CN103943839B - Surface forms the preparation method of Ti-F key graphite-doping lithium titanate anode material - Google Patents
Surface forms the preparation method of Ti-F key graphite-doping lithium titanate anode material Download PDFInfo
- Publication number
- CN103943839B CN103943839B CN201310556329.1A CN201310556329A CN103943839B CN 103943839 B CN103943839 B CN 103943839B CN 201310556329 A CN201310556329 A CN 201310556329A CN 103943839 B CN103943839 B CN 103943839B
- Authority
- CN
- China
- Prior art keywords
- lithium titanate
- key
- graphite
- hydrofluoric acid
- doping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 77
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 75
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000010405 anode material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 44
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 28
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- -1 modified lithium titanate Chemical class 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 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
- 238000012986 modification Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000005253 cladding Methods 0.000 claims description 3
- 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
- 230000004048 modification Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000004408 titanium dioxide Substances 0.000 abstract description 6
- 238000005530 etching Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000007423 decrease Effects 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 2
- 238000013019 agitation Methods 0.000 abstract 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 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
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 206010016766 flatulence Diseases 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910009866 Ti5O12 Inorganic materials 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
- 239000013078 crystal Substances 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
- 230000005611 electricity Effects 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 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
- 238000012545 processing Methods 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
- 238000005211 surface analysis Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses surface and form the preparation method of Ti F key graphite-doping lithium titanate anode material, pure phase lithium titanate material that the method synthesizes for different modes and modified lithium titanate material, the lithium titanate material taking multi-form synthesis is raw material, etching agent is done with the hydrofluoric acid of variable concentrations, lithium titanate material is carried out ultrasonic agitation etching, after etching, material dries up under an inert atmosphere, then carries out double sintering process in inert atmosphere, obtains surface F key graphite-doping lithium titanate anode material Han Ti.Surface prepared by present invention F key modified lithium titanate material Han Ti, particle diameter is uniform, the etching of hydrofluoric acid and double sintering process, on the one hand the titanium dioxide dephasign of remaining in lithium titanate material is eliminated, on the other hand hydrofluoric acid and particle surface lithium titanate react and define stable Ti F key after double sintering processes on material granule surface, improve the compatibility of material itself and electrolyte, improve material circulation efficiency, decrease the generation of side reaction.
Description
Technical field
The present invention relates to a kind of surface and form the preparation method of Ti-F key graphite-doping lithium titanate anode material.
Background technology
Developing rapidly of lithium ion battery depends on the exploitation of novel energy material and polytechnic progress.Its
Exploration and the research of middle new electrode materials especially negative material are just particularly important.The most business-like
Negative material uses the embedding lithium material with carbon elements such as graphite as negative pole mostly, although for lithium metal, is following
Ring performance and security performance aspect have had significant improvement, but when yet suffering from first charge-discharge, carbon surface generates
Passivating film and cause the problem that irreversible capacity loss is bigger.Additionally, the current potential of carbon electrode is close with lithium current potential,
Still it is likely to be formed Li dendrite when battery overcharge and causes battery short circuit, cause safety problem.Therefore,
When resource, environmental protection and the secure context searching preferable negative material of lithium ion battery is still the most suitable one section
Between the study hotspot of World chemical power supply circle.Spinel-type Li4Ti5O12Because of the electrochemical properties of its uniqueness
Cause the extensive concern of people.Li4Ti5O12Theoretical capacity be 175mAh/g, relative to lithium metal
Electrode voltage is 1.55V, and in charge and discharge process, crystal structure can keep the stability of height, hardly
Change.Therefore it is referred to as zero strain electrode material, there is longer cycle life.Therefore, metatitanic acid
Lithium has huge researching value and commercial application prospect as the preferable negative material of lithium-ion-power cell.
