CN110380053A - A kind of lithium titanate composite material and preparation method thereof, button cell and preparation method thereof - Google Patents
A kind of lithium titanate composite material and preparation method thereof, button cell and preparation method thereof Download PDFInfo
- Publication number
- CN110380053A CN110380053A CN201910708810.5A CN201910708810A CN110380053A CN 110380053 A CN110380053 A CN 110380053A CN 201910708810 A CN201910708810 A CN 201910708810A CN 110380053 A CN110380053 A CN 110380053A
- Authority
- CN
- China
- Prior art keywords
- lithium titanate
- composite material
- preparation
- titanate composite
- button cell
- 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.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 78
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 31
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 13
- -1 molybdenum ion Chemical class 0.000 claims abstract description 12
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 11
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 11
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 239000006258 conductive agent Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 229910013872 LiPF Inorganic materials 0.000 claims description 6
- 101150058243 Lipf gene Proteins 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000005030 aluminium foil Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- 239000011733 molybdenum Substances 0.000 abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 229910019934 (NH4)2MoO4 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- MERJTCXDDLWWSK-UHFFFAOYSA-N 1-methylpyrrole pyrrolidin-2-one Chemical group CN1C=CC=C1.N1C(CCC1)=O MERJTCXDDLWWSK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0422—Cells or battery with cylindrical casing
- H01M10/0427—Button cells
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- 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
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
-
- 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
-
- 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
The invention discloses a kind of lithium titanate composite materials and preparation method thereof, button cell and preparation method thereof, are related to battery technology field.The preparation method of the lithium titanate composite material includes obtaining mixed solution after titanium dioxide, lithium hydroxide and ammonium molybdate are mixed evenly；Lithium titanate composite material is obtained after mixed solution is carried out microwave hydrothermal processing in a nitrogen environment.Since the radius of molybdenum ion and titanium ion is very close to the addition for passing through molybdenum ion may replace position of the titanium ion in lithium titanate in this method.Meanwhile microwave hydrothermal reaction is carried out by being passed through for nitrogen, the position of lithium ion or titanium ion is replaced using nitrogen-atoms, the electric conductivity and chemical property of lithium titanate can be effectively improved by doping chemical property excellent ionic compartmentation lithium ion or titanium ion.
Description
Technical field
The present invention relates to battery technology fields, in particular to a kind of lithium titanate composite material and preparation method thereof, knob
Detain battery and preparation method thereof.
Background technique
Compared with traditional carbon negative pole material, lithium titanate (Li4Ti5O12) because having lithium ion three-dimensional diffusion channel, higher
Lithium ion diffusion coefficient and fast charging and discharging ability can effectively ensure the safety of lithium ion battery, thus to improve battery
Cyclical stability and service life provide the foundation.But since the conductivity of lithium titanate is lower, at normal temperature only 10-13S.cm-1, therefore limit its application.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
An object of the present invention includes providing the preparation method of lithium titanate composite material, can be prepared by this method
The lithium titanate composite material of conductivity and electrochemical performance.
The second object of the present invention includes providing a kind of preparation method of button cell, compound by above-mentioned lithium titanate
Button cell is prepared in material.Therefore, which has excellent chemical property.
The present invention is implemented as follows:
In a first aspect, the embodiment of the present invention provides a kind of preparation method of lithium titanate composite material, comprising:
Mixed solution is obtained after titanium dioxide, lithium hydroxide and ammonium molybdate are mixed evenly；
Lithium titanate composite material is obtained after mixed solution is carried out microwave hydrothermal processing in a nitrogen environment.
In alternative embodiments, mixed solution include 100~200 parts of titanium dioxide of parts by weight meter, 50~
100 parts of lithium hydroxide and 10~30 parts of ammonium molybdate.
In alternative embodiments, lithium titanate is obtained after mixed solution being carried out microwave hydrothermal processing in a nitrogen environment
The step of composite material, specifically includes:
It is precipitated after mixed solution is carried out microwave hydrothermal reaction in the environment of nitrogen；
Will precipitating be successively centrifuged, wash, dry after obtain precursor powder；
Lithium titanate composite material is obtained after precursor powder is calcined.
