CN103943839A - Preparation method of modified lithium titanate negative electrode materials having surface formed with Ti-F bonds - Google Patents
Preparation method of modified lithium titanate negative electrode materials having surface formed with Ti-F bonds Download PDFInfo
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- CN103943839A CN103943839A CN201310556329.1A CN201310556329A CN103943839A CN 103943839 A CN103943839 A CN 103943839A CN 201310556329 A CN201310556329 A CN 201310556329A CN 103943839 A CN103943839 A CN 103943839A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- -1 modified lithium titanate Chemical class 0.000 title abstract description 13
- 239000007773 negative electrode material Substances 0.000 title abstract 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 72
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 70
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 64
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 239000010405 anode material Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 6
- 239000004408 titanium dioxide Substances 0.000 abstract description 6
- 238000005530 etching Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 238000000861 blow drying Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000008151 electrolyte solution Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 8
- 238000010532 solid phase synthesis reaction Methods 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 206010016766 flatulence Diseases 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005502 phase rule Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of modified lithium titanate negative electrode materials having the surface formed with Ti-F bonds. Aiming at pure-phase lithium titanate materials and modified lithium titanate materials synthesized by different ways, the method comprises adopting the lithium titanate materials synthesized by the different ways as raw materials, taking hydrofluoric acid with different concentrations as an etching agent, and carrying out ultrasonic stirring etching on the lithium titanate materials; and after etching, blow-drying the materials under an inert atmosphere, then carrying out secondary sintering processing in the inert atmosphere, and thus obtaining the modified lithium titanate negative electrode materials having the surface containing the Ti-F bonds. The prepared modified lithium titanate materials having the surface containing the Ti-F bonds have uniform particle diameters; with hydrofluoric acid etching and secondary sintering processing, one hand, a residual titanium dioxide miscellaneous phase in the lithium titanate materials is eliminated, and on the other hand, after hydrofluoric acid and lithium titanate on the particle surface undergo a reaction and then are subjected to secondary sintering processing, the stable Ti-F bonds are formed on the material particle surface; and the compatibility of the materials with an electrolyte solution is improved, the material circulation efficiency is improved, and generation of side reactions is reduced.
Description
Technical field
The present invention relates to the preparation method that a kind of surface forms Ti-F key graphite-doping lithium titanate anode material.
Background technology
The develop rapidly of lithium ion battery depends on exploitation and the polytechnic progress of novel energy material.Wherein especially exploration and the research of negative material just seem particularly important to new electrode materials.Current business-like negative material adopts the embedding lithium material with carbon elements such as graphite as negative pole mostly, although for lithium metal, aspect cycle performance and security performance, having significant improvement, but while still there is first charge-discharge, carbon surface generates passivating film and causes the problem that irreversible capacity loss is larger.In addition, the current potential of carbon electrode is close with lithium current potential, still may form Li dendrite and cause battery short circuit in the time of battery overcharge, causes safety problem.Therefore, find the desirable negative material of lithium ion battery from resource, environmental protection and secure context and be still the study hotspot of quite a while World chemical power supply circle from now on.Spinel-type Li
4ti
5o
12because its unique electrochemical properties has caused people's extensive concern.Li
4ti
5o
12theoretical capacity be 175mAh/g, be 1.55V with respect to the electrode voltage of lithium metal, in charge and discharge process, crystal structure can keep height stability, change hardly.Therefore be called as zero strain electrode material, there is longer cycle life.Therefore, lithium titanate has huge researching value and commercial application prospect as the desirable negative material of lithium-ion-power cell.
