CN109768244A - A kind of tubulose titanium dioxide/carbon lithium ion cell negative electrode material and the preparation method and application thereof - Google Patents
A kind of tubulose titanium dioxide/carbon lithium ion cell negative electrode material and the preparation method and application thereof Download PDFInfo
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- CN109768244A CN109768244A CN201811642403.0A CN201811642403A CN109768244A CN 109768244 A CN109768244 A CN 109768244A CN 201811642403 A CN201811642403 A CN 201811642403A CN 109768244 A CN109768244 A CN 109768244A
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- 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 invention discloses a kind of tubulose titanium dioxide/carbon lithium ion cell negative electrode materials and the preparation method and application thereof.Specific preparation step is that (1) prepares precursor solution；(2) organic titanium precursors are prepared；(3) it is sintered.This method is with polyalcohol, and monohydric alcohol and ether are carbon source, and titanyl sulfate etc. is used as titanium source, using solvent-thermal process organotitanium precursor body, then calcines to obtain finished product through inert atmosphere.Obtained material is in the tubulose that nanometer sheet is assembled into, and has richer porosity, bigger specific surface area, shorter lithium ion transport channel, to just show excellent lithium electrical property.Preparation method raw material sources of the invention are extensive, and operating procedure is simple, easily controllable, reproducibility is high.Compared with traditional titanium base material, there is higher specific capacity, excellent high rate performance and long-term cycle stability, have wide practical use in lithium ion battery negative material.
Description
Technical field
The invention belongs to the preparations and application field of the energy and electrochemical material, and in particular to a kind of tubulose titanium dioxide/carbon
Lithium ion battery negative material and the preparation method and application thereof.
Background technique
Titanium dioxide can be shown since its chemical property is stable, specific capacity is larger, good cycling stability and environmentally friendly
It writes the safety for improving lithium ion battery while reducing production cost, be a kind of negative electrode material of excellent lithium ion battery.But
Since its electric conductivity is poor, high rate performance is poor when leading to it as electrode material.Traditional best solution is to pass through packet
It wraps up in carbon and increases electric conductivity, and lithium ion mobility path is shortened by synthesis special appearance.But mostly there is systems for these methods
The disadvantages of standby process very complicated, the cost of raw material is high.The present invention is directed to propose a kind of method of solvent heat, synthesizes the two of tubulose
Titanium oxide complex carbon material, as high performance lithium ion battery negative material.
Solvent-thermal process method is a kind of method of emerging synthesis of metal oxide, in solvent heat, the dissimilarity of solvent
Matter, such as viscosity, density, there is different reciprocal effect to reactant, to influence the molding of material.This method is for synthesizing material
The controllability of the granular size of material, crystal structure and pattern is preferable.Therefore, it is contemplated that solvent-thermal process method is applied to dioxy
In the synthesis for changing titanium negative electrode material, have a good application prospect.
Summary of the invention
The purpose of the present invention is to provide a kind of method of no templated synthesis tubular morphology titanium dioxide, needed for this method
Raw material sources are extensive, and operating procedure is simple, and easily controllable and reproducibility is high, the meaning with practical application.Increasing material
While the specific surface area and porosity of material, simplify its synthesis process, to reach reduction production cost, improve material property,
So that the commercialization further object of titanium dioxide cathode material.
Another object of the present invention is to provide a kind of titanium dioxide complex carbon materials in lithium ion battery
Using the negative electrode material has many advantages, such as that specific capacity height, charge and discharge good reversibility, high rate performance are excellent.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of tubulose titanium dioxide/carbon lithium ion cell negative electrode material, includes the following steps:
(1) preparation of precursor solution: by titanium source, polyalcohol, monohydric alcohol and ether according to molar ratio be 1-2: 100-200:
300-400: 50-150 ratio is uniformly mixed, and obtains precursor solution；
(2) precursor solution of step (1): being put into the reaction kettle of polytetrafluoroethyllining lining by the preparation of organotitanium precursor body,
100-200 DEG C reaction 1-3 days, after cooled to room temperature, the precipitating for reacting generation is washed, dry, obtains organotitanium precursor body；
(3) sintering stage: by 450-700 DEG C sintering 2-10 hours under an inert atmosphere of organotitanium precursor body made from step (2),
Cooled to room temperature obtains tubulose titanium dioxide/carbon compound cathode materials.
Preferably, the polyalcohol includes glycerine, ethylene glycol, at least one of erythrol and butantriol.
Preferably, the monohydric alcohol includes at least one of methanol, ethyl alcohol, propyl alcohol, the tert-butyl alcohol and benzyl alcohol.
Preferably, the ether includes at least one of ether, phenetole, isopropyl ether and n-butyl ether.
Preferably, the titanium source includes at least one of titanyl sulfate, titanium tetrachloride, titanium tetrabromide and titanium tetra iodide.
Preferably, in step (2), the washing is the solution centrifugation for being 1-2: 0.5-1 with the volume ratio of ethyl alcohol and water
Washing 3 ~ 6 times；The drying is dried in vacuo 12 ~ 36 hours at 60 DEG C ~ 100 DEG C.
A kind of tubulose titanium dioxide/carbon lithium ion cell negative electrode material as made from method made above.
A kind of above-described tubulose titanium dioxide/application of the carbon lithium ion cell negative electrode material in lithium ion battery.
Compared with prior art, the present invention has the advantage that and technical effect:
(1) tubular morphology that nanometer sheet is assembled into is presented in tubulose of the invention titanium dioxide/carbon lithium ion cell negative electrode material, greatly
Mesoporous and micropore coexisting structure is measured, titania nanoparticles have smaller partial size (10 nm of <), while having more uniformly
Carbon coating layer.So that the electric conductivity of material and leading lithium ion ability and being substantially improved.The material purity height of synthesis, structure composition
Good, mechanical performance is strong；
(2) tubulose of the invention titanium dioxide/carbon lithium ion cell negative electrode material is applied to lithium ion battery, in 180 mA g-1
Current density under stable reversible specific capacity be up to 534 mAh g-1, there is biggish energy density, while showing excellent
High rate performance and long-term cycle stability, have very high application prospect；
(3) the method for the present invention raw material sources are extensive, and operating procedure is simple, easily controllable, reproducibility is high, can significantly improve cathode
The specific capacity and cyclical stability of material, Yi Shixian industrial-scale production.
Detailed description of the invention
Fig. 1 is the tubulose titanium dioxide/carbon lithium ion cell negative electrode material scanning electron microscope prepared in embodiment 1
Figure；
Fig. 2 a and Fig. 2 b be in embodiment 1 tubulose titanium dioxide/carbon lithium ion cell negative electrode material for preparing respectively Bu Tong again
Transmission electron microscope picture under rate；
Fig. 3 be in embodiment 1 tubulose titanium dioxide/carbon lithium ion cell negative electrode material nitrogen adsorption desorption curve graph for preparing and
Graph of pore diameter distribution；
It in current density is 180 mA that Fig. 4, which is tubulose titanium dioxide/carbon lithium ion cell negative electrode material for preparing in embodiment 1,
g-1Under cyclic curve figure；
Fig. 5 is the tubulose titanium dioxide/carbon lithium ion cell negative electrode material high rate performance figure prepared in embodiment 1；
Fig. 6 be in embodiment 1 tubulose titanium dioxide/carbon lithium ion cell negative electrode material for preparing in 3500 mA of high current density
g-1Under long circulating stability curve graph.
Specific embodiment
Technical solution of the present invention is further illustrated below in conjunction with specific embodiments and drawings, but the present invention is not limited to
This.
Embodiment 1
The preparation of tubulose titanium dioxide/carbon lithium ion cell negative electrode material, specifically comprises the following steps:
(1) titanyl sulfate of 0.0013 mol, the glycerine of 0.13 mol, 0.35 mol the preparation of precursor solution: are weighed
Ethyl alcohol and 0.09 mol ether be uniformly mixed, obtain molecular sieve precursor solution；
(2) preparation of organotitanium precursor body: uniform precursor solution will be sufficiently mixed and be transferred to 50 mL threading polytetrafluoroethylene (PTFE)
The reaction kettle of liner, in 110 DEG C sustained response 2 days, after cooled to room temperature, the water of obtained final precipitated product ethyl alcohol
Solution, volume ratio 1:1, after centrifuge washing 3 times, 100 DEG C drying 12 hours, obtain organotitanium precursor body；
(3) sintering stage: under an argon atmosphere by obtained organotitanium precursor body, 600 DEG C are sintered 3 hours, naturally cool to room
Temperature obtains finished product tubulose titanium dioxide/carbon compound cathode materials.
(4) assembling of battery: by obtained negative electrode material, conductive agent acetylene black and binder PVDF are according to 7: 2: 1
Ratio weighs 70,20 and 10 mg respectively, and the NMP dispersion mixing of 0.4g is added after being fully ground, and is applied after sizing mixing uniformly with knife coating
It is distributed in copper foil, is placed in the drying 10 hours of 80 DEG C of convection oven, using metal lithium sheet as cathode in glove box, Celgard 2300 is
Diaphragm, 1mol/L LiPF6/ EC: DMC:EMC is electrolyte, and wherein EC: DMC:EMC volume ratio is 1:1:1, is assembled into
CR2025 button half-cell.At 25 DEG C, charge and discharge cycles are carried out between 0.01-3.0 V of potential window.
Tubulose titanium dioxide/carbon lithium ion cell negative electrode material scanning electron microscope diagram of preparation as shown in Figure 1, by
Fig. 1 can be seen, and the nanometer sheet that titanium dioxide composite carbon is formed is self-assembled into as tubular structure, about 500 nm of pipe diameter size.Tubulose
Transmission electron microscope picture difference of the titanium dioxide/carbon lithium ion cell negative electrode material under different multiplying is as shown in Figure 2 a and 2 b, can
With see material in apparent tubular morphology, 10 nm of titania nanoparticles partial size <, and be uniformly distributed in carbon-coating and work as
In.
Tubulose titanium dioxide/carbon lithium ion cell negative electrode material nitrogen adsorption desorption curve graph of preparation as shown in figure 3, by
Fig. 3 can be seen, and compared with carbon-free material, apparent hysteresis loop is demonstrated in titanium dioxide/carbon material adsorption desorption curve
Mesoporous presence, will also recognize that from graph of pore diameter distribution and sees, material is micro- mesoporous coexist a hierarchical porous structure.
Tubulose titanium dioxide/carbon lithium ion cell negative electrode material of preparation is assembled into button cell in current density and is
180 mA g-1Under cyclic curve figure as shown in figure 4, first charge-discharge capacity is up to 665.1 and, 815 mAh g-1, and
With 534 mAh g-1Stabilization reversible specific capacity.In terms of high rate performance, as can be seen from Figure 5, material shows excellent
High rate performance, be respectively 0.1,0.35,0.7,1.75, and 3.5 A g in current density-1When, reversible specific capacity point
Do not reach 524.3,474.5,437.3,372.1 and 322.8 mAh g-1.3500 mA g in Fig. 6-1High current is long
In circulation, material also shows excellent cyclical stability, still keeps 284.9 mA h g after 3000 circle long circulatings-1's
Reversible specific capacity.These performances compare the not material compound with carbon, and the titanium dioxide commercially produced, and all much want high.
Embodiment 2
The preparation of tubulose titanium dioxide/carbon lithium ion cell negative electrode material, specifically comprises the following steps:
(1) titanium tetrachloride of 0.001 mol, the ethylene glycol of 0.1 mol, the first of 0.3 mol the preparation of precursor solution: are weighed
The ether of alcohol and 0.05 mol are uniformly mixed, and obtain molecular sieve precursor solution；
(2) preparation of organotitanium precursor body: uniform precursor solution will be sufficiently mixed and be transferred to 50 mL threading polytetrafluoroethylene (PTFE)
The reaction kettle of liner, in 100 DEG C sustained response 3 days, after cooled to room temperature, the water of obtained final precipitated product ethyl alcohol
Solution, wherein the volume ratio of second alcohol and water is 1:0.5, after centrifuge washing 3 times, 60 DEG C drying 36 hours, obtain organotitanium precursor
Body；
(3) sintering stage: under an argon atmosphere by obtained organotitanium precursor body, 450 DEG C are sintered 10 hours, naturally cool to room
Temperature obtains finished product tubulose titanium dioxide/carbon compound cathode materials.
(4) assembling of battery: by obtained negative electrode material, conductive agent acetylene black and binder PVDF are according to 7: 2: 1
Ratio weighs 70,20 and 10 mg respectively, and the NMP dispersion mixing of 0.4 g is added after being fully ground, and uses knife coating after sizing mixing uniformly
It is coated on copper foil, is placed in the drying 10 hours of 90 DEG C of convection oven, using metal lithium sheet as cathode in glove box, Celgard 2300
For diaphragm, 1mol/L LiPF6/ EC: DMC:EMC is electrolyte, and wherein EC: DMC:EMC volume ratio is 1:1:1, is assembled into
CR2025 button half-cell.At 25 DEG C, charge and discharge cycles are carried out between 0.01-3.0 V of potential window.
Tubulose titanium dioxide/carbon lithium ion cell negative electrode material of preparation is similar to resulting materials pattern in example 1, is
The nanometer sheet that titanium dioxide composite carbon is formed is self-assembled into as tubular structure, and aperture is micro- mesoporous hierarchical porous structure coexisted.And
And it is better than material not compound with carbon in specific capacity, high rate performance and stability as lithium ion battery negative material,
And the titanium dioxide commercially produced.Material correlation appearance structure and performance parameter can refer to the respective drawings in embodiment 1.
Embodiment 3
The preparation of tubulose titanium dioxide/carbon lithium ion cell negative electrode material, specifically comprises the following steps:
(1) titanyl sulfate of 0.002 mol, the glycerine of 0.2 mol, the second of 0.4 mol the preparation of precursor solution: are weighed
The ether of alcohol and 0.15 mol are uniformly mixed, and obtain molecular sieve precursor solution；
(2) preparation of organotitanium precursor body: uniform precursor solution will be sufficiently mixed and be transferred to 100 mL threading polytetrafluoroethyl-ne
The reaction kettle of alkene liner, in 200 DEG C sustained response 1 day, after cooled to room temperature, obtained final precipitated product ethyl alcohol
Aqueous solution, wherein the volume ratio of second alcohol and water is 2:0.5, after centrifuge washing 6 times, 100 DEG C drying 12 hours, before obtaining organic titanium
Drive body；
(3) sintering stage: under an argon atmosphere by obtained organotitanium precursor body, 700 DEG C are sintered 2 hours, naturally cool to room
Temperature obtains finished product tubulose titanium dioxide/carbon compound cathode materials.
(4) assembling of battery: by obtained negative electrode material, conductive agent acetylene black and binder PVDF are according to 7: 2: 1
Ratio weighs 70,20 and 10 mg respectively, and the NMP dispersion mixing of 0.4g is added after being fully ground, and is applied after sizing mixing uniformly with knife coating
It is distributed in copper foil, is placed in the drying 10 hours of 80 DEG C of convection oven, using metal lithium sheet as cathode in glove box, Celgard 2300 is
Diaphragm, 1mol/L LiPF6/ EC: DMC:EMC, it is electrolyte, wherein EC: DMC:EMC volume ratio is 1:1:1, is assembled into
CR2025 button half-cell.At 25 DEG C, charge and discharge cycles are carried out between 0.01-3.0 V of potential window.
Tubulose titanium dioxide/carbon lithium ion cell negative electrode material of preparation is similar to resulting materials pattern in example 1, is
The nanometer sheet that titanium dioxide composite carbon is formed is self-assembled into as tubular structure, and aperture is micro- mesoporous hierarchical porous structure coexisted.And
And it is better than material not compound with carbon in specific capacity, high rate performance and stability as lithium ion battery negative material,
And the titanium dioxide commercially produced.Material correlation appearance structure and performance parameter can refer to the respective drawings in embodiment 1.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of tubulose titanium dioxide/carbon lithium ion cell negative electrode material, which is characterized in that including walking as follows
It is rapid:
(1) preparation of precursor solution: being 1-2: 100-200: 300- by titanium source, polyalcohol, monohydric alcohol and ether in molar ratio
400: 50-150 ratio is uniformly mixed, and obtains precursor solution；
(2) precursor solution of step (1): being put into the reaction kettle of polytetrafluoroethyllining lining by the preparation of organotitanium precursor body,
100-200 DEG C reaction 1-3 days, after cooled to room temperature, the precipitating for reacting generation is washed, dry, obtains organotitanium precursor body；
(3) sintering stage: by 450-700 DEG C sintering 2-10 hours under an inert atmosphere of organotitanium precursor body made from step (2),
Cooled to room temperature obtains tubulose titanium dioxide/carbon compound cathode materials.
2. the preparation method of tubulose titanium dioxide/carbon lithium ion cell negative electrode material according to claim 1, feature exist
In in step (1), the polyalcohol includes glycerine, ethylene glycol, at least one of erythrol and butantriol.
3. the preparation method of tubulose titanium dioxide/carbon lithium ion cell negative electrode material according to claim 1, feature exist
In in step (1), the monohydric alcohol includes at least one of methanol, ethyl alcohol, propyl alcohol, the tert-butyl alcohol and benzyl alcohol.
4. the preparation method of tubulose titanium dioxide/carbon lithium ion cell negative electrode material according to claim 1, feature exist
In in step (1), the ether includes at least one of ether, phenetole, isopropyl ether and n-butyl ether.
5. the preparation method of tubulose titanium dioxide/carbon lithium ion cell negative electrode material according to claim 1, feature exist
In in step (1), the titanium source includes at least one of titanyl sulfate, titanium tetrachloride, titanium tetrabromide and titanium tetra iodide.
6. the preparation method of tubulose titanium dioxide/carbon lithium ion cell negative electrode material according to claim 1, feature exist
In in step (2), the washing is be 1-2: 0.5-1 with the volume ratio of ethyl alcohol and water solution centrifuge washing for 3 ~ 6 times；Institute
Stating drying is dried in vacuo 12 ~ 36 hours at 60 DEG C ~ 100 DEG C.
7. a kind of tubulose titanium dioxide/carbon lithium ion battery as made from the described in any item preparation methods of claim 1 ~ 6 is negative
Pole material.
8. a kind of tubulose titanium dioxide/carbon lithium ion cell negative electrode material answering in lithium ion battery as claimed in claim 7
With.
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| US20090191458A1 (en) * | 2007-07-23 | 2009-07-30 | Matsushita Electric Industrial Co., Ltd. | Porous network negative electrodes for non-aqueous electrolyte secondary battery |
| CN101937985A (en) * | 2010-08-19 | 2011-01-05 | 北京科技大学 | Graphene/titanium dioxide lithium ion battery cathode material and preparation method |
| CN104868112A (en) * | 2015-05-12 | 2015-08-26 | 吉林大学 | Carbon-coated titanium dioxide nanosheet array and graphene composite electrode material and preparation method thereof |
| CN105406042A (en) * | 2015-11-16 | 2016-03-16 | 中国海洋大学 | Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery |
-
2018
- 2018-12-29 CN CN201811642403.0A patent/CN109768244A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090191458A1 (en) * | 2007-07-23 | 2009-07-30 | Matsushita Electric Industrial Co., Ltd. | Porous network negative electrodes for non-aqueous electrolyte secondary battery |
| CN101937985A (en) * | 2010-08-19 | 2011-01-05 | 北京科技大学 | Graphene/titanium dioxide lithium ion battery cathode material and preparation method |
| CN104868112A (en) * | 2015-05-12 | 2015-08-26 | 吉林大学 | Carbon-coated titanium dioxide nanosheet array and graphene composite electrode material and preparation method thereof |
| CN105406042A (en) * | 2015-11-16 | 2016-03-16 | 中国海洋大学 | Preparation method for carbon-coated super-long titanium dioxide nanotube negative electrode material of lithium ion battery |
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