CN103199236A - Doped lithium manganate precursor, modified lithium manganate positive electrode material and preparation method thereof - Google Patents
Doped lithium manganate precursor, modified lithium manganate positive electrode material and preparation method thereof Download PDFInfo
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002243 precursor Substances 0.000 title claims abstract description 42
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 230000002441 reversible effect Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 37
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- 239000010405 anode material Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 abstract description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 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
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a doped lithium manganate precursor, a modified lithium manganate positive electrode material and a preparation method thereof. Firstly, metal manganese and doping metal are used for preparing a metal alloy according to a certain molar ratio, and then the metal alloy is fully oxidized to obtain the doped lithium manganate precursor. The preparation method of a lithium ion battery positive electrode material by utilizing the doped lithium manganate precursor comprises the following steps of: crushing the doped lithium manganate precursor; and adding 45%-50% by mole of lithium salt into the crushed precursor, then performing ball milling and drying, and then calcining to obtain an initial doped lithium manganate positive electrode material. The tap density of the modified lithium manganate positive electrode material is not less than 2.6g/cm<3>, a button cell produced by the product is tested, 1C charge and discharge are performed, and when the discharge achieves 2.4V, the reversible discharge capacity is 175mAh/g- 260mAh/g; and when the discharge achieves 2.75V, the reversible discharge capacity is 135mAh/g-185mAh/g.
Description
Technical Field
The invention relates to a doped lithium manganate precursor, a modified lithium manganate positive electrode material and a preparation method thereof.
Background
In the composition of lithium ion batteries, the positive electrode material is the key to determine the performance of lithium ion batteries. In the commercial lithium ion batteries at present, lithium cobaltate, ternary materials (cobalt nickel lithium manganate), lithium manganate and lithium iron phosphate are mainly used as the positive electrode material. Lithium manganate has become a main choice for the anode material of power lithium ion batteries in the fields of electric automobiles, electric bicycles, electric tools and the like due to the characteristics of abundant resources, low price, good safety, no environmental pollution, relatively simple manufacturing process and the like.
LiMn with spinel structure of lithium manganate2O4And a layered LiMnO2Two types of LiMn, which have spinel structures for commercial applications2O4. Spinel structure LiMn2O4The potential for intercalation and deintercalation of metallic lithium is about 4V, the theoretical capacity is 148mAh/g, and the actual capacity is mostly 100-120 mAh/g.
The lithium manganate has the advantages, but also has the defects of low specific capacity, short cycle life and serious capacity attenuation in the high-temperature charge-discharge cycle process. The source of these problems is that the lithium manganate formed by combining a lithium manganate precursor (including manganese dioxide, manganese oxide, etc.) with a lithium salt has poor structural stability.
In order to improve the structural stability of lithium manganate, researchers have adopted various technical schemes, for example: carrying out bulk phase doping on a lithium manganate precursor by adopting a chemical method, and adding metal cations M (such as aluminum, cobalt, copper, nickel and the like) to stabilize crystal lattices (for example, a doping modification method is disclosed in Chinese patent with the publication number of CN 102201572A); the synthesis method of the lithium manganate precursor and the lithium salt is improved; coating the surface of lithium manganate; by using Mn3O4Substitution for MnO2As a precursor for synthesizing lithium manganate, etc. However, the modified lithium manganate battery products obtained by the methods have limited improvement degrees of cycle life and high-temperature performance, can not improve the specific capacity of lithium manganate, and mostly has the negative effect of reducing the battery capacity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a doped lithium manganate precursor, a modified lithium manganate positive electrode material and a preparation method thereof.
In order to solve the technical problems, the invention firstly provides a novel preparation method of a doped lithium manganate precursor, which comprises the following steps:
firstly, mixing manganese metal and doped metal according to a molar ratio of 1: preparing a metal alloy at a ratio of 0.02-1:0.35, and then completely oxidizing the metal alloy to obtain a doped lithium manganate precursor, wherein the doped metal is a metal corresponding to a metal oxide related to the existing oxide doping method.
