CN110061214A - Conducting polymer coats TiO2(B) preparation and application of negative electrode material - Google Patents
Conducting polymer coats TiO2(B) preparation and application of negative electrode material Download PDFInfo
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- CN110061214A CN110061214A CN201910310933.3A CN201910310933A CN110061214A CN 110061214 A CN110061214 A CN 110061214A CN 201910310933 A CN201910310933 A CN 201910310933A CN 110061214 A CN110061214 A CN 110061214A
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- electrode material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of conducting polymers to coat TiO2(B) preparation and application of negative electrode material, belongs to lithium ion battery material technical field.The TiO of conducting polymer cladding is prepared for by wet process coating technology2(B) 1-dimention nano belt composite；The preparation process is easy to operate, low in cost, and has good chemical property as lithium ion battery negative material.
Description
Technical field
The invention belongs to technical field of lithium batteries, and in particular to conducting polymer coats TiO2(B) preparation of negative electrode material
And application.
Background technique
TiO2(B) it is monoclinic system, there is open crystal structure, allows the reversible deintercalation of lithium/sodium ion.TiO2
(B) the removal lithium embedded thermodynamic study of material shows TiO2(B) crystal structure there are three position for lithium be embedded in (A1, A2 and C),
Total amount is up to Li1.25TiO2(B), and the practical lithium-inserting amount of electrochemistry is up to 0.75 ~ 0.9 (335 mA h g of theoretical electrochemistry capacity-1).During discharge, there are two phase reaction (LixTiO2, x=0.24 ~ 0.41), become the control for restricting lithium ion diffusion
Journey, the strong influence removal lithium embedded behavior of the system material.TiO2(B) material has the embedded fake capacitance of apparent lithium ion
There is capacitance behavior and ion to spread controlling behavior for effect, entire charge discharge process.Pass through the charge and discharge to the material
Dynamical property analysis in the process, in discharge regime (LixTiO2, x=0.24 ~ 0.41), electrochemical behavior is obviously by lithium
The control of ion dispersal behavior, and the charge discharge behavior in other stages is then controlled by capacitance behavior.TiO2(B) as lithium from
Sub- battery electrode material, heavy-current discharge performance (multiplying power property) is bad, and its poorly conductive, limits it and further applies.
Therefore TiO is improved2(B) ionic conductivity of negative electrode material and lithium ion diffusion rate are the key that improve its chemical property.
TiO at this stage2(B) study on the modification of material is based primarily upon material nano, surface cladding, using excellent electron conductor as substrate life
Long TiO2(B) and multi phase interface stores up lithium etc..Therefore it is wrapped by material nano (shortening ion diffusion length) and surface
Covering and (serve as conducting medium in surface) two methods collective effect makes its chemical property significantly improve.The present invention utilizes wet process
Coating technology successfully synthesizes conducting polymer cladding TiO2(B) electrode material, and applied in energy storage.
Summary of the invention
In view of this, it is an object of the invention to: a kind of conducting polymer cladding TiO (1) is provided2(B) electrode material
Preparation method, the preparation method are easy to operate, low in cost；(2) TiO is coated by conducting polymer prepared by the method2
(B) negative electrode material has the advantages such as unique pattern, chemical property be good；(3) conducting polymer coats TiO2(B) cathode material
Expect the application in terms of lithium ion battery.
In order to achieve the above objectives, the invention provides the following technical scheme:
1. a kind of conducting polymer coats TiO2(B) preparation method of negative electrode material, which comprises the steps of:
(1) precursor preparation: titanium dioxide being added in concentrated alkali solution and is stirred evenly, and passes through hydro-thermal method in homogeneous reaction instrument
Mixed liquid is synthesized, repeatedly washing is then carried out and filters, and suitable acid solution is added and stirs 12 hours, then wash solution for several times
It filters, is finally freeze-dried, obtains presoma；
(2) progress of presoma described in step (1) high-temperature heat treatment is obtained into TiO2(B)；
(3) wet process coating technology prepares conducting polymer cladding TiO2(B): by TiO described in step (2)2(B) be added to containing
In the solution of conducting polymer, after mixing evenly, then mixed liquid centrifuge washing is dried in vacuo to obtain conducting polymer packet
The TiO covered2(B)。
Further, in the step (1), the molar concentration of concentrated alkali solution is 10 ~ 15 mol/L, and concentrated alkali solution is hydroxide
One of sodium or potassium hydroxide；In the step (1), the molar ratio of titanium dioxide and high alkali liquid is 1:120 ~ 1:180；It is described
In step (1), acid solution is one of hydrochloric acid or nitric acid or a variety of；The molar concentration of acid is 0.1 mol/L.
