CN101580273A - High energy density spinel structural lithium titanate material and preparation method thereof - Google Patents

High energy density spinel structural lithium titanate material and preparation method thereof Download PDF

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CN101580273A
CN101580273A CNA2009100869463A CN200910086946A CN101580273A CN 101580273 A CN101580273 A CN 101580273A CN A2009100869463 A CNA2009100869463 A CN A2009100869463A CN 200910086946 A CN200910086946 A CN 200910086946A CN 101580273 A CN101580273 A CN 101580273A
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lithium
lithium titanate
energy density
high energy
preparation
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唐子龙
徐睿
张中太
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Tsinghua University
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Tsinghua University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • 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
    • Y02E60/13—Energy storage using capacitors
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Abstract

The invention relates to a high energy density spinel structural lithium titanate material and a preparation method thereof, belonging to the field of nano material preparation technology and energy. The preparation method comprises the following steps: taking cheap industrially produced titanium dioxide as a raw material and carrying out heat treatment on the titanium dioxide by an ultrasonic chemical water-heating method under reducing atmosphere to prepare a lithium titanate nano tube/wire, or taking lithium salt and titanium dioxide as raw materials and carrying out heat treatment on the lithium salt and titanium dioxide under reducing atmosphere to prepare lithium titanate submicron particulate, or carrying out heat treatment on the prepared spinel structural lithium titanate under reducing atmosphere. The high energy density lithium titanate materials obtained through heat treatment under reducing atmosphere can maintain higher capacity, better cyclical stability and longer service life under heavy current than the lithium titanate materials obtained through heat treatment in air, are suitable for serving as electrode materials of lithium ion batteries, supercapacitors or hybrid batteries and are expected to be applied to electric automobiles, etc.

Description

High energy density spinel structural lithium titanate material and preparation method thereof
Technical field
The present invention relates to the high charge-discharge magnification high energy density spinel structural lithium titanate, belong to nano material preparation technology and energy field.
Background technology
In recent years, spinel type lithium titanate comes into one's own day by day as the electrode materials of novel energy storage cell, this is because the lattice parameter of spinel type lithium titanate before and after lithium ion inserts and deviates from changes very little, be called " zero strain material " that lithium ion inserts, thereby can have excellent cyclical stability in theory.Simultaneously, characteristics such as spinel lithium titanate has good anti-over-charging performance and thermal stability, security is good and specific storage is big are a kind of novel lithium ion battery materials of excellence.Spinel type lithium titanate can also be applied to the electrode materials of ultracapacitor, for it provides high power density and energy density, has broad application prospects in fields such as electromobile and hybrid vehicles.
Li 4Ti 5O 12As the negative material of lithium ion battery, though capacity less than carbon negative pole material, it has the following advantages [127]: (1) embeds the stability that crystalline structure in the process of deviating from can keep height at lithium ion, makes it have good cycle performance and sparking voltage stably; (2) have higher electrode voltage, thereby avoided the generation of electrolyte decomposition phenomenon or protective membrane; (3) preparation Li 4Ti 5O 12Raw material sources abundanter.So Li 4Ti 5O 12A kind of more satisfactory lithium ion battery negative material that can replace carbon of can yet be regarded as.Present Li 4Ti 5O 12In the all-solid-state battery that adopts solid electrolyte, obtained suitable application.
The initial electronic conductivity of pure spinel lithium titanate is very low, has influenced the charge-discharge performance as lithium ion battery electrode material, and especially fast charging and discharging performance is very poor.Therefore, the level that reach practicability must be carried out modification to material.Modification is mainly carried out from two aspects, and the first improves its electronic conductivity, and it two is to reduce the path that grain-size shortens the lithium ion migration.