In alternative embodiments, microwave hydrothermal reaction be mixed solution is transferred in microwave hydrothermal reaction kettle, and
It is put into microwave abstracting resolution instrument after sealing and carries out hydro-thermal reaction.
In alternative embodiments, the temperature of microwave hydrothermal reaction is 120~200 DEG C, and the reaction time is 1~3h.
In alternative embodiments, calcine precursor powder calcination temperature be 300~600 DEG C, calcination time be 1~
4h。
Second aspect, the embodiment of the present invention provide a kind of lithium titanate composite material, and lithium titanate composite material passes through aforementioned reality
The preparation method for applying the lithium titanate composite material of any one of mode is prepared.
The third aspect, the embodiment of the present invention provide a kind of preparation method of button cell, comprising:
Positive plate is prepared using the lithium titanate composite material of aforementioned embodiments；
Positive plate and the lithium piece as negative electrode tab are assembled into button cell.
In alternative embodiments, positive plate is prepared by following steps:
Slurry is obtained after lithium titanate composite material is mixed with conductive agent, binder and solvent；
Slurry is coated on aluminium foil, and obtains positive plate after carrying out baking and roll-in.
In alternative embodiments, conductive agent is super carbon black, and binder is Kynoar, and solvent is N-methyl pyrrole
Pyrrolidone, and the amount ratio of lithium titanate composite material, conductive agent and binder is 91~93:3:5.
In alternative embodiments, assembling button cell specifically includes:
Using polypropylene micropore diaphragm as diaphragm, using the LiPF of 1mol/L6As electrolyte, and in the hand of argon gas protection
Positive plate and negative electrode tab are assembled into button cell in casing.
Fourth aspect, the embodiment of the present invention provide a kind of button cell, and button cell passes through any in aforementioned embodiments
The preparation method of the button cell of item is prepared.
The invention has the following advantages:
The embodiment provides a kind of preparation methods of lithium titanate composite material, mainly include by titanium dioxide
Titanium, lithium hydroxide and ammonium molybdate obtain mixed solution after being mixed evenly；Mixed solution is subjected to microwave in a nitrogen environment
Lithium titanate composite material is obtained after hydro-thermal process.Since the radius of molybdenum ion and titanium ion is very close to passing through in this method
The addition of molybdenum ion may replace position of the titanium ion in lithium titanate.Meanwhile microwave hydrothermal reaction is carried out by being passed through for nitrogen,
The position for replacing lithium ion or titanium ion using nitrogen-atoms, by the substitution lithium ion of the excellent ion of doping chemical property or
Titanium ion can effectively improve the electric conductivity and chemical property of lithium titanate.
The button cell that the embodiment of the present invention provides, is prepared by above-mentioned lithium titanate composite material.Therefore,
The button cell has excellent chemical property.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the normal temperature circulation of the embodiment of the present invention embodiment 1, embodiment 2 and comparative example that provide at 0.5C
Performance curve comparison diagram.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Feature and performance of the invention are described in further detail with reference to embodiments.
The embodiment of the present invention provides a kind of lithium titanate composite material and preparation method thereof, and its object is to improve existing skill
The technical problems such as the lithium titanate composite material conductivity in art is lower, and chemical property is poor.
In detail, in the prior art, the preparation method of spinel type lithium titanate mainly has sintering process, sol-gal process at present
With hydro-thermal method etc..Wherein sintering process is to the more demanding of equipment, and the particle size prepared is uneven, crystal form is irregular.Colloidal sol
Gel method operation is not easy to control, so that colloidal sol unstable quality.
For this purpose, the preparation method for the lithium titanate composite material that the embodiment of the present invention provides specifically includes that
Firstly, obtaining mixed solution after titanium dioxide, lithium hydroxide and ammonium molybdate are mixed evenly；Pass through titanium dioxide
The mixing of carbon, lithium hydroxide and ammonium molybdate may make the lithium titanate material that Mo can be used during the preparation process6+Replace lithium titanate
The position of middle titanium ion, to improve the electric conductivity of entire lithium titanate composite material.