Further, mixed liquid, including following reaction condition are synthesized by hydro-thermal method in homogeneous reaction instrument in step (1):
Phase reaction instrument revolving speed is 15 rpm, and hydrothermal temperature is 150 ~ 195 DEG C, and soaking time is 12 ~ 72 hours.
Further, the high-temperature heat treatment in step (2), including following reaction condition: calcination temperature is 400 DEG C, when heat preservation
Between be 4 hours.
Further, the wet process coating technology in step (3), including following reaction condition: magnetic agitation 12 hours；Vacuum is dry
Dry temperature is 80 DEG C, drying time 10 hours.
Further, in step (3) conducting polymer be polypyrrole, polyaniline, polythiophene one or more.
2. preparing conducting polymer cladding TiO by any of the above item the method2(B) negative electrode material.
3. coating TiO by the conducting polymer of preparation recited above2(B) negative electrode material answering in terms of lithium ion battery
With.
The beneficial effects of the present invention are: the present invention provides conducting polymers to coat TiO2(B) preparation of negative electrode material
And application.The preparation manipulation that the preparation method provides is simple, low in cost；Conducting polymer coats TiO2(B) ion battery is negative
Pole material has good high rate performance and cyclical stability.
Detailed description of the invention
In order to keep the purpose of the present invention, technical scheme and beneficial effects clearer, the present invention provides following attached drawing and carries out
Illustrate:
Fig. 1 is that 1 gained conducting polymer of embodiment coats TiO2(B) field emission scanning electron microscope figure.
Fig. 2 is that 1 gained conducting polymer of embodiment coats TiO2(B) object phase XRD diagram.
Fig. 3 is that 1 gained conducting polymer of example coats TiO2(B) the full spectrogram of x-ray photoelectron.
Fig. 4 is that conducting polymer described in embodiment 2 coats TiO2(B) half-cell of negative material preparation is in different current densities
Under charging and discharging curve figure.
Fig. 5 is that conducting polymer described in embodiment 2 coats TiO2(B) half-cell of negative material material preparation is under 1 C multiplying power
Cycle performance and efficiency for charge-discharge curve graph.
Fig. 6 is that conducting polymer described in embodiment 2 coats TiO2(B) half-cell of negative material material preparation is close in different electric currents
Spend lower circulating ratio figure.
Specific embodiment
Below in conjunction with attached drawing, a preferred embodiment of the present invention will be described in detail.
1 conducting polymer of embodiment coats TiO2(B) preparation of negative electrode material
Weigh 2 g titanium dioxide and sodium hydroxide (12 mol/L) solution be stirred at room temperature 1 hour, after aforesaid liquid is placed in
Poly- the four of 500 ml are covered in the stainless steel cauldron of ethylene liner, at 170 DEG C with 15 rpm tachyphylaxis 48 hours after, to anti-
It answers product to carry out washing suction filtration, until solution PH is neutrality, 0.1 mol/L hydrochloric acid is then added and is stirred at room temperature 12 hours, then will
Solution repeatedly washs suction filtration, is freeze-dried, and presoma is obtained.Take liter of the appropriate presoma in Muffle furnace with 3 DEG C/min
Warm rate is heat-treated 4 hours at 400 DEG C, obtains TiO2(B)。
It is molten that 670 μ l poly- (3,4- ethyldioxythiophene)-poly- (styrene sulfonate) is added in 20 ml deionized waters
Liquid (1.5 wt%), continual ultrasonic keeps its evenly dispersed.Then the TiO of 0.1 g is weighed2(B) it is added to above-mentioned evenly dispersed molten
In liquid, then magnetic agitation 10 hours, centrifugation obtain dark blue precipitate object.Then respectively by deionized water, acetone repeatedly from
Heart washing, is finally placed in a vacuum drying oven, 10 h is dried in vacuo at 80 DEG C, obtains conducting polymer cladding TiO2(B) material
Material.As shown in Figure 1, resulting materials object mutually characterizes XRD and the full spectrogram of x-ray photoelectron is as shown in Figure 2,3, explanation passes through its pattern
Such method can successfully prepare conducting polymer cladding TiO2(B) nanobelt material.
