CN106058182B - A kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance - Google Patents
A kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the good lithium titanate/polyaniline composite material of high rate performance, and lithium-containing solution is instilled in solution of tetrabutyl titanate, and emulsion A is made；Emulsion A is placed in baking oven, reaction to emulsion becomes solid product B；It is heat-treated after B is ground, obtains lithium titanate C；By lithium titanate and distilled water ultrasonic disperse, lithium titanate aqueous solution is obtained, a certain amount of surfactant is added, obtains solution D；Aniline monomer is instilled in solution D, E mixed solutions are obtained；E mixed solutions are put into cold bath stirring, hydrochloric acid solution is added dropwise to it, obtains mixed solution F；F solution is added dropwise in catalyst and oxidant mixed solution, obtains G solution；After a certain period of time by G solution magnetic agitation, reaction terminating agent stirring is added to G solution, obtains suspension H；It is finally precipitated after H is centrifuged, lithium titanate/polyaniline composite material can be obtained by finally carrying out vacuum drying.
Description
Technical field
The invention belongs to technical field of battery electrode materials, and in particular to a kind of good lithium titanate/polyphenyl of high rate performance
The preparation method of amine composite material.
Background technology
For lithium rechargeable battery since last century end comes out, development speed quickly, has received well-known enterprise of more families
The concern of industry, and research and develop to make it into energetically and commercially produce, there is a certain proportion of answer in electric vehicle field at present
With.Lithium ion battery has huge commercial promise on the products for civilian use such as electric vehicle, electric bicycle, also in space industry
There is great application.This requires this kind of batteries to have very high reliability and low-temperature working performance, while also requiring battery
Have extended cycle life, energy density is high, and volume and quality are small etc..Spinel type lithium titanate Li4Ti5O12(LTO) it is that one kind zero is answered
Become material, good cycle, charging/discharging voltage platform be steady, safe, price is low and easy preparation, is very promising dynamic
[Kang Xiaohong, the red conductive agents in river are to lithium ionic cell cathode material lithium titanate chemical property for power type lithium ion battery negative material
Influence, [J] Beijing Jiaotong University journal (2010) 34 3].
As heavy-duty battery material, Li4Ti5O12Have the advantages that it is many it is irreplaceable such as：Bulk effect when charge and discharge
Less than 1%；With apparent and higher charge and discharge platform, so as to effectively inhibit the decomposition of electrolyte and the production of Li dendrite
It is raw, it ensure that the safety of battery.However, electronic conductivity that the material is low (<10-13Scm-1) and Li+Diffusion coefficient (10-9-
10-13cm2s-1) Li is limited to a certain extent4Ti5O12The development of electrode material.In order to make up this shortcoming, scholar
Mainly studied in terms of following three：Material nano [Li X L, Meng Y, Liu S, et
al.Ionothermal synthesis of sponge-like nano Li4Ti5O12for high rate lithium-
ion batteries[J].Journal of Solid State Electrochemistry,2015,19(6):1745-
1753.], doping/compound high conductivity substance [Hao S, Xiao X, Hu Z, et al.Improving the
electrochemical performance of Li4Ti5O12anode through confinement into ordered
bimodal porous carbon frameworks[J].The Journal of Physical Chemistry C,2013,
117(51):26889-26895.], cladding high conductivity substance [Shi N N, Jiang X, Zhang Y, et
al.Preparation and performance of N-doped carbon coated Li4Ti5O12as anode
material for lithium-ion batteries[J].Chemical Journal of Chinese
Universities-Chinese,2015,36(5):981-988.].Since coated with conductive macromolecule can significantly improve material
Electric conductivity, in recent years conducting polymer cladding have been considered as improve electrode material electric conductivity economic, practical method.Together
When, flexibly easily controllable polymerization ratio can be very good to adapt to the volume expansion of material, improve chemical property to reach
Purpose.In miscellaneous high molecular material, polyaniline (PANI) is since its electric conductivity is good, synthetic method is simple, is easy to
Doping, stability is high low with production cost and is concerned [Zheng J, Yu X, Wang C, et al.Facile
synthesis of three-dimensional reinforced Sn@polyaniline/sodium alginate
nanofiber hydrogel network for high performance lithium-ion battery[J]
.Journal of Materials Science:Materials in Electronics,2016,27(5):4457-
4464.].So far, researchers have carried out many electrode materials with PANI compound, and it is compound after electrode material
Material shows good chemical property.Such as：Wang et al. is with TiO2It is primary raw material with aniline monomer, using in situ poly-
It closes and combines chemical etching method, prepared the TiO for the HCl doping haveing excellent performance2/ PANI composite materials [Wang W L, Park
J-Y,Nguyen V H,et al.Hierarchical mesoporous rutile TiO2/C composite
nanospheres as lithium-ion battery anode materials[J].Ceramics International,
2016,42(1):598-606.].Xu et al. is with SnO2It is that primary raw material is prepared using situ aggregation method with aniline
The SnO of H2SO4 doping2/ PANI core-shell materials considerably improve the lithium storage content of material and improve cyclical stability
[Xu W,Zhao K,Niu C,et al.Heterogeneous branched core-shell SnO2-PANI nanorod
arrays with mechanical integrity and three dimentional electron transport for
lithium batteries[J].Nano Energy,2014,8:196-204.].However up to now, about Li4Ti5O12/
The relevant report of PANI is seldom, and only He et al. was respectively at 2007 and 2010, with Li4Ti5O12Based on aniline monomer
Raw material is wanted, the Li of electrochemical performance has successfully been prepared using situ aggregation method4Ti5O12/ PANI composite materials [He Z-
Q,Xiong L Z,Chen S,et al.In situ polymerization preparation and
characterization of Li4Ti5O12-polyaniline anode material[J].Transactions of
Nonferrous Metals Society of China,2010,20(5):s262-s266.].But benzene in its preparation process
The polymerization temperature of amine is 30 DEG C, finally needs clean repeatedly with the HCl of various concentration and immersion treatment, is adulterated with reaching HCl
Purpose, so that preparation process complicate, it is difficult to large-scale production.So finding a kind of simple, easily-controllable, quick synthesis of titanium
The method of sour lithium/polyaniline, is of great significance to the research and development of high performance lithium ionic cell cathode material.
Invention content
The purpose of the present invention is to provide a kind of preparation sides of the good lithium titanate/polyaniline composite material of high rate performance
Method, to overcome the problems of the above-mentioned prior art, lithium titanate prepared by the present invention/polyaniline material purity is high, crystallinity is good
Good, the high conductivity substance polyaniline of cladding can significantly improve material conductivity, and can reach nanoscale, which has
Shorten to effect the diffusion path of lithium ion.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance, includes the following steps：
1) lithium-containing solution is instilled in butyl titanate, is stirred, Li and Ti in emulsion A, emulsion A is made
The ratio between the amount of substance be (0.7~1.5):1；
2) emulsion A is placed in baking oven and is reacted, obtain solid product B；
3) thermally treated to obtain lithium titanate C after grinding solid product B；
4) distilled water and ultrasonic disperse is added in lithium titanate C, obtains lithium titanate aqueous solution, add surfactant, obtains
To solution D；
5) by aniline monomer according to lithium titanate C:Aniline monomer=1:The molar ratio of (25~100) instills in solution D, obtains
Mixed solution E；
6) mixed solution E is put into after being stirred in 0-5 DEG C of cold bath, hydrochloric acid solution is added dropwise to it, is mixed
Solution F；
7) mixed solution F is added dropwise in catalyst and oxidant mixed solution, obtains solution G；
8) solution G is stirring evenly and then adding into reaction terminating agent, and continues to stir, obtain suspension H；
9) by finally being precipitated after suspension H centrifugation, finally it is dried in vacuo that obtain lithium titanate/polyaniline compound
Material.
Further, the lithium concentration in step 1) in lithium-containing solution is 0.2~5mol/L, and lithium-containing solution is carbonic acid
The aqueous solution of lithium, lithium oxalate, lithium acetate or lithium hydroxide.
Further, stirring is 20~120min of magnetic agitation at 20~100 DEG C in step 1).
