CN113764639A - Preparation method and application of layered lithium titanate - Google Patents
Preparation method and application of layered lithium titanate Download PDFInfo
- Publication number
- CN113764639A CN113764639A CN202111017561.9A CN202111017561A CN113764639A CN 113764639 A CN113764639 A CN 113764639A CN 202111017561 A CN202111017561 A CN 202111017561A CN 113764639 A CN113764639 A CN 113764639A
- Authority
- CN
- China
- Prior art keywords
- lithium titanate
- lithium
- titanium
- mortar
- layered lithium
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 112
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 111
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 105
- 239000010936 titanium Substances 0.000 claims abstract description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 30
- 238000004146 energy storage Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000000227 grinding Methods 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000004321 preservation Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000011232 storage material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000004570 mortar (masonry) Substances 0.000 description 77
- 239000000047 product Substances 0.000 description 36
- 238000005303 weighing Methods 0.000 description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 21
- 238000004140 cleaning Methods 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000003892 spreading Methods 0.000 description 14
- 230000007480 spreading Effects 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 239000006228 supernatant Substances 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
- 238000005485 electric heating Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000010406 cathode material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910009819 Ti3C2 Inorganic materials 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Images
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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method and application of layered lithium titanate.A titanium-based MXene is pretreated, then a pretreated material and a lithium source are mixed and ground, and the mixed material is heated, insulated, calcined and cooled to room temperature under the air atmosphere to obtain layered lithium titanate; the lithium titanate with the layered structure prepared from the titanium-based MXene improves the diffusion, embedding and separation of lithium ions in the electrode material, has a simple preparation method, can realize better electrochemical performance due to the good layered structure, and is easy to realize industrial popularization and application in the field of energy storage.
Description
Technical Field
The invention relates to the technical field of energy storage, in particular to layered lithium titanate prepared by titanium-based MXene, and the layered lithium titanate is applied to the technical field of energy storage.
Background
The lithium ion battery cathode material mainly comprises a carbon-based cathode material, an alloy-based cathode material and an oxide. The conventional lithium metal and graphite cathode materials have problems of life and safety, and therefore, a novel electrode material with good stability and safety needs to be developed.
Lithium titanate as a promising negative electrode material shows a stable voltage platform (1.55V vs Li/Li)+) There is almost no volume change and lithium dendrite problem, and it has zero strain property during lithium ion intercalation/deintercalation due to its unique crystal structure, thereby improving stability and safety.
MXene materials are also receiving more and more attention due to their unique advantages, excellent electronic conductivity, and competitive performance of adjustable layer structures in energy storage devices. The particles with large specific surface area of the layered structure can promote the electrolyte to be fully contacted with the active substance, and shorten the diffusion distance of lithium ions, thereby promoting the full contact, realizing high rate performance, and becoming a lithium ion battery cathode material with wide prospect.
Disclosure of Invention
The invention provides layered lithium titanate prepared based on titanium-based MXene and application of the layered lithium titanate in the field of energy storage battery cathodes.
The specific technical scheme of the invention is as follows:
after titanium-based MXene is pretreated, the pretreated material and a lithium source are mixed and ground, the mixed material is flatly laid in a crucible, put in a muffle furnace, heated, kept warm and calcined in the air atmosphere, and cooled to obtain the layered lithium titanate.
The titanium-based MXene material is Tin+1CnOr Tin+1CnTxWherein n is a natural number excluding 0, such as 1, 2, 3, 4xRepresents a surface functional group, is-O, -F or-OH; MXene materials are commercially available.
The titanium-based MXene material has two pretreatment methods, specifically the following steps:
the method comprises the following steps: weighing titanium-based MXene powder, pouring the titanium-based MXene powder into NaOH solution with the concentration of 1-2mol/L for etching to remove Al elements in MXene, stirring the mixture for 5-10min by using a glass rod, pouring the mixed solution into a centrifuge tube, pouring equivalent deionized water into a blank centrifuge tube, centrifuging the centrifuge tube for 20-40min at the speed of 4000-plus 5000rpm, pouring the centrifuged supernatant, drying the centrifugally collected material in a 50-60 ℃ drying oven for 12-24h, grinding the dried material for 30-60min by using a mortar due to agglomeration to obtain a pretreated material; the mass volume ratio g: mL of the titanium-based MXene powder to the NaOH solution is 1-2:100, and the dried material is a pretreatment material named as pretreatment material A;
the second method comprises the following steps: then, treating the pretreatment material A, heating, preserving heat and oxidizing the pretreatment material A in an oxygen atmosphere, continuously introducing oxygen and cooling to room temperature to obtain a pretreatment material, namely a pretreatment material B; the flow rate of oxygen is 2-5mL/min, the temperature rise, heat preservation and oxidation temperature is 560-.
The lithium source is lithium carbonate or lithium hydroxide.
The pretreatment material and a lithium source are mixed according to the molar ratio of titanium element in the pretreatment material to lithium element in the lithium source, namely Ti to Li, of 1:0.79-0.84, and ground for 30-60min after mixing, wherein the grinding method comprises the following steps: cleaning a mortar by using cleaning powder, washing the mortar by using deionized water for three times, washing the mortar by using absolute ethyl alcohol for three times, putting the washed mortar into an electrothermal blowing drying oven at 50-60 ℃ for 5-10min, drying the mortar, weighing the pretreatment material and a lithium source respectively, pouring the pretreatment material and the lithium source into the mortar, and manually grinding the mixture for 30-60 min.
The temperature rise and heat preservation calcining temperature of the material after the pretreatment material is mixed with the lithium source is 750-950 ℃, the time is 6-8h, and the temperature rise rate is 2 ℃/min.
The invention also provides application of the layered lithium titanate as an energy storage material in preparation of a lithium ion battery.
The invention has the following advantages:
(1) the method is simple and feasible, and only one device capable of circulating gas and heating is needed to be provided without complex preparation conditions and materials so that the MXene material and the mixed material can be calcined.
(2) The invention is green and environment-friendly, does not produce polluting and toxic gases and meets the environmental protection standard.
(3) The heating temperature is not over 1000 ℃ in the experimental process, and the safety standard is met.
(4) The method uses MXene material for pretreatment to prepare the layered lithium titanate, regulates and controls the diffusion, the embedding/the separation of lithium ions in the electrode material, hardly has volume change, improves the electrochemical performance and the like, and has good application prospect.
Drawings
FIG. 1 shows MXene-Ti in example 1 of the present invention2SEM image of material C;
FIG. 2 shows TiO prepared in step (2) of example 1 of the present invention2SEM picture of (1);
FIG. 3 is an SEM image of a lithium titanate prepared in example 1 of the present invention;
FIG. 4 is an XRD pattern of lithium titanate prepared in example 1 of the present invention;
FIG. 5 is a first charge-discharge curve diagram of the lithium ion battery of example 1 of the present invention;
fig. 6 is a plot of the cycling performance and coulombic efficiency of the lithium ion battery of example 1 of the present invention;
FIG. 7 is an SEM image of a lithium titanate prepared in comparative example 1 of the present invention;
FIG. 8 is a graph showing the first charge and discharge of a lithium ion battery according to comparative example 1 of the present invention;
fig. 9 is a graph of cycle performance and coulombic efficiency for the lithium ion battery of comparative example 1 of the present invention.
Detailed Description
In order that the invention may be better understood, reference will now be made to the following examples which illustrate the invention.
Example 1
A preparation method of layered lithium titanate comprises the following specific steps:
(1) business supportPretreating titanium base MXene: 10g of commercial MXene-Ti were weighed2Adding the powder C into 1000mL of NaOH solution with the concentration of 1mol/L to remove Al element in MXene, stirring for 5min by using a glass rod, pouring the mixed solution into centrifuge tubes, pouring equivalent deionized water into a blank centrifuge tube, centrifuging the centrifuge tubes for 20min at the speed of 4000rpm, pouring the centrifuged supernatant, drying the centrifugally collected material in a 60 ℃ drying oven for 12h, grinding the dried material for 30min by using a mortar due to agglomeration to obtain a pretreated material A;
(2) preparation of TiO2: spreading the pretreatment material A in a crucible, placing the crucible in a muffle furnace, heating to 560 ℃ at a heating rate of 2 ℃/min in an oxygen atmosphere, carrying out heat preservation oxidation treatment for 6 hours, wherein the oxygen flow rate is 4mL/min, continuously introducing oxygen to cool to room temperature after the heat preservation is finished, and collecting a product to obtain layered TiO2Namely, the pretreatment material B;
(3) preparing lithium titanate: weighing the product pretreatment material B-TiO prepared in the step (2)25g of powder and TiO2The molar ratio of the titanium element in the powder to the lithium element in the lithium source is 1:0.816, and lithium source lithium carbonate is weighed and mixed and ground by using a mortar, wherein the grinding method comprises the following steps: cleaning a mortar by using cleaning powder, rinsing the mortar by using deionized water for three times, rinsing the mortar by using absolute ethyl alcohol for three times, putting the washed mortar into a 60 ℃ electric heating blast drying oven for 5min, drying the mortar, weighing the product obtained in the step (1) and a lithium source respectively, pouring the product and the lithium source into the mortar, manually grinding the mixture for 30min, spreading the mixed material in a crucible, putting the crucible into a muffle furnace, heating the mixture to 850 ℃ at a heating rate of 2 ℃/min in an air atmosphere, carrying out heat preservation and calcination treatment for 6h, cooling the temperature to room temperature after the heat preservation is finished, and collecting the product to obtain the layered lithium titanate.
FIG. 1 shows Ti used in this example2C, SEM image of powder material, wherein the material is in a layered structure.
FIG. 2 shows TiO prepared in this example2SEM image of the material, from which it can be seen that the material is a layered structure.
Fig. 3 is an SEM image of the lithium titanate material prepared in this example, and it can be seen from the SEM image that the material has a layered structure.
Fig. 4 is an XRD pattern of the lithium titanate material prepared in this example, and it can be seen that the prepared material is lithium titanate.
Energy storage performance study:
1. mixing the prepared lithium titanate, conductive carbon black (SP) and polyvinylidene fluoride (PVDF) for 0.5h according to the mass ratio of 8:1:1, adding N-methylpyrrolidone (NMP) solvent, manually grinding for 5min to form black slurry, coating the slurry on a copper foil current collector according to the thickness of 100 mu m, drying the slurry in vacuum at 110 ℃ for 12h, taking a lithium titanate electrode plate as a lithium ion negative electrode battery, and assembling the battery in a glove box filled with argon, wherein the assembling process is as follows: cutting the dried pole piece into a round pole piece with the diameter of 13mm, namely 1.0MLiPF6And the battery is a button lithium ion negative electrode battery which is assembled by using inEC, DMC, DEC, 1:1:1 Vol% as an electrolyte, Celgard 2400 as a diaphragm, a lithium sheet with the diameter of 15mm as a reference electrode and a counter electrode and CR2016 type stainless steel as a battery shell.
Testing the electrochemical performance, and when the material is static for 8 hours at 25 ℃ and is subjected to charge-discharge circulation between 1.0V and 3.0V at the rate of 5C, the first charge-discharge specific capacity can reach 177mAh/g, and a first charge-discharge curve chart is shown in figure 5; after 100 cycles, the specific capacity is kept at 82%, the coulombic efficiency is kept at 100%, and a cycle performance and coulombic efficiency curve graph is shown in fig. 6, which shows that the layered lithium titanate prepared by the embodiment has excellent electrochemical performance when being applied to a lithium ion battery as a negative electrode material, and is a good negative electrode material in the lithium ion battery.
Example 2
A preparation method of layered lithium titanate comprises the following specific steps:
(1) pretreatment of commercial titanium-based MXene: weighing 10g of commercial titanium-based MXene-Ti2Adding the powder C into 1000mL of 2mol/L NaOH solution to remove Al element in MXene, stirring for 10min by using a glass rod, pouring the mixed solution into centrifuge tubes, pouring equivalent deionized water into a blank centrifuge tube, placing two centrifuge tubes on a centrifuge, centrifuging for 30min at 5000rpm, pouring out the centrifuged supernatant,drying the centrifugally collected materials in a 50 ℃ oven for 24h, grinding the dried materials for 60min by using a mortar due to agglomeration to obtain a pretreated material A;
(2) preparation of TiO2: spreading the pretreatment material A in a crucible, placing the crucible in a muffle furnace, heating to 660 ℃ at a heating rate of 2 ℃/min in an oxygen atmosphere, carrying out heat preservation oxidation treatment for 5 hours, wherein the oxygen flow rate is 2mL/min, continuously introducing oxygen to cool to room temperature after the heat preservation is finished, and collecting a product to obtain layered TiO2Namely, the pretreatment material B;
(3) preparing lithium titanate: weighing the product pretreatment material B-TiO prepared in the step (2)25g of powder and TiO2The molar ratio of the titanium element in the powder to the lithium element in the lithium source is 1:0.79, and lithium source lithium carbonate is weighed and mixed and ground by using a mortar, wherein the grinding method comprises the following steps: cleaning a mortar by using cleaning powder, rinsing the mortar by using deionized water for three times, rinsing the mortar by using absolute ethyl alcohol for three times, putting the washed mortar into a 50 ℃ electric heating forced air drying oven for 10min, drying the mortar, weighing the product obtained in the step (1) and a lithium source respectively, pouring the product and the lithium source into the mortar, manually grinding the mixture for 40min, spreading the mixed material in a crucible, putting the crucible into a muffle furnace, heating the mixture to 750 ℃ at a heating rate of 2 ℃/min under an air atmosphere, carrying out heat preservation and calcination treatment for 8h, cooling the temperature to room temperature after the heat preservation is finished, and collecting the product to obtain the layered lithium titanate.
The characterization was performed as in example 1, and a lithium ion battery was assembled to study the battery performance.
Example 3
A preparation method of layered lithium titanate comprises the following specific steps:
(1) pretreatment of commercial titanium-based MXene: weighing 10g of commercial titanium-based MXene-Ti3C2Adding the powder into 1000mL of NaOH solution with the concentration of 1mol/L to remove Al element in MXene, stirring for 8min by using a glass rod, pouring the mixed solution into centrifuge tubes, pouring equivalent deionized water into a blank centrifuge tube, placing two centrifuge tubes on a centrifuge, centrifuging for 30min at the speed of 4500rpm, pouring out the centrifuged supernatant, placing the centrifugally collected materials into a 55 ℃ oven for drying for 18h, and using grinding for the dried materials due to cakingGrinding in a bowl for 40min to obtain a pretreatment material A;
(2) preparation of TiO2: spreading the pretreatment material A in a crucible, placing the crucible in a muffle furnace, heating to 700 ℃ at a heating rate of 2 ℃/min in an oxygen atmosphere, carrying out heat preservation oxidation treatment for 4 hours, wherein the oxygen flow rate is 3mL/min, continuously introducing oxygen to cool to room temperature after the heat preservation is finished, and collecting a product to obtain layered TiO2Namely, the pretreatment material B;
(3) preparing lithium titanate: weighing the product pretreatment material B-TiO prepared in the step (2)25g of powder and TiO2The molar ratio of the titanium element in the powder to the lithium element in the lithium source is 1:0.84, the lithium source lithium hydroxide is weighed, mixed and ground by using a mortar, and the grinding method is as follows: cleaning a mortar by using cleaning powder, rinsing the mortar by using deionized water for three times, rinsing the mortar by using absolute ethyl alcohol for three times, putting the washed mortar into an electrothermal blowing drying oven with the temperature of 55 ℃ for 6min, drying the mortar, weighing the product obtained in the step (1) and a lithium source respectively, pouring the product and the lithium source into the mortar, manually grinding the mixture for 50min, spreading the mixed material in a crucible, putting the crucible into a muffle furnace, heating the mixture to 750 ℃ at the heating rate of 2 ℃/min under the air atmosphere, carrying out heat preservation and calcination treatment for 7h, cooling the temperature to room temperature after the heat preservation is finished, and collecting the product to obtain the layered lithium titanate.
The characterization was performed as in example 1, and a lithium ion battery was assembled to study the battery performance.
Example 4
A preparation method of layered lithium titanate comprises the following specific steps:
(1) pretreatment of commercial titanium-based MXene: weighing 15g of commercial titanium-based MXene-Ti3C2Adding the powder into 1000mL of NaOH solution with the concentration of 1.5mol/L to remove Al element in MXene, stirring for 5min by using a glass rod, pouring the mixed solution into centrifuge tubes, pouring equivalent deionized water into a blank centrifuge tube, placing two centrifuge tubes on a centrifuge, centrifuging for 40min at the speed of 4000rpm, pouring the centrifuged supernatant, placing the centrifugally collected material into a 50 ℃ oven for drying for 20h, grinding the dried material for 40min by using a mortar for grinding due to agglomeration to obtain a pretreated material A;
(2) system for makingPreparation of TiO2: spreading the pretreatment material A in a crucible, placing the crucible in a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min in an oxygen atmosphere, carrying out heat preservation oxidation treatment for 5 hours, wherein the flow rate of oxygen is 5mL/min, continuously introducing oxygen to cool to room temperature after the heat preservation is finished, and collecting a product to obtain layered TiO2Namely, the pretreatment material B;
(3) preparing lithium titanate: weighing the product pretreatment material B-TiO prepared in the step (2)25g of powder and TiO2The molar ratio of the titanium element in the powder to the lithium element in the lithium source is 1:0.82, and lithium source lithium carbonate is weighed and mixed and ground by using a mortar, wherein the grinding method comprises the following steps: cleaning a mortar by using cleaning powder, rinsing the mortar by using deionized water for three times, rinsing the mortar by using absolute ethyl alcohol for three times, putting the washed mortar into a 50 ℃ electric heating forced air drying oven for 10min, drying the mortar, weighing the product obtained in the step (1) and a lithium source respectively, pouring the product and the lithium source into the mortar, manually grinding the mixture for 60min, spreading the mixed material in a crucible, putting the crucible into a muffle furnace, heating the mixture to 950 ℃ at a heating rate of 2 ℃/min under an air atmosphere, carrying out heat preservation and calcination treatment for 6h, cooling the temperature to room temperature after the heat preservation is finished, and collecting the product to obtain the layered lithium titanate.
The characterization was performed as in example 1, and a lithium ion battery was assembled to study the battery performance.
Example 5
A preparation method of layered lithium titanate comprises the following specific steps:
(1) pretreatment of commercial titanium-based MXene: weighing 20g of commercial titanium-based MXene-Ti6C5Adding the powder into 1000mL of 2mol/L NaOH solution to remove Al element in MXene, stirring for 10min by using a glass rod, pouring the mixed solution into centrifuge tubes, pouring equivalent deionized water into a blank centrifuge tube, placing two centrifuge tubes on a centrifuge, centrifuging for 20min at 5000rpm, pouring the centrifuged supernatant, placing the centrifugally collected material into a 55 ℃ oven for drying for 18h, grinding the dried material for 50min by using a mortar due to agglomeration to obtain a pretreated material A;
(2) preparation of TiO2: spreading the pretreatment material A in a crucible, putting the crucible into a muffle furnace, and carrying out oxygen atmosphere treatmentHeating to 560 ℃ at a heating rate of 2 ℃/min, carrying out heat preservation oxidation treatment for 6h with the oxygen flow rate of 4mL/min, continuously introducing oxygen to reduce the temperature to room temperature after the heat preservation is finished, and collecting the product to obtain layered TiO2Namely, the pretreatment material B;
(3) preparing lithium titanate: weighing the product pretreatment material B-TiO prepared in the step (2)25g of powder and TiO2The molar ratio of the titanium element in the powder to the lithium element in the lithium source is 1:0.816, and the lithium source lithium hydroxide is weighed and mixed and ground by using a mortar, wherein the grinding method comprises the following steps: cleaning a mortar by using cleaning powder, rinsing the mortar by using deionized water for three times, rinsing the mortar by using absolute ethyl alcohol for three times, putting the washed mortar into a 60 ℃ electric heating blast drying oven for 5min, drying the mortar, weighing the product obtained in the step (1) and a lithium source respectively, pouring the product and the lithium source into the mortar, manually grinding the mixture for 30min, spreading the mixed material in a crucible, putting the crucible into a muffle furnace, heating the mixture to 850 ℃ at a heating rate of 2 ℃/min under the air atmosphere, carrying out heat preservation and calcination treatment for 7h, cooling the temperature to room temperature after the heat preservation is finished, and collecting the product to obtain the layered lithium titanate.
The characterization was performed as in example 1, and the lithium ion battery was assembled to investigate the battery performance.
With reference to the method of example 5, lithium titanate was prepared according to the following table 1 with different molar ratios of lithium to titanium and different calcination temperatures, and assembled into a lithium ion battery, the performance of the battery was investigated, and the specific capacity after 100 cycles at a rate of 3C was determined as follows table 1:
TABLE 1
Example 6
A preparation method of layered lithium titanate comprises the following specific steps:
(1) pretreatment of commercial titanium-based MXene: 20g of commercial MXene-Ti were weighed2Adding the C powder into 1000mL of 1mol/L NaOH solution to remove Al element in MXene, stirring for 8min by using a glass rod, pouring the mixed solution into centrifuge tubes, pouring an equal amount of deionized water into a blank centrifuge tube, and pouring two centrifuge tubes into the centrifuge tubesCentrifuging for 40min at 4000rpm on a centrifuge, pouring off the centrifuged supernatant, drying the centrifugally collected materials in a 60 ℃ oven for 12h, grinding the dried materials for 30min by using a mortar due to agglomeration to obtain a pretreated material A;
(2) preparing lithium titanate: weighing the pretreatment material A and lithium source lithium carbonate according to the molar ratio of the titanium element to the lithium element of 1:0.816, mixing and grinding by using a mortar, wherein the grinding method comprises the following steps: cleaning a mortar by using cleaning powder, rinsing the mortar by using deionized water for three times, rinsing the mortar by using absolute ethyl alcohol for three times, putting the washed mortar into a 60 ℃ electric heating blast drying oven for 5min, drying the mortar, weighing the product obtained in the step (1) and a lithium source respectively, pouring the product and the lithium source into the mortar, manually grinding the mixture for 60min, spreading the mixed material in a crucible, putting the crucible into a muffle furnace, heating the mixture to 850 ℃ at a heating rate of 2 ℃/min under the air atmosphere, carrying out heat preservation and calcination treatment for 7h, cooling the temperature to room temperature after the heat preservation is finished, and collecting the product to obtain the layered lithium titanate.
The characterization was performed as in example 1, and the lithium ion battery was assembled to investigate the battery performance.
Example 7
A preparation method of layered lithium titanate comprises the following specific steps:
(1) pretreatment of commercial titanium-based MXene: weighing 15g of commercial MXene-Ti3C2Adding the powder into 1000mL of NaOH solution with the concentration of 1.5mol/L to remove Al element in MXene, stirring for 10min by using a glass rod, pouring the mixed solution into centrifuge tubes, pouring equivalent deionized water into a blank centrifuge tube, centrifuging the centrifuge tubes for 20min at the speed of 5000rpm, pouring the centrifuged supernatant, drying the centrifugally collected material in a 50 ℃ drying oven for 24h, grinding the dried material for 40min by using a mortar due to agglomeration to obtain a pretreated material A;
(2) preparing lithium titanate: weighing the pretreatment material A and lithium source lithium carbonate according to the molar ratio of the titanium element to the lithium element of 1:0.84, mixing and grinding by using a mortar, wherein the grinding method comprises the following steps: cleaning a mortar by using cleaning powder, rinsing the mortar by using deionized water for three times, rinsing the mortar by using absolute ethyl alcohol for three times, putting the washed mortar into a 60 ℃ electric heating blast drying oven for 5min, drying the mortar, weighing the product obtained in the step (1) and a lithium source respectively, pouring the product and the lithium source into the mortar, manually grinding the mixture for 40min, spreading the mixed material in a crucible, putting the crucible into a muffle furnace, heating the mixture to 950 ℃ at a heating rate of 2 ℃/min under an air atmosphere, carrying out heat preservation and calcination treatment for 6h, cooling the temperature to room temperature after the heat preservation is finished, and collecting the product to obtain the layered lithium titanate.
The characterization was performed as in example 1, and the lithium ion battery was assembled to investigate the battery performance.
Example 8
A preparation method of layered lithium titanate comprises the following specific steps:
(1) pretreatment of commercial titanium-based MXene: 10g of commercial MXene-Ti were weighed6C5Adding the powder into 1000mL of 2mol/L NaOH solution to remove Al element in MXene, stirring for 5min by using a glass rod, pouring the mixed solution into centrifuge tubes, pouring equivalent deionized water into a blank centrifuge tube, centrifuging the centrifuge tubes for 25min at 4500rpm, pouring the centrifuged supernatant, drying the centrifugally collected material in a 55 ℃ oven for 18h, grinding the dried material for 60min by using a mortar due to agglomeration to obtain a pretreated material A;
(2) preparing lithium titanate: weighing the pretreatment material A and lithium source lithium hydroxide according to the molar ratio of the titanium element to the lithium element of 1:0.79, mixing and grinding by using a mortar, wherein the grinding method comprises the following steps: cleaning a mortar by using cleaning powder, rinsing the mortar by using deionized water for three times, rinsing the mortar by using absolute ethyl alcohol for three times, putting the washed mortar into a 60 ℃ electric heating blast drying oven for 5min, drying the mortar, weighing the product obtained in the step (1) and a lithium source respectively, pouring the product and the lithium source into the mortar, manually grinding the mixture for 30min, spreading the mixed material in a crucible, putting the crucible into a muffle furnace, heating the mixture to 750 ℃ at a heating rate of 2 ℃/min under an air atmosphere, carrying out heat preservation and calcination treatment for 8h, cooling the temperature to room temperature after the heat preservation is finished, and collecting the product to obtain the layered lithium titanate.
The characterization was performed as in example 1, and the lithium ion battery was assembled to investigate the battery performance.