The primary synthetic methods of lithium titanate has high temperature solid-state method, liquid phase method.Wherein liquid phase method includes again co-precipitation
And hydrothermal synthesis method.Lithium salts, titanium dioxide and carbon source and doped chemical are mainly mixed by solid-phase synthesis
After, under oxygen or inert gas shielding, under the conditions of uniform temperature, sintering synthesizes lithium titanate or Modified Titanium
Acid lithium material, the advantage of high temperature method is that synthesis technique is simple, is prone to carry out industrialization large-scale production, shortcoming
It is irregular to be that solid phase batch mixing process there may be batch mixing, miscellaneous containing titanium dioxide in gained lithium titanate material after sintering
Phase.Liquid phase rule is that to select the lithium source of solubility and titanium source be raw material, and two kinds of raw materials are configured to solution together
Reaching the other mixing of molecular level, make mixing evenly, liquid phase method is the most complicated with solid phase method processing step,
Lithium titanate material after sintering existence titanium dioxide impurity phase the most more or less.After the existence of impurity phase
The flatulence that may cause battery in the cell fabrication processes of phase is reacted.The problem of flatulence is also lithium titanate material
As one of battery material wide variety of fatal defects of energy, some researchers are also from different sides now
The flatulence problem of surface analysis lithium titanate material battery, reduces synthesis lithium titanate material by different method of modifying
In impurity phase, or reduce the direct of lithium titanate material and electrolyte by the method for cladding and contact, thus
Reduce the problem occurring to solve battery flatulence of side reaction.Therefore, improve lithium titanate material and electrolyte is compatible
The problem of property becomes one of current problem of concern.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of surface and forms Ti-F key modified lithium titanate negative pole material
The preparation method of material, exists in titanium dioxide dephasign and full battery for synthesis lithium titanate material and can cause flatulence
The defect of problem, the method can realize eliminate synthesis lithium titanate material in remaining titanium dioxide dephasign, and
The surface of material defines stable Ti-F key and adds the intermiscibility of lithium titanate material and electrolyte, reduces
The generation of side reaction in battery.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: surface forms Ti-F key and changes
The preparation method of property lithium titanate anode material, comprises the steps as follows:
(1) taking lithium titanate material is raw material；
(2) configuration solution concentration mass fraction is the hydrofluoric acid solution of 0.1%～10%；
(3) in plastic beaker, it is initially charged described hydrofluoric acid solution, then presses hydrofluoric acid solution and lithium titanate material
Material mass ratio is 5～100: 1 to weigh lithium titanate material, strength mechanic whirl-nett reaction 5 hours simultaneously；
(4) material filtering after stir process, is dried filter cake under an inert gas and processes；
(5) dried filter cake is put into tube furnace, under inert gas shielding, carry out double sintering process.
As preferably, the lithium titanate material described in step (1) is with high temperature solid-state, sol-gel hydro-thermal
Ion exchanges various methods and prepares gained, including with Mg2+、Al3+、Zr4+、Sr2+、F-、Sn2+、
W6+、Ni2+、Ba2+、Ag+、Cr3+、Fe3+In one or more element dopings and carbon doping cladding
The lithium titanate material of modification mode gained.
As preferably, inert gas selected in step (4) is in nitrogen, argon gas or helium
Kind.
As preferably, inert gas selected in step (5) is in nitrogen, argon gas or helium
Kind, sintering process is warming up to 400～1000 DEG C for first 1～8h, then is incubated 1～12h, heating rate be 2～
20℃/min。
The invention has the beneficial effects as follows:
In present technology final synthesis lithium titanate and graphite-doping lithium titanate anode material all can exist or many or
Few impurity phase, later stage side reaction is more causes the shortcoming that in circulation, capacity attenuation is fast, the present invention is directed to metatitanic acid
Subject matter elimination existing for lithium material can cause the impurity phase of side reaction, on lithium titanate material top layer through hydrogen
The etching of fluoric acid and sintering processes define stable Ti-F key, add lithium titanate material and electrolyte
Compatibility, improves cycle performance and the capability retention of material, decreases the generation of side reaction in battery.
There is the advantages such as easy and simple to handle, technique is simple, cost is relatively low simultaneously.
Accompanying drawing explanation
The present invention is further detailed explanation with detailed description of the invention below in conjunction with the accompanying drawings.
Fig. 1 be the embodiment of the present invention 3 preparation modified lithium titanate material first charge-discharge curve (1.0～
2.5V)。
Fig. 2 is modified lithium titanate and comparative example's pure phase lithium titanate material of the embodiment of the present invention 3 preparation
0.2C circulates correlation curve.
Fig. 3 is the modified lithium titanate material SEM photograph of the embodiment of the present invention 3 preparation.
Detailed description of the invention
Following example, only for further illustrating the present invention, are not limiting as present disclosure.
