CN105895878A - Lithium titanate modified material and preparation method thereof - Google Patents
Lithium titanate modified material and preparation method thereof Download PDFInfo
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- CN105895878A CN105895878A CN201610338193.0A CN201610338193A CN105895878A CN 105895878 A CN105895878 A CN 105895878A CN 201610338193 A CN201610338193 A CN 201610338193A CN 105895878 A CN105895878 A CN 105895878A
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- H01M4/00—Electrodes
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- 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
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a lithium titanate modified material, and belongs to the technical field of electrochemistry. The modified material has a micro-nano structure and comprises lithium titanate LTO, zinc titanate ZFO and nitrogen-doped carbon nanotube NCNTs. The preparation technology is simple; the conditions are mild; the cost is low; the repeatability is good; large-scale preparation is facilitated; the synthesized composite material are small in powder particles and uniform in distribution; and the problems of low electronic conductivity and low energy density when the lithium titanate is individually used as a negative electrode material of a lithium-ion battery are solved. The material has relatively high initial discharge capacity and cycling specific capacity and good rate capability and cycling stability in an electrochemical test. Compared with existing commercially applied lithium titanate, the material has the advantages that the energy density can be improved by 20%-40%; and the material is an ideal negative electrode material of the lithium-ion battery and has a potential application prospect in the fields of portable electronic equipment, an electric vehicle, aerospace and the like.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of lithium titanate material modified and preparation method thereof.
Background technology
Lithium ion battery has the advantages such as high-energy-density, high working voltage, memory-less effect and is used widely because of it.
Along with to higher energy density and the demand of power density battery, exploitation novel battery material is extremely urgent.Currently, business fossil
Although ink negative material has good cycle performance, but its specific capacity is relatively low, and is easily generated under the conditions of high current charge-discharge
Potential safety hazard, limits its application in extensive energy storage field.Spinel type lithium titanate (LTO) is in the embedding of lithium ion and de-
During going out, framing structure changes hardly, is a kind of " zero strain " material, and the charge and discharge cycles with excellence is stable
Property.Intercalation potential is high without causing a precipitation for brilliant lithium, is the ion cathode material lithium of a kind of high safety.But lithium titanate
Also having its weak point, the cell voltage that as low in theoretical specific capacity (175 mAh/g), high intercalation potential bring is low, in turn results in
The specific energy of battery is low；The own poorly conductive of material (intrinsic conductivity 10-9S/cm), is easily generated during high current charge-discharge simultaneously
Bigger polarization etc. and limit its application popularization.At present, mostly academia is that the mode using ion doping reduces metatitanic acid
The electrode potential (Electrochimica Acta 2008,53:7079) of lithium；By material nano, prepare special appearance
Lithium titanate or the method such as carbon or CNT (CNTs) cladding of employing solve lithium titanate material and cause owing to electronic conductivity is low
Problem (the J. Am. Chem. Soc. 2012,134:7874 that material high rate performance reduces; RSC Adv., 2012, 2:
10306).China Patent Publication No. CN201210163712.6, CN201010575269.4, CN 201310036005.5,
CN201010149910.8 reports CNT and the method for carbon modification lithium titanate, and this type of method all can improve metatitanic acid
The electronic conductivity of lithium.But all there are some problems in said method: (1) ion doping causes the electrode potential of lithium titanate material
Reduce limited extent, and then the energy density of material can not be increased substantially；(2) mostly carbon cladding is that employing is expensive has
Machine carbon source high temperature thermal decomposition realizes, and energy consumption is too high, the most unfriendly to environment；(3) CNT with front need surface acidifying or
Esterification treatment, process is complicated and unfriendly to environment；In order to realize CNT dispersed need to add expensive
Dispersant.
Nanostructured zinc ferrite (ZnFe2O4) it is superior binary spinelle ion cathode material lithium, show high power capacity
Feature, has stable intercalation potential platform (about 0.9V), will not produce analysis lithium phenomenon, substantially increase the safety of battery,
This material has the advantages such as nontoxic, pollution-free, security performance is high, and raw material sources is extensive simultaneously, and this is that it is combined with lithium titanate
The energy density promoting lithium titanate compound provides feasibility reference, but, pure phase ZnFe2O4The electric conductivity of material is poor；Material
Material Volumetric expansion is big, causes electrode matrix structure to be destroyed, thus affects the stable circulation performance of battery.
Summary of the invention
For making up the deficiencies in the prior art, the present invention provides a kind of lithium titanate material modified and preparation method thereof, this material
As Novel cathode material for lithium ion battery, there is higher recycle ratio capacity, high first charge-discharge efficiency, good multiplying power
Performance and cyclical stability.
The present invention is achieved through the following technical solutions:
A kind of lithium titanate is material modified, and it is characterized in that described material modified be made up of, including lithium titanate micro-nano structure
LTO, zinc titanate ZFO and nitrogen-doped carbon nanometer pipe NCNTs.Lithium titanate is that security performance is high as the advantage of negative material, circulation
Good stability, first charge-discharge efficiency is high, but the specific capacity of material is on the low side, electronic conductivity is low, high cost；Ask for this
The topic present invention uses cheap and height ratio capacity zinc ferrite to make up, but for zinc ferrite, its electronics electricity
Conductance is the lowest, and first charge-discharge efficiency is low, and material volumetric expansion in charge and discharge process simultaneously is excessive causes stability to decline；
For this problem, the present invention uses nitrogen-doped carbon nanometer pipe to stablize material to buffer zinc ferrite in the change in volume of charge and discharge process
Material, dredges heat, increases mechanical strength and the electronic conductivity of material, simultaneously micro-nano structure also contribute to lithium ion embedding and
Transmission.
Further, the lithium titanate of the present invention is material modified, and chemical composition is xZFO yNCNTs zLTO, x, y, z
Represent the content of ZFO, NCNTs and LTO, wherein, 0.01≤x≤0.50,0.01≤y≤0.10,0.4≤z≤0.98, x+ respectively
y+z=1；In NCNTs atom N content be the particle mean size of 0.01-6at%, LTO be 5-100 μm.
The lithium titanate of the present invention is material modified can be mixed to get by LTO, ZFO and NCNTs post processing, it is also possible to pass through
Fabricated in situ obtains.
The preparation method that the lithium titanate of the present invention is material modified, when using post processing to be mixed to get sample, including following step
Rapid:
(1) by NCNTs ultrasonic disperse in low-carbon alcohols；
(2) LTO, ZFO are joined in the NCNTs after ultrasonic disperse, ultrasonic after stirring, it is placed in oven for drying；
(3) the mixture ball milling mixing that will dry；
(4) sample that ball milling is good is annealed heat treatment under an inert atmosphere.
Wherein,
In step (1), low-carbon alcohols is the mixing of one or more in methanol, ethanol, propanol.
In step (4), inert atmosphere is He, N2Or Ar, heat treatment temperature is 200-700 DEG C, and the time is 0.1-10 h.
The preparation method that the lithium titanate of the present invention is material modified, when using fabricated in situ to obtain sample, comprises the following steps:
(1) by NCNTs ultrasonic disperse in low-carbon alcohols；
(2) iron salt, zinc salt are dissolved wiring solution-forming；
(3) NCNTs scattered for step (1) is mixed with iron salt, the zinc solution of step (2), after being sufficiently stirred for, carry out ultrasonic
Process；
(4) LTO is joined by several times in the solution of step (3), be sufficiently stirred for, dry；
(5) under an inert atmosphere, roasting after dried sample is heated up, cooling.
Wherein,
In step (2), iron salt is at least two in ferric chloride, ferric nitrate, ferric citrate, ferric acetate, and zinc salt is anhydrous slufuric acid
One or more in zinc, zinc chloride, zinc sulfate；In zinc salt, iron salt, zinc is 1:1.8-2.2 with the mol ratio of ferrum.
In step (3), NCNTs and iron salt, the hybrid mode of zinc solution are that by several times scattered NCNTs is joined step
Suddenly joining in scattered NCNTs by several times in the solution of (2) or by the solution of step (2), adition process ceaselessly stirs.
In step (4), mixing time is 0-20h.
In step (5), inert atmosphere is He, N2Or Ar, gas flow rate is 20-1000sccm, and sintering temperature is 500-1000
DEG C, the process time is 0.1-10h.
The material modified electrochemical property test that carries out of the lithium titanate present invention prepared, test is carried out in following condition: will
The active material prepared is mixed by the weight ratio of 8:1:1 with Kynoar (PVDF) and conductive agent, with N-Methyl pyrrolidone
(NMP) it is solvent, is applied to equably on Copper Foil after stirring 6 hours, 110 DEG C of vacuum drying tablettings, obtains working electrode sheet.Electrolysis
Liquid is LiPF6/ ethylene carbonate (the EC)-dimethyl carbonate (DMC) (volume ratio 1:1) of 1 mol/L；Barrier film is polypropylene/poly-
Ethylene microporous membrane (Celgard2500).All of battery (2032 type button cell) all assembles in the glove box of anhydrous and oxygen-free
Becoming, lithium sheet is as to electrode.Battery is measured after assembling postactivated 12 hours, so that electrolyte is sufficiently wet on electrode.?
Carrying out charge-discharge test on battery performance testing system, voltage range is 0.5-3.0 V.
The invention has the beneficial effects as follows:
(1) negative material prepared by the present invention is novel tri compound negative material；
(2) composite negative pole material granular powder is tiny and is evenly distributed, and has good electrical conductivity；
(3) as material of main part, lithium titanate can ensure that material has high security performance, excellent cyclical stability, high head
Secondary efficiency for charge-discharge；Add zinc ferrite and can reduce the cost of material, improve the energy density of material；Add nitrogen-doped carbon nanometer
Pipe can effectively suppress material change in volume in charge and discharge process violent, causes that capacity attenuation is fast, poor the asking of cycle performance
Topic, increases mechanical strength and the electronic conductivity of material, and micro-nano structure also contributes to embedding and the transmission of lithium ion simultaneously；
(4) compared to having been commercialized the lithium titanate of application at present, the material energy densities of the present invention can improve 20-40%；
(5) preparation technology of the present invention is simple, low cost, environmental friendliness, and safety is high, and experimental repeatability is good.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the sample of the embodiment of the present invention 12.
Fig. 2 is the difference sample of the present invention cyclical stability comparison diagram under 1C multiplying power.
Fig. 3 is the cyclical stability test figure of the sample of the embodiment of the present invention 13.
Detailed description of the invention
The present invention is further detailed explanation with detailed description of the invention below in conjunction with the accompanying drawings, but is not limited to this
Bright protection domain.
Embodiment 1
The present embodiment uses the method for post processing mixing to prepare lithium titanate material modified 0.02ZFO 0.02NCNTs
0.96LTO。
By in the ultrasonic disperse of the NCNTs of 0.2g to methanol, after being subsequently adding the ZFO stirring 30min of 0.2g, continue ultrasonic 1
H, adds the LTO of 9.6g, repeats stirring and ultrasonic step, is placed in oven for drying, by ball mill, compound is carried out secondary
Stirring mixing, after sample is dried, at N2The lower 200 DEG C of heat treatment time 1h of atmosphere.
Button electrical test results, under 0.2C, first discharge specific capacity is 193mAh g-1, first charge-discharge efficiency 85%, under 1C
Specific discharge capacity be 190 mAh g-1。
Embodiment 2
The present embodiment uses the method for post processing mixing to prepare lithium titanate material modified 0.05ZFO 0.02NCNTs
0.93LTO。
By in the ultrasonic disperse of the NCNTs of 0.2g to alcohol, after being subsequently adding the ZFO stirring 30min of 0.5g, continue ultrasonic 1
H, adds the LTO of 9.3g, repeats stirring and ultrasonic step, is placed in oven for drying, by ball mill, compound is carried out secondary
Stirring mixing, after sample is dried, at N2The lower 500 DEG C of heat treatment time 0.5h of atmosphere.
Button electrical test results, under 0.2C, first discharge specific capacity is 228mAh g-1, first charge-discharge efficiency 82%, under 1C
Specific discharge capacity be 195 mAh g-1。
Embodiment 3
The present embodiment uses the method for post processing mixing to prepare lithium titanate material modified 0.1ZFO 0.05NCNTs
0.88LTO。
By in the ultrasonic disperse of the NCNTs of 0.2g to propanol, after being subsequently adding the ZFO stirring 30min of 1.0g, continue ultrasonic 1
H, adds the LTO of 8.8g, repeats stirring and ultrasonic step, is placed in oven for drying, by ball mill, compound is carried out secondary
Stirring mixing, after sample is dried, at N2The lower 300 DEG C of heat treatment time 1h of atmosphere.
Button electrical test results, under 0.2C, first discharge specific capacity is 258mAh g-1, first charge-discharge efficiency 77%, under 1C
Specific discharge capacity be 210 mAh g-1。
Embodiment 4
The present embodiment uses the method for post processing mixing to prepare lithium titanate material modified 0.5ZFO 0.05NCNTs
0.4LTO。
By in the ultrasonic disperse of the NCNTs of 0.5g to methanol, after being subsequently adding the ZFO stirring 30min of 5.0g, continue ultrasonic 1
H, adds the LTO of 4.5g, repeats stirring and ultrasonic step, is placed in oven for drying, by ball mill, compound is carried out secondary
Stirring mixing, after sample is dried, at N2The lower 500 DEG C of heat treatment time 1h of atmosphere.
Button electrical test results, under 0.2C, first discharge specific capacity is 538mAh g-1, first charge-discharge efficiency 65%, under 1C
Specific discharge capacity be 350 mAh g-1。
Embodiment 5
The present embodiment uses the method for post processing mixing to prepare lithium titanate material modified 0.5ZFO 0.1NCNTs
0.4LTO。
By in the ultrasonic disperse of the NCNTs of 1.0g to alcohol, after being subsequently adding the ZFO stirring 30min of 5.0g, continue ultrasonic 1
H, adds the LTO of 4.0g, repeats stirring and ultrasonic step, is placed in oven for drying, by ball mill, compound is carried out secondary
Stirring mixing, after sample is dried, 700 DEG C of heat treatment time 10h under N2 atmosphere.
Button electrical test results, under 0.2C, first discharge specific capacity is 658mAh g-1, and first charge-discharge efficiency 70%, under 1C
Specific discharge capacity be 558 mAh g-1.
Embodiment 6
The present embodiment, with ferric nitrate as source of iron, uses in-situ synthetic method to prepare the material modified 0.02ZFO of lithium titanate
0.02NCNTs 0.96LTO (stoichiometric proportion of zinc and ferrum is 1:2).
The ferric nitrate of the zinc nitrate and 0.67g that weigh 0.25g is dissolved in ethanol solution, by the NCNTs ultrasonic disperse of 0.2g
In methanol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, is stirred continuously 10h supersound process 10h,
The LTO being subsequently adding 9.6 g is sufficiently stirred for being placed on oven for drying, at gas flow rate 100 sccm N2Under inert gas, 700
DEG C heat treatment time 10h, then cools down, obtains this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 198mAh g-1, first charge-discharge efficiency 89%, under 1C
Specific discharge capacity be 193 mAh g-1。
Embodiment 7
The present embodiment, with ferric nitrate as source of iron, uses the method for fabricated in situ to prepare the material modified 0.02ZFO of lithium titanate
0.02NCNTs 0.96LTO (stoichiometric proportion of zinc and ferrum is 1:1.8).
The ferric nitrate of the zinc nitrate and 0.60g that weigh 0.25g is dissolved in ethanol solution, by the NCNTs ultrasonic disperse of 0.2g
In methanol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, is stirred continuously 10h supersound process 10h,
The LTO being subsequently adding 9.6 g is sufficiently stirred for being placed on oven for drying, at gas flow rate 500 sccm N2Under inert gas, 700
DEG C heat treatment time 10h, then cools down, obtains this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 195mAh g-1, first charge-discharge efficiency 90%, under 1C
Specific discharge capacity be 190 mAh g-1。
Embodiment 8
The present embodiment, with ferric nitrate as source of iron, uses the method for fabricated in situ to prepare the material modified 0.02ZFO of lithium titanate
0.02NCNTs 0.96LTO (stoichiometric proportion of zinc and ferrum is 1:2.2).
The ferric nitrate of the zinc nitrate and 0.74g that weigh 0.25g is dissolved in ethanol solution, by the NCNTs ultrasonic disperse of 0.2g
In alcohol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, is stirred continuously 10h supersound process 10h,
The LTO being subsequently adding 9.6 g is sufficiently stirred for being placed on oven for drying, at gas flow rate 100 sccm N2Under inert gas, 800
DEG C heat treatment time 10h, then cools down, obtains this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 190mAh g-1, first charge-discharge efficiency 85%, under 1C
Specific discharge capacity be 185 mAh g-1。
Embodiment 9
The present embodiment, with ferric chloride as source of iron, uses the method for fabricated in situ to prepare the material modified 0.02ZFO of lithium titanate
0.02NCNTs · 0.96LTO。
The ferric chloride of the zinc nitrate and 0.44g that weigh 0.25g is dissolved in ethanol solution, by ultrasonic for the NCNTs of 0.2g point
It is scattered in methanol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, be stirred continuously 10h supersound process
10h, the LTO being subsequently adding 9.6 g are sufficiently stirred for being placed on oven for drying, at gas flow rate 50 sccm N2Under inert gas,
700 DEG C of heat treatment time 10h, then cool down, and obtain this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 180mAh g-1, first charge-discharge efficiency 80%, under 1C
Specific discharge capacity be 173 mAh g-1。
Embodiment 10
The present embodiment, with ferric acetate as source of iron, uses the method for fabricated in situ to prepare the material modified 0.02ZFO of lithium titanate
0.02NCNTs · 0.96LTO。
The ferric acetate of the zinc nitrate and 0.70g that weigh 0.25g is dissolved in propanol solution, by the NCNTs ultrasonic disperse of 0.2g
In methanol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, is stirred continuously 10h supersound process 10h,
The LTO being subsequently adding 9.6 g is sufficiently stirred for being placed on oven for drying, under gas flow rate 100 sccm N2 inert gas, and 600
DEG C heat treatment time 10h, then cools down, obtains this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 175mAh g-1, and first charge-discharge efficiency 89%, under 1C
Specific discharge capacity be 165 mAh g-1.
Embodiment 11
The present embodiment, with zinc chloride for zinc source, uses the method for fabricated in situ to prepare the material modified 0.02ZFO of lithium titanate
0.02NCNTs · 0.96LTO。
The ferric chloride of the zinc chloride and 0.44g that weigh 0.20g is dissolved in ethanol solution, by ultrasonic for the NCNTs of 0.2g point
It is scattered in methanol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, be stirred continuously 10h supersound process
10h, the LTO being subsequently adding 9.6 g are sufficiently stirred for being placed on oven for drying, at gas flow rate 1000 sccm N2Inert gas
Under, 700 DEG C of heat treatment time 10h, then cool down, obtain this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 178mAh g-1, first charge-discharge efficiency 88%, under 1C
Specific discharge capacity be 174 mAh g-1。
Embodiment 12
The present embodiment, with ferric nitrate as source of iron, uses the method for fabricated in situ to prepare the material modified 0.1ZFO of lithium titanate
0.02NCNTs · 0.88LTO。
The ferric nitrate of the zinc nitrate and 3.35g that weigh 1.23g is dissolved in ethanol solution, by the NCNTs ultrasonic disperse of 0.2g
In methanol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, is stirred continuously 10h supersound process 10h,
The LTO being subsequently adding 8.8 g is sufficiently stirred for being placed on oven for drying, at gas flow rate 100 sccm N2Under inert gas, 700
DEG C heat treatment time 10h, then cools down, obtains this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 250mAh g-1, first charge-discharge efficiency 84%, under 1C
Specific discharge capacity be 200 mAh g-1。
Embodiment 13
The present embodiment, with ferric nitrate as source of iron, uses the method for fabricated in situ to prepare the material modified 0.1ZFO of lithium titanate
0.02NCNTs · 0.88LTO。
The ferric nitrate of the zinc nitrate and 3.68g that weigh 1.23g is dissolved in ethanol solution, by the NCNTs ultrasonic disperse of 0.2g
In methanol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, be stirred continuously 5h supersound process 10h, so
The LTO of rear addition 8.8 g is sufficiently stirred for being placed on oven for drying, at gas flow rate 80 sccm N2Under inert gas, 600 DEG C
Heat treatment time 5h, then cools down, and obtains this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 230mAh g-1, first charge-discharge efficiency 87%, under 1C
Specific discharge capacity be 195 mAh g-1。
Embodiment 14
The present embodiment, with ferric nitrate as source of iron, uses the method for fabricated in situ to prepare the material modified 0.1ZFO of lithium titanate
0.1NCNTs · 0.8LTO。
The ferric nitrate of the zinc nitrate and 3.68g that weigh 1.23g is dissolved in ethanol solution, by the NCNTs ultrasonic disperse of 1.0g
In methanol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, be stirred continuously 5h supersound process 10h, so
The LTO of rear addition 8.0 g is sufficiently stirred for being placed on oven for drying, at gas flow rate 100 sccm N2Under inert gas, 800 DEG C
Heat treatment time 10h, then cools down, and obtains this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 230mAh g-1, first charge-discharge efficiency 82%, under 1C
Specific discharge capacity be 205 mAh g-1。
Embodiment 15
The present embodiment, with ferric nitrate as source of iron, uses the method for fabricated in situ to prepare the material modified 0.5ZFO of lithium titanate
0.02NCNTs · 0.48LTO。
The ferric nitrate of the zinc nitrate and 16.76g that weigh 6.17g is dissolved in ethanol solution, by the NCNTs ultrasonic disperse of 0.2g
In methanol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, be stirred continuously 5h supersound process 10h, so
The LTO of rear addition 4.8 g is sufficiently stirred for being placed on oven for drying, at gas flow rate 100 sccm N2Under inert gas, 1000
DEG C heat treatment time 10h, then cools down, obtains this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 650mAh g-1, first charge-discharge efficiency 65%, under 1C
Specific discharge capacity be 589mAh g-1。
Embodiment 16
The present embodiment, with ferric nitrate as source of iron, uses the method for fabricated in situ to prepare the material modified 0.5ZFO of lithium titanate
0.1NCNTs · 0.4LTO。
The ferric nitrate of the zinc nitrate and 16.76g that weigh 6.17g is dissolved in ethanol solution, by the NCNTs ultrasonic disperse of 1.0g
In methanol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, be stirred continuously 5h supersound process 10h, so
The LTO of rear addition 4.0 g is sufficiently stirred for being placed on oven for drying, at gas flow rate 100 sccm N2Under inert gas, 700 DEG C
Heat treatment time 10h, then cools down, and obtains this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 670mAh g-1, first charge-discharge efficiency 75%, under 1C
Specific discharge capacity be 600mAh g-1。
Embodiment 17
The present embodiment, with ferric chloride as source of iron, uses the method for fabricated in situ to prepare the material modified 0.5ZFO of lithium titanate
0.1NCNTs · 0.4LTO。
The ferric chloride of the zinc nitrate and 11.2g that weigh 6.17g is dissolved in propanol solution, by ultrasonic for the NCNTs of 1.0g point
It is scattered in methanol, and then the NCNTs after ultrasonic disperse is joined in above-mentioned solution, be stirred continuously 10h supersound process
10h, the LTO being subsequently adding 4.0 g are sufficiently stirred for being placed on oven for drying, at gas flow rate 100 sccm N2Under inert gas,
1000 DEG C of heat treatment time 10h, then cool down, and obtain this material.
Button electrical test results, under 0.2C, first discharge specific capacity is 560mAh g-1, first charge-discharge efficiency 79%, under 1C
Specific discharge capacity be 520mAh g-1。
Comparative example
The present embodiment carries out electro-chemical test using LTO and ZFO as electrode material respectively.
The specific capacity recorded under different multiplying for the sample of above-mentioned different embodiments is as shown in the table:
Claims (10)
1. a lithium titanate is material modified, it is characterised in that: described material modified be made up of micro-nano structure, including lithium titanate LTO,
Zinc titanate ZFO and nitrogen-doped carbon nanometer pipe NCNTs.
A kind of lithium titanate the most according to claim 1 is material modified, it is characterised in that: described material modified chemical composition
For xZFO yNCNTs zLTO, x, y, z represents the content of ZFO, NCNTs and LTO respectively, wherein, and 0.01≤x≤
0.50,0.01≤y≤0.10,0.4≤z≤0.98, x+y+z=1.
A kind of lithium titanate the most according to claim 1 and 2 is material modified, it is characterised in that: in described NCNTs, atom N contains
Amount is 5-100 μm for the particle mean size of 0.01-6at%, LTO.
The preparation method that a kind of lithium titanate the most according to claim 1 is material modified, it is characterised in that: use post processing to mix
Conjunction obtains sample, comprises the following steps:
(1) by NCNTs ultrasonic disperse in low-carbon alcohols；
(2) LTO, ZFO are joined in the NCNTs after ultrasonic disperse, ultrasonic after stirring, it is placed in oven for drying；
(3) the mixture ball milling mixing that will dry；
(4) sample that ball milling is good is annealed heat treatment under an inert atmosphere.
The preparation method that a kind of lithium titanate the most according to claim 4 is material modified, it is characterised in that: low in step (1)
Carbon alcohol is the mixing of one or more in methanol, ethanol, propanol.
The preparation method that a kind of lithium titanate the most according to claim 4 is material modified, it is characterised in that: lazy in step (4)
Property atmosphere is He, N2Or Ar, heat treatment temperature is 200-700 DEG C, and the time is 0.1-10 h.
The preparation method that a kind of lithium titanate the most according to claim 1 is material modified, it is characterised in that: use fabricated in situ
Obtain sample, comprise the following steps:
(1) by NCNTs ultrasonic disperse in low-carbon alcohols；
(2) iron salt, zinc salt are dissolved wiring solution-forming；
(3) NCNTs scattered for step (1) is mixed with iron salt, the zinc solution of step (2), after being sufficiently stirred for, carry out ultrasonic
Process；
(4) LTO is joined by several times in the solution of step (3), be sufficiently stirred for, dry；
(5) under an inert atmosphere, roasting after dried sample is heated up, cooling.
The preparation method that a kind of lithium titanate the most according to claim 7 is material modified, it is characterised in that: ferrum in step (2)
Salt is at least two in ferric chloride, ferric nitrate, ferric citrate, ferric acetate, and zinc salt is anhydro-zinc sulfate, zinc chloride, sulphuric acid
One or more in zinc；In zinc salt, iron salt, zinc is 1:1.8-2.2 with the mol ratio of ferrum.
The preparation method that a kind of lithium titanate the most according to claim 7 is material modified, it is characterised in that: in step (3)
NCNTs and iron salt, the hybrid mode of zinc solution are in the solution that scattered NCNTs joins step (2) by several times or will
The solution of step (2) joins in scattered NCNTs by several times, and adition process ceaselessly stirs.
The preparation method that a kind of lithium titanate the most according to claim 7 is material modified, it is characterised in that: step is stirred in (4)
The time of mixing is 0-20h；In step (5), inert atmosphere is He, N2Or Ar, gas flow rate is 20-1000sccm, and sintering temperature is
500-1000 DEG C, the process time is 0.1-10h.
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| CN108318821A (en) * | 2017-12-14 | 2018-07-24 | 合肥国轩高科动力能源有限公司 | A kind of method of fast prediction lithium electricity ternary material cycle performance |
| CN109980223A (en) * | 2017-12-28 | 2019-07-05 | 张家港市国泰华荣化工新材料有限公司 | A kind of lithium titanate/carbon/carbon nano tube composite material and preparation method and application |
| CN110104677A (en) * | 2019-04-01 | 2019-08-09 | 桂林电子科技大学 | Composite titanic acid lithium material and the preparation method and application thereof |
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| CN109378463A (en) * | 2018-11-27 | 2019-02-22 | 中南大学 | Composite cathode material for lithium ion cell and preparation method thereof |
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