CN106784607A - A kind of preparation method of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of lithium - Google Patents
A kind of preparation method of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of lithium Download PDFInfo
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- CN106784607A CN106784607A CN201710076523.8A CN201710076523A CN106784607A CN 106784607 A CN106784607 A CN 106784607A CN 201710076523 A CN201710076523 A CN 201710076523A CN 106784607 A CN106784607 A CN 106784607A
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
- H01M4/0426—Sputtering
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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
- H01M10/058—Construction or manufacture
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A kind of preparation method of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of lithium, belongs to new energy materialses field.Nano tube array of titanium dioxide after heat treatment by vacuumizing, heating, pre-sputtering, after sputtering, is cooled to 40~80 DEG C of taking-ups, wherein being sputtered to as matrix：Open radio-frequency power supply sputtered silicon；In sputter procedure matrix heating, after the completion of be cooled to 40~80 DEG C after take out sample.As negative pole carrier material, silicon is splashed to by titanic oxide nano tube thin-film surface and inside using magnetron sputtering technique, deposition efficiency is high, method is easy, reproducible.
Description
Technical field
A kind of preparation method of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of lithium, belongs to new energy materialses neck
Domain.
Background technology
Graphite being used in China market practical lithium battery at this stage as negative material, it is advantageous that reserves are rich more
Richness, with low cost and preferable electric conductivity.But relatively low theoretical capacity (372mAh/g) and poor high rate performance, it is impossible to full
Demand of the sufficient people to high power capacity high voltage high-energy-density lithium battery.Silicon is a kind of common material, and theoretical capacity is
4200mAh/g, is the second abundant element in the earth's crust, and it is relatively low to prepare simple cost, and effect on environment is small, is expected to substitution stone
Ink is used as novel high-capacity lithium cell cathode material.Current people study more to silicon materials, but there are two subject matters, one
Be silicon as semi-conducting material, electric conductivity is poor, can influence the insertion and abjection of lithium ion；Two is the coefficient of cubical expansion of silicon
About 300%, it is broken to there is silicon in the dilation in charge and discharge process, departs from conductive network, causes capacitance loss.The present invention
Using the stability and resistance to acids and bases of titania nanotube, as negative pole carrier material, will using magnetron sputtering technique
Silicon is splashed to titanic oxide nano tube thin-film surface and inside, and deposition efficiency is high, and method is easy, reproducible.Can overcome above-mentioned
Problem.
The content of the invention
The present invention overcomes the application problem of prior art silicon, there is provided a kind of immobilized silicon of electric Nano tube array of titanium dioxide of lithium
The preparation method of negative material, silicon is supported on titania nanotube, is limited the expansion of silicon and is improved electric conductivity.
To achieve the above object, the system of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of a kind of lithium of the invention
Preparation Method, the titania nanotube of high-sequential as magnetron sputtering matrix material is prepared by the use of anodizing；Using penetrating
Silicon is splashed on Nano tube array of titanium dioxide frequency power the silicon that definite shape structure is formed in nanotube mouthful；By what is prepared
Sample is dried (such as 80 DEG C insulation 12h) in being put into vacuum drying chamber；Being put into after being taken out from vacuum drying chamber in glove box is carried out
The assembling of battery.Test the charge-discharge performance of battery.The immobilized silicon of nano-tube array under the conditions of radio frequency parameter is 100W, 40min
The battery that film preparation goes out first circle discharge capacity under 5C multiplying powers can reach 1246.8mAh/g, with the increase of discharge and recharge number of times,
The capacity of battery has decay, and 834.6mAh/g is reduced to the 50th circle discharge capacity, but the 200th circle discharge capacity still has
248.9mAh/g, is the 20% of initial discharge capacity；First circle discharge capacity can reach 1050.0mAh/g under 10C multiplying powers, after 50 circles
Discharge capacity still has 485.1mAh/g.And directly silicon is splashed on Titanium base, first circle charge/discharge capacity is only under 5C multiplying powers
490.9mAh/g, the 50th circle discharge capacity is reduced to 167.0mAh/g, and the 200th circle discharge capacity only has 100.0mAh/g, is just
The 20.4% of beginning discharge capacity；The 1st circle discharge capacity is 0.26mAh/g under 10C current densities, and the 50th circle time discharge capacity has
0.37mAh/g.Two methods gap substantially, shows that the cell negative electrode material that the immobilized silicon of Nano tube array of titanium dioxide is prepared holds
Amount is obviously improved, and method is reliable and stable.
