CN103956474A - Method for supercritically preparing lithium titanate aerosol nano-particles by using organic solvent - Google Patents

Method for supercritically preparing lithium titanate aerosol nano-particles by using organic solvent Download PDF

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CN103956474A
CN103956474A CN201410161924.XA CN201410161924A CN103956474A CN 103956474 A CN103956474 A CN 103956474A CN 201410161924 A CN201410161924 A CN 201410161924A CN 103956474 A CN103956474 A CN 103956474A
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organic solvent
lithium
nano particle
lithium titanate
titanate
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CN103956474B (en
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杨伟
王胜伟
王瑛
陈双喜
赵成龙
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Shandong Yuhuang New Energy Technology 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
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Inorganic Compounds Of Heavy Metals (AREA)
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Abstract

The invention relates to a preparation method of lithium titanate serving as a lithium battery anode material, and particularly relates to a method for supercritically preparing lithium titanate aerosol nano-particles by using an organic solvent. The method takes a titanium source, a lithium compound and an organic solvent as raw materials and is characterized by comprising the following steps: respectively dissolving the titanium source and the lithium compound in a part of the organic solvent under room temperature, then transferring to a high-pressure reactor lining, adding the rest of organic solvent, sealing and blowing; starting a heating and stirring reaction, and recycling the reacted organic solvent in a circulation condensing device, thus obtaining aerosol nano-particles; and carrying out heat treatment on the nano-particles to obtain a nanoscale product. The preparation method provided by the invention has the advantages that the preparation is simple, the cost is low, the effects of high stability and reliability are achieved, and the prepared lithium titanate powder has the excellent high rate capability and stability.

Description

The overcritical method of preparing lithium titanate aerosol shape nano particle of organic solvent
(1) technical field
The present invention relates to the preparation method of lithium battery cathode material lithium titanate, particularly a kind of overcritical method of preparing lithium titanate aerosol shape nano particle of organic solvent.
(2) background technology
The negative material of lithium ion battery adopts various material with carbon elements mostly at present, in use, material with carbon element easily with electrolyte generation solid electrolyte interface (Solid electrolyte interface, the SEI) film that easily reacts, thereby cause the decay of capacity, in addition Li +in the stratiform of material with carbon element, embed, the easy precipitating metal lithium of carbon material surface, this likely causes active lithium metal to react with electrolyte, can cause the inefficacy of structure after repeatedly circulating, and makes lithium ion battery cannot continue to use.Therefore, preparation has suitable embedding lithium current potential, good cyclical stability, and the Novel anode material of higher energy density is one of very significant problem.
Lithium titanate (the Li with spinel structure 4ti 5o 12) because its lattice constant in doff lithium process changes hardly, being called as " zero strain " material, lithium ion embeds therein and deviates from the structure of material in process and changes hardly, has in theory the cycle life of endless.Its theoretical embedding lithium current potential is 1.55V (vs.Li +/ Li) theoretical specific capacity safe, the advantage such as charge-discharge performance good, cycle performance is good, charging/discharging voltage platform stable that is that 175mAh/g. has, as cathode material of lithium-ion power battery, the rapid charge characteristic and the security performance that are expected to solve lithium ion battery, have good development and application prospect; Titanium resource is abundant, cheap in addition.These advantages become the lithium-ion-power cell electrode material that has development prospect.
Spinel-type Li 4ti 5o 12charge/discharge capacity and the cycle life impact that is subject to its synthetic method and condition very large, main synthetic method has the methods such as high temperature solid-state method, sol-gal process, spray heating decomposition, combustion method.Solid phase method is a kind of traditional powder preparation method, has the advantages such as cost is low, output is large, preparation technology is simple, is the conventional method of suitability for industrialized production.Conventionally, solid phase method (Hsiao K C, Liao S C, Chen J M, Microstructure effect on the electrochemical property of Li 4ti 5o 12as an anode material for lithium-ion batteries [J] .Electrochim.Acta, 2008 53 (24): 7242 ~ 7247.) can not provide gratifying granular size, pattern and uniformity, this will have influence on the chemical property of material greatly.The Li that uses sol-gal process to be synthesized 4ti 5o 12conventionally have the comparatively near cubical pattern of homogeneous, and particle diameter distribution is very narrow, chemical property is good, has shown higher electric discharge initial capacity and excellent stable circulation performance.Shortcoming is the synthetic cost of raw material higher (Zhang C M, Zhang Y Y, Wang J, Wang D, He D N, Xia Y Y, Li 4ti 5o 12prepared by a modified citric acid sol – gel method for lithium-ion battery[J] .J.Power Sources, 2013,236:118-125), therefore this method be not suitable for actual production application.Combustion synthesis method (Yuan T, Wang K, Cai R, et al. Cellulose-assisted combustion synthesis of Li 4ti 5o 12adopting anatase TiO 2solid as raw material with high electrochemical performance [J] .J.Alloys Compd., 2009,477 (1-2): 665 ~ 672.) its main process is that the nitrate of metal and flammable auxiliary material (as citric acid, urea, glycine) etc. are soluble in water, then it being warmed up to rapidly to solution seethes with excitement until smolder on fire, whole process finishes very soon, obtains loose powder.Prepared by combustion method is loose sample, but now the bulk density of powder obviously declines, and is unfavorable for improving energy density, and technique is very loaded down with trivial details, and the particle size distribution of sample is inhomogeneous.
In a word, about Li 4ti 5o 12present Research analysis, for synthetic powder, require particle size to be evenly distributed, granularity reaches micron or Nano grade, specific area is large, stable performance, batch consistent a grade for product become domestic and international preparation Li 4ti 5o 12main direction of studying.Because supercritical fluid has special physicochemical property, the character such as its surface tension, dielectric constant, density are very responsive to the variation of temperature and pressure, therefore, control by pressure and temperature just can regulate the character of supercritical fluid, shooting flow precursor reactant has become one of focus of people's research, supercritical fluid is as a kind of green and the adjustable reaction medium of physicochemical property, aspect synthesizing inorganic nano material, there is obvious advantage, synthesizing many metallic compound nano materials.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides a kind of overcritical method of preparing lithium titanate aerosol shape nano particle of simple, with low cost, reliable and stable organic solvent of preparing.
The present invention is achieved through the following technical solutions:
The overcritical method of preparing lithium titanate aerosol shape nano particle of organic solvent, take titanium source, lithium compound and organic solvent as raw material, comprises the steps:
(1), under room temperature, titanium source and lithium compound are utilized to ultrasonic wave is auxiliary to be dissolved in respectively in part organic solvent;
(2) above-mentioned two kinds of organic solvents are transferred in autoclave liner, add remaining organic solvent, enclosed high pressure reactor, with pure gas purging autoclave three times, get rid of oxygen in still, start heating and stir, band temperature rises to after 235-290 ℃, maintains reaction 30-300min;
(3) after reaction finishes, until temperature, reach after 180-200 ℃, open vent valve, in circulation condensation device, the organic solvent of reaction is reclaimed, to organic solvent-free outflow, reactor is naturally cooling, can obtain the nano particle of aerosol shape;
(4) collect aerosol shape nano particle, in gas atmosphere, be heated to 500-800 ℃, reaction is held time as 1-24h, obtains nanoscale product after heat treatment.
The mole of described titanium source and lithium compound is than being 0.5-1.5:0.4-1.2, and total consumption of organic solvent is 600-900ml.
Described organic solvent is a kind of in absolute methanol, absolute ethyl alcohol, normal propyl alcohol, isopropyl alcohol, n-butanol and isobutanol.
Described titanium source is a kind of in butyl titanate, tetraisopropyl titanate and titanium tetrachloride, preferably butyl titanate.
Described lithium compound is in nitric acid, one or more in lithium hydroxide, lithium chloride, lithium acetate and lithium oxalate.
In step (2), pure gas is a kind of in nitrogen, hydrogen, carbon dioxide and helium, preferred nitrogen.
Compared with prior art, the overcritical method of preparing lithium titanate aerosol shape nano particle of organic solvent involved in the present invention has following characteristics:
A) organic solvent that the present invention uses can, by cool solidifying device recycling, be conducive to cost-saving;
B) gained lithium titanate of the present invention is Nano grade, and nano-scale is 10nm, and distribution of sizes is compared with homogeneous;
C) lithium titanate in the present invention is very pure well coincide with the corresponding angle of diffraction of standard card JCPDS #49-0207 diffraction maximum;
The chemical property of the coated lithium titanate nano composite material of carbon that d) prepared by the present invention is superior, at 0.2C, puts in a situation, puts first more than a specific capacity reaches 170mAh/g.
The present invention is prepared simply, with low cost, reliable and stable, the Li preparing 4ti 5o 12powder, shows good high rate capability and stability.
(4) accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Fig. 1 is the x-ray diffractogram of powder spectrum (XRD) of embodiment 1 sample;
Fig. 2 is the transmission electron microscope figure (TEM) of embodiment 1 sample;
Fig. 3 is the charging and discharging curve under 0.2C of embodiment 1 sample;
Fig. 4 is the x-ray diffractogram of powder spectrum (XRD) of embodiment 2 samples;
Fig. 5 is the transmission electron microscope figure (TEM) of embodiment 2 samples;
Fig. 6 is the charging and discharging curve under 0.2C of embodiment 2 samples;
Fig. 7 is the x-ray diffractogram of powder spectrum (XRD) of embodiment 3 samples;
Fig. 8 is the x-ray diffractogram of powder spectrum (XRD) of embodiment 4 samples.
(5) embodiment
Below in conjunction with accompanying drawing explanation and embodiment, the present invention is further described.
Embodiment 1:
At room temperature, utilize ultrasonic wave assist in dissolving in dissolving in 200mol absolute ethyl alcohol 36.464g butyl titanate; At room temperature, according to stoichiometric proportion, according to formula M lI=M ti* 0.162079, calculate and add LiNO 3quality be 5.9101g, accurately weigh, by LiNO 3utilize ultrasonic wave assist in dissolving in dissolving in 200mol absolute ethyl alcohol; Above-mentioned two kinds of mixed solutions are added in reactor, in adding the absolute ethyl alcohol of 400ml, cumulative volume is 800ml, and regulating the Temperature Setting of reactor is 245 ℃, reactor initial speed is made as 500 turn/min, the rotating speed end time is 1h, before reaction starts, uses nitrogen blowing autoclave three times, make it get rid of the oxygen in still, open heating and stir switch, question response temperature in the kettle arrives after design temperature, maintains reaction time 1h.After reaction finishes, regulate reactor voltage, making heating voltage is 0V, opens the cool solidifying device of circulation, and temperature drops to 210 ℃ by the time, and general pressure is 2.1MPa, and the intake valve (or air outlet valve) of opening reactor regulates the flow velocity of giving vent to anger, and collects organic solvent.Treat that organic solvent-free flows out off-response device.The nano particle of collecting aerosol shape, in gas atmosphere, is heated to 700 ℃, and reaction is held time as 4h.After heat treatment, obtain nano level Li 4ti 5o 12sample.
Embodiment 2:
At room temperature, utilize ultrasonic wave assist in dissolving in dissolving in 200mol isopropyl alcohol 35.416g butyl titanate; At room temperature, according to stoichiometric proportion, according to formula M lI=M ti* 0.162079, calculate and add LiNO 3quality be 5.740g, accurately weigh, by LiNO 3utilize ultrasonic wave assist in dissolving in dissolving in 200mol isopropyl alcohol; Above-mentioned two kinds of mixed solutions are added in reactor, in adding the isopropyl alcohol of 400ml, cumulative volume is 800ml, and regulating the Temperature Setting of reactor is 235 ℃, reactor initial speed is made as 500 turn/min, the rotating speed end time is 1h, before reaction starts, uses nitrogen blowing autoclave three times, make it get rid of the oxygen in still, open heating and stir switch, question response temperature in the kettle arrives after design temperature, maintains reaction time 1h.After reaction finishes, regulate reactor voltage, making heating voltage is 0V, opens the cool solidifying device of circulation, and temperature drops to 205 ℃ by the time, and general pressure is 2MPa, and the intake valve (or air outlet valve) of opening reactor regulates the flow velocity of giving vent to anger, and collects anhydrous organic solvent.Treat that organic solvent-free flows out off-response device.The nano particle of collecting aerosol shape, in gas atmosphere, is heated to 700 ℃, and reaction is held time as 4h.After heat treatment, obtain nano level Li 4ti 5o 12sample.
Embodiment 3:
At room temperature, utilize ultrasonic wave assist in dissolving in dissolving in 200mol absolute methanol 19.530g butyl titanate; At room temperature, according to stoichiometric proportion, according to formula M lI=M ti* 0.0963, calculate that to add the quality of LiOH be 1.926g, accurately weigh, by LiNO 3utilize ultrasonic wave assist in dissolving in dissolving in 200mol absolute methanol; Above-mentioned two kinds of mixed solutions are added in reactor, in adding the absolute methanol of 400ml, cumulative volume is 700ml, and regulating the Temperature Setting of reactor is 241 ℃, reactor initial speed is made as 450 turn/min, the rotating speed end time is 1h, before reaction starts, uses nitrogen blowing autoclave three times, make it get rid of the oxygen in still, open heating and stir switch, question response temperature in the kettle arrives after design temperature, maintains reaction time 2h.After reaction finishes, regulate reactor voltage, making heating voltage is 0V, opens the cool solidifying device of circulation, and temperature drops to 210 ℃ by the time, and general pressure is 2.1MPa, and the intake valve (or air outlet valve) of opening reactor regulates the flow velocity of giving vent to anger, and collects organic solvent.Treat that organic solvent-free flows out off-response device.The nano particle of collecting aerosol shape, in gas atmosphere, is heated to 500 ℃, and reaction is held time as 4h.After heat treatment, obtain nano level Li 4ti 5o 12sample.
Embodiment 4:
At room temperature, utilize ultrasonic wave assist in dissolving in dissolving in 200mol n-butanol 34.813g butyl titanate; At room temperature, according to stoichiometric proportion, according to formula M lI=M ti* 0.162079, calculate and add LiNO 3quality be 5.643g, accurately weigh, by LiNO 3utilize ultrasonic wave assist in dissolving in dissolving in 200mol n-butanol; Above-mentioned two kinds of mixed solutions are added in reactor, in adding the n-butanol of 450ml, cumulative volume is 850ml, and regulating the Temperature Setting of reactor is 290 ℃, reactor initial speed is made as 500 turn/min, the rotating speed end time is 2h, before reaction starts, uses nitrogen blowing autoclave three times, make it get rid of the oxygen in still, open heating and stir switch, question response temperature in the kettle arrives after design temperature, maintains reaction time 2h.After reaction finishes, regulate reactor voltage, making heating voltage is 0V, opens the cool solidifying device of circulation, and temperature drops to 232 ℃ by the time, and general pressure is 0.2MPa, and the intake valve (or air outlet valve) of opening reactor regulates the flow velocity of giving vent to anger, and collects organic solvent.Treat that organic solvent-free flows out off-response device.The nano particle of collecting aerosol shape, in gas atmosphere, is heated to 700 ℃, and reaction is held time as 4h.After heat treatment, obtain nano level Li 4ti 5o 12sample.
Embodiment 5:
At room temperature, utilize ultrasonic wave assist in dissolving in dissolving in 200mol normal propyl alcohol 18.741 butyl titanates; At room temperature, according to stoichiometric proportion, according to formula M lI=M ti* 0.162079, calculate and add LiNO 3quality be 3.041g, accurately weigh, by LiNO 3utilize ultrasonic wave assist in dissolving in dissolving in 200mol normal propyl alcohol; Above-mentioned two kinds of mixed solutions are added in reactor, in adding the normal propyl alcohol of 450ml, cumulative volume is 850ml, and regulating the Temperature Setting of reactor is 235 ℃, reactor initial speed is made as 500 turn/min, the rotating speed end time is 1h, before reaction starts, uses nitrogen blowing autoclave, make it get rid of the oxygen in still, open heating and stir switch, question response temperature in the kettle arrives after design temperature, maintains reaction time 1h.After reaction finishes, regulate reactor voltage, making heating voltage is 0V, opens the cool solidifying device of circulation, and temperature drops to 200 ℃ by the time, and general pressure is 2MPa, and the intake valve (or air outlet valve) of opening reactor regulates the flow velocity of giving vent to anger, and collects anhydrous organic solvent.Treat that organic solvent-free flows out off-response device.The nano particle of collecting aerosol shape, in gas atmosphere, is heated to 700 ℃, and reaction is held time as 4h.After heat treatment, obtain nano level Li 4ti 5o 12sample.

Claims (6)

1. the overcritical method of preparing lithium titanate aerosol shape nano particle of organic solvent, take titanium source, lithium compound and organic solvent as raw material, it is characterized by, and comprises the steps:
(1), under room temperature, titanium source and lithium compound are utilized to ultrasonic wave is auxiliary to be dissolved in respectively in part organic solvent;
(2) above-mentioned two kinds of organic solvents are transferred in autoclave liner, add remaining organic solvent, enclosed high pressure reactor, with pure gas purging autoclave, get rid of oxygen in still, start heating and stir, band temperature rises to after 235-290 ℃, maintains reaction 30-300min;
(3) after reaction finishes, until temperature, reach after 180-200 ℃, open vent valve, in circulation condensation device, the organic solvent of reaction is reclaimed, to organic solvent-free outflow, reactor is naturally cooling, can obtain the nano particle of aerosol shape;
(4) collect aerosol shape nano particle, in gas atmosphere, be heated to 500-800 ℃, reaction is held time as 1-24h, obtains nanoscale product after heat treatment.
2. the overcritical method of preparing lithium titanate aerosol shape nano particle of organic solvent according to claim 1, is characterized in that: the mole of described titanium source and lithium compound is than being 0.5-1.5:0.4-1.2, and total consumption of organic solvent is 600-900ml.
3. the overcritical method of preparing lithium titanate aerosol shape nano particle of organic solvent according to claim 1, is characterized in that: described organic solvent is a kind of in absolute methanol, absolute ethyl alcohol, normal propyl alcohol, isopropyl alcohol, n-butanol and isobutanol.
4. the overcritical method of preparing lithium titanate aerosol shape nano particle of organic solvent according to claim 1, is characterized in that: described titanium source is a kind of in butyl titanate, tetraisopropyl titanate and titanium tetrachloride.
5. the overcritical method of preparing lithium titanate aerosol shape nano particle of organic solvent according to claim 1, is characterized in that: described lithium compound is in nitric acid, one or more in lithium hydroxide, lithium chloride, lithium acetate and lithium oxalate.
6. the overcritical method of preparing lithium titanate aerosol shape nano particle of organic solvent according to claim 1, is characterized in that: in step (2), pure gas is a kind of in nitrogen, hydrogen, carbon dioxide and helium.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1710742A (en) * 2004-06-18 2005-12-21 中国科学院过程工程研究所 Method for low-temp. preparing nano-crystal zirconium-oxide base solid electrolyte
US20120202120A1 (en) * 2011-02-07 2012-08-09 Korea Institute Of Science And Technology Synthesizing method for lithium titanium oxide nanoparticle using supercritical fluids
CN103094549A (en) * 2012-10-12 2013-05-08 合肥国轩高科动力能源股份公司 Supercritical hydro-thermal synthesizing method of lithium ion battery negative material lithium titanate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1710742A (en) * 2004-06-18 2005-12-21 中国科学院过程工程研究所 Method for low-temp. preparing nano-crystal zirconium-oxide base solid electrolyte
US20120202120A1 (en) * 2011-02-07 2012-08-09 Korea Institute Of Science And Technology Synthesizing method for lithium titanium oxide nanoparticle using supercritical fluids
CN103094549A (en) * 2012-10-12 2013-05-08 合肥国轩高科动力能源股份公司 Supercritical hydro-thermal synthesizing method of lithium ion battery negative material lithium titanate

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