Enforcement row 1:
Taking the pure phase lithium titanate material prepared by solid phase synthesis process is raw material, adds in the plastic beaker of 1L
Enter the hydrofluoric acid solution 500mL that concentration is 2%, add lithium titanate dried feed 10g after break process, with stirring
Oar quickly stirs.Carrying out suction filtration after stirring reaction 5h, filter cake dries up under a nitrogen atmosphere.Dried feed is put
Entering in tube furnace, under argon shield, 5 DEG C/min is warming up to 750 DEG C and is incubated 5h.
Gained graphite-doping lithium titanate anode material prepares electrode as follows: lithium titanate material, binding agent, lead
Electricity agent be in mass ratio 82: 8: 10 ratio be prepared as electrode, using lithium as to electrode, with 1M-LiPF6
EC/EMC solution does electrolyte, and microporous polypropylene membrane is barrier film, is assembled into button cell.And it is little to stand 6
Time.Battery after standing is placed on LAND tester and carries out electric performance test, with the current density of 0.2C
Carrying out constant current charge-discharge experiment, test charging/discharging voltage scope is 1V～2.5V, and what the present embodiment obtained changes
Property lithium titanate material, its first discharge specific capacity is 165mAh/g, and efficiency is 98.1% first.
Embodiment 2:
Taking the pure phase lithium titanate material prepared by solid phase synthesis process is raw material, adds in the plastic beaker of 1L
Enter the hydrofluoric acid solution 500mL that concentration is 0.1%, add lithium titanate dried feed 10g after break process, with stirring
Mix oar quickly to stir.Carrying out suction filtration after stirring reaction 5h, filter cake dries up under a nitrogen atmosphere.Dried feed
Putting into tube furnace, under argon shield, 2 DEG C/min is warming up to 750 DEG C and is incubated 1h.
Gained lithium titanate anode material is tested by embodiment 1 method of testing, and first discharge specific capacity is
160mAh/g, efficiency is 90.1% first.
Embodiment 3
Taking the magnesium elements doping vario-property lithium titanate material prepared by solid phase synthesis process is raw material, moulding at 1L
Material beaker adds the hydrofluoric acid solution 400mL that concentration is 3%, adds break process post-modification lithium titanate and be dried
Material 10g, quickly stirs with paddle.Carrying out suction filtration after stirring reaction 5h, filter cake is under a nitrogen atmosphere
Dry up.Dried feed puts into tube furnace, and under argon shield, 5 DEG C/min is warming up to 800 DEG C and is incubated 6h.
Gained lithium titanate anode material is tested by embodiment 1 method of testing, provides this enforcement in accompanying drawing 1
The material modified first discharge specific capacity of example gained is 169mAh/g, and efficiency is 98.8% first.Accompanying drawing 2
Provide the capacity of the circulation in 100 weeks of latter two material before modified and keep situation, surface-modified after material 100
After Zhou Xunhuan, capability retention is apparently higher than lithium titanate material before modified, and from accompanying drawing 3, this embodiment gained changes
Property lithium titanate material SEM photograph can be seen that the lithium titanate after HF acid etch double sintering process
Material granule uniform diameter, surface smoother.
Embodiment 4:
Taking the coated modified carbon lithium titanate material prepared by solid phase synthesis process is raw material, and the plastics at 1L burn
Add the hydrofluoric acid solution 300mL that concentration is 4% in Bei, add break process post-modification lithium titanate dried feed
10g, quickly stirs with paddle.Carrying out suction filtration after stirring reaction 5h, filter cake dries up under a nitrogen atmosphere.
Dried feed puts into tube furnace, and under argon shield, 6 DEG C/min is warming up to 800 DEG C and is incubated 8h.
Gained lithium titanate anode material is tested by embodiment 1 method of testing, and first discharge specific capacity is
163mAh/g, efficiency is 97.8% first.
Embodiment 5:
Taking the magnesium elements doping vario-property lithium titanate material prepared by solid phase synthesis process is raw material, moulding at 1L
Material beaker adds the hydrofluoric acid solution 200mL that concentration is 5%, adds lithium titanate dried feed after break process
10g, quickly stirs with paddle.Carrying out suction filtration after stirring reaction 5h, filter cake dries up under a nitrogen atmosphere.
Dried feed puts into tube furnace, and under argon shield, 4 DEG C/min is warming up to 800 DEG C and is incubated 10h.
Gained lithium titanate anode material is tested by embodiment 1 method of testing, and first discharge specific capacity is
167mAh/g, efficiency is 97.6% first.
Embodiment 6
Taking the magnesium elements doping vario-property lithium titanate material prepared by solid phase synthesis process is raw material, moulding at 1L
Material beaker adds the hydrofluoric acid solution 200mL that concentration is 10%, adds lithium titanate dried feed after break process
10g, quickly stirs with paddle.Carrying out suction filtration after stirring reaction 5h, filter cake dries up under a nitrogen atmosphere.
Dried feed puts into tube furnace, and under argon shield, 10 DEG C/min is warming up to 1000 DEG C and is incubated 12h.
Gained lithium titanate anode material is tested by embodiment 1 method of testing, and first discharge specific capacity is
158mAh/g, efficiency is 93.6% first.
Comparative example:
Lithium, magnesium and titanium elements press molecular formula Li3.88Mg0.12Ti5O12Proportioning weighs lithium source, magnesium source and titanium source, uses
Analyzing pure absolute ethyl alcohol and do dispersant, ratio of grinding media to material is 6: 1.Rotating speed is 450r/min, ball milling 5h, 80 DEG C
Vacuum drying obtains presoma, and presoma is placed in Muffle furnace sintering, and sin-tering mechanism is: first 3h liter
Temperature is to 200 DEG C, then 5 DEG C/min is warming up to 800 DEG C and is incubated 17h, naturally cools to room temperature, obtains magnesium
Element doping graphite-doping 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, efficiency is 94.5% first.
Claims (4)
1. surface formed Ti-F key graphite-doping lithium titanate anode material preparation method, it is characterised in that include as
Lower step is as follows:
(1) taking lithium titanate material is raw material；
(2) configuration solution concentration mass fraction is the hydrofluoric acid solution of 0.1%～10%；
(3) in plastic beaker, it is initially charged described hydrofluoric acid solution, then presses hydrofluoric acid solution and lithium titanate material
Material mass ratio is 5～100: 1 to weigh lithium titanate material, strength mechanic whirl-nett reaction 5 hours simultaneously；
(4) material filtering after stir process, is dried filter cake under an inert gas and processes；
(5) dried filter cake is put into tube furnace, under inert gas shielding, carry out double sintering process.
Surface the most according to claim 1 forms the preparation side of Ti-F key graphite-doping lithium titanate anode material
Method, it is characterised in that: the lithium titanate material described in step (1) is with high temperature solid-state or sol-gel water
Thermal ion exchange method prepares gained, including with Mg2+、Al3+、Zr4+、Sr2+、F-、Sn2+、
W6+、Ni2+、Ba2+、Ag+、Cr3+、Fe3+In one or more element dopings and carbon doping cladding
The lithium titanate material of modification mode gained.
Surface the most according to claim 1 forms the preparation side of Ti-F key graphite-doping lithium titanate anode material
Method, it is characterised in that: inert gas selected in step (4) is in nitrogen, argon gas or helium
A kind of.