The preparation method that the present invention is provided, it is characterised in that preparation process is comprised the following steps：
(1) titanium substrate pretreatment：The oxide layer that titanium metal substrate surface oily matter is produced with rolling with storage process is led to
Physics ultrasound and the removal of chemical pickling process are crossed, specially using acetone, ethanol, deionized water ultrasound, pickling after drying is taken out,
Pickle is preferably HF (analysis is pure), HNO3(analysis is pure), H2O (preferably 1：3：6 volume ratios) mixed solution, gone after pickling
Ultrasound 5~30min, dry for standby in ionized water；
(2) pretreated titanium sheet uses pulse anodic oxidation：Anode is carried out in the water solution system containing fluorine ion
Oxidation；As pulse oxidation voltage carries out oxygen under 20V (30min), 10V (10min), 20V (30min), 10V (10min) respectively
Change, 4h is finally aoxidized under 20V, by sample taking-up deionized water rinsing after oxidation, drying；Preferably comprise the water-soluble of fluorine ion
Liquid is NH4HF2、NH4H2PO4With the mixed solution of water, further preferably every 3gNH4HF2Correspondence 1L water and 0.5mol NH4H2PO4；
(3) it is heat-treated：Sample after step (2) is aoxidized carries out crystallization and thermal treatment at 300~500 DEG C, is incubated 1-3h, so
After cool to room temperature with the furnace；
(4) magnetron sputtering prepares cathode of lithium battery film：It is with the Nano tube array of titanium dioxide after step (3) heat treatment
Matrix, by vacuumizing, heating, after pre-sputtering, sputtered silicon, is cooled to 40~80 DEG C of taking-ups, and wherein sputtered silicon process is：Open
Radio-frequency power supply sputtered silicon；In sputter procedure matrix heating, after the completion of be cooled to 40~80 DEG C after take out sample, wherein back end vacuum
Degree (i.e. the vacuum of reative cell) is 4 × 10-4Pa~6 × 10-4Pa。
Further preferably：During radio-frequency power supply sputtered silicon：The preferred 100W of sputtering power in radio-frequency power supply sputtering parameter, sputtering
Time preferably 20~60min, preferably 400 DEG C of sputter temperature.Wherein pre-sputtering and the argon pressure of sputtering are 1.5Pa.
Pre-sputtering is that target is carried out " cleaning ".Pre-sputtering time such as 180s,
The assembling of lithium battery：The sample that step (4) is obtained is put into 80 DEG C of vacuum drying 12h in vacuum drying chamber, then
Sample is put into glove box, the assembling of battery is carried out, assembling sequence is anode cover, the immobilized silicon of Nano tube array of titanium dioxide is born
Pole piece, electrolyte, barrier film, lithium piece, stainless steel substrates, shell fragment, negative electrode casing.Pressure is set to 52Kg/cm on assembling post package machine2Enter
Row encapsulation, tests after standing one day.
Compared with prior art, the beneficial effects of the invention are as follows：
The Nano tube array of titanium dioxide of high-sequential as the matrix material of immobilized silicon is prepared by the use of anodizing；Profit
Silicon is splashed on Nano tube array of titanium dioxide with radio-frequency power supply so that silicon is splashed to the inside and one, surface of nanotube
Point, negative material capacity can not only be improved, and the special structure of nanotube causes to inhibit the swollen of silicon in the two-dimensional direction
Crushed caused by swollen contraction；The battery that the immobilized silicon thin film of nano-tube array is prepared under the conditions of radio frequency parameter is 100W, 40min
First circle discharge capacity can reach 1246.8mAh/g under 5C multiplying powers, and with the increase of discharge and recharge number of times, the capacity of battery has and declines
Subtract, 834.6mAh/g is reduced to the 50th circle discharge capacity, but the 200th circle discharge capacity still has 248.9mAh/g, is initially to put
The 20% of capacitance；Up to 1050.0mAh/g, discharge capacity still has 485.1mAh/ to first circle discharge capacity after 50 circles under 10C multiplying powers
g.And directly silicon is splashed on Titanium base, first circle charge/discharge capacity is only 490.9mAh/g under 5C multiplying powers, the 50th circle electric discharge
Capacity is reduced to 167.0mAh/g, and the 200th circle discharge capacity only has 100.0mAh/g, is the 20.4% of initial discharge capacity；10C
The 1st circle discharge capacity is 0.26mAh/g under current density, and the 50th circle time discharge capacity has 0.37mAh/g.Two methods gap is bright
It is aobvious, show that the cell negative electrode material capacity that the immobilized silicon of Nano tube array of titanium dioxide is prepared is obviously improved, method is reliable and stable.
Brief description of the drawings
Fig. 1：Titania nanotube SEM figures under 20V voltages prepared by anodizing.
Fig. 2：Ti-TiO after magnetron sputtering 40min2The SEM figures of-Si laminated films.
Fig. 3：The SEM figures of Ti-Si films after magnetron sputtering 40min.
Fig. 4：Radio frequency parameter is 100W, 40min, 400 DEG C of sample multiplying power lab diagram.
Fig. 5：Radio frequency parameter is 100W, 40min, Ti-TiO at 400 DEG C2- Si sample discharge capacity figures.
Fig. 6：Radio frequency parameter is 100W, 40min, Ti-Si sample discharge capacity figures at 400 DEG C.
Specific embodiment
A kind of preparation side of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of lithium of the invention illustrated below
The specific embodiment of method, but the present invention is not limited to following examples.
The technological parameter of the pretreated pulse anodic oxidation of metal titanium sheet in following examples：Pulse oxidation voltage is distinguished
Aoxidized in 20V (30min), 10V (10min), 20V (30min), 10V (10min), finally aoxidized 4h under 20V, aoxidized
Afterwards by sample taking-up deionized water rinsing, drying；The aqueous solution containing fluorine ion is NH4HF2、NH4H2PO4Mixing with water is molten
Liquid, per 3gNH4HF2Correspondence 1L water and 0.5mol NH4H2PO4。
Embodiment 1
Metal titanium sheet is cleaned, pickling, after ultrasonic 5min treatment, in the organic solution middle arteries chongyang containing fluorine ion
Pole aoxidizes, and is dried after being heat-treated through 300 DEG C；The titanium sheet and pretreated titanium sheet for aoxidizing out are put into magnetron sputtering overlay film system
In, radio-frequency power supply sputtered silicon parameter has sputtering power for 100W, and sputtering time is 20min, and sputter temperature is 400 DEG C.Wherein carry on the back
Bottom vacuum is 4 × 10-4Pa, the pre-sputtering time is that 180s removes impurity and oxide, and argon pressure is 1.5Pa.It is true by taking out
After sky, heating, pre-sputtering, sputtering, 40 DEG C of taking-ups are cooled to.Then the assembling test of electrode slice vacuum drying and battery is carried out.
Embodiment 2
Metal titanium sheet is cleaned, pickling, after ultrasonic 15min treatment, the pulse in the organic solution containing fluorine ion
Anodic oxidation, dries after being heat-treated through 450 DEG C；The titanium sheet and pretreated titanium sheet for aoxidizing out are put into magnetron sputtering overlay film system
In, radio-frequency power supply sputtered silicon parameter has sputtering power for 100W, and sputtering time is 40min, and sputter temperature is 400 DEG C.Wherein carry on the back
Bottom vacuum is 5 × 10-4Pa, the pre-sputtering time is that 180s removes impurity and oxide, and argon pressure is 1.5Pa.It is true by taking out
After sky, heating, pre-sputtering, sputtering, 60 DEG C of taking-ups are cooled to.Then the assembling test of electrode slice vacuum drying and battery is carried out,
It is shown in Table 1.
Embodiment 3
Metal titanium sheet is cleaned, pickling, after ultrasonic 30min treatment, the pulse in the organic solution containing fluorine ion
Anodic oxidation, dries after being heat-treated through 500 DEG C；The titanium sheet and pretreated titanium sheet for aoxidizing out are put into magnetron sputtering overlay film system
In, radio-frequency power supply sputtered silicon parameter has sputtering power for 100W, and sputtering time is 60min, and sputter temperature is 400 DEG C.Wherein carry on the back
Bottom vacuum is 6 × 10-4Pa, the pre-sputtering time is that 180s removes impurity and oxide, and argon pressure is 1.5Pa.It is true by taking out
After sky, heating, pre-sputtering, sputtering, 80 DEG C of taking-ups are cooled to.Then the assembling test of electrode slice vacuum drying and battery is carried out,
It is shown in Table 2.
Above-described embodiment is reproducible, the similar technique effect for obtaining.
The radio frequency parameter of table 1 is 100W, 40min, test result summary sheet at 400 DEG C
The radio frequency parameter of table 2 is 100W, 60min, test result summary sheet at 400 DEG C
Claims (9)
1. a kind of preparation method of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of lithium, it is characterised in that process bag
Include following steps：
(1) titanium substrate pretreatment：The oxide layer that titanium metal substrate surface oily matter is produced with rolling with storage process passes through thing
Reason ultrasound and the removal of chemical pickling process, specially using acetone, ethanol, deionized water ultrasound, take out pickling, pickling after drying
Ultrasound 5~30min, dry for standby in deionized water afterwards；
(2) pretreated titanium sheet uses pulse anodic oxidation：Anodic oxidation is carried out in the water solution system containing fluorine ion；
(3) it is heat-treated：Sample after step (2) is aoxidized is heat-treated at 300~500 DEG C, is incubated 1-3h, then cold with stove
But to room temperature；
(4) magnetron sputtering prepares cathode of lithium battery film：With the Nano tube array of titanium dioxide after step (3) heat treatment as base
Body, by vacuumizing, heating, pre-sputtering, after sputtering, is cooled to 40~80 DEG C of taking-ups, wherein being sputtered to：Radio-frequency power supply is opened to splash
Radiosilicon；In sputter procedure matrix heating, after the completion of be cooled to 40~80 DEG C after take out sample.
2. according to the method for claim 1, it is characterised in that pickle is preferably HF, HNO3、H2The mixed solution of O.
3. according to the method for claim 2, it is characterised in that HF (analysis is pure), HNO3(analysis is pure), H2O volume ratios 1：3：6.
4. according to a kind of preparation side of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of lithium described in claim 1
Method, it is characterised in that step (2) pulse oxidation voltage is respectively in 20V (30min), 10V (10min), 20V (30min), 10V
Aoxidized under (10min), 4h is finally aoxidized under 20V, by sample taking-up deionized water rinsing after oxidation, drying.
5. according to a kind of preparation side of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of lithium described in claim 1
Method, it is characterised in that sputtering power in step (4) radio-frequency power supply sputtering parameter using 100W, sputtering time 20-60min, splash
Temperature is penetrated for 400 DEG C.
6. according to a kind of preparation side of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of lithium described in claim 1
Method, it is characterised in that the aqueous solution containing fluorine ion is NH4HF2、NH4H2PO4With the mixed solution of water.
7. according to a kind of preparation side of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of lithium described in claim 6
Method, it is characterised in that per 3gNH in the aqueous solution containing fluorine ion4HF2Correspondence 1L water and 0.5mol NH4H2PO4。
8. according to a kind of preparation side of the immobilized silicium cathode material of the electric Nano tube array of titanium dioxide of lithium described in claim 1
Method, it is characterised in that pre-sputtering and the argon pressure of sputtering are 1.5Pa, pre-sputtering time such as 180s.
9. the immobilized silicium cathode material group of Nano tube array of titanium dioxide for being prepared using the method for claim any one of 1-8
The method of packed battery, it is characterised in that step (4) is obtained into sample and is put into 80 DEG C of vacuum drying 12h in vacuum drying chamber, then
Be put into glove box, carry out the assembling of battery, assembling sequence be anode cover, the immobilized silicium cathode piece of Nano tube array of titanium dioxide,
Electrolyte, barrier film, lithium piece, stainless steel substrates, shell fragment, negative electrode casing, all processes of battery assembling are carried out in glove box.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110474033A (en) * | 2019-08-22 | 2019-11-19 | 中南大学 | TiO2The preparation method and cathode of nano-array confinement antimony oxide cathode |
| CN111270288A (en) * | 2020-01-21 | 2020-06-12 | 黑龙江科技大学 | Preparation method of novel titanium dioxide negative electrode material |
| CN111448342A (en) * | 2017-09-15 | 2020-07-24 | 欧瑞康表面处理解决方案股份公司普费菲孔 | Method for producing a coating with a coloured surface |
| CN112366322A (en) * | 2020-01-03 | 2021-02-12 | 万向一二三股份公司 | Current collector for improving structural stability and cycle performance of silicon-carbon negative electrode, preparation method of current collector and battery comprising current collector |
| CN112909223A (en) * | 2021-03-10 | 2021-06-04 | 湖北大学 | Lithium ion battery cathode and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111448342A (en) * | 2017-09-15 | 2020-07-24 | 欧瑞康表面处理解决方案股份公司普费菲孔 | Method for producing a coating with a coloured surface |
| CN110474033A (en) * | 2019-08-22 | 2019-11-19 | 中南大学 | TiO2The preparation method and cathode of nano-array confinement antimony oxide cathode |
| CN110474033B (en) * | 2019-08-22 | 2021-09-07 | 中南大学 | TiO2Preparation method of nano-array confined antimony oxide cathode and cathode |
| CN112366322A (en) * | 2020-01-03 | 2021-02-12 | 万向一二三股份公司 | Current collector for improving structural stability and cycle performance of silicon-carbon negative electrode, preparation method of current collector and battery comprising current collector |
| CN112366322B (en) * | 2020-01-03 | 2022-01-07 | 万向一二三股份公司 | Current collector for improving structural stability and cycle performance of silicon-carbon negative electrode, preparation method of current collector and battery comprising current collector |
| CN111270288A (en) * | 2020-01-21 | 2020-06-12 | 黑龙江科技大学 | Preparation method of novel titanium dioxide negative electrode material |
| CN112909223A (en) * | 2021-03-10 | 2021-06-04 | 湖北大学 | Lithium ion battery cathode and preparation method and application thereof |
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Application publication date: 20170531 |