Further, oven temperature is 70~100 DEG C in step 2), and the reaction time is 1~48h.
Further, heat treatment is specially in step 3)：It is warming up to 400~1000 with the heating rate of 6~10 DEG C/min
2~15h is kept the temperature after DEG C, is then cooled to room temperature.
Further, 1~3mol lithium titanate C are added in step 4) per 1L distilled water, the ultrasonic disperse time is 1~5h,
Surfactant is according to lithium titanate C：Surfactant is 1:0.1~1:0.3 mass ratio is added, and the surfactant is bromine
Change cetrimonium, neopelex or lauryl sodium sulfate.
Further, stirring is magnetic agitation in step 6), and mixing time is 1~5h, a concentration of 1mol/ of hydrochloric acid solution
L~3mol/L.
Further, catalyst is tungstic acid, vanadic anhydride or titanium dioxide in step 7)；Oxidant is dioxygen
Water, potassium permanganate or ferric trichloride, the reaction terminating agent in step 8) are potassium iodide.
Further, in step 5) to step 8) aniline monomer, hydrochloric acid, catalyst, oxidant, reaction terminating agent addition
Amount is successively 1 according to the ratio between amount of substance:1:0.02:5:0.006 is added.
Further, reaction terminating agent will be added in step 8) after solution G magnetic agitation 1~5h times, and will stirring temperature
Degree is adjusted to 60 DEG C, after continuing 1~5h of stirring, obtains suspension H；Vacuum drying temperature is 90~110 DEG C in step 9), the time
For 6~12h.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention uses lithium titanate and polyaniline for raw material, is uniformly dispersed using situ aggregation method preparation, high conductivity
Lithium ion battery negative material lithium titanate/polyaniline.Lithium titanate/polyaniline material the purity prepared through the method for the present invention
Height, crystallinity are good, and the high conductivity substance polyaniline of cladding can significantly improve material conductivity, and can reach nanometer
Grade, the material are effectively shortened the diffusion path of lithium ion.Meanwhile flexible easily controllable polymerization ratio can be very good to fit
The volume expansion for answering material improves its high rate performance, has good chemical property.In this method, by the polymerization of aniline
Temperature is set as 0-5 DEG C so that aniline monomer can fully polymerize and hydrochloric acid can be adulterated effectively, and final product only needs
Final product is can be obtained by simply centrifuging, significantly shortens manufacturing cycle in this way, and preparation method is simple, reaction temperature
It is low, it is not necessarily to subsequent processing, it is environmentally friendly.
Description of the drawings
Fig. 1 is the XRD diagram piece of lithium ion battery negative material lithium titanate/polyaniline prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM photograph of lithium ion battery negative material lithium titanate/polyaniline prepared by the embodiment of the present invention 1；
Fig. 3 is the high rate performance of lithium ion battery negative material lithium titanate/polyaniline prepared by the embodiment of the present invention 1
Figure.
Specific implementation mode
Embodiments of the present invention are described in further detail below：
A kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance, includes the following steps：
1) lithium-containing solution that lithium concentration is 0.2~5mol/L is instilled in butyl titanate, the magnetic at 20~100 DEG C
Power stirs 20~120min, and the ratio between the amount of substance of Li and Ti in emulsion A, emulsion A that is made is (0.7~1.5):1, wherein
Lithium-containing solution is the aqueous solution of lithium carbonate, lithium oxalate, lithium acetate or lithium hydroxide；
2) emulsion A is placed in 1~48h of reaction in 70~100 DEG C of baking oven, obtains solid product B；
3) it by after solid product B grinding, is placed in Muffle furnace, 400 are warming up to the heating rate of 6~10 DEG C/min~
2~15h is kept the temperature after 1000 DEG C, is then cooled to room temperature, is obtained lithium titanate C；
4) distilled water and 1~5h of ultrasonic disperse is added in lithium titanate C, obtains lithium titanate aqueous solution, adds surface-active
Agent obtains solution D, 1~3mol lithium titanate C is added in every 1L distilled water, surfactant is according to lithium titanate C：Surfactant
It is 1:0.1~1:0.3 mass ratio is added, and the surfactant is cetab, dodecyl benzene sulfonic acid
Sodium or lauryl sodium sulfate；
5) by aniline monomer according to lithium titanate C:Aniline monomer=1:The molar ratio of (25~100) instills in solution D, obtains
Mixed solution E；
6) mixed solution E is put into 0-5 DEG C of cold bath after 1~5h of magnetic agitation, hydrochloric acid solution is added dropwise to it,
Obtain mixed solution F, wherein a concentration of 1mol/L~3mol/L of hydrochloric acid solution；
7) mixed solution F is added dropwise in catalyst and oxidant mixed solution, obtains solution G, wherein catalyst is three
Tungsten oxide, vanadic anhydride or titanium dioxide；Oxidant is hydrogen peroxide, potassium permanganate or ferric trichloride；
8) reaction terminating agent will be added after solution G magnetic agitation 1~5h times, and whipping temp is adjusted to 60 DEG C, continue
After stirring 1~5h, obtain suspension H, wherein reaction terminating agent is potassium iodide, aniline monomer in step 5) to step 8), hydrochloric acid,
Catalyst, oxidant, reaction terminating agent additive amount successively according to the ratio between amount of substance be 1:1:0.02:5:0.006 is added；
9) it will finally be precipitated after suspension H centrifugations, 6~12h is finally dried in vacuo at a temperature of 90~110 DEG C is
Obtain lithium titanate/polyaniline composite material.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
(1) the lithium oxalate solution that lithium concentration is 0,2mol/L is slowly dropped into butyl titanate, the magnetic at 20 DEG C
Power stirs 120min, and the ratio between the amount of substance of Li and Ti in emulsion A, emulsion A that is made is 0.7:1；
(2) emulsion A is put into baking oven to react, the temperature of baking oven is 80 DEG C, and solid production will be had been changed to after 1h
Object takes out from baking oven, obtains solid product B；
(3) by after solid product B grinding, be placed in Muffle furnace, with the heating rate of 6 DEG C/min be warming up at 600 DEG C into
Row heat treatment 2h, then cools to room temperature, obtains lithium titanate C；
(4) distilled water and ultrasonic disperse 1h is added in lithium titanate C, lithium titanate aqueous solution is obtained, according still further to lithium titanate C：Table
Face activating agent is 1:Surfactant cetab is added in 0.1 mass ratio, solution D is obtained, wherein being steamed per 1L
1mol lithium titanates C is added in distilled water；
(5) by aniline monomer according to lithium titanate:Aniline monomer=1:25 molar ratio instills in solution D, obtains mixing molten
Liquid E；
(6) mixed solution E is put into 0 DEG C of cold bath, after magnetic agitation 1h, hydrochloric acid solution is added dropwise to it, is mixed
Close solution F, the wherein a concentration of 1mol/L of hydrochloric acid solution；
(7) mixed solution F is added dropwise in catalyst tungstic oxide and oxidant hydrogen peroxide mixed solution, obtains solution G；
(8) by after the solution G magnetic agitation 1h times, potassium iodide is added to solution G, and whipping temp is adjusted to 60 DEG C, stirs
After mixing the 1h times, suspension H is obtained, aniline monomer, hydrochloric acid, catalyst, oxidant, reaction are whole wherein in step 5) to step 8)
Only the additive amount of agent is successively 1 according to the ratio between amount of substance:1:0.02:5:0.006 is added；
(9) it will finally be precipitated after suspension H centrifugations, 12h is finally dried in vacuo at a temperature of 90 DEG C obtains titanium
Sour lithium/polyaniline composite material.
Embodiment 2
(1) the lithium acetate solution that lithium concentration is 1mol/L is slowly dropped into butyl titanate, the magnetic force at 100 DEG C
20min is stirred, the ratio between the amount of substance of Li and Ti in emulsion A, emulsion A that is made is 0.85:1；
(2) emulsion A is put into baking oven to react, the temperature of baking oven is 70 DEG C, and solid production will be had been changed to after 5h
Object takes out from baking oven, obtains solid product B；
(3) it by after solid product B grindings, is placed in Muffle furnace, is warming up at 1000 DEG C with the heating rate of 10 DEG C/min
Heat treatment 8h is carried out, is then cooled to room temperature, lithium titanate C is obtained；
(4) distilled water and ultrasonic disperse 2h is added in lithium titanate C, lithium titanate aqueous solution is obtained, according still further to lithium titanate C：Table
Face activating agent is 1:Surfactant sodium dodecyl base benzene sulfonic acid sodium salt is added in 0.15 mass ratio, obtains solution D, wherein being distilled per 1L
1.5mol lithium titanates C is added in water；
(5) by aniline monomer according to lithium titanate:Aniline monomer=1:50 molar ratio instills in solution D, obtains mixing molten
Liquid E；
(6) mixed solution E is put into 1 DEG C of cold bath, after magnetic agitation 2h, hydrochloric acid solution is added dropwise to it, is mixed
Close solution F, the wherein a concentration of 3mol/L of hydrochloric acid solution；
(7) mixed solution F is added dropwise in catalyst vanadic anhydride and oxidant potassium permanganate mixed solution, obtained molten
Liquid G；
(8) by after the solution G magnetic agitation 2h times, potassium iodide is added to solution G, and whipping temp is adjusted to 60 DEG C, stirs
After mixing the 2h times, suspension H is obtained, aniline monomer, hydrochloric acid, catalyst, oxidant, reaction are whole wherein in step 5) to step 8)
Only the additive amount of agent is successively 1 according to the ratio between amount of substance:1:0.02:5:0.006 is added；
(9) it will finally be precipitated after suspension H centrifugations, 6h is finally dried in vacuo at a temperature of 110 DEG C obtains titanium
Sour lithium/polyaniline composite material.
Embodiment 3
(1) lithium hydroxide solution that lithium concentration is 2mol/L is slowly dropped into butyl titanate, the magnetic at 40 DEG C
Power stirs 60min, and the ratio between the amount of substance of Li and Ti in emulsion A, emulsion A that is made is 1.2:1；
(2) emulsion A is put into baking oven to react, the temperature of baking oven is 100 DEG C, and solid production will be had been changed to after 8h
Object takes out from baking oven, obtains solid product B；
(3) by after solid product B grinding, be placed in Muffle furnace, with the heating rate of 8 DEG C/min be warming up at 800 DEG C into
Row heat treatment 6h, then cools to room temperature, obtains lithium titanate C；
(4) distilled water and ultrasonic disperse 3h is added in lithium titanate C, lithium titanate aqueous solution is obtained, according still further to lithium titanate C：Table
Face activating agent is 1:Surfactant SDS is added in 0.2 mass ratio, obtains solution D, wherein per 1L distilled water
Middle addition 2mol lithium titanates C；
(5) by aniline monomer according to lithium titanate:Aniline monomer=1:100 molar ratio instills in solution D, obtains mixing molten
Liquid E；
(6) mixed solution E is put into 2 DEG C of cold baths, after magnetic agitation 3h, hydrochloric acid solution is added dropwise to it, is mixed
Close solution F, the wherein a concentration of 2mol/L of hydrochloric acid solution；
(7) mixed solution F is added dropwise in catalyst titanium dioxide and oxidant ferric oxide mixed solution, obtains solution
G；
(8) by after the solution G magnetic agitation 3h times, potassium iodide is added to solution G, and whipping temp is adjusted to 60 DEG C, stirs
After mixing the 3h times, suspension H is obtained, aniline monomer, hydrochloric acid, catalyst, oxidant, reaction are whole wherein in step 5) to step 8)
Only the additive amount of agent is successively 1 according to the ratio between amount of substance:1:0.02:5:0.006 is added；
(9) it will finally be precipitated after suspension H centrifugations, 8h is finally dried in vacuo at a temperature of 100 DEG C obtains titanium
Sour lithium/polyaniline composite material.
Embodiment 4
(1) Lithium carbonate solution that lithium concentration is 3mol/L is slowly dropped into butyl titanate, the magnetic force at 60 DEG C
80min is stirred, the ratio between the amount of substance of Li and Ti in emulsion A, emulsion A that is made is 1.5:1；
(2) emulsion A is put into baking oven to react, the temperature of baking oven is 90 DEG C, and solid production will be had been changed to after 48h
Object takes out from baking oven, obtains solid product B；
(3) by after solid product B grinding, be placed in Muffle furnace, with the heating rate of 10 DEG C/min be warming up at 800 DEG C into
Row heat treatment 10h, then cools to room temperature, obtains lithium titanate C；
(4) distilled water and ultrasonic disperse 4h is added in lithium titanate C, lithium titanate aqueous solution is obtained, according still further to lithium titanate C：Table
Face activating agent is 1:Surfactant SDS is added in 0.25 mass ratio, obtains solution D, wherein per 1L distilled water
Middle addition 2.5mol lithium titanates C；
(5) by aniline monomer according to lithium titanate:Aniline monomer=1:25 molar ratio instills in solution D, obtains mixing molten
Liquid E；
(6) mixed solution E is put into 3 DEG C of cold baths, after magnetic agitation 4h, hydrochloric acid solution is added dropwise to it, is mixed
Close solution F, the wherein a concentration of 3mol/L of hydrochloric acid solution；
(7) mixed solution F is added dropwise in catalyst tungstic oxide and oxidant hydrogen peroxide mixed solution, obtains solution G；
(8) by after the solution G magnetic agitation 4h times, potassium iodide is added to solution G, and whipping temp is adjusted to 60 DEG C, stirs
After mixing the 4h times, suspension H is obtained, aniline monomer, hydrochloric acid, catalyst, oxidant, reaction are whole wherein in step 5) to step 8)
Only the additive amount of agent is successively 1 according to the ratio between amount of substance:1:0.02:5:0.006 is added；
(9) it will finally be precipitated after suspension H centrifugations, 10h is finally dried in vacuo at a temperature of 100 DEG C obtains titanium
Sour lithium/polyaniline composite material.
Embodiment 5
(1) the lithium oxalate solution that lithium concentration is 5mol/L is slowly dropped into butyl titanate, the magnetic force at 80 DEG C
100min is stirred, the ratio between the amount of substance of Li and Ti in emulsion A, emulsion A that is made is 1:1；
(2) emulsion A is put into baking oven to react, the temperature of baking oven is 70 DEG C, and solid production will be had been changed to after 48h
Object takes out from baking oven, obtains solid product B；
(3) by after solid product B grinding, be placed in Muffle furnace, with the heating rate of 12 DEG C/min be warming up at 400 DEG C into
Row heat treatment 15h, then cools to room temperature, obtains lithium titanate C；
(4) distilled water and ultrasonic disperse 5h is added in lithium titanate C, lithium titanate aqueous solution is obtained, according still further to lithium titanate C：Table
Face activating agent is 1:Surfactant sodium dodecyl base benzene sulfonic acid sodium salt is added in 0.3 mass ratio, obtains solution D, wherein being distilled per 1L
3mol lithium titanates C is added in water；
(5) by aniline monomer according to lithium titanate:Aniline monomer=1:50 molar ratio instills in solution D, obtains mixing molten
Liquid E；
(6) mixed solution E is put into 5 DEG C of cold baths, after magnetic agitation 5h, hydrochloric acid solution is added dropwise to it, is mixed
Close solution F, the wherein a concentration of 1mol/L of hydrochloric acid solution；
(7) mixed solution F is added dropwise in catalyst vanadic anhydride and oxidant potassium permanganate mixed solution, obtained molten
Liquid G；
(8) by after the solution G magnetic agitation 5h times, potassium iodide is added to solution G, and whipping temp is adjusted to 60 DEG C, stirs
After mixing the 5h times, suspension H is obtained, aniline monomer, hydrochloric acid, catalyst, oxidant, reaction are whole wherein in step 5) to step 8)
Only the additive amount of agent is successively 1 according to the ratio between amount of substance:1:0.02:5:0.006 is added；
(9) it will finally be precipitated after suspension H centrifugations, 6h is finally dried in vacuo at a temperature of 90 DEG C obtains metatitanic acid
Lithium/polyaniline composite material.