With reference to the method of example 8, lithium titanate was prepared according to the following table 2 with different molar ratios of lithium to titanium and different calcination temperatures, and assembled into a lithium ion battery, the performance of the battery was investigated, and the specific capacity after 100 cycles at a rate of 3C was found to be as follows in table 2:
TABLE 2
Comparative example 1
A preparation method of granular lithium titanate comprises the following specific steps:
according to the molar ratio of the titanium element to the lithium element of 1:0.79, weighing commercial granular titanium oxide and lithium carbonate, mixing and grinding by using a mortar, wherein the grinding method comprises the following steps: cleaning a mortar by using cleaning powder, rinsing the mortar by using deionized water for three times, rinsing the mortar by using absolute ethyl alcohol for three times, putting the washed mortar into an electrothermal blowing drying oven with the temperature of 60 ℃ for 5min, drying the mortar, weighing the product obtained in the step (1) and a lithium source respectively, pouring the product and the lithium source into the mortar, manually grinding the mixture for 30min, spreading the mixed material in a crucible, putting the crucible into a muffle furnace, heating the mixture to 850 ℃ at the heating rate of 2 ℃/min in the air atmosphere, carrying out heat preservation oxidation treatment for 6h, and then cooling the mixture to the room temperature to prepare the granular lithium titanate.
Fig. 7 is an SEM image of the lithium titanate material prepared in comparative example 1, and it can be seen from the SEM image that the material has a granular structure, the morphology structure of which is greatly different from the porous layered structure prepared in the above example, and the granular structure is not favorable for migration of lithium ions, resulting in low battery capacity and poor cycle performance.
The lithium ion battery is assembled according to the method in the embodiment 1, the battery performance is researched, the initial charge-discharge specific capacity of the assembled lithium ion battery is only 99mAh/g, the initial charge-discharge curve graph is shown in fig. 8, the capacity retention rate of 100 cycles is about 63%, the cycle performance and coulombic efficiency curve graph is shown in fig. 9, and the result shows that the electrochemical performance of the granular lithium titanate applied to the lithium ion battery cathode is poor and the granular lithium titanate is not suitable for being applied to the lithium ion battery cathode.
Although the present invention has been described above by reference to the exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of layered lithium titanate is characterized by comprising the following specific steps:
after titanium-based MXene is pretreated, the pretreated material and a lithium source are mixed and ground, the mixed material is heated, insulated and calcined in the air atmosphere, and the layered lithium titanate is obtained after cooling.
2. The method for preparing layered lithium titanate as claimed in claim 1, wherein the titanium-based MXene material is Tin+1CnOr Tin+1CnTxWherein n is a natural number excluding 0, TxRepresents a surface functional group and is-O, -F or-OH.
3. The method for preparing layered lithium titanate according to claim 1, wherein the titanium-based MXene material is pretreated by the following method: adding titanium-based MXene powder into a NaOH solution with the concentration of 1-2mol/L, stirring for 5-10min, centrifuging the mixed solution at the speed of 4000-5000rpm for 20-40min, drying the centrifugally collected material at 50-60 ℃ for 12-24h, grinding the dried material for 30-60min, and taking the dried material as a pretreatment material A.
4. The method for preparing layered lithium titanate according to claim 3, wherein the mass-to-volume ratio g/mL of the titanium-based MXene powder to the NaOH solution is 1-2: 100.
5. The method for preparing layered lithium titanate according to claim 1, wherein the titanium-based MXene material is pretreated by the following method: adding titanium-based MXene powder into a NaOH solution with the concentration of 1-2mol/L, stirring for 5-10min, centrifuging the mixed solution at the speed of 4000 plus 5000rpm for 20-40min, drying the centrifugally collected material at 50-60 ℃ for 12-24h, grinding the dried material for 30-60min, heating, preserving heat and oxidizing the dried material in an oxygen atmosphere, continuously introducing oxygen, and cooling to room temperature to obtain a pretreated material B.
6. The method for preparing layered lithium titanate as claimed in claim 5, wherein the flow rate of oxygen is 2-5mL/min, the temperature rise and temperature preservation oxidation temperature is 560-700 ℃, the time is 4-6h, and the temperature rise rate is 2 ℃/min.
7. The method for producing layered lithium titanate as claimed in claim 1, wherein the lithium source is lithium carbonate or lithium hydroxide.
8. The method for producing layered lithium titanate according to claim 1, wherein the pretreatment material is mixed with a lithium source in such a ratio that the molar ratio of titanium to lithium elements, Ti to Li, is 1:0.79 to 0.84, and the mixture is ground for 30 to 60 minutes.
9. The method for preparing layered lithium titanate as claimed in claim 1, wherein the temperature-raising and temperature-maintaining calcination temperature is 750-.
10. Use of the layered lithium titanate of claim 1 as an energy storage material in the preparation of a lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111017561.9A CN113764639A (en) | 2021-08-31 | 2021-08-31 | Preparation method and application of layered lithium titanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111017561.9A CN113764639A (en) | 2021-08-31 | 2021-08-31 | Preparation method and application of layered lithium titanate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113764639A true CN113764639A (en) | 2021-12-07 |
Family
ID=78792334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111017561.9A Pending CN113764639A (en) | 2021-08-31 | 2021-08-31 | Preparation method and application of layered lithium titanate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113764639A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085920A (en) * | 2014-07-09 | 2014-10-08 | 河海大学 | Preparation method for two-dimensional sheet-shaped titanium dioxide nanosheet material |
| CN105197992A (en) * | 2015-09-10 | 2015-12-30 | 同济大学 | Preparation method of lamellar stacking titanium dioxide nanoparticles |
| CN112520785A (en) * | 2020-11-02 | 2021-03-19 | 江苏理工学院 | Preparation method of lithium titanate nanoparticles with layered structure |
-
2021
- 2021-08-31 CN CN202111017561.9A patent/CN113764639A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085920A (en) * | 2014-07-09 | 2014-10-08 | 河海大学 | Preparation method for two-dimensional sheet-shaped titanium dioxide nanosheet material |
| CN105197992A (en) * | 2015-09-10 | 2015-12-30 | 同济大学 | Preparation method of lamellar stacking titanium dioxide nanoparticles |
| CN112520785A (en) * | 2020-11-02 | 2021-03-19 | 江苏理工学院 | Preparation method of lithium titanate nanoparticles with layered structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104022266B (en) | A kind of silicon-based anode material and preparation method thereof | |
| CN107732205B (en) | Method for preparing sulfur-nitrogen co-doped carbon-coated nano flower-shaped lithium titanate composite negative electrode material | |
| CN102394305A (en) | Foamy copper oxide/copper lithium ion battery anode and preparation method thereof | |
| CN109659511B (en) | SiO (silicon dioxide)2Coated ternary positive electrode material and preparation method thereof | |
| CN115259132B (en) | Preparation method and application of ultra-high first-effect hard carbon anode material | |
| CN111244414A (en) | Method for preparing silicon-carbon negative electrode material by magnesiothermic reduction | |
| CN107302083A (en) | A kind of solid reaction process preparation method of nickel lithium manganate cathode material | |
| CN106654245A (en) | Preparation method of cobalt-doped nano tungsten oxide negative electrode material | |
| CN106611847A (en) | Preparation method of titanium-doped nano tungsten oxide negative electrode material | |
| CN103490040A (en) | Preparation method of lithium titanate-graphene composite material | |
| CN110767901A (en) | Preserved plum-shaped iron diselenide electrode material and preparation method and application thereof | |
| CN110589791A (en) | Preparation method of tin-doped titanium pyrophosphate | |
| CN110627031A (en) | Preparation method of molybdenum-doped cobalt phosphide-carbon coral sheet composite material | |
| CN111646510A (en) | High-rate titanium niobium oxide microsphere and preparation method and application thereof | |
| CN109286002B (en) | Multi-bark biomass carbon-loaded red phosphorus sodium ion battery negative electrode material and preparation method thereof | |
| CN105047870A (en) | Nitrogen-doped carbon-coated silicon composite material and preparation method thereof | |
| CN111017903A (en) | High-performance carbon anode PAN hard carbon material and preparation method thereof | |
| CN112803018B (en) | Silicon-doped graphene composite material and preparation method and application thereof | |
| CN116425170B (en) | Pre-lithiated silicon-based composite material with stable structure, and preparation method and application thereof | |
| CN103296266B (en) | Zinc titanate lithium titanate cathode material of doped with Cu and preparation method thereof | |
| CN103378355A (en) | Alkali metal secondary battery as well as negative active substance, negative material and negative electrode thereof, and preparation method of negative active substance | |
| CN113410454A (en) | Preparation method and application of porous layered titanium dioxide | |
| CN116177520A (en) | High-performance hard carbon negative electrode material for low-temperature sodium ion battery and preparation method thereof | |
| CN115548290A (en) | Surface modification modified lithium-rich manganese-based cathode material and preparation method thereof | |
| CN113764639A (en) | Preparation method and application of layered lithium titanate |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20211207 |