CN103825002B - It is composite and the application thereof that framing structure is coated with phosphorus with titanium dioxide - Google Patents
It is composite and the application thereof that framing structure is coated with phosphorus with titanium dioxide Download PDFInfo
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- CN103825002B CN103825002B CN201410043623.7A CN201410043623A CN103825002B CN 103825002 B CN103825002 B CN 103825002B CN 201410043623 A CN201410043623 A CN 201410043623A CN 103825002 B CN103825002 B CN 103825002B
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- composite
- phosphorus
- titanium dioxide
- framing structure
- structure cladding
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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
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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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
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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 invention discloses a kind of with titanium dioxide be the framing structure cladding composite of phosphorus and application thereof, the preparation method of described composite comprises the steps: that (1) takes red phosphorus powder and dispersant, dissolve in ethanol ultrasonic 2～4h, then natural subsidence 48～96h；(2) upper liquid obtained after taking sedimentation, adds titanium source, is slowly added to deionized water after stirring, centrifugal collection lower sediment thing, calcines 2～4 hours at 300～400 DEG C after drying, obtains with the composite that titanium dioxide is framing structure cladding phosphorus.Present invention also offers the described application using composite that titanium dioxide is framing structure cladding phosphorus as lithium ion battery negative material and thus obtained lithium ion battery.When the composite that the present invention prepares is applied as lithium ion battery negative material, it is possible to performance its high current charge-discharge under the conditions of is greatly improved, and there is the highest safety.
Description
(1) technical field
The present invention relates to one and be coated with phosphorus (TiO with titanium dioxide for framing structure2/ P) composite and conduct
The application of lithium ion battery negative material, and thus obtained lithium ion battery.
(2) background technology
Lithium ion battery, as a kind of High-performance green energy, receives extensive concern in recent years.Develop high property
The research and development of one of energy lithium battery key technology negative material just.Titanium dioxide is as a kind of emerging lithium ion
Cell negative electrode material, more traditional negative material graphite-phase ratio, security and stability and big times can be greatly improved
Rate charge-discharge performance.And along with mobile energy source use to the requirement of high rate during charging-discharging and safety not
Disconnected raising (such as hybrid vehicle), these 2 the most very important.Although having above-mentioned advantage,
Its relatively low energy density (theoretical capacity) means to occupy under identical energy higher volume, greatly limits
Make its application.This project utilizes the electrochemical stability of titanium dioxide, using titanium dioxide as skeleton, adds
Adding energy density height but the red phosphorus of cycle performance instability, the two is had complementary advantages.This imitate build at coagulation
Soil adds the structure of reinforcing bar, can promote the energy of titanium dioxide while ensureing stability greatly
Metric density.
(3) summary of the invention
First purpose of the present invention is that providing a kind of titanium dioxide is that framing structure is coated with phosphorus (TiO2/ P) answer
Condensation material, to improve the energy density of titanium dioxide and to reduce cost, is suitable to industrialized production.
Second object of the present invention is that providing described titanium dioxide is that framing structure is coated with phosphorus (TiO2/ P) answer
Condensation material is as the application of lithium ion battery negative material, and described titanium dioxide is that framing structure is coated with phosphorus
(TiO2/ P) composite can be effectively reduced titanium dioxide and apply the one-tenth at lithium ion battery negative material
This, improve its energy density, and keep the structural stability during this material large current density, for it
Large-scale commercial provides may.
Third object of the present invention is that offer is coated with phosphorus (TiO with described titanium dioxide for framing structure2/ P)
Composite, as the lithium ion battery of negative material, has volume energy density height, circulation and big multiplying power and fills
The advantage that discharge performance is excellent, safety is high.
Below technical scheme is illustrated.
The invention provides one and be coated with phosphorus (TiO with titanium dioxide for framing structure2/ P) composite, its system
Preparation Method comprises the steps:
(1) take red phosphorus powder and dispersant, dissolve in ethanol ultrasonic 2～4h, then natural subsidence 48～96
h；
(2) upper liquid obtained after taking sedimentation, adds titanium source, is slowly added to deionized water after stirring, centrifugal
Collect lower sediment thing, calcine 2～4 hours at 300～400 DEG C after drying, obtain end product TiO2/P。
As preferably, step (1) described red phosphorus powder is 4～10:1 with the mass ratio of dispersant, solvent
Consumption is calculated as 5～20mL/g with the quality of red phosphorus powder, preferably 10mL/g.
As preferably, the dispersant described in step (1) is selected from a kind of or the most several following combination: poly-second
Glycol, sodium lignin sulfonate, polyvinylpyrrolidone, glyceryl monostearate.
As preferably, in step (2), described titanium source is a kind of or the most several following combination: sulphuric acid
Titanium, titanous chloride., titanium tetrachloride, isopropyl titanate, butyl titanate.
As preferably, in step (2), the addition quality in titanium source is calculated as 20～50g/L with the volume of upper liquid.
The titanium dioxide that the present invention prepares is that framing structure is coated with phosphorus (TiO2/ P) composite be nanoscale
TiO2Red phosphorus is mixed for agent structure.
Present invention also offers described titanium dioxide is that framing structure is coated with phosphorus (TiO2/ P) composite is as lithium
The application of ion battery cathode material.
Finally, the invention provides and be coated with phosphorus (TiO with described titanium dioxide for framing structure2/ P) composite
As the lithium ion battery of negative material, wherein the preparation of lithium ion battery uses routine operation.
Compared with prior art, the beneficial effects of the present invention is:
A) titanium dioxide of the present invention is that framing structure is coated with phosphorus (TiO2/ P) composite can improve titanium dioxide
Energy density and reduce cost, be suitable to industrialized production.
B) titanium dioxide that the present invention prepares is that framing structure is coated with phosphorus (TiO2/ P) composite is as lithium-ion electric
During the negative material application of pond, it is possible to performance its high current charge-discharge under the conditions of is greatly improved, and has the highest
Safety, this characteristic can meet what lithium ion battery was improved constantly by current mobile energy source use field
The requirement (such as electric automobile) of high rate during charging-discharging and safety.
(4) accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 prepare titanium dioxide be framing structure be coated with phosphorus (TiO2/ P) composite
Electron scanning micrograph, it can be seen that outer layer a large amount of nano-scale TiO2。
Fig. 2 be the embodiment of the present invention 2 prepare titanium dioxide be framing structure be coated with phosphorus (TiO2/ P) composite
Transmission electron microscope photo and power spectrum, it was demonstrated that the material of described preparation method gained is that nano titanium oxide is
Framing structure cladding phosphorus (TiO2/ P) composite.
Fig. 3 be the titanium dioxide that the embodiment of the present invention 1 prepares be that framing structure is coated with phosphorus (TiO2/ P) composite
Chemical property figure as lithium ion battery negative material, it is seen that its stable electrochemical property, large current density
Electrical property is good.
(5) detailed description of the invention
With specific embodiment, technical scheme is described further below, but the protection model of the present invention
Enclose and be not limited to this.
Embodiment 1
First block red phosphorus is inserted the rotating speed ball milling 40h with 300r/min in planetary ball mill.Take ball milling
After red phosphorus 20g add 4g polyvinylpyrrolidone, dissolve in ultrasonic 4h in 200ml ethanol, then treat
Its natural subsidence 96h.Take upper liquid 100ml after sedimentation, add isopropyl titanate 4g, slowly add after stirring
Enter 50ml deionized water, then by it with the centrifugation of 8000r/min, time 10min.Collect lower floor
Precipitate dry after after in high-temperature atmosphere furnace 350 DEG C calcining 3h.Obtain end product TiO2/ P(is shown in Fig. 1).
TiO is weighed respectively with the mass ratio of 70:15:152/ P composite: acetylene black: polyvinylidene fluoride,
Being coated on Copper Foil after grinding uniformly and make electrode, employing metal lithium sheet is positive pole, and electrolyte is 1mol/L
LiPF6/ EC-DMC(volume ratio is 1:1), polypropylene microporous film is barrier film (Celgard2300), assembles
Become button cell (CR2025).Fig. 3 is respective battery 0.01-3.0V electricity under the electric current density of 0.1A/g
Long-time cyclic curve in the range of pressure, it appeared that this combination electrode material has excellent cyclical stability,
After 50 circulations, specific capacity remains above 400mAh/g.
Embodiment 2
First block red phosphorus is inserted the rotating speed ball milling 35h with 250r/min in planetary ball mill.Take ball milling
After red phosphorus 20g add 5g sodium lignin sulfonate, dissolve in ultrasonic 3.5h in 200ml ethanol, then treat it
Natural subsidence 72h.Take upper liquid 100ml after sedimentation, add titanium sulfate 4g, after stirring, be slowly added to 50ml
Deionized water, then by it with the centrifugation of 8000r/min, time 10min, collects lower sediment thing
After after drying in high-temperature atmosphere furnace 380 DEG C calcining 2h.Obtain end product TiO2/P.Product morphology is similar to
Fig. 1.
With obtained TiO2/ P composite material is prepared as electrode as described in Example 1, is assembled into mould
Intending battery, under the electric current density of 0.1A/g, its reversible capacity reaches 430mAh/g.
Embodiment 3
First block red phosphorus is inserted the rotating speed ball milling 38h with 200r/min in planetary ball mill.Take ball milling
After red phosphorus 20g add 3g glyceryl monostearate, dissolve in ultrasonic 3h in 200ml ethanol, then treat it
Natural subsidence 48h.Take upper liquid 100ml after sedimentation, add butyl titanate 4g, be slowly added to after stirring
50ml deionized water, then by it with the centrifugation of 8000r/min, time 10min, collects lower floor and sinks
Shallow lake thing dry after after in high-temperature atmosphere furnace 390 DEG C of calcining 2.5h.Obtain end product TiO2/P.Product shape
Looks are similar to Fig. 1.
With obtained TiO2/ P composite material is prepared as electrode as described in Example 1, is assembled into mould
Intending battery, under the electric current density of 0.1A/g, its reversible capacity reaches 440mAh/g.
Embodiment 4
First block red phosphorus is inserted the rotating speed ball milling 38h with 200r/min in planetary ball mill.Take ball milling
After red phosphorus 20g add 2g Polyethylene Glycol, dissolve in ultrasonic 3h in 200ml ethanol, then treat its naturally sink
Fall 60h.Take upper liquid 100ml after sedimentation, add isopropyl titanate 5g, after stirring, be slowly added to 50ml
Deionized water, then by it with the centrifugation of 8000r/min, time 10min, collects lower sediment thing
After after drying in high-temperature atmosphere furnace 360 DEG C calcining 4h.Obtain end product TiO2/P.Product morphology is similar to
Fig. 1.
With obtained TiO2/ P composite material is prepared as electrode as described in Example 1, is assembled into mould
Intending battery, under the electric current density of 0.1A/g, its reversible capacity reaches 420mAh/g.
Claims (7)
1. the composite being framing structure cladding phosphorus with titanium dioxide, its preparation method includes walking as follows
Rapid:
(1) taking red phosphorus powder and dispersant, described dispersant is selected from following a kind of or the most several
Combination: Polyethylene Glycol, sodium lignin sulfonate, polyvinylpyrrolidone, glyceryl monostearate, dissolves in second
In alcohol ultrasonic 2～4h, then natural subsidence 48～96h；
(2) upper liquid obtained after taking sedimentation, adds titanium source, and described titanium source is following a kind of or the most several
The combination planted: titanium sulfate, titanous chloride., titanium tetrachloride, isopropyl titanate, butyl titanate, after stirring
It is slowly added to deionized water, centrifugal collection lower sediment thing, calcine 2～4 hours at 300～400 DEG C after drying,
Obtain the composite being framing structure cladding phosphorus with titanium dioxide.
2. the composite being framing structure cladding phosphorus with titanium dioxide as claimed in claim 1, its feature
It is: step (1) described red phosphorus powder is 4～10:1 with the mass ratio of dispersant.
3. the composite being framing structure cladding phosphorus with titanium dioxide as claimed in claim 2, its feature
It is: step (1) ethanol consumption is calculated as 5～20mL/g with the quality of red phosphorus powder.
4. the composite being framing structure cladding phosphorus with titanium dioxide as claimed in claim 3, its feature
It is: step (1) ethanol consumption is calculated as 10mL/g with the quality of red phosphorus powder.
5. the composite being framing structure cladding phosphorus with titanium dioxide as claimed in claim 3, its feature
Being: in step (2), the addition quality in titanium source is calculated as 20～50g/L with the volume of upper liquid.
6. titanium dioxide as claimed in claim 1 is that framing structure cladding phosphorus composite material is as lithium-ion electric
The application of pond negative material.
7. using the titanium dioxide described in claim 1 for framing structure cladding phosphorus composite material as negative material
The lithium ion battery prepared.
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| CN201410043623.7A CN103825002B (en) | 2014-01-29 | 2014-01-29 | It is composite and the application thereof that framing structure is coated with phosphorus with titanium dioxide |
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| CN201410043623.7A CN103825002B (en) | 2014-01-29 | 2014-01-29 | It is composite and the application thereof that framing structure is coated with phosphorus with titanium dioxide |
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| CN103825002B true CN103825002B (en) | 2017-01-04 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105226246B (en) * | 2015-09-08 | 2017-08-29 | 武汉理工大学 | Graphene coated P@SnO2Core-shell quanta dots electrode material and its preparation method and application |
| KR102076035B1 (en) * | 2018-01-04 | 2020-02-11 | 포항공과대학교 산학협력단 | Elemental coating on oxide materials for lithium rechargeable battery |
| CN108899528B (en) * | 2018-07-13 | 2020-11-10 | 中国地质大学（北京） | Lithium ion battery negative electrode material P + TiO2+ CNT preparation method |
| CN109301209B (en) * | 2018-09-27 | 2022-03-18 | 三峡大学 | Preparation method of titanium dioxide modified phosphorus/carbon composite negative electrode material |
| CN111628143B (en) * | 2019-02-28 | 2021-07-09 | 比亚迪股份有限公司 | Lithium ion battery anode material and preparation method thereof, lithium ion battery anode and lithium ion battery |
| CN110838580B (en) * | 2019-11-20 | 2023-03-31 | 长沙理工大学 | Titanium dioxide ultrathin carbon bubble confinement high-load red phosphorus composite electrode material and preparation method thereof |
| CN114937768A (en) * | 2022-06-10 | 2022-08-23 | 浙江大学 | Titanium dioxide/red phosphorus composite material, preparation method thereof and sodium ion half cell |
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| CN1824730A (en) * | 2006-02-16 | 2006-08-30 | 杨第伦 | Manufacture of ultra fine red phosphorus composite fire retardant and its product using air bubble liquid film method |
| CN101343542A (en) * | 2008-08-25 | 2009-01-14 | 温州大学 | Method for preparing ultra-fine red phosphorus microcapsule |
| CN101648147A (en) * | 2009-08-28 | 2010-02-17 | 南京工业大学 | Mesoporous compound titanium oxide and preparation method thereof |
| WO2011022888A1 (en) * | 2009-08-28 | 2011-03-03 | 南京工业大学 | Mesoporous composite titania and preparing method thereof |
| CN103337611A (en) * | 2013-07-10 | 2013-10-02 | 厦门大学 | Preparation method of graphene-titanium dioxide composite material |
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| CN1824730A (en) * | 2006-02-16 | 2006-08-30 | 杨第伦 | Manufacture of ultra fine red phosphorus composite fire retardant and its product using air bubble liquid film method |
| CN101343542A (en) * | 2008-08-25 | 2009-01-14 | 温州大学 | Method for preparing ultra-fine red phosphorus microcapsule |
| CN101648147A (en) * | 2009-08-28 | 2010-02-17 | 南京工业大学 | Mesoporous compound titanium oxide and preparation method thereof |
| WO2011022888A1 (en) * | 2009-08-28 | 2011-03-03 | 南京工业大学 | Mesoporous composite titania and preparing method thereof |
| CN103337611A (en) * | 2013-07-10 | 2013-10-02 | 厦门大学 | Preparation method of graphene-titanium dioxide composite material |
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