Secondly, obtaining lithium titanate composite material after mixed solution is carried out microwave hydrothermal processing in a nitrogen environment.Pass through
Hydro-thermal method can make reactant reach the other mixing of molecular level, the uniform nano material of easily prepared object phase, pattern.Also, it is micro-
Wave hydro-thermal method is to be combined together hydro-thermal method and microwave, and this method has the characteristics that heating rapidly and without hysteresis effect, thus
Manufacturing cycle is substantially reduced, production efficiency is improved.It is also desirable to explanation is to bring nitrogen by microwave-hydrothermal method,
It may make nitrogen-atoms that can replace the position of lithium ion, or replace the position of titanium ion, so as to further improve titanium
The electric conductivity of sour lithium.
Alternatively, in the present embodiment, mixed solution includes 100~200 parts of dioxy of parts by weight meter
Change titanium, 50~100 parts of lithium hydroxide and 10~30 parts of ammonium molybdate.And specifically, when the quality of titanium dioxide is selected as
When 200g, lithium hydroxide may be selected to be 100g, and ammonium molybdate may be selected to be 30g.When the quality of titanium dioxide is selected as 100g, hydrogen
Lithia may be selected to be 50g, and ammonium molybdate may be selected to be 10g.By controlling the dosage of each raw material, it may make and be finally prepared
Chemical formula is (Li4Ti4.95Mo0.05O12) presoma powder, guarantee the electrification that lithium titanate composite material is finally prepared with this
Learn performance.Certainly, in other embodiments of the invention, each raw material with than that can also be adjusted according to demand, the present invention
Embodiment without limitation.
Specifically, in an embodiment of the present invention, it is obtained after mixed solution to be carried out to microwave hydrothermal processing in a nitrogen environment
It is specifically included to the step of lithium titanate composite material:
Firstly, being precipitated after mixed solution is carried out microwave hydrothermal reaction in the environment of nitrogen；In detail, by micro-
The material for being doped with molybdenum and nitrogen can be prepared after wave hydro-thermal reaction.
Secondly, obtaining precursor powder after precipitating is successively centrifuged, is washed, is dried；Wherein, centrifugation can be used dedicated
Centrifugation apparatus, can also be centrifuged using mixing plant high agitation, washing is to remove the impurity in mixture.
Then, lithium titanate composite material is obtained after precursor powder being calcined, chemical formula can be expressed as (Li4(TiN)4.95Mo0.05O4.5).Since it is doped with molybdenum and nitrogen, so that its conductivity and chemical property are effectively improved.
It should be noted that in the present embodiment, microwave hydrothermal reaction temperature is 120 DEG C~200 DEG C, reaction time 1h
~3h.High-temperature calcination temperature is 300 DEG C~600 DEG C, and calcination time is 1h~4h.As the temperature of reaction increases, when reacting
Between can accordingly carry out shortening adjustment, in other embodiments of the invention, the selection of specific temperature and time can also be according to need
It asks and is adjusted, the embodiment of the present invention is without limitation.
The embodiments of the present invention also provide a kind of button cell, it is prepared by the following method to obtain:
With the molybdenum of preparation and nitrogen co-doped lithium titanate composite material (Li4(TiN)4.95Mo0.05O4.5) it is active matter, SP
(super carbon black) is conductive agent, and PVDF (Kynoar) is binder, and NMP (N-methyl pyrrolidones) is solvent.According to work
Property object: conductive agent: binder=92:3:5 is tuned into slurry and is applied on aluminium foil, and 12h is toasted in 110 DEG C of vacuum oven,
Later to its roll-in, and it is washed into the sequin that diameter is 1cm size, as the positive plate of button cell, using lithium piece as cathode
Piece, diaphragm of the polypropylene micropore diaphragm as battery, electrolyte are the LiPF of 1mol/L6, in group in the glove box of argon gas protection
Dress up button cell.
Since it is prepared by the above-mentioned lithium titanate composite material being prepared, the button being prepared is electric
Pond conductivity with higher and chemical property.
It is described in detail below by embodiment.
Embodiment 1
A kind of lithium titanate composite material is present embodiments provided, is prepared by the following method to obtain:
S1: 200gTiO is weighed2、100gLiOH.H2O and 30g (NH4)2MoO4, it is added in 100mL deionized water, machinery stirs
1h is mixed and be ultrasonically treated, obtains mixed solution after so that it is uniformly dispersed.