Among the present invention, adopting cheap industrial production titanium dioxide is starting material, heat-treat preparation lithium titanate nanotube/line through the sonochemistry hydrothermal method with under reducing atmosphere, or be raw material, under reducing atmosphere, heat-treat preparation lithium titanate submicron particles with lithium salts and titanium dioxide.These high specific energy lithium titanate materials that thermal treatment obtains through reducing atmosphere are compared with the lithium titanate material that thermal treatment in air obtains, and can keep higher capacity, better cyclical stability and longer work-ing life under big electric current.Be fit to the electrode materials of development, and be expected to be applied to aspect such as electromobile as lithium ion battery, ultracapacitor or hybrid battery.
Summary of the invention
The objective of the invention is to adopt cheap industrial production titanium dioxide is starting material, heat-treat preparation lithium titanate nanotube/line through the sonochemistry hydrothermal method with under reducing atmosphere, or be raw material with lithium salts and titanium dioxide, under reducing atmosphere, heat-treat preparation lithium titanate submicron particles, or under reducing atmosphere, the spinel header structure lithium titanate that has prepared is heat-treated.These high specific energy lithium titanate materials that thermal treatment obtains through reducing atmosphere are compared with the lithium titanate that thermal treatment in air obtains, and can keep higher capacity, better cyclical stability and longer work-ing life under big electric current.Wherein pass through in nitrogen heat treated lithium titanate submicron particles and (promptly put whole electric weight in 3.2min) under the high magnification of 19C loading capacity can reach 107mAh/g, loading capacity also can reach 60mAh/g and 40mAh/g under the ultra-high magnifications of 85C (promptly having put whole electric weight in 42.4s) and 212C (promptly having put whole electric weight in 17s).Under the charge-discharge magnification of 6C and 16.3C through 400 times the circulation after, still kept 100% capacity, be respectively 135mAh/g and 109mAh/g.This has shown in reducing atmosphere heat-treats lithium titanate, compare in air and heat-treat, not only can improve the high rate during charging-discharging of electrode, can also improve its cycle performance under high magnification greatly, be fit to the electrode materials of development, and be expected to be applied to aspect such as electromobile as lithium ion battery, ultracapacitor or hybrid battery.
The present invention is achieved through the following technical solutions:
The preparation method of common spinel lithium titanate nanotube/line: with 5g TiO 2With 70mL concentration is that the NaOH solution of 10M mixes, and is 0.2～0.5W/cm at power 2Following sonochemistry reaction 30 minutes, to move into volume then be 100mL, have in the autoclave of teflon lined and carry out hydro-thermal reaction 24-40h, hydrothermal temperature is 150-180 ℃.After reaction finishes, take out reactor, naturally cool to room temperature, opening the kettle cover after-filtration, is that the product to hydrothermal method washed 30 minutes under 3 the condition at pH with the nitric acid of 0.2M concentration, behind the vacuum filtration, product obtains the fluffy powder product of white after 80 ℃ of dryings, be H 2Ti 3O 7Nanotube/line.With 1.5g H 2Ti 3O 7Nanotube/line and 40mL LiOH aqueous solution stir, and moving into volume then is 50mL, have in the autoclave of teflon lined to carry out more than the hydro-thermal reaction 24h, and preparation nanotube/line hydrothermal temperature is 120-180 ℃.After reaction finishes, take out reactor, naturally cool to room temperature, open the kettle cover after-filtration, for several times with deionized water wash.Behind the vacuum filtration, filter cake with absolute ethanol washing for several times, product obtains the product of white after 80 ℃ of vacuum-drying.Product obtains having the Li of spinel structure after 350～600 ℃ of thermal treatment in air atmosphere 4Ti 5O 12Nanotube/line.
Above-mentioned common spinel lithium titanate nanotube/line is obtained high specific energy lithium titanate nanotube/line in reducing atmosphere after 300～600 ℃ of thermal treatment.Perhaps in the last heat treatment step of said process, change into directly and under reducing atmosphere, obtain high specific energy lithium titanate nanotube/line through 350～600 ℃ of thermal treatments.
The preparation method of common spinel lithium titanate submicron particles: a certain amount of lithium salts is dissolved in 20～40ml ethanol, add 3g titania powder (mol ratio of elemental lithium and titanium elements is 0.8: 1～1.08: 1), stir 4～6h, then at 100 ℃ of down dry 7～10h.Dried powder takes out, and grinds, sieves, thermal treatment 3h in 800 ℃ air atmosphere then, furnace cooling.
