CN104538611B - One kind doping Na+Nano lithium titanate preparation method - Google Patents

One kind doping Na+Nano lithium titanate preparation method Download PDF

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CN104538611B
CN104538611B CN201410728404.2A CN201410728404A CN104538611B CN 104538611 B CN104538611 B CN 104538611B CN 201410728404 A CN201410728404 A CN 201410728404A CN 104538611 B CN104538611 B CN 104538611B
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lithium
sodium
lithium titanate
solution
doping
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CN104538611A (en
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何丹农
郭元
张春明
姚露露
郭松涛
宁子杨
黄昭
贺旷驰
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Shanghai Jiaotong University
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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

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  • General Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention provides one kind to adulterate Na+Nano lithium titanate preparation method, microemulsion reaction is carried out by Triton X-100/n-hexyl alcohol/hexamethylene microemulsion system and adulterates sodium ion, obtains LixNa4‑XTi5O12Negative material.Sodium lithium titanate particle dispersion effect prepared by the present invention is good, and particle agglomeration phenomenon is significantly improved and can more preferably control particle size.Obtained LiXNa4‑XTi5O12Possess higher charging and discharging capacity and relatively stable cycle performance, under room temperature condition, during 0.5C multiplying powers its discharge capacity has reached 177mAh/g first, close to theoretical capacity.Its discharge capacity has also reached more than 90mAh/g under 10C multiplying powers, and possesses relatively stable cycle performance, has broad application prospects in civilian portable electric appts or even power-equipment field.

Description

One kind doping Na+Nano lithium titanate preparation method
Technical field
It is especially a kind of the present invention relates to a kind of preparation method of lithium ion secondary battery cathode material lithium titanate sodium contaminated Adulterate Na+Nano lithium titanate preparation method.
Background technology
At present, lithium ion battery occupies the maximum capture of chargeable battery, is widely used in mobile phone, notebook electricity The civilian portable electric appts such as brain, MP3, in recent years, people are also gradually applied to power-equipment, lithium ion battery and stone The hybrid vehicle of oil also has been enter into market.Negative material is mostly carbon material used by commercially available lithium ion battery, but it In the presence of one it is fatal the problem of, i.e., when battery fast charge or when overcharging, electrode material surface may precipitating metal lithium, and form branch Crystalline substance causes short circuit, and this can not only reduce product service life, while there is also potential safety hazard.It is fast with lithium ion battery market Speed increase, there is an urgent need to the more preferable novel anode material of security performance.And spinelle Li4Ti5O12Just because of its zero strain, Gao An Full property starts to receive significant attention.
Li4Ti5O12With deficiency spinel structure, this special construction is determined during embedding and removing, its Lattice constant and Volume Changes are no more than 1%, thus its long lifespan, stable performance and safer.Li4Ti5O12With respect to lithium electricity The current potential of pole is about 1.55V, and discharge platform is gentle, theoretical specific capacity 175mAh/g, and because its reversible de- lithium ratio connects Nearly 100%, thus, the actual capacity for testing gained is closer to theoretical capacity, can reach 160 more than mAh/g substantially. But spinelle Li4Ti5O12A problem be present in the negative material as lithium ion battery --- due to Li4Ti5O12It is a kind of Intrinsic conductivity is only 10-9S/cm insulating materials, therefore electric conductivity extreme difference, cause under the conditions of high-multiplying power discharge, and electronics holds Easily enrichment, produce electrode polarization and then the insertion of limiting lithium ion and abjection, the final performance for influenceing battery.In order to solve this Problem, universal ameliorative way are to reduce Li4Ti5O12Particle size introduces the lifting that conductive materials realize electrical conductivity. Using the particle diameter and degree of scatter of microemulsion reaction controlling lithium titanate nano material, and Na is carried out to original crystal simultaneously and mixed It is miscellaneous.These two aspects acts on the particle size and size dispersity and introducing conductive materials of product simultaneously, influences its electrification Learn performance：Particle size is smaller, Li+Migration distance reduces, and chemical property is more preferably；Ratio of the sodium ion on 8a positions is more proper As Li+Deintercalation process just more smoothly, chemical property is more preferably.
The application tied up on Emulsions in lithium battery material synthesis, most classical is exactly to be synthesized using microemulsion system Barium titanate positive electrode, the present invention are based on this direction, it is intended to which microemulsion method is applied into doped lithium titanate nano material Synthesis in, so as to reach control granular size and using doping improve chemical property double achievement purposes.
The content of the invention
For in the prior art the defects of, it is an object of the invention to break through currently used a series of to prepare lithium titanate material The method of material, such as sol-gal process, high temperature solid-state method and hydro-thermal method, there is provided one kind is prepared with excellent using microemulsion reaction The method of the sodium lithium titanate negative material of chemical property.Sodium lithium titanate negative material prepared by this method shows excellent multiplying power Performance and cycle performance.
The present invention is achieved by the following technical solutions：
The present invention provides a kind of doping Na+Nano lithium titanate preparation method, methods described is by configuring polyethylene glycol Octyl phenyl ether/n-hexyl alcohol/hexamethylene microemulsion system carries out microemulsion reaction and adulterates sodium ion, obtains LiXNa4-XTi5O12 Negative material, comprise the following steps that：
Step 1, by surfactant, cosurfactant, deionized water (1~3) in mass ratio:1:30 premixs, are obtained mixed Solution is closed, deionized water is as follow-up Li and Na slightly solubles or the lytic agent of soluble compound；
Step 2, the mixed solution is subjected to magnetic agitation under normal temperature, makes solution clarification uniform, obtain solution A；
Step 3, by lithium and the slightly soluble or soluble compound of sodium, according to Li:Na=(3.9~3.98):(0.02~0.1) Mol ratio mixed, add appropriate amount of deionized water, obtain solution B；
Step 4, the solution B solution is added in the solution A, water bath with thermostatic control magnetic agitation, obtains homogeneous transparent Microemulsion system；
Step 5, Ti is compared by the amount of material:(Li+Na)=5:4 take appropriate soluble titanium compound, are dissolved in hexamethylene, Solution C, the mass ratio of hexamethylene and titanium source is 5:(1~3)；
Step 6, the microemulsion system is placed on the magnetic stirring apparatus of water bath with thermostatic control, then in the process being slowly stirred In dropwise plus the solution C, continue constant temperature stirring and be allowed to react, be aged；
Step 7, after the product after being aged in step 6 is centrifuged by supercentrifuge, organic solvent washing residual Surfactant；
Step 8, the product after step 7 is washed is placed in vacuum drying, finally gives white pigmented samples；
Step 9, the white pigmented samples are cleaned by ultrasonic 5 minutes with acetic acid, to remove the change of the lithium remained in sample and sodium Compound, centrifugal drying obtain pure sodium lithium titanate powder, sample segment are placed in air atmosphere after being heat-treated and produce lithium titanate Sodium.
Preferably, in step 1, the surfactant is Triton X-100.
Preferably, in step 1, the cosurfactant is the medium alcohols cosurfactant n-hexyl alcohol of chain length.
Preferably, in step 3, the slightly soluble or soluble lithium compounds are lithium carbonate, lithium chloride, lithium acetate, citric acid One kind in lithium, lithium oxalate, lithium formate, lithium lactate, isopropyl lithium alkoxide, long-chain or short-chain alkyl lithium.
Preferably, in step 3, the slightly soluble or soluble sodium compound are sodium carbonate, sodium acetate, sodium citrate, oxalic acid One kind in sodium, sodium formate, sodium lactate, sodium isopropylate, long-chain or short-chain alkyl sodium.
Preferably, in step 5, the soluble titanium compound is the chlorine of tetra-n-butyl titanate, tetraisopropyl titanate or titanium Compound.
Preferably, in step 6, continue constant temperature stirring and be allowed to react 1 hour, be aged 24 hours.
Preferably, in step 7, the organic solvent is absolute ethyl alcohol, isooctane or chloroform.
Preferably, in step 8, the vacuum drying temperature is 60~100 DEG C.
Preferably, in step 9, the temperature of the heat treatment is 600~900 DEG C, and the time is 6 hours, heating rate 5 ℃/h.Preferably, the acetic acid concentration is 0.05mol/L.
Compared with prior art, the present invention has following beneficial effect：
(1) Triton X-100/n-hexyl alcohol/hexamethylene microemulsion system of the present invention can be carried significantly High reactant controls particle size in the mixing homogeneity of molecular level, alleviation particle agglomeration phenomenon, is that one kind prepares carbonic acid The relatively new mode of lithium.
(2) the inventive method can further lift chemical property by adulterating process, be prepared with the present invention Product --- LiXNa4-XTi5O12It can be applied in the negative material field of lithium ion battery.
(3) Li made from the inventive methodXNa4-XTi5O12Possess higher charging and discharging capacity and relatively stable cyclicity Can, under room temperature condition, during 0.5C multiplying powers its discharge capacity has reached 177mAh/g first, close to theoretical capacity.Under 10C multiplying powers its Discharge capacity has also reached more than 90mAh/g, and possesses relatively stable cycle performance, in civilian portable electric appts or even Power-equipment field has broad application prospects.
Brief description of the drawings
The detailed description made by reading with reference to the following drawings to non-limiting example, further feature of the invention, Objects and advantages will become more apparent upon：
Fig. 1 is that the SEM of the product of the embodiment of the present invention 1 schemes；
Fig. 2 is that the TEM of the product of the embodiment of the present invention 2 schemes；
Fig. 3 is charge and discharge cycles curve of the product of the embodiment of the present invention 3 under different multiplying；
Fig. 4 be the product of the embodiment of the present invention 4 cyclic voltammetry curve figure.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention Protection domain.
Embodiment 1
The present embodiment is related to a kind of doping Na+Nano lithium titanate preparation method, specially following steps：
Step 1, it is 2mL Triton X-100s (chemistry is pure) and 2mL n-hexyl alcohols (analysis is pure) is mixed by premix composition Solution is closed, appropriate deionized water is added and forms 64mL lytic agents；
Step 2, this lytic agent is subjected to magnetic agitation under normal temperature, until solution clarification is uniform, obtains solution A；
Step 3, according to mol ratio Li:Na=3.98：0.02, take 0.4969g lithium carbonates (analysis is pure, wears into fine powder in advance) Mixed with 0.00358g sodium carbonate (analysis is pure), add 2mL deionized waters and shake up, obtain solution B；
Step 4, solution B is poured into the solution (solution A) that Triton X-100 and n-hexyl alcohol are well mixed, it is permanent Tepidarium magnetic agitation 20 minutes, obtains the microemulsion system of homogeneous transparent；
Step 5, Ti is compared by the amount of material:(Li+Na)=5:4 take 5.751g tetra-n-butyl titanates (analysis is pure), and its is molten Solution obtains solution C in 30mL hexamethylenes (analysis is pure)；
Step 6, microemulsion system before is continued to be placed on the magnetic stirring apparatus of water bath with thermostatic control, be then slowly stirred During the hexamethylene dissolved with tetra-n-butyl titanate is added dropwise, continue constant temperature stirring is allowed to react 1 hour, ageing 24 Hour；
Step 7, the product after being aged in step 6 is centrifuged by supercentrifuge, it is washed more with absolute ethyl alcohol Surfactant；
Step 8, above-mentioned product is dried in vacuo at 60 DEG C, final arrives white pigmented samples；
Step 9, obtained white pigmented samples are cleaned by ultrasonic 5 minutes with 0.05mol/L acetic acid, centrifugal drying obtains pure Sodium lithium titanate powder, by sample segment be placed in 600 DEG C be heat-treated 5h after it is standby, the product SEM figures of the present embodiment are shown in Fig. 1.
Embodiment 2
The present embodiment is related to a kind of doping Na+Nano lithium titanate preparation method, specially following steps：
Step 1, it is 4mL Triton X-100s (chemistry is pure) and 2mL n-hexyl alcohols (analysis is pure) is mixed by premix composition Solution is closed, appropriate deionized water is added and forms 66mL lytic agents；
Step 2, this lytic agent is subjected to magnetic agitation under normal temperature, until solution clarification is uniform, obtains solution A；
Step 3, according to mol ratio Li:Na=3.95：0.05, take 0.4932g lithium carbonates (analysis is pure, wears into fine powder in advance) Mixed with 0.00896g sodium carbonate (analysis is pure), add 2mL deionized waters and shake up, obtain solution B；
Step 4, solution B is poured into the solution that Triton X-100 and n-hexyl alcohol are well mixed, water bath with thermostatic control Magnetic agitation 20 minutes, obtains the microemulsion system of homogeneous transparent；
Step 5, Ti is compared by the amount of material:(Li+Na)=5:4 take 5.751g tetra-n-butyl titanates (analysis is pure), and its is molten Solution obtains solution C in 15mL hexamethylenes (analysis is pure)；
Step 6, microemulsion system before is continued to be placed on the magnetic stirring apparatus of water bath with thermostatic control, be then slowly stirred During the hexamethylene dissolved with tetra-n-butyl titanate is added dropwise, continue constant temperature stirring is allowed to react 1 hour, ageing 24 Hour；
Step 7, the product after being aged in step 6 is centrifuged by supercentrifuge, it is washed more with absolute ethyl alcohol Surfactant；
Step 8, above-mentioned product is dried in vacuo at 60 DEG C, final arrives white pigmented samples；
Step 9, obtained white pigmented samples are cleaned by ultrasonic 5 minutes with 0.05mol/L acetic acid, centrifugal drying obtains pure Sodium lithium titanate powder, by sample segment be placed in 700 DEG C be heat-treated 5h after it is standby, the product TEM figures of the present embodiment are shown in Fig. 2.
Embodiment 3
The present embodiment is related to a kind of doping Na+Nano lithium titanate preparation method, specially following steps：
Step 1, it is 6mL Triton X-100s (chemistry is pure) and 2mL n-hexyl alcohols (analysis is pure) is mixed by premix composition Solution is closed, appropriate deionized water is added and forms 68mL lytic agents；
Step 2, this lytic agent is subjected to magnetic agitation under normal temperature, until solution clarification is uniform, obtains solution A；
Step 3, according to mol ratio Li:Na=3.92：0.08, take 0.4894g lithium carbonates (analysis is pure, wears into fine powder in advance) Mixed with 0.0143g sodium carbonate (analysis is pure), add 2mL deionized waters and shake up, obtain solution B；
Step 4, solution B is poured into the solution that Triton X-100 and n-hexyl alcohol are well mixed, water bath with thermostatic control Magnetic agitation 20 minutes, obtains the microemulsion system of homogeneous transparent；
Step 5, Ti is compared by the amount of material:(Li+Na)=5:4 take 5.751g tetra-n-butyl titanates (analysis is pure), and its is molten Solution obtains solution C in 10mL hexamethylenes (analysis is pure)；
Step 6, microemulsion system before is continued to be placed on the magnetic stirring apparatus of water bath with thermostatic control, be then slowly stirred During the hexamethylene dissolved with tetra-n-butyl titanate is added dropwise, continue constant temperature stirring is allowed to react 1 hour.Ageing 24 Hour；
Step 7, the product after being aged in step 6 is centrifuged by supercentrifuge, it is washed more with absolute ethyl alcohol Surfactant；
Step 8, above-mentioned product is dried in vacuo at 60 DEG C, final arrives white pigmented samples；
Step 9, obtained white pigmented samples are cleaned by ultrasonic 5 minutes with 0.05mol/L acetic acid, centrifugal drying obtains pure Sodium lithium titanate powder, by sample segment be placed in 800 DEG C be heat-treated 5h after it is standby, the present embodiment product is under different multiplying Charge and discharge cycles curve map is shown in Fig. 3.
Embodiment 4
The present embodiment is related to a kind of doping Na+Nano lithium titanate preparation method, specially following steps：
Step 1, it is 6mL Triton X-100s (chemistry is pure) and 2mL n-hexyl alcohols (analysis is pure) is mixed by premix composition Solution is closed, appropriate deionized water is added and forms 68mL lytic agents；
Step 2, this lytic agent is subjected to magnetic agitation under normal temperature, until solution clarification is uniform, obtains solution A；
Step 3, according to mol ratio Li:Na=3.9：0.1, take 0.4869g lithium carbonates (analysis pure, wear into fine powder in advance) and 0.0179g sodium carbonate (analysis is pure) is mixed, and is added 2mL deionized waters and is shaken up, obtains solution B；
Step 4, solution B is poured into the solution that Triton X-100 and n-hexyl alcohol are well mixed, water bath with thermostatic control Magnetic agitation 20 minutes, obtains the microemulsion system of homogeneous transparent；
Step 5, Ti is compared by the amount of material:(Li+Na)=5:4 take 5.751g tetra-n-butyl titanates (analysis is pure), and its is molten Solution obtains solution C in 30mL hexamethylenes (analysis is pure)；
Step 6, microemulsion system before is continued to be placed on the magnetic stirring apparatus of water bath with thermostatic control, be then slowly stirred During the hexamethylene dissolved with tetra-n-butyl titanate is added dropwise, continue constant temperature stirring and be allowed to react 1 hour, ageing is 24 small When；
Step 7, the product after being aged in step 6 is centrifuged by supercentrifuge, it is washed more with absolute ethyl alcohol Surfactant.