S2: mixed solution is transferred in microwave hydrothermal reaction kettle, and is passed through 5min nitrogen into reaction kettle to exclude instead
Answer the air in kettle, finally sealed and being put into after microwave abstracting resolution instrument carries out microwave hydrothermal reaction is precipitated；Wherein, microwave
Hydrothermal temperature is 120 DEG C, reaction time 3h.
S3: after reaction, precipitating centrifugation, washing, and spray-dried device handles to obtain solid powder product
(Li4Ti4.95Mo0.05O12)。
S4: by solid powder product (Li4Ti4.95Mo0.05O12) be placed in crucible, be put into the high temperature furnace for be connected with ammonia into
Row high-temperature calcination；Wherein, calcination temperature is 600 DEG C, calcination time 1h, and final products therefrom is that molybdenum is nitrogen co-doped after calcining
Lithium titanate composite material (Li4(TiN)4.95Mo0.05O4.5)。
Experimental example 1
The molybdenum and nitrogen co-doped lithium titanate composite material (Li that embodiment 1 is prepared4(TiN)4.95Mo0.05O4.5) make
For active matter, SP (super carbon black) is conductive agent, and PVDF (Kynoar) is binder, and NMP (N-methyl pyrrolidones) is
Solvent, according to active matter: conductive agent: binder=92:3:5 is tuned into slurry and is applied on aluminium foil, and in 110 DEG C of vacuum oven
Interior baking 12h later to its roll-in, and is washed into the sequin that diameter is 1cm size, as the positive plate of button cell, with lithium
Piece is the LiPF of 1mol/L as negative electrode tab, diaphragm of the polypropylene micropore diaphragm as battery, electrolyte6, in argon gas protection
Button cell is assembled into glove box.
Then, normal temperature circulation test, test method are as follows: in 25 ± 5 DEG C of environment, with 0.5C electric current constant current are carried out to battery
3.0V is charged to, is shelved 10 minutes, then with 0.5C electric current constant-current discharge to 1.0V, is shelved 10 minutes；The above charge and discharge are repeated to follow
Ring step, test results are shown in figure 1.
Embodiment 2
A kind of lithium titanate composite material is present embodiments provided, is prepared by the following method to obtain:
S1: 100gTiO is weighed2、50gLiOH.H2O and 10g (NH4)2MoO4, it is added in 100mL deionized water, mechanical stirring
And it is ultrasonically treated 1h, mixed solution is obtained after so that it is uniformly dispersed.
S2: mixed solution is transferred in microwave hydrothermal reaction kettle, and is passed through 5min nitrogen into reaction kettle to exclude instead
Answer the air in kettle, finally sealed and being put into after microwave abstracting resolution instrument carries out microwave hydrothermal reaction is precipitated；Wherein, microwave
Hydrothermal temperature is 200 DEG C, reaction time 1h.
S3: after reaction, precipitating centrifugation, washing, and spray-dried device handles to obtain solid powder product
(Li4Ti4.95Mo0.05O12)。
S4: by solid powder product (Li4Ti4.95Mo0.05O12) be placed in crucible, be put into the high temperature furnace for be connected with ammonia into
Row high-temperature calcination.Calcination temperature is 300 DEG C, calcination time 4h.Final products therefrom is molybdenum and nitrogen co-doped lithium titanate
Composite material (Li4(TiN)4.95Mo0.05O4.5)。
Experimental example 2
The molybdenum and nitrogen co-doped lithium titanate composite material (Li that embodiment 2 is prepared4(TiN)4.95Mo0.05O4.5) make
For active matter, SP (super carbon black) is conductive agent, and PVDF (Kynoar) is binder, and NMP (N-methyl pyrrolidones) is
Solvent, according to active matter: conductive agent: binder=92:3:5 is tuned into slurry and is applied on aluminium foil, and in 110 DEG C of vacuum oven
Interior baking 12h later to its roll-in, and is washed into the sequin that diameter is 1cm size, as the positive plate of button cell, with lithium
Piece is the LiPF of 1mol/L as negative electrode tab, diaphragm of the polypropylene micropore diaphragm as battery, electrolyte6, in argon gas protection
Button cell is assembled into glove box.
Then, normal temperature circulation test, test method are as follows: in 25 ± 5 DEG C of environment, with 0.5C electric current constant current are carried out to battery
3.0V is charged to, is shelved 10 minutes, then with 0.5C electric current constant-current discharge to 1.0V, is shelved 10 minutes；The above charge and discharge are repeated to follow
Ring step, test results are shown in figure 1.
Comparative example
A kind of lithium titanate composite material is present embodiments provided, is prepared by the following method to obtain:
S1: 100gTiO is weighed2And 50gLiOH.H2O is added in 100mL deionized water, and mechanical stirring is simultaneously ultrasonically treated 1h,
Mixed solution is obtained after so that it is uniformly dispersed.
S2: mixed solution is transferred in microwave hydrothermal reaction kettle, and is passed through 5min nitrogen into reaction kettle to exclude instead
Answer the air in kettle, finally sealed and being put into after microwave abstracting resolution instrument carries out microwave hydrothermal reaction is precipitated；Wherein, microwave
Hydrothermal temperature is 200 DEG C, reaction time 1h.
S4: after reaction, precipitating centrifugation, washing, and spray-dried device handles to obtain solid powder product
(Li4Ti5O12)。
S5: by above-mentioned resulting solid powder product (Li4Ti5O12) be placed in crucible, it is put into high temperature furnace and carries out high temperature
Calcining.Calcination temperature is 300 DEG C, calcination time 4h.Final products therefrom is lithium titanate material.
For the lithium titanate composite material that comparative example is prepared as active matter, SP (super carbon black) is conductive agent, PVDF
(Kynoar) is binder, and NMP (N-methyl pyrrolidones) is solvent, according to active matter: conductive agent: binder=92:
3:5 is tuned into slurry and is applied on aluminium foil, and 12h is toasted in 110 DEG C of vacuum oven, later to its roll-in, and is washed into diameter
For the sequin of 1cm size, as the positive plate of button cell, using lithium piece as negative electrode tab, polypropylene micropore diaphragm is as electricity
The diaphragm in pond, electrolyte are the LiPF of 1mol/L6, in argon gas protection glove box in be assembled into button cell.
Then, normal temperature circulation test, test method are as follows: in 25 ± 5 DEG C of environment, with 0.5C electric current constant current are carried out to battery
3.0V is charged to, is shelved 10 minutes, then with 0.5C electric current constant-current discharge to 1.0V, is shelved 10 minutes；The above charge and discharge are repeated to follow
Ring step, test results are shown in figure 1.
According to Fig. 1 result shown it is found that the electrification for the lithium titanate composite material that embodiment 1 and embodiment 2 are prepared
Learn the lithium titanate material that performance is substantially better than comparative example offer.And it is preferred scheme that embodiment 1, which is opposite,.
In conclusion due to molybdenum ion and titanium in the preparation method for the lithium titanate composite material that the embodiment of the present invention provides
The radius of ion is very close to therefore may replace position of the titanium ion in lithium titanate by the addition of molybdenum ion.Meanwhile passing through nitrogen
Being passed through for gas carries out microwave hydrothermal reaction, and the position of lithium ion or titanium ion is replaced using nitrogen-atoms, by adulterating chemically
The substitution lithium ion or titanium ion of ion that can be excellent can effectively improve the electric conductivity and chemical property of lithium titanate.Also,
Reactant can also be made to reach the other mixing of molecular level, the uniform nanometer of easily prepared object phase, pattern by microwave hydrothermal reaction
Material.Also, microwave-hydrothermal method is to be combined together hydro-thermal method and microwave, and this method has heating rapidly and without hysteresis effect
The features such as, thus manufacturing cycle is substantially reduced, improve production efficiency.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (12)
1. a kind of preparation method of lithium titanate composite material characterized by comprising
Mixed solution is obtained after titanium dioxide, lithium hydroxide and ammonium molybdate are mixed evenly；
The lithium titanate composite material is obtained after the mixed solution is carried out microwave hydrothermal processing in a nitrogen environment.
2. the preparation method of lithium titanate composite material according to claim 1, it is characterised in that:
The mixed solution includes 100~200 parts of the titanium dioxide of parts by weight meter, 50~100 parts of the hydrogen-oxygen
Change lithium and 10~30 parts of the ammonium molybdate.
3. the preparation method of lithium titanate composite material according to claim 1 or 2, which is characterized in that the mixing is molten
Liquid carries out the step of obtaining the lithium titanate composite material after microwave hydrothermal processing in a nitrogen environment and specifically includes:
It is precipitated after the mixed solution is carried out microwave hydrothermal reaction in the environment of the nitrogen；
By it is described precipitating be successively centrifuged, wash, dry after obtain precursor powder；
The lithium titanate composite material will be obtained after precursor powder calcining.
4. the preparation method of lithium titanate composite material according to claim 3, it is characterised in that:
The microwave hydrothermal reaction is the mixed solution to be transferred in microwave hydrothermal reaction kettle, and be put into microwave after sealing
Extraction resolution instrument carries out hydro-thermal reaction.
5. the preparation method of lithium titanate composite material according to claim 4, it is characterised in that:
The temperature of the microwave hydrothermal reaction is 120~200 DEG C, and the reaction time is 1~3h.
6. the preparation method of lithium titanate composite material according to claim 3, it is characterised in that:
The calcination temperature for calcining the precursor powder is 300~600 DEG C, and calcination time is 1~4h.
7. a kind of lithium titanate composite material, which is characterized in that the lithium titanate composite material passes through any in claim 1 to 6
The preparation method of lithium titanate composite material described in is prepared.
8. a kind of preparation method of button cell characterized by comprising
Positive plate is prepared using lithium titanate composite material as claimed in claim 7；
The positive plate and the lithium piece as negative electrode tab are assembled into the button cell.
9. the preparation method of button cell according to claim 8, which is characterized in that the positive plate passes through following steps
It is prepared:
Slurry is obtained after the lithium titanate composite material is mixed with conductive agent, binder and solvent；
The slurry is coated on aluminium foil, and obtains the positive plate after carrying out baking and roll-in.
10. the preparation method of button cell according to claim 9, it is characterised in that:
The conductive agent is super carbon black, and the binder is Kynoar, and the solvent is N-methyl pyrrolidones, and institute
The amount ratio for stating lithium titanate composite material, the conductive agent and the binder is 91~93:3:5.
11. the preparation method of button cell according to claim 8, which is characterized in that it is specific to assemble the button cell
Include:
Using polypropylene micropore diaphragm as diaphragm, using the LiPF of 1mol/L6As electrolyte, and in the glove box of argon gas protection
It is interior that the positive plate and the negative electrode tab are assembled into the button cell.
12. a kind of button cell, which is characterized in that the button cell passes through knob described in any one of claim 8 to 11
The preparation method of button battery is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910708810.5A CN110380053A (en) | 2019-08-01 | 2019-08-01 | A kind of lithium titanate composite material and preparation method thereof, button cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910708810.5A CN110380053A (en) | 2019-08-01 | 2019-08-01 | A kind of lithium titanate composite material and preparation method thereof, button cell and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110380053A true CN110380053A (en) | 2019-10-25 |
Family
ID=68257634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910708810.5A Pending CN110380053A (en) | 2019-08-01 | 2019-08-01 | A kind of lithium titanate composite material and preparation method thereof, button cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110380053A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496706A (en) * | 2011-12-09 | 2012-06-13 | 东莞市迈科科技有限公司 | Modified lithium titanate and preparation method thereof |
| CN102891304A (en) * | 2012-09-24 | 2013-01-23 | 合肥国轩高科动力能源有限公司 | Lithium titanate and lithium ion battery using lithium titanate as anode active substance |
| CN103055846A (en) * | 2012-11-07 | 2013-04-24 | 陕西科技大学 | Method for preparing tungstate with visible-light photocatalytic activity by microwave hydrothermal process |
| CN103956475A (en) * | 2014-05-08 | 2014-07-30 | 上海电力学院 | Method for preparing lithium titanate of lithium ion battery cathode material |
| CN104370303A (en) * | 2014-11-27 | 2015-02-25 | 陕西科技大学 | Preparing method of lithium titanate with good rate performance |
-
2019
- 2019-08-01 CN CN201910708810.5A patent/CN110380053A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496706A (en) * | 2011-12-09 | 2012-06-13 | 东莞市迈科科技有限公司 | Modified lithium titanate and preparation method thereof |
| CN102891304A (en) * | 2012-09-24 | 2013-01-23 | 合肥国轩高科动力能源有限公司 | Lithium titanate and lithium ion battery using lithium titanate as anode active substance |
| CN103055846A (en) * | 2012-11-07 | 2013-04-24 | 陕西科技大学 | Method for preparing tungstate with visible-light photocatalytic activity by microwave hydrothermal process |
| CN103956475A (en) * | 2014-05-08 | 2014-07-30 | 上海电力学院 | Method for preparing lithium titanate of lithium ion battery cathode material |
| CN104370303A (en) * | 2014-11-27 | 2015-02-25 | 陕西科技大学 | Preparing method of lithium titanate with good rate performance |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Machida et al. | Electrochemical properties of all-solid-state batteries with ZrO2-coated LiNi1/3Mn1/3Co1/3O2 as cathode materials | |
| Huang et al. | A novel carbamide-assistant hydrothermal process for coating Al2O3 onto LiMn1. 5Ni0. 5O4 particles used for cathode material of lithium-ion batteries | |
| CN109461928B (en) | High-energy-density multi-element positive electrode material and preparation method thereof | |
| CN107768663B (en) | Method for preparing transition metal oxide having oxygen defect | |
| Wang et al. | Synthesis of LiNi0. 5Mn1. 5O4 cathode material with improved electrochemical performances through a modified solid-state method | |
| Meng et al. | Surface modification of Li-rich layered Li [Li0. 17Ni0. 17Co0. 10Mn0. 56] O2 oxide with LiV3O8 as a cathode material for Li-ion batteries | |
| Lu et al. | Electrochemical characteristics of LiNi1/3Co1/3Mn1/3O2 powders prepared from microwave-hydrothermally derived precursors | |
| CN105355871B (en) | A kind of combination electrode material, preparation method and solid lithium battery | |
| Zhou et al. | Preparation and electrochemical properties of spinel LiMn2O4 prepared by solid-state combustion synthesis | |
| JP2023507212A (en) | Method for preparing lithium manganese iron phosphate precursor and method for preparing lithium manganese iron phosphate | |
| KR101272042B1 (en) | Lithuium manganese complex oxide and the manufacturing method thereof | |
| CN109873140B (en) | Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material | |
| CN105977460B (en) | A kind of graphene composite material, preparation method and application | |
| CN109473641A (en) | A kind of preparation method of coated modified carbon high magnification titanium niobium oxide material | |
| CN106450265A (en) | In-situ nitrogen-doped carbon coated lithium titanate composite electrode material and preparation method thereof | |
| CN104282886A (en) | Carbon coating method for electrode active material of lithium ion battery | |
| WO2016202173A1 (en) | Method for preparing high-purity lithium titanate negative electrode material and use thereof | |
| Wu et al. | Simultaneously fabricating homogeneous nanostructured ionic and electronic pathways for layered lithium-rich oxides | |
| TWI651272B (en) | Process for producing lr-lnmo composite materials and use the same | |
| He et al. | An improved solid-state method for synthesizing LiNi0. 5Mn1. 5O4 cathode material for lithium ion batteries | |
| CN108598439A (en) | A kind of preparation method of tungstic acid/graphene composite negative pole | |
| CN106067539B (en) | A kind of method that electrode material is fluorinated modified | |
| Wu et al. | Study on Li1+ xV3O8 synthesized by microwave sol–gel route | |
| Li et al. | Effect of Nb 5+ doping on LiNi 0.5 Co 0.25 Mn 0.25 O 2 cathode material | |
| CN108767231A (en) | A kind of LiNixCoyMnl-x-yO2/Li2O·B2O3The preparation method of composite positive pole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |