CN110380021A - A kind of TiO of organic conductive polymer/carbon dual cladding2(B) negative electrode material and preparation method thereof - Google Patents
A kind of TiO of organic conductive polymer/carbon dual cladding2(B) negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of organic conductive polymer/carbon dual cladding TiO2(B) negative electrode material and preparation method thereof, the negative electrode material are core-shell structure, and wherein kernel is TiO2(B) and superconductive carbon black, shell are organic conductive polymer layer and carbon-coating；The superconductive carbon black is filled in TiO2(B) in the gap grid of particle, the filling rate of superconductive carbon black is 0.1 ~ 6%；The organic conductive polymer layer between kernel and carbon-coating, organic conductive polymer layer with a thickness of 0.1 ~ 20 μm, carbon-coating with a thickness of 0.1 ~ 15 μm.The negative electrode material is prepared using hydro-thermal method in the present invention, and preparation method is simple and easy to control, simple process, and environmental-friendly pollution-free, negative electrode material obtained has excellent high rate performance, is suitble to industrialized production.
Description
Technical field
The present invention relates to negative electrode material fields, more particularly, to a kind of organic conductive polymer/carbon dual cladding
TiO2(B) negative electrode material and preparation method thereof.
Background technique
With the fast development of emerging economies, global energy consumption sharp increase.Lithium ion battery is with its high voltage, height
Energy density, the advantages that having extended cycle life, have a safety feature, is low in cost, are in portable electrics such as computer, camera and mobile phones
It has been obtained and is widely applied in sub- equipment.Nowadays, the Main way that field of lithium ion battery is assaulted fortified position is to improve battery
Energy density, and therefore the defect that an important factor for limiting energy density is negative electrode material strives to find the cathode material of high capacity
Material becomes the major tasks of researcher.
Lithium titanate is a kind of zero strain material, and lithium ion does not make its crystal form change in deintercalation behavior wherein, lattice
Volume change has good cycle performance and stable discharge platform less than 1%.However, the theoretical ratio of lithium titanate
Capacity only has 175mAh/g, and actual specific capacity is lower, limits its large-scale commercial application.TiO2(B) crystal structure
For monoclinic system, C2/ m space group, by the TiO on total side and vertex6Octahedron is constituted, TiO2(B) design feature par excellence is
There are the feature parallel channels along [010] direction in its crystal structure, theoretical and experiment all shows that this is conducive to lithium ion logical
Combination and diffusion in road are a kind of ideal negative electrode materials for substituting lithium titanate.However, TiO2(B) it is used as negative electrode material
When, have the defects that ionic conductivity is low.For the ion conductivity for improving titanium dioxide, the prior art is often using using carbon
Coat TiO2Negative electrode material promotes TiO using carbon2The electric conductivity of negative electrode material, but there are titanium dioxide and carbon-coating defective tightness,
The problems such as carbon-coating is not uniform enough causes its chemical property to need to be improved.And TiO is coated using carbon-coating2When negative electrode material,
The tap density of material is not only reduced, so that the decrease of power density, increases the volume and weight of material, is unfavorable for applying,
And carbon coating during be easy to appear the problems such as carbon coating layer falls off, drops off with aluminium foil, meanwhile, carbon-coated thickness with
Uniformity is also difficult to control.Therefore, the compactness between the ionic conductivity and clad of TiO2 (B) negative electrode material is improved
It is of great significance.
Summary of the invention
The present invention is to overcome above-mentioned the deficiencies in the prior art, provides a kind of organic conductive polymer/carbon dual packet
The TiO covered2(B) negative electrode material.Negative electrode material of the present invention has core-shell structure, is filled in first using superconductive carbon black
TiO2(B) inner casing is formed in gap grid, then is successively coated using organic conductive polymer and carbon, and organic conducting polymer is formed
Object/carbon double-coating TiO2(B) negative electrode material improves TiO by the organic conductive polymer layer and carbon-coating of specific thicknesses2
(B) ionic conductivity of negative electrode material.Meanwhile the introducing of organic conductive polymer realizes TiO2(B), organic conductive polymer
Close cladding between layer and carbon-coating.