The basis of the invention of the precursor preparation method is as follows: most of the existing lithium manganate doping modification adopts a chemical doping method, namely how to obtain a uniform mixture of metal-doped oxide and manganese oxide, and then calcining the mixture to form a precursor. However, the difference between the activity of the lithium manganate prepared by the precursor and the ideal value is large. The main reason is that manganese oxide (manganese dioxide, manganese sesquioxide and manganomanganic oxide) can not form stable compounds with other metal oxides except alkali metal and alkaline earth metal oxides, and is easily decomposed to form respective crystal grains in the subsequent lithium adding sintering process. Thus, the interaction between the lithium manganate crystal grains and the doped metal oxide crystal grains is limited to the crystal grain surfaces. In the working process of the lithium ion battery, lithium ions are inserted and extracted in the material crystal lattice. This is the theoretical basis for the less than ideal chemical doping effect.
The preparation method of the doped lithium manganate precursor comprises the following steps: firstly, obtaining an alloy of doped metal and metal manganese, wherein the doped metal and the metal manganese are uniformly dispersed in an atomic scale; and then, the alloy is completely oxidized to form a doped lithium manganate precursor with a compact structure. This precursor has the following characteristics: (1) the tap density is higher than that of chemical doping by more than 15%; (2) the doped metal oxide and the manganese oxide are uniformly dispersed in small-sized crystal grains, and the activity of the crystal grains is high; (3) the lattices are staggered with each other, so that the manganese oxide lattices are distorted, more lattice gaps are formed, and the activity of the manganese oxide is higher. Therefore, the doped lithium manganate prepared by the precursor material not only has improved cycle performance, but also has greatly improved capacity.
The resulting metal alloy can, in theory, be formed using any process and method that results in an alloy. Preferably, any one of the following two process methods is adopted:
one is the melting method. And putting the manganese metal and the doped metal into a melting furnace according to the molar ratio, filling protective gas, heating to 1250-. The method is simple, and the components are stable and uniformly dispersed.
The second is powder metallurgy. And putting the metal manganese powder and the doped metal powder into a high-speed ball mill according to the molar ratio, introducing argon gas for protection, and performing dry ball milling to achieve full mixing uniformity and preliminary alloying. And placing the mixed metal powder into a graphite die, and pressing and molding by using a press machine. Then heating the mixture by a hot isostatic pressing sintering furnace under the protection of argon, keeping the temperature for 1 to 2 hours when the temperature reaches 800 to 1200 ℃. This method does not require reaching the melting point of the alloy, but the compositional uniformity is inferior to the former.
The metal alloy is completely oxidized, and theoretically, any metal oxidation method can be adopted, including natural oxidation in the air. Preferably, a solid-phase calcination oxidation process is used, namely: calcining the metal alloy in a muffle furnace, and oxidizing the alloy by using oxygen in the air at the temperature of 600 ℃ and 900 ℃ for more than 10 hours.
The invention selects zinc, nickel, copper, indium, aluminum, cobalt and antimony, and comprises several of the metals which are matched according to any proportion. The basic idea of such a selection is: first, the strength and melting point of the metal are low; second, the atomic weight of the metal element is greater than that of manganese; thirdly, the calcined oxide of the metal is capable of combining with manganese oxide; fourth, the metal oxide should have some activity.
Based on the doped lithium manganate precursor, the invention further provides a doped lithium manganate cathode material and a preparation method thereof, wherein the preparation method comprises the following steps:
step one, crushing the precursor. Because of metal calcination, the particle size is too large, and if the particles are not crushed, lithium is difficult to diffuse uniformly during calcination with lithium. And if the lithium manganate particles are too large in size, the cohesion is too large, so that the lithium ion transmission resistance is too large, and the electrochemical performance is influenced. After the precursor is crushed, the calcination and the oxidation are fully facilitated.
The precursor crushing process comprises the following steps: the alloy is crushed and then calcined. The high-speed ball mill can be used for grinding, and other methods can also be used. Preferably, the crushing and the calcining are alternately carried out: calcining for more than 1 hour after primarily crushing the alloy, and performing dry ball milling for more than 0.5 hour by using a high-speed ball mill; calcining for 5-20 hours, and performing dry ball milling for more than 0.5 hour; then continuing calcining until all the catalyst is oxidized; and performing dry ball milling and wet ball milling for 0.5-4 hours again, drying and screening for later use.
And secondly, adding lithium salt with a molar ratio of 45-60% into the crushed precursor, wherein the lithium salt comprises lithium hydroxide, lithium carbonate and lithium acetate. And then, after ball milling (wet milling) and drying, firstly calcining at the low temperature of 500-600 ℃ for 1-10h in a muffle furnace, and then calcining at the high temperature of 700-900 ℃ for 10-60h (the temperature and the time are properly shortened), thus obtaining the initial doped lithium manganate cathode material.