Step 8, above-mentioned product is dried in vacuo at 60 DEG C, final arrives white pigmented samples；
Step 9, obtained white pigmented samples are cleaned by ultrasonic 5 minutes with 0.05mol/L acetic acid, centrifugal drying obtains pure Sodium lithium titanate powder, sample segment is placed in 900 DEG C be heat-treated it is standby after 5h, the present embodiment product cyclic voltammetric it is bent Line chart is shown in Fig. 4.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow Ring the substantive content of the present invention.

Claims (8)

1. one kind doping Na+Nano lithium titanate preparation method, it is characterised in that comprise the following steps：
Step 1, by surfactant, cosurfactant, deionized water (1~3) in mass ratio:1:30 premixs, must be mixed molten Liquid；The surfactant is Triton X-100, and the cosurfactant is n-hexyl alcohol；
Step 2, mixed solution described in step 1 is subjected to magnetic agitation under normal temperature, makes solution clarification uniform, obtain solution A；
Step 3, by lithium and the slightly soluble or soluble compound of sodium, according to Li:Na=(3.9~3.98):(0.02~0.1) rubs You are mixed ratio, are added appropriate amount of deionized water, are obtained solution B；
Step 4, the solution B is added in the solution A, water bath with thermostatic control magnetic agitation, obtains the microemulsion of homogeneous transparent System；
Step 5, Ti is compared by the amount of material:(Li+Na)=5:4 take soluble titanium compound, are dissolved in hexamethylene, obtain solution C, ring Hexane and the mass ratio of titanium source are 5:(1~3)；
Step 6, microemulsion system described in step 4 is placed on the magnetic stirring apparatus of water bath with thermostatic control, then in the mistake being slowly stirred Add the solution C in journey dropwise, continue constant temperature stirring and is allowed to react, is aged；
Step 7, after the product after being aged in step 6 is centrifuged by supercentrifuge, the table of organic solvent washing residual Face activating agent；
Step 8, the product vacuum after step 7 is washed is dried, and obtains white pigmented samples；
Step 9, the white pigmented samples are cleaned by ultrasonic with acetic acid, to remove the compound of the lithium remained in sample and sodium, centrifugation Dry pure sodium lithium titanate powder, sample segment is placed in air atmosphere after being heat-treated and produces sodium lithium titanate.
2. doping Na according to claim 1+Nano lithium titanate preparation method, it is characterised in that it is described in step 3 Slightly soluble or soluble lithium compounds are lithium carbonate, lithium chloride, lithium acetate, lithium citrate, lithium oxalate, lithium formate, lithium lactate, isopropyl One kind in lithium alkoxide, long-chain or short-chain alkyl lithium.
3. doping Na according to claim 1+Nano lithium titanate preparation method, it is characterised in that it is described in step 3 Slightly soluble or soluble sodium compound are sodium carbonate, sodium acetate, sodium citrate, sodium oxalate, sodium formate, sodium lactate, sodium isopropylate, length One kind in chain or short-chain alkyl sodium.
4. doping Na according to claim 1+Nano lithium titanate preparation method, it is characterised in that it is described in step 5 Soluble titanium compound is the chloride of tetra-n-butyl titanate, tetraisopropyl titanate or titanium.
5. according to the doping Na described in claim any one of 1-4+Nano lithium titanate preparation method, it is characterised in that step In 6, continue constant temperature stirring and be allowed to react 1 hour, be aged 24 hours.
6. according to the doping Na described in claim any one of 1-4+Nano lithium titanate preparation method, it is characterised in that step In 7, the organic solvent is absolute ethyl alcohol, isooctane or chloroform.
7. according to the doping Na described in claim any one of 1-4+Nano lithium titanate preparation method, it is characterised in that step In 8, the vacuum drying temperature is 60~100 DEG C.
8. according to the doping Na described in claim any one of 1-4+Nano lithium titanate preparation method, it is characterised in that step In 9, the temperature of the heat treatment is 600~900 DEG C, and the time is 6 hours, and heating rate is 5 DEG C/h；The acetic acid concentration is 0.05mol/L。
CN201410728404.2A 2014-12-03 2014-12-03 One kind doping Na+Nano lithium titanate preparation method Expired - Fee Related CN104538611B (en)

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