Surface the most according to claim 1 forms the preparation side of Ti-F key graphite-doping lithium titanate anode material
Method, it is characterised in that: inert gas selected in step (5) is in nitrogen, argon gas or helium
One, sintering process is for first 1～8h being warming up to 400～1000 DEG C, then is incubated 1～12h, and heating rate is
2～20 DEG C/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310556329.1A CN103943839B (en) | 2013-11-08 | 2013-11-08 | Surface forms the preparation method of Ti-F key graphite-doping lithium titanate anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310556329.1A CN103943839B (en) | 2013-11-08 | 2013-11-08 | Surface forms the preparation method of Ti-F key graphite-doping lithium titanate anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103943839A CN103943839A (en) | 2014-07-23 |
| CN103943839B true CN103943839B (en) | 2016-09-07 |
Family
ID=51191410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310556329.1A Active CN103943839B (en) | 2013-11-08 | 2013-11-08 | Surface forms the preparation method of Ti-F key graphite-doping lithium titanate anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103943839B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102347484A (en) * | 2010-07-29 | 2012-02-08 | 株式会社东芝 | Active material for battery, nonaqueous electrolyte battery, battery pack, and vehicle |
| CN103199232A (en) * | 2013-03-06 | 2013-07-10 | 宁德新能源科技有限公司 | Surface-modified lithium titanate and preparation method thereof |
| CN103219505A (en) * | 2012-01-19 | 2013-07-24 | 株式会社东芝 | Active material, active material production method, nonaqueous electrolyte battery, and battery pack |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130095386A1 (en) * | 2011-10-12 | 2013-04-18 | Battelle Memorial Institute | Metal Fluoride Electrode Protection Layer and Method of Making Same |
-
2013
- 2013-11-08 CN CN201310556329.1A patent/CN103943839B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102347484A (en) * | 2010-07-29 | 2012-02-08 | 株式会社东芝 | Active material for battery, nonaqueous electrolyte battery, battery pack, and vehicle |
| CN103219505A (en) * | 2012-01-19 | 2013-07-24 | 株式会社东芝 | Active material, active material production method, nonaqueous electrolyte battery, and battery pack |
| CN103199232A (en) * | 2013-03-06 | 2013-07-10 | 宁德新能源科技有限公司 | Surface-modified lithium titanate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103943839A (en) | 2014-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105742602B (en) | A kind of sodium-ion battery cathode Sn/MoS2/ C composite and preparation method thereof | |
| CN102790217B (en) | Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof | |
| CN108321366A (en) | A kind of method for coating improving nickelic ternary nickel cobalt manganese anode material chemical property | |
| CN104124431B (en) | A kind of lithium ion battery graphite cathode material and preparation method thereof | |
| CN106025260A (en) | Ternary cathode material of hollow spherical nano-structure and preparing method thereof | |
| CN110429268A (en) | A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof | |
| CN108493458B (en) | High-performance echinoid nickel oxide/nickel cobaltate microsphere lithium oxygen battery positive electrode catalytic material and preparation method thereof | |
| CN106058238A (en) | Modified spherical nickel cobalt lithium manganate NCM622 anode material and preparation method thereof | |
| CN106340633A (en) | Composite nano material for high performance lithium ion battery and preparation method thereof | |
| CN104993116B (en) | A kind of self assembly anode material for lithium-ion batteries V2O5Preparation method | |
| CN105977484A (en) | Iron sesquioxide nanotube material as well as preparation method and application thereof | |
| CN104466139A (en) | Preparation method of polyaniline-clad germanium-doped lithium manganate composite cathode material | |
| CN102903918A (en) | Preparation method for manganese phosphate lithium nanosheet | |
| CN105481004A (en) | Stannic oxide nanotubes with high electrical properties and preparation method therefor | |
| CN108598463B (en) | Preparation method of nano flaky lithium-rich manganese-based positive electrode material | |
| CN110336017A (en) | A kind of modified lithium manganate and its preparation method and application | |
| CN104253270A (en) | Lithium iron phosphate coated lithium manganate composite electrode material and its preparation method | |
| CN102544468B (en) | Mesoporous lithium titanate lithium ion battery negative material of carbon cladding and preparation method thereof | |
| CN106299276A (en) | A kind of preparation method of ion cathode material lithium silver surface modified lithium titanate | |
| CN109428068A (en) | A kind of anode material for lithium-ion batteries gradient precursor preparation method | |
| CN107055613A (en) | One kind is without substrate niobium pentoxide nano chip arrays negative material and its preparation method and application | |
| CN104300136B (en) | One-dimensional manganese oxide/carbon coaxial hollow nanorod as well as preparation method and application of nanorod | |
| CN104505502B (en) | Lithium titanate composite negative material for lithium ion battery and preparation method of lithium titanate composite negative material | |
| CN103943839B (en) | Surface forms the preparation method of Ti-F key graphite-doping lithium titanate anode material | |
| CN107256962B (en) | A kind of the tertiary cathode material nickel cobalt aluminium and preparation method and application of aluminium foil growth in situ |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 230000 Yaohai Industrial Zone, Hefei New District, Anhui, No. D weft Road, No. 7 Applicant after: Gotion High-tech Co., Ltd. Address before: 230000 Yaohai Industrial Park, Anhui, Hefei No. D weft Road, No. 7 Applicant before: Hefei Guoxuan High-Tech Power Energy Co.,Ltd. |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |