CN109244387B - Method for improving capacity of 1.55V carbon-coated lithium titanate battery - Google Patents
Method for improving capacity of 1.55V carbon-coated lithium titanate battery Download PDFInfo
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- CN109244387B CN109244387B CN201810940706.4A CN201810940706A CN109244387B CN 109244387 B CN109244387 B CN 109244387B CN 201810940706 A CN201810940706 A CN 201810940706A CN 109244387 B CN109244387 B CN 109244387B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000007773 negative electrode material Substances 0.000 claims abstract description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008103 glucose Substances 0.000 claims abstract description 10
- 229910003451 terbium oxide Inorganic materials 0.000 claims abstract description 10
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 10
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 5
- 229910009864 Ti5/3O4 Inorganic materials 0.000 abstract description 4
- 238000012216 screening Methods 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- 238000007599 discharging Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000007600 charging Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910009866 Ti5O12 Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/48—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
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for improving the capacity of a 1.55V carbon-coated lithium titanate battery, which comprises the steps of grinding and uniformly mixing lithium hydroxide, titanium oxide, terbium oxide and glucose according to a certain proportion, calcining for 5-10 hours in a high-temperature furnace under the argon atmosphere, wherein the calcining temperature is 700-900 ℃, naturally cooling, crushing and screening to obtain a lithium titanate negative electrode material Li coated with C0.99Tb0.01Li1/3Ti5/3O4. The capacity of a 1.55V battery of lithium titanate synthesized by the hydrothermal reaction is 252 mAh/g.
Description
Technical Field
The invention relates to a lithium titanate battery, and particularly provides a method for improving the capacity of a 1.55V carbon-coated lithium titanate battery.
Background
20 nineties of the 20 th century, lithium titanate Li4Ti5O12The lithium ion battery cathode material is used as a novel lithium battery cathode material, and is valued for the characteristics of high safety, high stability, long service life and environmental protection. Lithium titanate is used as a negative electrode material to replace graphite, and can be combined with lithium manganate, ternary materials or lithium iron phosphate and other positive electrode materials to form a 2.4V or 1.9V lithium ion secondary battery. The lithium titanate battery has obvious advantages and obvious defects, such as relatively low energy density and weak cruising ability, which are determined by the voltage of a single battery to a great extent, and tests show that the gram capacity of lithium titanate is 174mAh/g theoretically when the lithium potential is 1.5V, and is only half of that of the traditional graphite cathode material, so that the lithium titanate battery has high requirement on the battery capacityLithium titanate batteries do not have much advantage, so the low capacity limits the amount of lithium titanate batteries, which is an objective shorthand for this technical route.
There are also methods for improving the capacity of lithium titanate batteries in the existing published documents, but most of them are realized by adding compounds or compounding or modifying silicon and carbon elements, such as the preparation method of a high-capacity lithium titanate negative electrode material disclosed in chinese patent application No. 201310219768.3; a preparation method of a high-capacity lithium titanate negative electrode material disclosed in Chinese patent application No. 201510331370.8; chinese patent application No. 201410541098.1 discloses a composite negative electrode material for a lithium ion battery, a preparation method thereof, a lithium ion battery negative electrode sheet, a lithium ion battery and the like. The techniques described in these publications apparently show that the capacity of the battery is high, but the methods adopted are all palliative and non-radical methods, and in practice, these methods have the following problems: firstly, although the capacity of the battery is high, the other performances of the battery are lost, for example, after silicon is doped, the cycle number of the battery formed by compounding is greatly reduced, so that the service life of the battery is shortened; secondly, the capacity of the battery is high, and the safety of the battery is reduced due to the unsafety of silicon materials.
Chinese patent application No. 201410541098.1 discloses a composite negative electrode material for a lithium ion battery, a preparation method thereof, a lithium ion battery negative electrode sheet and the lithium ion battery. The composite negative electrode material is prepared by ball-milling and mixing a proper amount of acetate or oxalate of at least one of nickel, cerium and chromium, a lithium source and a titanium source, sintering in an inert atmosphere to obtain a lithium titanate matrix material doped with carbon and at least one metal element of nickel, chromium and cerium, uniformly mixing the matrix material, a soluble carbon-containing organic binder, a nitrogen-containing carbon material and a solvent to obtain slurry, and carrying out spray drying and carbonization on the slurry. Although the composite negative electrode material has higher specific capacity, according to the advantages recorded in the specification (0027), the electrochemical performance of the composite negative electrode material can be effectively improved by effectively preventing the lithium titanate from reacting with the electrolyte in the charging and discharging process. According to the common knowledge in the art, the voltage of the lithium titanate battery synthesized by the mechanism is below 1.5, so that the document also cannot improve the capacity of the 1.55V lithium titanate battery.
Therefore, in order to improve the capacity of the 1.55V lithium titanate battery, a technical breakthrough must be made, starting from the improvement of the synthesis mechanism of the lithium titanate battery, so as to break the use bottleneck of the lithium titanate battery, and make the lithium titanate battery become a vital force of the new energy automobile battery technology.
Disclosure of Invention
In order to overcome the defects of the existing technology for improving the capacity of the lithium titanate battery, the invention provides a method for improving the capacity of the 1.55V carbon-coated lithium titanate battery, which has a different synthetic mechanism from the prior art, on the premise of not losing other performances of the battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for improving the capacity of a 1.55V carbon-coated lithium titanate battery is characterized by comprising the following steps:
the first step is as follows: weighing lithium hydroxide, titanium oxide, terbium oxide and glucose according to a certain proportion, wherein the molar ratio of lithium, titanium and terbium is required to be in accordance with 1.323:1.666:0.01, and the weight of the glucose is 20% of the total weight of the three raw materials of the lithium hydroxide, the titanium oxide and the terbium oxide;
step two, uniformly mixing the lithium hydroxide, the titanium oxide, the terbium oxide and the glucose with the grinding particle size smaller than 50nm according to the proportion, calcining for 5-10 hours in a high-temperature furnace under the argon atmosphere, wherein the calcining temperature is 700-900 ℃, naturally cooling, crushing and screening to obtain the lithium titanate negative electrode material Li coated with C0.99Tb0.01Li1/3Ti5/3O4。
The feasibility and positive effects of the invention are illustrated below from the crystal structure characteristics of lithium titanate and the reaction mechanism of the invention.
As is well known in the art, the basic principle of a lithium titanate battery is that corresponding lithium ions are inserted and released back and forth between a positive electrode and a negative electrode in the charging and discharging processes to complete the charging and discharging of the battery and the power supply to a load. However, due to Li4Ti5O12With stable spinelStone structure, space group Fd3m, wherein O2At the 32e position, constituting the FCC lattice, part of the Li + is located in the tetrahedral 8a interstitials, the remainder of the Li + and Ti4+ are located in the octahedral 16d interstitials, when foreign Li + intercalates into Li +4Ti5O12The lattice of (1) is such that these Li + initially occupy the 16c position and the Li + in the original tetrahedral 8a position also initially migrates to the octahedral 16c position, and finally all 16c positions are occupied by Li +, so its capacity is limited mainly by the number of octahedral voids that can accommodate Li +, i.e. the number of 16c, and therefore theoretically 3mol of lithium ions enter the 16c position at 1.55V of lithium titanate, the capacity of lithium titanate being 175 mAh/g.
According to the invention, terbium oxide is added into lithium hydroxide and titanium oxide, and the proportion of raw materials is designed, so that Tb occupies Li position, and Li at 8a position can not enter 16c position in the process of charging and discharging lithium ions due to the interaction between Li and Tb, therefore, theoretically, Li with molecular formula of Li can be obtained4Ti5O125mol of lithium ions of the lithium titanate enter a 16c position, so that the capacity of the 1.55V lithium titanate battery is improved, and the Li synthesized by the method is detected0.99Tb0.01Li1/3Ti5/3O4The capacity of a lithium titanate 1.55V battery is 252mAh/g, and the specific detection method is as follows:
the sample material prepared in the experiment is ground in a ceramic mortar for 30min and then is dried in a vacuum drying oven for 10h at 100 ℃ together with acetylene black and PVDF. The electrode active material, the acetylene black and the PVDF are prepared into slurry according to the mass ratio of 85:9:6 and evenly coated on an aluminum foil, the coated pole piece is dried in a vacuum drying oven at 120 ℃ for 12 hours, and then taken out and stamped to be weighed, and a battery is assembled.
The charge and discharge test system is as follows: standing → constant current discharging → standing → constant current charging → constant voltage charging, and the cut-off voltage is 1V-3V. And 0.1C is selected for multiplying power test.
And (3) testing temperature: at 25 ℃.
The capacity of the 1.55V lithium titanate monomer battery synthesized by the invention reaches 252mAh/g, so that the lithium titanate synthesized by the invention can be used as a negative electrode material to replace graphite, can be combined with a ternary material positive electrode material to form a 2.4V lithium ion secondary battery, the specific capacity of the battery can reach 108wh/kg, and the lithium titanate monomer battery can be used in occasions with higher battery capacity requirements, such as electric automobiles, so that the use bottleneck of lithium titanate batteries is broken.
Drawings
FIG. 1 is a charge-discharge curve plot for lithium titanate synthesized using the present invention;
fig. 2 SEM image of the synthesized lithium titanate.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings and the detailed implementation mode.
A method for improving the capacity of a 1.55V carbon-coated lithium titanate battery is characterized by comprising the following steps:
the first step is as follows: preparing the raw materials
Weighing four raw materials of lithium hydroxide, titanium oxide, terbium oxide and glucose, wherein the molar ratio of lithium, titanium and terbium is 1.323:1.666:0.01, and the weight of glucose is 20 percent of the total weight of the rest three raw materials
Step two, uniformly mixing the lithium hydroxide, the titanium oxide, the terbium oxide and the glucose with the grinding particle size smaller than 50nm, placing the mixture in a high-temperature furnace in an argon atmosphere, heating the mixture to 700-plus-material 900 ℃ at the heating rate of 12-18 ℃/min, then preserving the heat for 5-10 hours in the temperature section, naturally cooling the mixture, crushing and screening the mixture to obtain the lithium titanate negative electrode material Li coated with C shown in figure 20.99Tb0.01Li1/3Ti5/3O4。
Fig. 1 is a charge-discharge capacity curve diagram of the lithium titanate powder of the present invention, and it is seen from the graph that the 1.55V battery charge capacity of the lithium titanate material synthesized by the present invention is 252mAh/g when discharging at 0.1C rate within 1-3V voltage, and the specific test method is the test method described in the positive effect.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800307A (en) * | 2010-02-05 | 2010-08-11 | 中国科学院新疆理化技术研究所 | Method for preparing carbon-coated manganese-doped lithium titanate negative electrode material of lithium ion battery |
| CN102376945A (en) * | 2010-08-20 | 2012-03-14 | 三星Sdi株式会社 | Negative active material, method of preparing same, and rechargeable lithium battery including same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800307A (en) * | 2010-02-05 | 2010-08-11 | 中国科学院新疆理化技术研究所 | Method for preparing carbon-coated manganese-doped lithium titanate negative electrode material of lithium ion battery |
| CN102376945A (en) * | 2010-08-20 | 2012-03-14 | 三星Sdi株式会社 | Negative active material, method of preparing same, and rechargeable lithium battery including same |
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