Common spinel lithium titanate submicron particles is obtained high energy density spinel lithium titanate submicron particles in reducing atmosphere after 300～400 ℃ of thermal treatment.Perhaps in the last heat treatment step of said process, change into directly and under reducing atmosphere, obtain high energy density spinel lithium titanate submicron particles through 800 ℃ of thermal treatments.
Material is carried out the composition of the test battery electrode diaphragm of electro-chemical test: anodal diaphragm adds a certain proportion of conductive agent acetylene black and binding agent polyvinylidene difluoride (PVDF) (PVDF) with heat treated spinel lithium titanate nanotube/line or submicron particles under the process reducing atmosphere as active substance.Wherein the quality of active substance accounts for 80% altogether, and the quality of conductive agent acetylene black and binding agent respectively accounts for 10%.
The process of assembling test battery: in through active substance, conductive agent acetylene black and binding agent PVDF after disperseing, add dispersion agent N-Methyl pyrrolidone (NMP) and form slurry, it was mixed fully in 4 hours the slurry stirring, and it is ultrasonic to place ultrasonic generator to carry out, and ultrasonic power is 0.2～0.5W/cm 2, 1 hour time.Coat equably on the conductive current collector aluminium foil with scraping the skill in using a kitchen knife in cookery then, in 85 ℃ of following vacuum, carry out punching after dry 1.5 hours.Packaged battery carries out in the glove box of argon gas atmosphere.Electrolytic solution adopts 1mol/L LiPF 6EC: DMC (1: 1) mixed solution, barrier film adopt Celgard 2400.
Description of drawings
Fig. 1 is the SEM image that does not pass through heat treated material under the nitrogen atmosphere among present method embodiment 1.
Fig. 2 is the SEM image of the material among present method embodiment 1.
Fig. 3 is that the specific storage of the test battery of the material among present method embodiment 1 contrasts with the discharge-rate change trend curve.
Fig. 4 is the cycle performance contrast of the test battery of the material among present method embodiment 1.
Fig. 5 is the cycle performance of the test battery of the material among present method embodiment 1.
Fig. 6 is the TEM image of the material among present method embodiment 2.
Fig. 7 is that the specific storage of test battery of the material among present method embodiment 2 is with the discharge-rate change trend curve.
Fig. 8 is the SEM image of the material among present method embodiment 3.
Fig. 9 is that the specific storage of test battery of the material among present method embodiment 3 is with the discharge-rate change trend curve.
Embodiment
Adopting cheap industrial production titanium dioxide is starting material, heat-treat preparation lithium titanate nanotube/line through the sonochemistry hydrothermal method with under reducing atmosphere, or be raw material with Lithium Acetate or Quilonum Retard and titanium dioxide, under reducing atmosphere, heat-treat preparation lithium titanate submicron particles, or under reducing atmosphere, the spinel header structure lithium titanate that has prepared is heat-treated.These high specific energy lithium titanate materials that thermal treatment obtains through reducing atmosphere are compared with the lithium titanate material that thermal treatment in air obtains, and can keep higher capacity, better cyclical stability and longer work-ing life under big electric current.Be fit to the electrode materials of development, and be expected to be applied to aspect such as electromobile as lithium ion battery, ultracapacitor or hybrid battery.
Embodiment 1
The lithium titanate with spinel structure submicron particles heat-treated under 350 ℃ of nitrogen atmospheres obtain the high energy density spinel structural lithium titanate submicron particles, test its performance, and compare with performance without the heat treated lithium titanate with spinel structure submicron particles of nitrogen:
3～4g Lithium Acetate is dissolved in 20～40ml ethanol, adds the 3g titania powder, stir 4～6h, then at 100 ℃ of down dry 7～10h.Dried powder takes out, and grinds, sieves, thermal treatment 3h in 800 ℃ air atmosphere then, furnace cooling.The common spinel lithium titanate submicron particles that obtains is being obtained high energy density spinel lithium titanate submicron particles under the nitrogen atmosphere, and testing its performance after 350 ℃ of thermal treatment.SEM image without heat treated lithium titanate with spinel structure submicron particles of nitrogen and product is seen Fig. 1 and Fig. 2.