Step three: and crushing, drying and screening the initially doped lithium manganate anode material to obtain the required doped lithium manganate anode material.
As a more optimized method, the preparation method of the modified lithium manganate cathode material further comprises the following four steps: and (3) reducing the doped lithium manganate positive electrode material prepared in the step (three) by using reducing gas (such as hydrogen, methane and the like) at the temperature of 100-300 ℃ for 30-180 minutes to obtain a better modified lithium manganate positive electrode material. The technical principle of the invention is that in the process of calcining the crushed precursor added with lithium salt in the step two, the crystal lattice of the precursor is propped open by lithium oxide, the activity is increased, and the lithium oxide has strong oxygen attraction to form lithium peroxide, so that a small amount of excessive oxygen permeates into lithium manganate. The amount of these oxygen, though small, seriously affects the material capacity (decrease in lithium ion charge) and cycle performance. So that the reduction reaction is adopted to remove the excessive oxygen permeated in the lithium manganate.
The tap density of the modified lithium manganate cathode material prepared by the method is more than or equal to 2.6g/cm3And the electrode filling processability is good. The button cell prepared by the product is detected, 1C is charged and discharged, when the voltage is discharged to 2.4V, the reversible discharge capacity is 175mAh/g-260 mAh/g; when the discharge voltage is 2.75V, the reversible discharge capacity is 135mAh/g-185 mAh/g. The theoretical capacity of the anode material 148mAh/g of the lithium manganate lithium ion battery with the spinel structure is obviously exceeded. Therefore, the method has great commercial application prospect and is worthy of wide popularization and application.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, which describe in detail and fully the preparation method from the preparation of doped lithium manganate precursor to the preparation of modified lithium manganate positive electrode material. The specific implementation steps are as follows:
step 1, preparing the manganese metal and the doped metal in the table into alloy according to the corresponding mol ratio. One skilled in the relevant art will appreciate that all methods of forming an alloy may be used to form the alloy. The specific methods employed in the examples include,
the method comprises the following steps: putting manganese metal and surface doped metal into a corundum crucible, putting the crucible into a melting furnace, filling protective gas argon, heating to 1250-. Or,
the method II comprises the following steps: mixing metal manganese powder and surface doped metal powder, placing the mixture in a high-speed ball mill, introducing argon gas for protection, and performing dry ball milling for 2-3 hours. And placing the ball-milled metal powder in a graphite die, and pressing and molding by using a press machine. Then heating the mixture by a hot isostatic pressing sintering furnace under the protection of argon, keeping the temperature for 1 to 2 hours when the temperature reaches 800 to 1200 ℃. And taking out the alloy after cooling, and primarily crushing.
And 2, oxidizing the alloy. One skilled in the relevant art will appreciate that all methods available for oxidation of alloys, even natural oxidation in air, may be used. Based on the convenience of industrial application, the oxidation steps adopted in the embodiment are as follows: calcining and oxidizing the alloy in a muffle furnace in an air atmosphere, heating to 600-900 ℃ at a heating rate of 5-10 ℃/min, then preserving heat for 2-3h, taking out and air-cooling; carrying out dry ball milling on the calcined material for 1-2 hours by using a high-speed ball mill, calcining and oxidizing the alloy for 12-15 hours again in the air atmosphere in a muffle furnace, and carrying out dry ball milling for 1-2 hours again by using the high-speed ball mill; and continuing calcining and oxidizing to complete oxidation.
And 3, preparing doped lithium manganate precursor powder. The method comprises the following specific steps: carrying out dry ball milling on the calcined and oxidized material for 1-2 hours by using a high-speed ball mill, and then carrying out wet ball milling for 2-4 hours; drying after ball milling at the temperature of 120 ℃ and 150 ℃; sieving with 200 mesh sieve to obtain doped lithium manganate precursor powder.
And 4, preparing the initial doped lithium manganate positive electrode material. The method comprises the following specific steps: adding lithium carbonate or lithium hydroxide with the amount corresponding to the molar ratio of lithium shown in the table into the doped lithium manganate precursor powder; dry grinding and wet grinding by using a high-speed ball mill for 2-3 hours; drying after ball milling at the temperature of 120 ℃ and 150 ℃. Heating the powder in a muffle furnace to 500 ℃ and 600 ℃ at the heating rate of 5 ℃/min, and then preserving the heat for 1-10 h; then heating to 700 and 900 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 10-60 h; and cooling along with the furnace to obtain the initial doped lithium manganate cathode material.
And 5, crushing the initially doped lithium manganate positive electrode material after calcination. The method comprises the following specific steps: and (4) crushing the initial doped lithium manganate positive electrode material obtained in the step (4) again by using a high-speed ball mill, drying, screening, and obtaining the doped lithium manganate positive electrode material, wherein the moisture content of the dried material is lower than 1.5%, the average particle size of the doped lithium manganate positive electrode material is 10-24 mu m, and the tap density of the doped lithium manganate positive electrode material is shown in the table.
And 6, carrying out reduction reaction on the doped lithium manganate positive electrode material. The method comprises the following specific steps: and (3) placing the doped lithium manganate anode material in a porcelain boat, and placing the porcelain boat in a normal-pressure atmosphere furnace. Heating to 100-300 ℃ at the heating rate of 5 ℃/min, and simultaneously filling argon (normal pressure) for half an hour. Then the reaction solution is reduced for 30 to 180 minutes by hydrogen (normal pressure) and cooled along with the furnace. And preparing the modified lithium manganate cathode material.
Table one, concrete embodiment table
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (7)
1. The preparation method of the doped lithium manganate precursor is characterized by comprising the following steps of:
firstly, mixing manganese metal and doped metal according to a molar ratio of 1: preparing a metal alloy at a ratio of 0.02-1:0.35, and then completely oxidizing the metal alloy to obtain a doped lithium manganate precursor, wherein the doped metal is a metal corresponding to a metal oxide related to the existing oxide doping method.
2. The method for preparing a doped lithium manganate precursor of claim 1, wherein said doping metal is one of zinc, nickel, copper, indium, aluminum, cobalt, antimony, or a combination of several of said metals.
3. The method for preparing the doped lithium manganate precursor of claim 1 or 2, wherein the metal alloy is completely oxidized by a solid-phase calcination oxidation method, that is: calcining the metal alloy in a muffle furnace, and oxidizing the alloy by using oxygen in the air at the temperature of 600 ℃ and 900 ℃ for more than 10 hours.
4. A preparation method of a modified lithium manganate positive electrode material doped with a lithium manganate precursor is characterized by comprising the following steps:
crushing the doped lithium manganate precursor;
and secondly, adding lithium salt with the molar ratio of 45-60% into the crushed precursor, then carrying out ball milling and drying, calcining for 1-10h at the temperature of 500-600 ℃ in a muffle furnace, and then calcining for 10-60h at the temperature of 700-900 ℃ to obtain the initial doped lithium manganate anode material.
5. The method for preparing the modified lithium manganate positive electrode material using the doped lithium manganate precursor of claim 4, further comprising the third step of: and crushing, drying and screening the initially doped lithium manganate anode material to obtain the required doped lithium manganate anode material.
6. The method for preparing the modified lithium manganate positive electrode material using the doped lithium manganate precursor of claim 5, further comprising the step four of: and reducing the doped lithium manganate positive electrode material prepared in the step three by using reducing gas at the temperature of 100-300 ℃ for 30-180 minutes to obtain the modified lithium manganate positive electrode material.
7. The modified lithium manganate cathode material is characterized in that the modified manganeseThe tap density of the lithium anode material is more than or equal to 2.6g/cm3The button cell prepared by the product is detected, 1C is charged and discharged, when the voltage is discharged to 2.4V, the reversible discharge capacity is 175mAh/g-260 mAh/g; when the discharge voltage is 2.75V, the reversible discharge capacity is 135mAh/g-185 mAh/g.
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| CN107994227A (en) * | 2017-12-16 | 2018-05-04 | 淄博国利新电源科技有限公司 | The preparation method of 523 ternary material precursor of zinc doping |
| CN111640934A (en) * | 2020-04-18 | 2020-09-08 | 浙江金鹰新能源技术开发有限公司 | High-temperature solid-phase sintering method for lithium ion anode material |
| CN112490436A (en) * | 2020-12-02 | 2021-03-12 | 湖北文理学院 | Preparation method of nickel-doped spinel lithium manganate serving as lithium ion battery anode material |
| CN114604899A (en) * | 2022-04-11 | 2022-06-10 | 安徽工业大学 | Lithium ion battery anode material precursor and preparation method thereof |
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| CN114604899A (en) * | 2022-04-11 | 2022-06-10 | 安徽工业大学 | Lithium ion battery anode material precursor and preparation method thereof |
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