It is yet another object of the invention to provide a kind of organic conductive polymer/carbon dual cladding TiO2(B) negative electrode material
Preparation method.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of TiO of organic conductive polymer/carbon dual cladding2(B) negative electrode material, the negative electrode material are nucleocapsid knot
Structure, wherein kernel is TiO2(B) and superconductive carbon black, shell are organic conductive polymer layer and carbon-coating；The superconductive carbon black
It is filled in TiO2(B) in the gap grid of particle, the filling rate of superconductive carbon black is 0.1~6%；The organic conductive polymer
Layer between kernel and carbon-coating, organic conductive polymer layer with a thickness of 0.1~20 μm, carbon-coating with a thickness of 0.1~15 μm.
The present invention is by being filled in TiO for the superconductive carbon black of special ratios range2(B) the gap grid of particle, can have
Effect improves the ion and electron transfer rate of negative electrode material, then the organic conductive polymer of specific thicknesses is closely coated outside kernel
Layer, on the one hand can further fill negative electrode material gap, on the other hand can also combine closely carbon-coating, promote big multiplying power discharging and follow
Ring ability realizes fitting closely between layers, the carbon-coating of specific thicknesses is finally coated, between organic conductive polymer layer
The electric conductivity of the negative electrode material is improved by mutually acting synergistically, while carbon-coating can also play the role of that electrolyte, shape is isolated
At protective shell, prevent negative electrode material by electrolyte etch.
When superconductive carbon black filling rate is too low, high rate capability is become negatively affected；When superconductive carbon black filling rate mistake
Gao Shi will affect battery capacity.
When the thickness of organic conductive polymer layer and carbon-coating is too thick, it is unfavorable for Li+Transmission；Work as organic conductive polymer
When the thickness of layer and carbon-coating is too low, the electric conductivity of negative electrode material cannot be effectively promoted, while electrolyte can not be completely cut off well,
Protective effect is not had.
Inventor has found that, when the filling rate of superconductive carbon black is between 0.1~6%, organic conductive polymerize by many experiments
Nitride layer with a thickness of 0.1~20um, carbon-coating with a thickness of 0.1~15 μm when, by mutual synergistic effect between three,
Negative electrode material shows better high rate performance.
Preferably, the filling rate of the superconductive carbon black is 2~4%.
It is highly preferred that the filling rate of the superconductive carbon black is 2.5%.
Preferably, the organic conductive polymer layer with a thickness of 6~8 μm, carbon-coating with a thickness of 5~8 μm.
It is highly preferred that the organic conductive polymer layer with a thickness of 5 μm, carbon-coating with a thickness of 5 μm.
Preferably, the TiO2(B) partial size is 1~1000nm.
Preferably, the specific volume of the superconductive carbon black is 4~5cm3/ g, partial size are 1~500nm.
A kind of TiO of organic conductive polymer/carbon dual cladding2(B) preparation method of negative electrode material, including following step
It is rapid:
S1. presoma is prepared: by TiO2(B) mixed with superconductive carbon black, dispersing agent 70~90:2 in mass ratio~7:8~13
It closes, solvent, spray drying is added, powder is processed to obtain presoma；
S2. organic conductive polymer coating is coated: by presoma described in S1 and organic conductive polymer mass ratio 1:0.03
~1:0.15 heating is mixed and dried, and ball milling obtains first time covering material；
S3. it coats carbon-coating: first time covering material described in S2 being mixed with carbon source 1:1~1:30 in mass ratio, vacuum
Stirring, 400~1000 DEG C of 0.5~8h of calcining obtain the negative electrode material.
Preferably, TiO described in S12(B), superconductive carbon black, dispersing agent mixing mass ratio be 80~90:3~5:8~
10。
Preferably, the mass ratio of presoma described in S2 and organic conductive polymer is 1:0.03~1:0.07.
Preferably, the organic conductive polymer is polypyrrole, polythiophene, polyaniline, one of PEDOT-PSS or several
Kind.
It is highly preferred that the organic conductive polymer is polypyrrole.
Preferably, carbon source described in S3 is phenol, pitch, epoxy resin, phenolic resin, furfural resin, polyvinyl chloride, gathers
One or more of ethylene glycol, polyethylene oxide, acrylic resin and polyacrylonitrile.
Preferably, TiO described in S12(B) it is prepared by hydro-thermal method, comprising the following steps:
S11. titanium source, acetic acid are added into ethylene glycol solvent, adds NaOH and carries out hydro-thermal reaction, protected in 130~250 DEG C
Temperature 5~for 24 hours, it washs to neutrality, obtains sediment；
S12. sediment described in S11 is added in HCL solution, is washed, it is dry, in 200~700 DEG C of 8~16h of calcining,
Obtain the TiO2(B)。
It is highly preferred that calcination temperature described in S12 is 300~600 DEG C, calcination time is 10~14h.
Preferably, titanium source described in S11 is titanium oxide powder, butyl titanate, titanium tetrachloride, titanium tetrafluoride and vulcanization
One or more of titanium.
Preferably, dispersing agent described in S1 is sodium tripolyphosphate, calgon, sodium pyrophosphate, vinyl stearic bicine diester
Amine, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, guar gum, fat
At least one of acid polyethylene glycol ester；The solvent is one or more of furans, amide, pure and mild ketone.
It is highly preferred that dispersing agent described in S1 is sodium tripolyphosphate.
Preferably, jitter time described in S1 is 1~100h.
Preferably, solvent described in S1 be furans, amide, it is one or more of in pure and mild ketone.
Preferably, the hot-air inlets temperature of spray drying described in S1 be 150~300 DEG C, outlet temperature be 100~
190℃。
Preferably, the material median partial size after the processing of powder described in S1 is 5~30 μm, and specific surface area is 1~80m2/g。
Preferably, the carbon source of carbon-coating described in S3 is phenol, pitch, epoxy resin, phenolic resin, furfural resin, polychlorostyrene
One or more of ethylene, polyethylene glycol, polyethylene oxide, acrylic resin and polyacrylonitrile.
It is highly preferred that carbon source described in S3 is epoxy resin.
Compared with prior art, the invention has the following beneficial effects:
The present invention provides a kind of organic conductive polymer/carbon dual cladding TiO2(B) negative electrode material and its preparation side
Method, the negative electrode material have core-shell structure, and wherein kernel is filled in TiO using the superconductive carbon black of special ratios2(B) particle
Gap grid, play the role of promoted negative electrode material electric conductivity；Shell is the organic conductive polymer and carbon pair of specific thicknesses
Layer structure, coats the organic conductive polymer layer of a layer specific thickness outside inner casing first, not only realizes between layers
Combine closely, also improve the electric conductivity of negative electrode material；One layer of certain thickness carbon-coating is finally coated, cathode can be effectively completely cut off
Contact of the material with electrolyte, while the electric conductivity for improving negative electrode material surface can also be played.The present invention uses hydro-thermal legal system
Standby to obtain the negative electrode material, preparation method is simple and easy to control, simple process, environmental-friendly pollution-free, negative electrode material tool obtained
Standby excellent high rate performance, is suitble to industrialized production.
Detailed description of the invention
Fig. 1 is organic conductive polymer/carbon dual cladding TiO in embodiment 12(B) the SEM figure of negative electrode material.
Fig. 2 is organic conductive polymer/carbon dual cladding TiO in embodiment 12(B) negative electrode material is prepared into 18650
Battery different multiplying curve, charging curve fill for 0.5C, and discharge curve is 0.5C, 1C, 2C, 5C, 10C from right to left.