Conducting polymer is coated TiO by embodiment 22(B) assembling and electrochemical property test of the negative electrode material for battery
(1) the conducting polymer cladding TiO prepared in Example 12(B) negative electrode material is as active material and conductive additive
After evenly mixing, it is molten that suitable ethyl alcohol is added in (acetylene black) and binder (sodium carboxymethylcellulose, CMS) 8:1:1 in mass ratio
Liquid (volume fraction 65%) is simultaneously ground into uniform slurry.Then it is uniformly coated in area is about 1.3 cm2Copper sheet base
On bottom, then coated copper sheet is placed in a vacuum drying oven, 12 h are dried in vacuo at 80 DEG C.Up to working electrode.
(2) half-cell assembles: by anode cover, working electrode, diaphragm (Celgard2400), 1 mol L-1LiPF6Electrolysis
Liquid (fluorinated ethylene carbonate FEC: dimethyl carbonate DMC volume ratio be 1:1), lithium piece, gasket, spring leaf, negative electrode casing successively into
Row assembling.After encapsulation, by battery removal glove box, after being stored at room temperature 6 hours；Electrochemistry is carried out on blue electrical measurement test system
The test of performance, test voltage range are 1.0 ~ 3.0V, and acquired results are as shown in Figure 4,5, 6.
As can be seen from Figure 4: obtained conducting polymer coats TiO2(B) negative electrode material is inclined 1.8 ~ 1.0 V are gentle
Oblique region, specific discharge capacity are more than 90% or more of total capacity, have good commercial application value.
As can be seen from Figure 5: for the material under the multiplying power of 1 C, first circle specific discharge capacity is 209 mA h g-1, by 600
Still there are 179.6 mA hg after secondary circulation-1Specific discharge capacity, total capacity conservation rate be 86 %；And its coulombic efficiency is always
It is maintained at 100 % or so.Therefore TiO is coated by conducting polymer prepared by this method2(B) negative electrode material cycle performance is good
It is good.
As can be seen from Figure 6: the conducting polymer under the multiplying power of 0.1 C, 0.5 C, 1 C, 5 C, 10 C, 20 C and 30 C
Coat TiO2(B) specific discharge capacity of negative electrode material is respectively 256.7 mA h g-1、227.5 mA h g-1、200.6 mA h
g-1、146.6 mA h g-1、132.2 mA h g-1、107.2 mA h g-1With 96.5 mA h g-1.Show close in different electric currents
Good rate capability, the security performance for spending the lower lithium ion battery negative material are high.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (7)
1. a kind of conducting polymer coats TiO2(B) preparation method of negative electrode material, which is characterized in that including following preparation step:
(1) preparation of presoma: titanium dioxide being added in concentrated alkali solution and is stirred evenly, and passes through hydro-thermal in homogeneous reaction instrument
Method synthesizes mixed liquid, then carries out repeatedly washing and filters, and suitable acid solution is added and stirs 12 hours, then washes solution for several times
Suction filtration is washed, is finally freeze-dried, presoma is obtained；
(2) progress of presoma described in step (1) high-temperature heat treatment is obtained into TiO2(B)；
(3) wet process coating technology prepares conducting polymer cladding TiO2(B): by TiO described in step (2)2(B) be added to containing
In the solution of conducting polymer, after mixing evenly, then mixed liquid centrifuge washing is dried in vacuo to obtain conducting polymer packet
The TiO covered2(B)。
2. a kind of conducting polymer according to claim 1 coats TiO2(B) preparation method of negative electrode material, feature exist
In in the step (1), the molar concentration of concentrated alkali solution is 10 ~ 15 mol/L, and concentrated alkali solution is sodium hydroxide or potassium hydroxide
One of；In the step (1), the molar ratio of titanium dioxide and concentrated alkali solution is 1:120 ~ 1:180；In the step (1),
Acid solution is one of hydrochloric acid or nitric acid, and the molar concentration of acid solution is 0.1 mol/L；In the step (1) homogeneous
React in instrument and synthesize mixed liquid, including following reaction condition by hydro-thermal method: homogeneous reaction instrument revolving speed is 15 rpm, and hydrothermal temperature is
150 ~ 195 DEG C, soaking time is 12 ~ 72 hours.