The main synthetic method of lithium titanate has high temperature solid-state method, liquid phase method.Wherein liquid phase method comprises again co-precipitation and hydrothermal synthesis method.Solid-phase synthesis is mainly by after lithium salts, titanium dioxide and carbon source and doped chemical mixing; under oxygen or inert gas shielding, under uniform temperature condition, sintering synthesizes lithium titanate or modified lithium titanate material; the advantage of high temperature method be synthesis technique simple, be easy to carry out large-scale industrialization production; shortcoming is that solid phase batch mixing process may exist batch mixing irregular, contains titanium dioxide dephasign after sintering in gained lithium titanate material.Liquid phase rule is that the He Tai source, lithium source of selection solubility is raw material, two kinds of raw materials are mixed with to solution together and reach other mixing of molecular level, make to mix more even, liquid phase method relatively and solid phase method processing step more complicated, the lithium titanate material after sintering also more or less there is titanium dioxide impurity phase.In the battery manufacturing process that has the later stage due to impurity phase, may cause the flatulence reaction of battery.The problem of flatulence is also lithium titanate material as one of fatal shortcoming of battery material energy extensive use, some researchers are also analyzed the flatulence problem of lithium titanate material battery from different aspects now, reduce the impurity phase in synthetic lithium titanate material by different method of modifying, or reduce lithium titanate material by coated method and contact with the direct of electrolyte, thereby the generation of minimizing side reaction solves the problem of battery flatulence.Therefore the problem of, improving lithium titanate material and compatibility of electrolyte becomes one of problem that current people pay close attention to.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of surface formation Ti-F key graphite-doping lithium titanate anode material, there is the defect that can cause flatulence problem in titanium dioxide dephasign and full battery for synthetic lithium titanate material, the method can realize eliminates remaining titanium dioxide dephasign in synthetic lithium titanate material, and formed stable Ti-F key on the surface of material and increased the intermiscibility of lithium titanate material and electrolyte, reduce the generation of side reaction in battery.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: surface forms the preparation method of Ti-F key graphite-doping lithium titanate anode material, comprises the steps as follows:
(1) getting lithium titanate material is raw material;
(2) hydrofluoric acid solution that configuration solution concentration mass fraction is 0.1%～10%;
(3) in plastic beaker, first add described hydrofluoric acid solution, then be that 5～100:1 takes lithium titanate material by hydrofluoric acid solution and lithium titanate material mass ratio, simultaneously the powerful mechanical agitation regular hour;
(4) material filtering after stir process, filter cake dry processing under inert gas;
(5) will be dried rear filter cake and put into tube furnace, under inert gas shielding, carry out double sintering processing.
As preferably, the lithium titanate material described in step (1) is to prepare gained with high temperature solid-state, sol-gel hydro-thermal ion-exchange the whole bag of tricks, comprising with Mg
2+, Al
3+, Zr
4+, Sr
2+, F
-, Sn
2+, W
6+, Ni
2+, Ba
2+, Ag
+, Cr
3+, Fe
3+deng the lithium titanate material of element doping and the coated modification mode gained of carbon doping.
As preferably, in step (4), selected inert gas is the one in nitrogen, argon gas or helium.
As preferably, in step (5), selected inert gas is the one in nitrogen, argon gas or helium, and sintering process is warming up to 400～1000 DEG C of insulation 1～12h for first 1～8h, and heating rate is 2～20 DEG C/min.
The invention has the beneficial effects as follows:
In present technology all can there is impurity phase more or less in final synthetic lithium titanate and graphite-doping lithium titanate anode material, later stage side reaction is more causes the fast shortcoming of capacity attenuation in circulation, the present invention is directed to the impurity phase that the existing subject matter elimination of lithium titanate material can cause side reaction, etching and sintering processes on lithium titanate material top layer through hydrofluoric acid have formed stable Ti-F key, increase the compatibility of lithium titanate material and electrolyte, improve cycle performance and the capability retention of material, reduced the generation of side reaction in battery.There is the advantages such as easy and simple to handle, technique simple, cost is lower simultaneously.
Brief description of the drawings
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is modified lithium titanate material first charge-discharge curve (1.0～2.5V) prepared by the embodiment of the present invention 3.
Fig. 2 is modified lithium titanate and comparative example's pure phase lithium titanate material 0.2C circulation correlation curve prepared by the embodiment of the present invention 3.
Fig. 3 is modified lithium titanate material SEM photo prepared by the embodiment of the present invention 3.
Embodiment
Following examples only, in order to further illustrate the present invention, do not limit content of the present invention.
