CN112614967A - Preparation method of lithium ion battery anode material and product thereof - Google Patents
Preparation method of lithium ion battery anode material and product thereof Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- 239000010405 anode material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000011572 manganese Substances 0.000 claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 25
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229910003378 NaNbO3 Inorganic materials 0.000 claims description 7
- 229910052961 molybdenite Inorganic materials 0.000 claims description 7
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 7
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 4
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- MUPJWXCPTRQOKY-UHFFFAOYSA-N sodium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Na+].[Nb+5] MUPJWXCPTRQOKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910002983 Li2MnO3 Inorganic materials 0.000 claims description 3
- 229910013191 LiMO2 Inorganic materials 0.000 claims description 3
- 229910002993 LiMnO2 Inorganic materials 0.000 claims description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000004927 fusion Effects 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 3
- 239000004020 conductor Substances 0.000 abstract description 2
- 239000010416 ion conductor Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 229910001428 transition metal ion Inorganic materials 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001000 micrograph Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910006873 Li1+xMO2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 1
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 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
- 238000009776 industrial production Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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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- Engineering & Computer Science (AREA)
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- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lithium ion battery anode material and a product thereof, belonging to the technical field of electrochemical batteries, wherein the method comprises the following steps: mixing, granulating and sintering the lithium ion battery manganese-based positive electrode material and the modifier to obtain the lithium ion battery positive electrode material; the invention adopts the solid-phase fusion technology to uniformly modify the surface of the anode material by taking a high-electron conductor or a high-ion conductor as a modifier, and the thickness of the modification layer can be controlled by adjusting the mass ratio of the manganese-based anode material of the lithium ion battery to the modification body; the surface of the modified lithium ion battery anode material is more stable, the dissolution of transition metal ions and the generation of cracks among particles in the circulation process are slowed down, and the specific capacity and the circulation stability of the lithium ion battery anode material are effectively improved; the preparation method of the invention is environment-friendly, pollution-free and low in process cost.
Description
Technical Field
The invention belongs to the technical field of electrochemical cells, and particularly relates to a preparation method of a lithium ion battery anode material and a product thereof.
Background
At present, commercial lithium ion batteries are widely applied to portable electronic products, meanwhile, the conventional lithium ion batteries are being converted into power battery systems for high-power fields such as energy storage, pure electric vehicles, hybrid electric vehicles and the like, and the specific energy requirement of the high-power lithium ion power battery system reaches 300Wh/kg, so that the improvement of the specific capacity of the anode material plays a decisive role in the construction of the high-specific-capacity lithium ion batteries. Manganese-based materials such as Li for conventional lithium ion batteries2MnO4、LiMnO2And the requirement of the high-specific-capacity lithium ion battery is difficult to meet due to the lower theoretical specific capacity (less than 200 mAh/g); currently, based on Li2MnO3The layered lithium-rich cathode material Li1+xMO2The specific capacity of (M ═ Ni, Co and Mn) can reach more than 250mAh/g, and the lithium ion battery is one of the most possible positive electrode materials for realizing 300Wh/kg high specific energy lithium ion battery systems. In recent years, researchers have proposed using Li2MnO3Lithium-rich composite layered cathode material xLi as stable phase2MnO31-x LiMO2(wherein M ═ Mn, Ni, Co, Fe, Sn, Mo, etc.) (as in documents J. Mater. chem., 2007,17, 3112; J. Power sources,2010,195,834; electric. acta,2015,174,1167; electric. acta,2015,168,234; CN102088085A), it has the advantages of stable structure, high specific capacity, abundant manganese resource, low price and environmental protection, and is the most potential positive electrode material for power lithium ion batteries.
However, in practical application and production, the manganese-based material of the lithium ion battery is easy to dissolve from the positive electrode and deposit on the negative electrode under higher voltage. Manganese deposited on the negative electrode further catalyzes the decomposition of the electrolyte, so that an SEI film is thickened, the impedance is increased, and the cycle life, the capacity attenuation speed, the rate capability and the low-temperature performance of the material are poor. Therefore, a new method for preparing and modifying the manganese-based material is urgently found, so that the manganese-based material has better reversible capacity, cycle performance and rate charge-discharge performance, is simple in synthesis and manufacturing process, low in cost and good in batch stability, and meets the performance requirements of the power battery.
Currently, the commonly used modification methods for manganese-based Materials of lithium ion batteries mainly include coprecipitation (e.g., Applied Surface Science 355(2015) 1222- & 1228, Journal of alloys and Compounds 715(2017)105- & 111), sol-gel (e.g., Journal of Power Source 2002, 112(2) & 634; Journal of Power Source 2010,195 (21) & 7391; electrochemical acta 168(2015) 234- & 239), atomic layer deposition (ACS Applied Materials & Interfaces,2018,10(49),43131- & 43143), magnetron sputtering (Applied Materials & Interfaces,2014,6(12),9185- & 9193), and so on. The modification methods can enable the mixing of the raw materials to reach an atomic level, but the reaction process needs to strictly control experimental conditions, and the process is very complex, so that the industrial production is not facilitated.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a lithium ion battery anode material and a product thereof.
One of the technical schemes of the invention is as follows: a preparation method of a lithium ion battery anode material comprises the following steps:
and mixing, granulating and sintering the lithium ion battery manganese-based positive electrode material and the modifier to obtain the lithium ion battery positive electrode material.
Furthermore, the mass ratio of the manganese-based positive electrode material of the lithium ion battery to the modification body is 1: 0.01-0.1.
Furthermore, the mass ratio of the manganese-based positive electrode material of the lithium ion battery to the modified body is 1 to (0.03-0.06).
Further, the manganese-based positive electrode material of the lithium ion battery is one of a lithium manganese oxide, a nickel-cobalt-manganese ternary material and a lithium-rich manganese-based material.
Further, the lithium manganese oxide is LiMn2O4And LiMnO2At least one of (1).
Further, the lithium-rich manganese-based material is xLi2MnO3·(1-x)LiMO2Wherein x is more than 0 and less than 1, and M is at least one of Fe, Ni, Co and Mn.
Further, the nickel-cobalt-manganese ternary material is LiNi1-x-yCoxMnyO2。
Further, the modification body is MoS2And/or NaNbO3。
Further, the granulation is carried out in a granulator, the power is 1-5 KW, and the time is 3-15 min.
Furthermore, the granulation time is 5-12 min.
Further, the sintering is carried out in an air atmosphere or an oxygen-enriched atmosphere, the temperature is 300-500 ℃, and the time is 2-8 hours.
Still further, the oxygen-rich atmosphere has an oxygen volume fraction of 30%.
The second technical scheme of the invention is as follows: the lithium ion battery cathode material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the solid-phase fusion technology to uniformly modify the surface of the anode material by taking a high-electron conductor or a high-ion conductor as a modifier, and the thickness of the modification layer can be controlled by adjusting the mass ratio of the manganese-based anode material of the lithium ion battery to the modification body; the surface of the modified lithium ion battery anode material is more stable, the generation of intergranular cracks is slowed down, and the specific capacity and the cycling stability of the lithium ion battery anode material are effectively improved.
(2) The preparation method of the invention is environment-friendly, pollution-free and low in process cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a transmission electron microscope image of the lithium ion battery cathode material prepared in example 1.
Fig. 2 is a transmission electron microscope image of the lithium ion battery positive electrode material prepared in comparative example 1.
Fig. 3 is a scanning electron micrograph of the lithium ion battery positive electrode material prepared in example 1 before and after 250 charge and discharge cycles, wherein fig. 3a is the scanning electron micrograph before the charge and discharge cycles, and fig. 3b is the scanning electron micrograph after 250 charge and discharge cycles.
Fig. 4 is a scanning electron microscope image of the lithium ion battery positive electrode material prepared in comparative example 1 before and after a charge-discharge cycle, wherein fig. 4a is a scanning electron microscope image before a charge-discharge cycle, and fig. 4b is a scanning electron microscope image after a charge-discharge cycle of 250 times.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
The preparation method of the lithium ion battery anode material comprises the following steps:
weighing LiNi according to the mass ratio of 1: 0.030.5Co0.2Mn0.3O2，MoS2Uniformly mixing, placing in a mixing granulator, adjusting the power to 5KW, reacting for 5 minutes, taking out, placing in an atmosphere furnace, sintering for 7 hours at 350 ℃ in the air atmosphere, and naturally cooling to room temperature to obtain the lithium ion battery cathode material, wherein a transmission electron microscope image of the lithium ion battery cathode material is shown in figure 1.
Battery production and testing: 0.8g of the prepared lithium ion battery positive electrode material is weighed, 0.1g of acetylene black and 0.1g of PVDF (polyvinylidene fluoride) adhesive dissolved in N-dimethyl pyrrolidone are added, the mixture is uniformly mixed to form slurry, the slurry is uniformly coated on an aluminum foil, a metal lithium sheet is used as a counter electrode, Celgard2400 is a diaphragm, lmol/L LIPF6(EC: DEC: DMC ═ 1:1:1) is used as an electrolyte in an argon atmosphere glove box, a CR type button cell is assembled, a testing instrument is a LANDCT2001 type battery testing system, the battery is subjected to a charge-discharge cycle experiment at 25 ℃, the voltage range of 2.0V-4.6V and the multiplying power of 0.2C, the cycle number is 250, the first discharge specific capacity and the discharge specific capacity after the cycle number is 250 are recorded, and the results are shown in Table 1.
Example 2
Preparing a lithium ion battery anode material:
weighing Li according to the mass ratio of 1: 0.015: 0.0251.2Mn0.54Ni0.13Co0.13O2、MoS2And NaNbO3Uniformly mixing, placing in a mixing granulator, adjusting the power to 3KW, reacting for 7 minutes, taking out, placing in an atmosphere furnace, sintering for 3 hours at 450 ℃ in an oxygen-rich atmosphere (the volume fraction of oxygen is 30%), and naturally cooling to room temperature to obtain the lithium ion battery cathode material.
The battery was fabricated and tested in the same manner as in example 1 except that the voltage range was 2.0V-4.8V.
Example 3
Weighing Li according to the mass ratio of 1: 0.061.2Mn0.6Ni0.2O2And NaNbO3Uniformly mixing, placing in a mixing granulator, adjusting the power to 1KW, reacting for 12 minutes, taking out, placing in an atmosphere furnace, sintering for 2 hours at 500 ℃ in an oxygen-rich atmosphere (the volume fraction of oxygen is 30%), and naturally cooling to room temperature to obtain the lithium ion battery cathode material.
The battery was fabricated and tested in the same manner as in example 1 except that the voltage range was 2.0V-4.8V.
Example 4
Weighing LiMn according to the mass ratio of 1: 0.12O4And MoS2Uniformly mixing, placing in a mixing granulator, adjusting the power to 4KW, reacting for 6 minutes, taking out, placing in an atmosphere furnace, sintering at 300 ℃ for 8 hours in the air atmosphere, and naturally cooling to room temperature to obtain the lithium ion battery cathode material.
The battery was fabricated and tested in the same manner as in example 1 except that the voltage range was 3.0V-4.5V.
Example 5
Weighing LiMnO according to the mass ratio of 1: 0.0052、MoS2And NaNbO3Uniformly mixing, placing in a mixing granulator, adjusting power to 2KW, reacting for 8 minutes, taking out, placing in an atmosphere furnace, and placing in oxygen-enriched atmosphere (oxygen volume fraction is 30%) Sintering at 400 ℃ for 5h, and naturally cooling to room temperature to obtain the lithium ion battery anode material.
The battery was fabricated and tested in the same manner as in example 1 except that the voltage range was 2.0V-4.6V.
Comparative example 1
The difference from example 1 is that no MoS is added to the starting material2The transmission electron micrograph of the lithium ion battery cathode material prepared in this way is shown in fig. 2.
Comparative example 2
The difference from example 2 is that no MoS is added to the starting material2And NaNbO3。
Comparative example 3
The difference from example 3 is that NaNbO is not added to the starting material3。
Comparative example 4
The difference from example 4 is that no MoS is added to the starting material2。
Comparative example 5
The difference from example 5 is that no MoS is added to the starting material2And NaNbO3。
Comparative example 6
The difference from example 1 is that MoS2Replacement with CaCl2。
Observing the lithium ion battery anode materials prepared in the example 1 and the comparative example 1 by using a transmission electron microscope, wherein the lithium ion battery anode materials are respectively shown in a figure 1 and a figure 2;
observing the lithium ion battery cathode material prepared in example 1 before and after 250 charge-discharge cycles by using a scanning electron microscope, as shown in fig. 3, wherein fig. 3a is a scanning electron microscope image before the charge-discharge cycles, and fig. 3b is a scanning electron microscope image after 250 charge-discharge cycles;
the cross sections of the lithium ion battery positive electrode material prepared in the comparative example 1 before and after the charge-discharge cycle were observed by using a scanning electron microscope, as shown in fig. 4, wherein fig. 4a is a scanning electron microscope image before the charge-discharge cycle, and fig. 4b is a scanning electron microscope image after the charge-discharge cycle was 250 times.
TABLE 1
As can be seen from FIGS. 1 and 2, MoS is used2The surface of the modified anode material is provided with a modified layer with the thickness of 10 nm. As can be seen from fig. 1-4 and table 1, the lithium ion battery cathode material with a surface modification layer prepared by the solid-phase fusion technology of the present invention can effectively improve the structural stability of the lithium ion battery cathode material, and can effectively improve the specific capacity and the cycle stability of the lithium battery, thereby laying a foundation for realizing long cycle of the lithium ion battery high-voltage cathode material.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (8)
1. A preparation method of a lithium ion battery anode material is characterized by comprising the following steps:
and mixing, granulating and sintering the lithium ion battery manganese-based positive electrode material and the modifier to obtain the lithium ion battery positive electrode material.
2. The preparation method according to claim 1, wherein the mass ratio of the manganese-based positive electrode material to the modified body of the lithium ion battery is 1: 0.01-0.1.
3. The method of claim 1, wherein the lithium ion battery manganese-based positive electrode material is one of a lithium manganese oxide, a nickel-cobalt-manganese ternary material, and a lithium-rich manganese-based material.
4. The method according to claim 3, wherein the lithium manganese oxide is LiMn2O4And LiMnO2At least one of (1).
5. The method of claim 3, wherein the lithium-rich manganese-based material isXLi2MnO3·(1-x)LiMO2Wherein x is more than 0 and less than 1, and M is at least one of Fe, Ni, Co and Mn.
6. The production method according to claim 1, wherein the modified body is MoS2And/or NaNbO3。
7. The method according to claim 1, wherein the sintering is performed in an air atmosphere or an oxygen-rich atmosphere at a temperature of 300 to 500 ℃ for 2 to 8 hours.
8. The lithium ion battery positive electrode material prepared by the preparation method according to any one of claims 1 to 7.
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