As seen from Figure 1, each diffraction maximum of the product prepared by embodiment 1 is all very sharp, and intensity is all very high, and
And also without the appearance of other dephasigns, it is pure phase lithium titanate to show product.The diffraction maximum of uneven protrusion between 20-30 °
For the characteristic peak of PANI.Figure it is seen that lithium titanate/polyaniline that embodiment is prepared is nanoscale little particle, and it is in
Reveal loose structure, the electrode material of this class formation is conducive to lithium ion and electronics is embedded and abjection, can also fully with
Electrolyte contacts, thus can have good chemical property.It can significantly be obtained from Fig. 3, metatitanic acid prepared by embodiment 1
Lithium/polyaniline material has higher specific discharge capacity and good high rate performance.
Claims (7)
1. a kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance, which is characterized in that including following step
Suddenly：
1) lithium-containing solution is instilled in butyl titanate, at 20~100 DEG C, emulsion is made in 20~120min of magnetic agitation
The ratio between amount of substance of Li and Ti is (0.7~1.5) in A, emulsion A:1；
2) emulsion A is placed in baking oven and is reacted, oven temperature is 70~100 DEG C, and the reaction time is 1~48h, obtains solid-state production
Object B；
3) by after solid product B grindings, thermally treated to obtain lithium titanate C, heat treatment is specially：With the heating of 6~10 DEG C/min
Rate keeps the temperature 2~15h after being warming up to 400~1000 DEG C, then cools to room temperature；
4) distilled water and ultrasonic disperse is added in lithium titanate C, obtains lithium titanate aqueous solution, add surfactant, obtains molten
Liquid D；
5) by aniline monomer according to lithium titanate C:Aniline monomer=1:The molar ratio of (25~100) instills in solution D, is mixed
Solution E；
6) mixed solution E is put into after being stirred in 0-5 DEG C of cold bath, hydrochloric acid solution is added dropwise to it, obtains mixed solution
F；
7) mixed solution F is added dropwise in catalyst and oxidant mixed solution, obtains solution G；
8) solution G is stirring evenly and then adding into reaction terminating agent, and continues to stir, obtain suspension H；
9) it will finally be precipitated after suspension H centrifugations, be finally dried in vacuo and obtain lithium titanate/polyaniline composite wood
Material.
2. a kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance according to claim 1,
Be characterized in that, the lithium concentration in step 1) in lithium-containing solution be 0.2~5mol/L, lithium-containing solution be lithium carbonate, lithium oxalate,
The aqueous solution of lithium acetate or lithium hydroxide.
3. a kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance according to claim 1,
It is characterized in that, 1~3mol lithium titanate C are added in step 4) in every 1L distilled water, and the ultrasonic disperse time is 1~5h, surface-active
Agent is according to lithium titanate C：Surfactant is 1:0.1~1:0.3 mass ratio is added, and the surfactant is cetyl
Base trimethylammonium, neopelex or lauryl sodium sulfate.
4. a kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance according to claim 1,
It is characterized in that, stirring is magnetic agitation in step 6), and mixing time is 1~5h, a concentration of 1mol/L~3mol/ of hydrochloric acid solution
L。
5. a kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance according to claim 1,
It is characterized in that, catalyst is tungstic acid, vanadic anhydride or titanium dioxide in step 7)；Oxidant is hydrogen peroxide, permanganic acid
Potassium or ferric trichloride, the reaction terminating agent in step 8) are potassium iodide.
6. a kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance according to claim 1,
Be characterized in that, aniline monomer in step 5) to step 8), hydrochloric acid, catalyst, oxidant, reaction terminating agent additive amount press successively
It is 1 according to the ratio between amount of substance:1:0.02:5:0.006 is added.
7. a kind of preparation method of the good lithium titanate/polyaniline composite material of high rate performance according to claim 1,
It is characterized in that, reaction terminating agent will be added after solution G magnetic agitation 1~5h times in step 8), and whipping temp is adjusted to 60
DEG C, after continuing 1~5h of stirring, obtain suspension H；In step 9) vacuum drying temperature be 90~110 DEG C, the time be 6~
12h。
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