rate is only 74.8% after 300 cycles at the rate of 1C; under a plurality of different multiplying powers, the specific capacity of only 65mAh/g is obtained under the 10C multiplying power.
the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a pure-phase lithium titanate negative electrode material is characterized by comprising the following steps:
step 1, mixing a titanium source, a lithium source and a solvent to obtain a mixture;
Step 2, freezing the mixture to prepare an ice-cube-shaped solid mixture;
step 3, carrying out vacuum drying treatment on the ice-cake-shaped solid mixture to obtain a dried substance;
And 4, grinding the dried substance and then sintering to obtain the lithium titanate negative electrode material.
2. The method according to claim 1, wherein in step 1, the lithium source is one or more selected from lithium carbonate, lithium bromide, and lithium nitrate.
3. The method according to claim 1, wherein in step 1, the titanium source is one or more selected from titanium dioxide P25, anatase titanium dioxide, butyl titanate, titanium isopropoxide, and titanium tetrachloride.
4. The method according to claim 1, wherein the mixing temperature is 80 to 100 ℃ and the mixing time is 15 to 30min in step 1.
5. The preparation method according to claim 1, wherein in the step 2, the freezing temperature of the freezing treatment is-10 ℃ to-75 ℃, and the freezing time of the freezing treatment is 12-24 h.
6. The method according to claim 1, wherein in step 3, the drying temperature of the vacuum drying treatment is 10 to 40 ℃, and the time of the vacuum drying treatment is 18 to 50 hours.
7. The preparation method according to claim 1, wherein in the step 4, the temperature rise rate of the sintering is 3-5 ℃/min, the sintering temperature of the sintering is 800-850 ℃, and the sintering holding time of the sintering is 12-15 h.
8. The pure-phase lithium titanate negative electrode material is characterized by comprising the pure-phase lithium titanate negative electrode material prepared by the preparation method according to any one of claims 1 to 8.
9. A negative electrode comprising the pure-phase lithium titanate negative electrode material prepared by the preparation method of any one of claims 1 to 8.
10. A battery comprising the negative electrode according to claim 9.
CN201910872209.XA 2019-09-16 2019-09-16 Pure-phase lithium titanate negative electrode material, preparation method thereof, negative electrode and battery Pending CN110571428A (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103771500A (en) * 2012-10-18 2014-05-07 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of lithium ion secondary battery with nanometer lithium titanate simultaneously doped at A and B site
CN104332604A (en) * 2014-11-05 2015-02-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of negative electrode material lithium titanate of lithium battery
CN106477623A (en) * 2016-09-12 2017-03-08 苏州大学 A kind of method for preparing bobbles shape lithium titanate
CN107226454A (en) * 2017-07-14 2017-10-03 东莞市迈科科技有限公司 A kind of preparation method of lithium titanate graphene composite negative pole
CN107706408A (en) * 2017-08-17 2018-02-16 中国第汽车股份有限公司 A kind of preparation method of nanofiber lithium titanate composite material
CN109360968A (en) * 2018-11-15 2019-02-19 成都新柯力化工科技有限公司 A kind of lithium titanate anode material and preparation method of the load of lamellar graphite alkene
EP3471179A1 (en) * 2017-03-21 2019-04-17 LG Chem, Ltd. Anode active material having high output characteristics, and lithium secondary battery comprising same
CN109786705A (en) * 2019-01-17 2019-05-21 禹城贝尔新材料有限公司 A kind of lithium titanate anode material and its preparation method and application with multistage carbon coating network structure
CN110092413A (en) * 2019-05-09 2019-08-06 云南中烟工业有限责任公司 A kind of method that spray drying-solid phase method prepares lithium titanate

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103771500A (en) * 2012-10-18 2014-05-07 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of lithium ion secondary battery with nanometer lithium titanate simultaneously doped at A and B site
CN104332604A (en) * 2014-11-05 2015-02-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of negative electrode material lithium titanate of lithium battery
CN106477623A (en) * 2016-09-12 2017-03-08 苏州大学 A kind of method for preparing bobbles shape lithium titanate
EP3471179A1 (en) * 2017-03-21 2019-04-17 LG Chem, Ltd. Anode active material having high output characteristics, and lithium secondary battery comprising same
CN107226454A (en) * 2017-07-14 2017-10-03 东莞市迈科科技有限公司 A kind of preparation method of lithium titanate graphene composite negative pole
CN107706408A (en) * 2017-08-17 2018-02-16 中国第汽车股份有限公司 A kind of preparation method of nanofiber lithium titanate composite material
CN109360968A (en) * 2018-11-15 2019-02-19 成都新柯力化工科技有限公司 A kind of lithium titanate anode material and preparation method of the load of lamellar graphite alkene
CN109786705A (en) * 2019-01-17 2019-05-21 禹城贝尔新材料有限公司 A kind of lithium titanate anode material and its preparation method and application with multistage carbon coating network structure
CN110092413A (en) * 2019-05-09 2019-08-06 云南中烟工业有限责任公司 A kind of method that spray drying-solid phase method prepares lithium titanate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
吴宇平，等: "《锂离子电池——应用与实践》", 31 January 2012 *

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