Implementation column 1:
Getting the prepared pure phase lithium titanate material of solid phase synthesis process is raw material, and in the plastic beaker of 1L, adding concentration is 2% hydrofluoric acid solution 500mL, adds lithium titanate dried feed 10g after break process, stirs fast with paddle.After stirring reaction 5h, carry out suction filtration, filter cake dries up under condition of nitrogen gas.Dried feed is put into tube furnace, and under argon shield, 5 DEG C/min is warming up to 750 DEG C and be incubated 5h.
Gained graphite-doping lithium titanate anode material is prepared electrode as follows: lithium titanate material, binding agent, conductive agent are in mass ratio for the ratio of 82:8:10 is prepared into electrode, using lithium as to electrode, do electrolyte with 1M-LiPF6EC/EMC solution, microporous polypropylene membrane is barrier film, is assembled into button cell.And leave standstill 6 hours.After leaving standstill, battery is placed on and on LAND tester, carries out electric performance test, current density with 0.2C is carried out constant current charge-discharge experiment, test charging/discharging voltage scope is 1V～2.5V, the modified lithium titanate material that the present embodiment obtains, its first discharge specific capacity is 165mAh/g, and efficiency is 98.1% first.
Embodiment 2:
Getting the prepared pure phase lithium titanate material of solid phase synthesis process is raw material, and in the plastic beaker of 1L, adding concentration is 0.1% hydrofluoric acid solution 500mL, adds lithium titanate dried feed 10g after break process, stirs fast with paddle.After stirring reaction 5h, carry out suction filtration, filter cake dries up under condition of nitrogen gas.Dried feed is put into tube furnace, and under argon shield, 2 DEG C/min is warming up to 750 DEG C and be incubated 1h.
Gained lithium titanate anode material is tested by embodiment 1 method of testing, and first discharge specific capacity is 160mAh/g, and efficiency is 90.1% first.
Embodiment 3
Getting the prepared magnesium elements doping vario-property lithium titanate material of solid phase synthesis process is raw material, and in the plastic beaker of 1L, adding concentration is 3% hydrofluoric acid solution 400mL, adds break process post-modification lithium titanate dried feed 10g, stirs fast with paddle.After stirring reaction 5h, carry out suction filtration, filter cake dries up under condition of nitrogen gas.Dried feed is put into tube furnace, and under argon shield, 5 DEG C/min is warming up to 800 DEG C and be incubated 6h.
Gained lithium titanate anode material is tested by embodiment 1 method of testing, and in accompanying drawing 1, providing the material modified first discharge specific capacity of this embodiment gained is 169mAh/g, and efficiency is 98.8% first.Accompanying drawing 2 provides the Capacitance reserve situation of modification front and back bi-material circulation in 100 weeks, after the circulation in 100 weeks of material after surface modification, capability retention is apparently higher than lithium titanate material before modification, from accompanying drawing 3 the SEM photo of this embodiment gained modified lithium titanate material can find out through HF acid etch double sintering lithium titanate material particle diameter after treatment even, surperficial smoother.
Embodiment 4:
Getting the prepared coated modified carbon lithium titanate material of solid phase synthesis process is raw material, and in the plastic beaker of 1L, adding concentration is 4% hydrofluoric acid solution 300mL, adds break process post-modification lithium titanate dried feed 10g, stirs fast with paddle.After stirring reaction 5h, carry out suction filtration, filter cake dries up under condition of nitrogen gas.Dried feed is put into tube furnace, and under argon shield, 6 DEG C/min is warming up to 800 DEG C and be incubated 8h.
Gained lithium titanate anode material is tested by embodiment 1 method of testing, and first discharge specific capacity is 163mAh/g, and efficiency is 97.8% first.
Embodiment 5:
Getting the prepared magnesium elements doping vario-property lithium titanate material of solid phase synthesis process is raw material, and in the plastic beaker of 1L, adding concentration is 5% hydrofluoric acid solution 200mL, adds lithium titanate dried feed 10g after break process, stirs fast with paddle.After stirring reaction 5h, carry out suction filtration, filter cake dries up under condition of nitrogen gas.Dried feed is put into tube furnace, and under argon shield, 4 DEG C/min is warming up to 800 DEG C and be incubated 10h.
Gained lithium titanate anode material is tested by embodiment 1 method of testing, and first discharge specific capacity is 167mAh/g, and efficiency is 97.6% first.
Embodiment 6
Getting the prepared magnesium elements doping vario-property lithium titanate material of solid phase synthesis process is raw material, and in the plastic beaker of 1L, adding concentration is 10% hydrofluoric acid solution 200mL, adds lithium titanate dried feed 10g after break process, stirs fast with paddle.After stirring reaction 5h, carry out suction filtration, filter cake dries up under condition of nitrogen gas.Dried feed is put into tube furnace, and under argon shield, 10 DEG C/min is warming up to 1000 DEG C and be incubated 12h.
Gained lithium titanate anode material is tested by embodiment 1 method of testing, and first discharge specific capacity is 158mAh/g, and efficiency is 93.6% first.
Comparative example:
Lithium, magnesium and titanium elements are by molecular formula Li
3.88mg
0.12ti
5o
12proportioning takes lithium source, He Tai source, magnesium source, does dispersant with analyzing pure absolute ethyl alcohol, and ratio of grinding media to material is 6:1.Rotating speed is 450r/min, ball milling 5h, 80 DEG C of vacuumizes obtain presoma, presoma is placed in to Muffle furnace sintering, sintering machine is made as: first 3h is warming up to 200 DEG C, 5 DEG C/min is warming up to 800 DEG C and be incubated 17h again, naturally cools to room temperature, obtains magnesium elements doping vario-property lithium titanate anode material material.
Gained lithium titanate anode material is tested by embodiment 1 method of testing, and first discharge specific capacity is 167mAh/g, and efficiency is 94.5% first.
Claims (4)
1. surface forms the preparation method of Ti-F key graphite-doping lithium titanate anode material, it is characterized in that comprising the steps as follows:
(1) getting lithium titanate material is raw material;
(2) hydrofluoric acid solution that configuration solution concentration mass fraction is 0.1%～10%;
(3) in plastic beaker, first add described hydrofluoric acid solution, then be that 5～100:1 takes lithium titanate material by hydrofluoric acid solution and lithium titanate material mass ratio, simultaneously the powerful mechanical agitation regular hour;
(4) material filtering after stir process, filter cake dry processing under inert gas;
(5) will be dried rear filter cake and put into tube furnace, under inert gas shielding, carry out double sintering processing.
2. surface according to claim 1 forms the preparation method of Ti-F key graphite-doping lithium titanate anode material, it is characterized in that: the lithium titanate material described in step (1) is to prepare gained with high temperature solid-state or sol-gel hydro-thermal ion-exchange process, comprising with Mg
2+, A1
3+, Zr
4+, Sr
2+, F
-, Sn
2+, W
6+, Ni
2+, Ba
2+, Ag
+, Cr
3+, Fe
3+deng the lithium titanate material of element doping and the coated modification mode gained of carbon doping.
3. surface according to claim 1 forms the preparation method of Ti-F key graphite-doping lithium titanate anode material, it is characterized in that: in step (4), selected inert gas is the one in nitrogen, argon gas or helium.
4. surface according to claim 1 forms the preparation method of Ti-F key graphite-doping lithium titanate anode material, it is characterized in that: in step (5), selected inert gas is the one in nitrogen, argon gas or helium, sintering process is incubated 1～12h for first 1～8h is warming up to 400～1000 DEG C, and heating rate is 2～20 DEG C/min.
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Cited By (1)
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| CN108777300A (en) * | 2018-06-07 | 2018-11-09 | 王丹亮 | A kind of preparation method of Al, F, R doped titanic acid lithium titanate cathode material and application |
| CN108777300B (en) * | 2018-06-07 | 2021-07-06 | 王丹亮 | Preparation method and application of Al, F and R doped lithium titanate negative electrode material |
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