Specific embodiment
In order to become apparent from, completely describe technical solution of the present invention, further specifically below by way of specific embodiment
The bright present invention, it should be understood that described herein the specific embodiments are only for explaining the present invention, is not intended to limit the present invention,
Various changes can be carried out in the range of right of the present invention limits.
Embodiment 1
A kind of TiO of polypyrrole/carbon-coating dual cladding2(B) negative electrode material, the negative electrode material are core-shell structure, wherein
Kernel is TiO2(B) and superconductive carbon black, shell are polypyrrole layer and carbon-coating；The superconductive carbon black is filled in TiO2(B) particle
Gap grid in, the filling rate of superconductive carbon black is 2.5%, specific volume 4cm3/ g, partial size 50nm, TiO2(B) partial size is
50nm；The polypyrrole layer between kernel and carbon-coating, polypyrrole layer with a thickness of 5 μm, carbon-coating with a thickness of 5 μm, it is described
The carbon source of carbon-coating is epoxy resin.
Embodiment 2~6
A kind of TiO of polypyrrole/carbon-coating dual cladding2(B) negative electrode material, substantially the same manner as Example 1, difference is shown in Table
1, wherein A is the filling rate (%) of superconductive carbon black, and B is the thickness (μm) of polypyrrole layer, and C is the thickness (μm) of carbon-coating.
Table 1
| Project | A | B | C |
| Embodiment 2 | 0.1 | 5 | 5 |
| Embodiment 3 | 6 | 5 | 5 |
| Embodiment 4 | 2.5 | 6 | 5 |
| Embodiment 5 | 2.5 | 8 | 5 |
| Embodiment 6 | 2.5 | 5 | 8 |
Embodiment 7
A kind of TiO of polypyrrole/carbon-coating dual cladding2(B) negative electrode material, comprising the following steps:
S1. presoma is prepared: by TiO2(B) it mixes, is added with superconductive carbon black, sodium tripolyphosphate 80:4:9 in mass ratio
Furans, spray drying, powder are processed to obtain presoma；
S2. it coats organic conductive polymer coating: presoma described in S1 and polypyrrole 1:0.07 in mass ratio being heated mixed
It closes, drying, ball milling obtains first time covering material；
S3. it coats carbon-coating: first time covering material described in S2 is mixed with phenol 1:15 in mass ratio, be stirred under vacuum,
The negative electrode material is obtained in 800 DEG C of calcining 6h；
Wherein, the hot-air inlets temperature of spray drying described in S1 is 200 DEG C, and outlet temperature is 150 DEG C；
Material median partial size after the processing of powder described in S1 is 20 μm, specific surface area 60m2/g；
TiO described in S12(B) it is prepared by hydro-thermal method, comprising the following steps:
S11. 6ml butyl titanate, 3ml acetic acid are added into 20ml ethylene glycol solvent, adds 30ml13mol/L
NaOH solution carries out hydro-thermal reaction, in 150 DEG C of heat preservation 14h, washs to neutrality, obtains sediment；
S12. it will be added in 0.1mol/L HCL solution in sediment described in S11, washing, in 80 DEG C of dry 12h, in
400 DEG C of calcining 12h, obtain the TiO2(B)。
Embodiment 8
A kind of TiO of polypyrrole/carbon-coating dual cladding2(B) preparation method of negative electrode material, it is substantially the same manner as Example 7,
Its difference is, TiO described in S12It (B) is 90:7:13 with the mass ratio of superconductive carbon black, sodium tripolyphosphate.
Embodiment 9
A kind of TiO of polypyrrole/carbon-coating dual cladding2(B) preparation method of negative electrode material, it is substantially the same manner as Example 7,
Its difference is that the mass ratio of presoma described in S2 and polypyrrole is 1:0.03.
Comparative example 1~9
A kind of TiO of polypyrrole/carbon-coating dual cladding2(B) negative electrode material, substantially the same manner as Example 1, difference is shown in Table
2, wherein A is the filling rate (%) of superconductive carbon black, and B is the thickness (μm) of polypyrrole layer, and C is the thickness (μm) of carbon-coating.
Table 2
| Project | A | B | C |
| Comparative example 1 | - | 3 | 5 |
| Comparative example 2 | 0.05 | 3 | 5 |
| Comparative example 3 | 7 | 3 | 5 |
| Comparative example 4 | 2.5 | - | 5 |
| Comparative example 5 | 2.5 | 0.05 | 5 |
| Comparative example 6 | 2.5 | 22 | 5 |
| Comparative example 7 | 2.5 | 3 | - |
| Comparative example 8 | 2.5 | 3 | 0.05 |
| Comparative example 9 | 2.5 | 3 | 17 |
Comparative example 10
A kind of TiO of polypyrrole/carbon-coating dual cladding2(B) preparation method of negative electrode material, it is substantially the same manner as Example 7,
Its difference is, TiO described in S12It (B) is 60:1:7 with the mass ratio of superconductive carbon black, sodium tripolyphosphate.
Comparative example 11
A kind of TiO of polypyrrole/carbon-coating dual cladding2(B) preparation method of negative electrode material, it is substantially the same manner as Example 7,
Its difference is, TiO described in S12It (B) is 95:8:15 with the mass ratio of superconductive carbon black, sodium tripolyphosphate.
Comparative example 12
A kind of TiO of polypyrrole/carbon-coating dual cladding2(B) preparation method of negative electrode material, it is substantially the same manner as Example 7,
Its difference is that the mass ratio of presoma described in S2 and polypyrrole is 1:0.01.
Comparative example 13
A kind of TiO of polypyrrole/carbon-coating dual cladding2(B) preparation method of negative electrode material, it is substantially the same manner as Example 7,
Its difference is that the mass ratio of presoma described in S2 and polypyrrole is 1:0.19.
Performance test and interpretation of result
The negative electrode material of embodiment and comparative example and conductive agent, binder PVDF 94:3:3 mixed dissolution in mass ratio are existed
In NMP, control solid content is coated in copper foil current collector 35%, and negative electrode tab is made in vacuum drying.Again by traditional maturation
The LiPF of iron phosphate lithium positive pole piece, 1mol/L6/ EC+DMC (v/v=1:4) electrolyte, Celgard2400 diaphragm, shell use
Conventional production process assembles 18650 cylinder single batteries.The cylindrical battery discharge performance of preparation is tested, test condition is room temperature,
0.2C constant current charge-discharge, charging/discharging voltage are 1.0~2.5V.Test the results are shown in Table 3.
Table 3
Obviously, the above embodiment of the present invention is only intended to clearly illustrate examples made by the present invention, and is not to this
The restriction of the embodiment of invention.It will be appreciated by those skilled in the art that can also make on the basis of the above description other
Various forms of variations or variation, there is no necessity and possibility to exhaust all the enbodiments.It is all in spirit of the invention
With any modifications, equivalent replacements, and improvements made within principle etc., the protection scope of the claims in the present invention should be included in
Within.
Claims (10)
1. a kind of organic conductive polymer/carbon dual cladding TiO2(B) negative electrode material, which is characterized in that the negative electrode material is
Core-shell structure, wherein kernel is TiO2(B) and superconductive carbon black, shell are organic conductive polymer layer and carbon-coating；The superconduction
Electricity is carbon black filled in TiO2(B) in the gap grid of particle, the filling rate of superconductive carbon black is 0.1 ~ 6%；The organic conductive is poly-
Nitride layer is closed between kernel and carbon-coating, organic conductive polymer layer with a thickness of 0.1 ~ 20 μm, carbon-coating with a thickness of 0.1 ~ 15 μ
m。
2. negative electrode material as described in claim 1, which is characterized in that the filling rate of the superconductive carbon black is 2 ~ 4%.
3. negative electrode material as described in claim 1, which is characterized in that the filling rate of the superconductive carbon black is 2.5%.
4. negative electrode material as described in claim 1, which is characterized in that the organic conductive polymer layer with a thickness of 6 ~ 8 μm,
Carbon-coating with a thickness of 5 ~ 8 μm.
5. such as the preparation method of any one of claim 1 ~ 4 negative electrode material, which comprises the following steps:
S1. presoma is prepared: by TiO2(B) it mixes, is added with superconductive carbon black, dispersing agent 70 ~ 90:2 in mass ratio ~ 7:8 ~ 13
Solvent, spray drying, powder are processed to obtain presoma；
S2. coat organic conductive polymer coating: by presoma described in S1 and organic conductive polymer 1:0.03 in mass ratio ~
1:0.15 heating is mixed and dried, and ball milling obtains first time covering material；
S3. it coats carbon-coating: first time covering material described in S2 is mixed with carbon source 1:1 ~ 1:30 in mass ratio, be stirred under vacuum,
400 ~ 1000 DEG C of 0.5 ~ 8h of calcining, obtain the negative electrode material.
6. preparation method as claimed in claim 5, which is characterized in that TiO described in S12(B), superconductive carbon black, dispersing agent it is mixed
Conjunction mass ratio is 80 ~ 90:3 ~ 5:8 ~ 10.
7. preparation method as claimed in claim 5, which is characterized in that the quality of presoma described in S2 and organic conductive polymer
Than for 1:0.03 ~ 1:0.07.
8. negative electrode material as claimed in claim 5, which is characterized in that organic conductive polymer described in S2 is polypyrrole, poly- thiophene
Pheno, polyaniline, one or more of PEDOT-PSS.
9. preparation method as claimed in claim 5, which is characterized in that carbon source described in S3 is phenol, pitch, epoxy resin, phenol
One of urea formaldehyde, furfural resin, polyvinyl chloride, polyethylene glycol, polyethylene oxide, acrylic resin and polyacrylonitrile are several
Kind.
10. preparation method as claimed in claim 5, which is characterized in that TiO described in S12(B) it is prepared by hydro-thermal method, including
Following steps:
S11. titanium source, acetic acid are added into ethylene glycol solvent, adds NaOH solution and carries out hydro-thermal reaction, protected in 130 ~ 250 DEG C
Temperature 5 ~ for 24 hours, it washs to neutrality, obtains sediment；
S12. sediment described in S1 is added in HCL solution, is washed, it is dry, in 200 ~ 700 DEG C of 8 ~ 16h of calcining, obtain institute
State TiO2(B)。
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| CN113889593A (en) * | 2020-07-02 | 2022-01-04 | 洛阳月星新能源科技有限公司 | Preparation method of hard carbon-coated soft carbon composite material |
| US20220089917A1 (en) * | 2020-09-23 | 2022-03-24 | HKC Corporation Limited | Conductive particle and manufacturing method thereof, adhesive and application thereof |
| CN115548363A (en) * | 2022-11-29 | 2022-12-30 | 山东海化集团有限公司 | Weldable bipolar plate for flow battery and preparation method and application thereof |
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2019
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| CN111924848A (en) * | 2020-08-10 | 2020-11-13 | 中南大学 | Silicon-based negative electrode material for lithium ion battery and preparation method thereof |
| US20220089917A1 (en) * | 2020-09-23 | 2022-03-24 | HKC Corporation Limited | Conductive particle and manufacturing method thereof, adhesive and application thereof |
| US12024660B2 (en) * | 2020-09-23 | 2024-07-02 | HKC Corporation Limited | Conductive particle and manufacturing method thereof, adhesive and application thereof |
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