3. a kind of conducting polymer according to claim 1 coats TiO2(B) preparation method of negative electrode material, feature exist
In the high-temperature heat treatment in the step (2) includes following reaction condition: calcination temperature is 400 DEG C, and soaking time is 4 hours.
4. conducting polymer according to claim 1 coats TiO2(B) method of negative electrode material preparation, which is characterized in that institute
State the wet process coating technology in step (3), including following reaction condition: magnetic agitation 12 hours, vacuum drying temperature was 80 DEG C,
Drying time 10 hours.
5. a kind of conducting polymer according to claim 1 coats TiO2(B) preparation method of negative electrode material, feature exist
In in the step (3), conducting polymer is one or more of polypyrrole, polyaniline, polythiophene.
6. any one the method prepares conducting polymer cladding TiO according to claim 1 ~ 52(B) negative electrode material.
7. coating TiO by the conducting polymer of claim 6 the method preparation2(B) negative electrode material answering on lithium ion battery
With.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111762814A (en) * | 2020-07-02 | 2020-10-13 | 西南大学 | TiO2(B) Preparation and application of @ RGO aerogel negative electrode material |
| CN112794365A (en) * | 2021-01-05 | 2021-05-14 | 西南大学 | Phosphorus-doped conductive carbon-coated metal oxide composite material, preparation method thereof and application thereof in sodium-ion battery cathode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172800A (en) * | 2017-12-28 | 2018-06-15 | 福建翔丰华新能源材料有限公司 | A kind of polypyrrole coats TiO2(B) negative material and preparation method thereof |
| CN108305998A (en) * | 2017-12-28 | 2018-07-20 | 福建翔丰华新能源材料有限公司 | A kind of polyaniline-coated TiO2(B) negative material and preparation method thereof |
| CN108899549A (en) * | 2018-07-14 | 2018-11-27 | 西南大学 | Carbon coating TiO in situ2(B) preparation method and application of negative electrode material |
-
2019
- 2019-04-18 CN CN201910310933.3A patent/CN110061214A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108172800A (en) * | 2017-12-28 | 2018-06-15 | 福建翔丰华新能源材料有限公司 | A kind of polypyrrole coats TiO2(B) negative material and preparation method thereof |
| CN108305998A (en) * | 2017-12-28 | 2018-07-20 | 福建翔丰华新能源材料有限公司 | A kind of polyaniline-coated TiO2(B) negative material and preparation method thereof |
| CN108899549A (en) * | 2018-07-14 | 2018-11-27 | 西南大学 | Carbon coating TiO in situ2(B) preparation method and application of negative electrode material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111762814A (en) * | 2020-07-02 | 2020-10-13 | 西南大学 | TiO2(B) Preparation and application of @ RGO aerogel negative electrode material |
| CN112794365A (en) * | 2021-01-05 | 2021-05-14 | 西南大学 | Phosphorus-doped conductive carbon-coated metal oxide composite material, preparation method thereof and application thereof in sodium-ion battery cathode material |
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Application publication date: 20190726 |