Get high energy density spinel lithium titanate submicron particles 2.4g, binding agent polyvinylidene difluoride (PVDF) (PVDF) 0.3g and conductive agent acetylene black 0.3g.Mix the back and add the about 15ml of dispersion agent N-Methyl pyrrolidone (NMP), stirred 4 hours.On aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 85 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The process of assembling test battery: with anodal diaphragm diameter is 12 millimeters drift punching, and negative pole adopts the lithium sheet, assembling CR2032 type button test battery.Packaged battery carries out in the glove box of argon gas atmosphere.Electrolytic solution adopts 1mol/L LiPF 6EC: DMC (1: 1) mixed solution, barrier film adopt Celgard 2400.
The testing method of high energy density spinel lithium titanate submicron particles chemical property: under multiplying powers such as 0.1C, 0.5C, 1C, 6C, 16.3C, 19C, 85C, 103C, 212C, battery is carried out charge-discharge test respectively, and compare with common spinel lithium titanate submicron particles, obtain specific storage with discharge-rate changing trend diagram (Fig. 3) and cycle performance (Fig. 4 and Fig. 5).
Embodiment 2
Heat-treat with the sonochemistry hydrothermal method and under 3% (volume) hydrogen/argon gas atmosphere of 350 ℃ and to obtain the high energy density spinel structural lithium titanate nanotube, and test its performance:
With 5g TiO 2With 70mL concentration is that the NaOH solution of 10M mixes, and is 0.2～0.5W/cm at power 2Following sonochemistry reaction 30 minutes, to move into volume then be 100mL, have in the autoclave of teflon lined and carry out hydro-thermal reaction 24h, hydrothermal temperature is 150 ℃.After reaction finishes, take out reactor, naturally cool to room temperature, opening the kettle cover after-filtration, is that the product to hydrothermal method washed 30 minutes under 3 the condition at pH with the nitric acid of 0.2M concentration, behind the vacuum filtration, product obtains the fluffy powder product of white after 80 ℃ of dryings, be H 2Ti 3O 7Nanotube.With 1.5g H 2Ti 3O 7Nanotube and 40mL LiOH aqueous solution stir, and moving into volume then is 50mL, have in the autoclave of teflon lined to carry out more than the hydro-thermal reaction 40h, and preparation nanotube hydrothermal temperature is 150 ℃.After reaction finishes, take out reactor, naturally cool to room temperature, open the kettle cover after-filtration, for several times with deionized water wash.Behind the vacuum filtration, filter cake with absolute ethanol washing for several times, product obtains the product of white after 80 ℃ of vacuum-drying.Product obtains the Li of high energy density spinel structural after 350 ℃ of thermal treatment in 3% (volume) hydrogen/argon gas atmosphere 4Ti 5O 12Nanotube.The TEM image of product is seen Fig. 6.
Get high energy density spinel lithium titanate nanotube 2.4g, binding agent polyvinylidene difluoride (PVDF) (PVDF) 0.3g and conductive agent acetylene black 0.3g.Mix the back and add the about 15ml of dispersion agent N-Methyl pyrrolidone (NMP), stirred 4 hours, and the excusing from death wavelength-division that places the excusing from death wave producer to carry out 1 hour is loose.On aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 85 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The process of assembling test battery: with anodal diaphragm diameter is 12 millimeters drift punching, and negative pole adopts the lithium sheet, assembling CR2032 type button test battery.Packaged battery carries out in the glove box of argon gas atmosphere.Electrolytic solution adopts 1mol/L LiPF 6EC: DMC (1: 1) mixed solution, barrier film adopt Celgard 2400.
The testing method of the chemical property of high energy density spinel lithium titanate nanotube: under multiplying powers such as 0.1C, 0.5C, 1C, 2.3C, 6C, 13.7C, 26.7C, 40C, battery is carried out charge-discharge test respectively, obtain specific storage with discharge-rate variation tendency (Fig. 7).
Embodiment 3
Heat-treat under 800 ℃ of nitrogen atmospheres with solid phase method and to obtain the high energy density spinel structural lithium titanate submicron particles, and test its performance:
3～4g Lithium Acetate is dissolved in 20～40ml ethanol, adds the 3g titania powder, stir 4～6h, then at 100 ℃ of down dry 7～10h.Dried powder takes out, and grind, sieve, thermal treatment 3h in 800 ℃ nitrogen atmosphere atmosphere then, furnace cooling obtains high energy density spinel lithium titanate submicron particles, and tests its performance.The SEM image of product is seen Fig. 8.
Get high energy density spinel lithium titanate submicron particles 2.4g, binding agent polyvinylidene difluoride (PVDF) (PVDF) 0.3g and conductive agent acetylene black 0.3g.Mix the back and add the about 15ml of dispersion agent N-Methyl pyrrolidone (NMP), stirred 4 hours.On aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 85 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The process of assembling test battery: with anodal diaphragm diameter is 12 millimeters drift punching, and negative pole adopts the lithium sheet, assembling CR2032 type button test battery.Packaged battery carries out in the glove box of argon gas atmosphere.Electrolytic solution adopts 1mol/L LiPF 6EC: DMC (1: 1) mixed solution, barrier film adopt Celgard 2400.
The testing method of high energy density spinel lithium titanate submicron particles chemical property: under multiplying powers such as 0.1C, 0.5C, 1C, 3C, 7C, 15C, 30C, 80C, 100C, battery is carried out charge-discharge test respectively, obtain specific storage with discharge-rate variation tendency (Fig. 9).
Embodiment 4
The lithium titanate with spinel structure submicron particles heat-treated under 300 ℃ of nitrogen atmospheres obtain the high energy density spinel structural lithium titanate submicron particles and test its performance.
3～4g Lithium Acetate is dissolved in 20～40ml ethanol, adds the 3g titania powder, stir 4～6h, then at 100 ℃ of down dry 7～10h.Dried powder takes out, and grinds, sieves, thermal treatment 3h in 800 ℃ air atmosphere then, furnace cooling.The common spinel lithium titanate submicron particles that obtains is obtained high energy density spinel lithium titanate submicron particles after thermal treatment under 300 ℃ of nitrogen atmospheres, and test its performance.
Get high energy density spinel lithium titanate submicron particles 2.4g, binding agent polyvinylidene difluoride (PVDF) (PVDF) 0.3g and conductive agent acetylene black 0.3g.Mix the back and add the about 15ml of dispersion agent N-Methyl pyrrolidone (NMP), stirred 4 hours.On aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 85 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The process of assembling test battery: with anodal diaphragm diameter is 12 millimeters drift punching, and negative pole adopts the lithium sheet, assembling CR2032 type button test battery.Packaged battery carries out in the glove box of argon gas atmosphere.Electrolytic solution adopts 1mol/L LiPF 6EC: DMC (1: 1) mixed solution, barrier film adopt Celgard 2400.
The testing method of high energy density spinel lithium titanate submicron particles chemical property: under multiplying powers such as 0.1C, 0.5C, 1C, 5C, 10C, 20C, 50C, 100C, 200C, battery is carried out charge-discharge test respectively, obtain its specific storage and be respectively 157mAh/g, 156mAh/g, 155mAh/g, 135mAh/g, 117mAh/g, 100mAh/g, 80mAh/g, 52mAh/g, 32mAh/g.
Embodiment 5
The lithium titanate with spinel structure submicron particles heat-treated through 400 ℃ under 3% (volume) hydrogen/argon gas atmosphere obtain the high energy density spinel structural lithium titanate submicron particles and test its performance.
3～4g Lithium Acetate is dissolved in 20～40ml ethanol, adds the 3g titania powder, stir 4～6h, then at 100 ℃ of down dry 7～10h.Dried powder takes out, and grinds, sieves, thermal treatment 3h in 800 ℃ air atmosphere then, furnace cooling.The common spinel lithium titanate submicron particles that obtains is obtained high energy density spinel lithium titanate submicron particles under 3% (volume) hydrogen/argon gas atmosphere, and test its performance after 400 ℃ of thermal treatment.
Get high energy density spinel lithium titanate submicron particles 2.4g, binding agent polyvinylidene difluoride (PVDF) (PVDF) 0.3g and conductive agent acetylene black 0.3g.Mix the back and add the about 15ml of dispersion agent N-Methyl pyrrolidone (NMP), stirred 4 hours.On aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 85 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The process of assembling test battery: with anodal diaphragm diameter is 12 millimeters drift punching, and negative pole adopts the lithium sheet, assembling CR2032 type button test battery.Packaged battery carries out in the glove box of argon gas atmosphere.Electrolytic solution adopts 1mol/L LiPF 6EC: DMC (1: 1) mixed solution, barrier film adopt Celgard 2400.
The testing method of high energy density spinel lithium titanate submicron particles chemical property: under multiplying powers such as 0.1C, 0.5C, 1C, 5C, 10C, 20C, 50C, 100C, 200C, battery is carried out charge-discharge test respectively, obtain its specific storage and be respectively 157mAh/g, 154mAh/g, 154mAh/g, 133mAh/g, 115mAh/g, 102mAh/g, 81mAh/g, 52mAh/g, 33mAh/g.
Embodiment 6
The lithium titanate with spinel structure submicron particles heat-treated under 450 ℃ of nitrogen atmospheres obtain the high energy density spinel structural lithium titanate submicron particles and test its performance.
3～4g Lithium Acetate is dissolved in 20～40ml ethanol, adds the 3g titania powder, stir 4～6h, then at 100 ℃ of down dry 7～10h.Dried powder takes out, and grinds, sieves, thermal treatment 3h in 800 ℃ air atmosphere then, furnace cooling.The common spinel lithium titanate submicron particles that obtains is obtained high energy density spinel lithium titanate submicron particles at nitrogen atmosphere after 450 ℃ of thermal treatment, and test its performance.
Get high energy density spinel lithium titanate submicron particles 2.4g, binding agent polyvinylidene difluoride (PVDF) (PVDF) 0.3g and conductive agent acetylene black 0.3g.Mix the back and add the about 15ml of dispersion agent N-Methyl pyrrolidone (NMP), stirred 4 hours.On aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 85 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The process of assembling test battery: with anodal diaphragm diameter is 12 millimeters drift punching, and negative pole adopts the lithium sheet, assembling CR2032 type button test battery.Packaged battery carries out in the glove box of argon gas atmosphere.Electrolytic solution adopts 1mol/L LiPF 6EC: DMC (1: 1) mixed solution, barrier film adopt Celgard 2400.
The testing method of high energy density spinel lithium titanate submicron particles chemical property: under multiplying powers such as 0.1C, 0.5C, 1C, 5C, 10C, 20C, 50C, 100C, 200C, battery is carried out charge-discharge test respectively, obtain its specific storage and be respectively 156mAh/g, 156mAh/g, 155mAh/g, 132mAh/g, 116mAh/g, 101mAh/g, 81mAh/g, 51mAh/g, 34mAh/g.
Embodiment 7
Heat-treat with the sonochemistry hydrothermal method and under 3% (volume) hydrogen/argon gas atmosphere of 400 ℃ and to obtain the high energy density spinel structural lithium titanate nanotube, and test its performance:
With 5g TiO 2With 70mL concentration is that the NaOH solution of 10M mixes, and is 0.2～0.5W/cm at power 2Following sonochemistry reaction 30 minutes, to move into volume then be 100mL, have in the autoclave of teflon lined and carry out hydro-thermal reaction 24h, hydrothermal temperature is 150 ℃.After reaction finishes, take out reactor, naturally cool to room temperature, opening the kettle cover after-filtration, is that the product to hydrothermal method washed 30 minutes under 3 the condition at pH with the nitric acid of 0.2M concentration, behind the vacuum filtration, product obtains the fluffy powder product of white after 80 ℃ of dryings, be H 2Ti 3O 7Nanotube.With 1.5g H 2Ti 3O 7Nanotube and 40mL LiOH aqueous solution stir, and moving into volume then is 50mL, have in the autoclave of teflon lined to carry out more than the hydro-thermal reaction 40h, and preparation nanotube hydrothermal temperature is 150 ℃.After reaction finishes, take out reactor, naturally cool to room temperature, open the kettle cover after-filtration, for several times with deionized water wash.Behind the vacuum filtration, filter cake with absolute ethanol washing for several times, product obtains the product of white after 80 ℃ of vacuum-drying.Product obtains the Li of high energy density spinel structural after 400 ℃ of thermal treatment in 3% (volume) hydrogen/argon gas atmosphere 4Ti 5O 12Nanotube.The TEM image of product is seen Fig. 6.
Get high energy density spinel lithium titanate nanotube 2.4g, binding agent polyvinylidene difluoride (PVDF) (PVDF) 0.3g and conductive agent acetylene black 0.3g.Mix the back and add the about 15ml of dispersion agent N-Methyl pyrrolidone (NMP), stirred 4 hours, and the excusing from death wavelength-division that places the excusing from death wave producer to carry out 1 hour is loose.On aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 85 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The process of assembling test battery: with anodal diaphragm diameter is 12 millimeters drift punching, and negative pole adopts the lithium sheet, assembling CR2032 type button test battery.Packaged battery carries out in the glove box of argon gas atmosphere.Electrolytic solution adopts 1mol/L LiPF 6EC: DMC (1: 1) mixed solution, barrier film adopt Celgard 2400.
The testing method of the chemical property of high energy density spinel lithium titanate nanotube: under multiplying powers such as 0.1C, 0.5C, 1C, 2C, 5C, 10C, 30C, 50C, battery is carried out charge-discharge test respectively, obtain its specific storage and be respectively 165mAh/g, 154mAh/g, 151mAh/g, 148mAh/g, 145mAh/g, 138mAh/g, 128mAh/g, 124mAh/g.
Embodiment 8
Heat-treat with the sonochemistry hydrothermal method and under 450 ℃ nitrogen atmosphere and to obtain the high energy density spinel structural lithium titanate nanotube, and test its performance:
With 5g TiO 2With 70mL concentration is that the NaOH solution of 10M mixes, and is 0.2～0.5W/cm at power 2Following sonochemistry reaction 30 minutes, to move into volume then be 100mL, have in the autoclave of teflon lined and carry out hydro-thermal reaction 24h, hydrothermal temperature is 150 ℃.After reaction finishes, take out reactor, naturally cool to room temperature, opening the kettle cover after-filtration, is that the product to hydrothermal method washed 30 minutes under 3 the condition at pH with the nitric acid of 0.2M concentration, behind the vacuum filtration, product obtains the fluffy powder product of white after 80 ℃ of dryings, be H 2Ti 3O 7Nanotube.With 1.5g H 2Ti 3O 7Nanotube and 40mL LiOH aqueous solution stir, and moving into volume then is 50mL, have in the autoclave of teflon lined to carry out more than the hydro-thermal reaction 40h, and preparation nanotube hydrothermal temperature is 150 ℃.After reaction finishes, take out reactor, naturally cool to room temperature, open the kettle cover after-filtration, for several times with deionized water wash.Behind the vacuum filtration, filter cake with absolute ethanol washing for several times, product obtains the product of white after 80 ℃ of vacuum-drying.Product obtains the Li of high energy density spinel structural after 450 ℃ of thermal treatment in nitrogen atmosphere 4Ti 5O 12Nanotube.The TEM image of product is seen Fig. 6.
Get high energy density spinel lithium titanate nanotube 2.4g, binding agent polyvinylidene difluoride (PVDF) (PVDF) 0.3g and conductive agent acetylene black 0.3g.Mix the back and add the about 15ml of dispersion agent N-Methyl pyrrolidone (NMP), stirred 4 hours, and the excusing from death wavelength-division that places the excusing from death wave producer to carry out 1 hour is loose.On aluminium foil, carry out curtain coating with scraping the skill in using a kitchen knife in cookery then, and place 85 ℃ of following vacuum to obtain anodal diaphragm after dry 1.5 hours.
The process of assembling test battery: with anodal diaphragm diameter is 12 millimeters drift punching, and negative pole adopts the lithium sheet, assembling CR2032 type button test battery.Packaged battery carries out in the glove box of argon gas atmosphere.Electrolytic solution adopts 1mol/L LiPF 6EC: DMC (1: 1) mixed solution, barrier film adopt Celgard 2400.
The testing method of the chemical property of high energy density spinel lithium titanate nanotube: under multiplying powers such as 0.1C, 0.5C, 1C, 2C, 5C, 10C, 30C, 50C, battery is carried out charge-discharge test respectively, obtain its specific storage and be respectively 161mAh/g, 152mAh/g, 151mAh/g, 145mAh/g, 142mAh/g, 135mAh/g, 124mAh/g, 120mAh/g.

Claims (7)

1, high energy density spinel structural lithium titanate material is characterized in that, described material is by hydrothermal method and heat-treats the high energy density spinel structural lithium titanate nanotube or the line of preparation under reducing atmosphere.
2, the method for preparation high energy density spinel structural lithium titanate material as claimed in claim 1, this method contains following steps:
(1) with TiO 2Mix with NaOH solution, carry out sonochemistry reaction after, carry out hydro-thermal reaction, hydrothermal temperature is 150-180 ℃:
(2) after reaction finishes, wash with the product of diluted acid to hydrothermal method, behind the vacuum filtration, product obtains the fluffy powder product of white after drying, is H 2Ti 3O 7Nanotube or line;
(3) with H 2Ti 3O 7Nanotube or line and LiOH aqueous solution are carried out hydro-thermal reaction, and preparation nanotube or line hydrothermal temperature are 120-180 ℃;
(4) after reaction finishes, use the deionized water wash product, behind the vacuum filtration, filter cake absolute ethanol washing, product obtain the product of white after vacuum-drying;
It is characterized in that,
(5) with the product of above-mentioned white in reducing atmosphere after 350～600 ℃ of thermal treatment, obtain having the Li of spinel structure 4Ti 5O 12Nanotube or line.
3, high energy density spinel structural lithium titanate material is characterized in that, described material is by solid phase method and heat-treats the high energy density spinel structural lithium titanate submicron particles of preparation under reducing atmosphere.
4, the method for preparation high energy density spinel structural lithium titanate submicron particles as claimed in claim 4, this method contains following steps:
(1) lithium salts is dissolved in 20～40ml ethanol, adds titania powder, the mol ratio of described elemental lithium and titanium elements is 0.8: 1～1.08: 1;
(2) stir and carry out drying;
(3) dried powder takes out, and grinds, sieves, thermal treatment 3 hours in 800 ℃ reducing atmosphere then, furnace cooling.
5, preparation method according to claim 5 is characterized in that, this method is that common spinel lithium titanate submicron particles is obtained high energy density spinel lithium titanate submicron particles in reducing atmosphere after 300～400 ℃ of thermal treatment.
6, preparation method according to claim 4, it is characterized in that, described lithium salts is organic lithium salt or inorganic lithium salt, comprises a kind of in lithium hydroxide, Lithium Oxide 98min, Quilonum Retard, lithium nitrate, Lithium Sulphate, Trilithium phosphate, lithium chloride, lithium chlorate or Lithium Acetate, lithium oxalate, lithium benzoate, the vinylformic acid lithium.
According to claim 2,3,4 or 5 described preparation methods, it is characterized in that 7, the reducing atmosphere that described material is heat-treated comprises nitrogen, hydrogen or argon gas or their gas mixture.
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