CN112850792A - Method for doping molybdenum in lithium battery positive electrode material - Google Patents
Method for doping molybdenum in lithium battery positive electrode material Download PDFInfo
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- molybdenum
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 38
- 239000011733 molybdenum Substances 0.000 title claims abstract description 38
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 32
- 239000007774 positive electrode material Substances 0.000 title claims description 27
- 239000000463 material Substances 0.000 claims abstract description 99
- 239000002243 precursor Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000010405 anode material Substances 0.000 claims abstract description 19
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 6
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 7
- 239000012452 mother liquor Substances 0.000 abstract description 6
- 238000001704 evaporation Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000002194 synthesizing effect Effects 0.000 description 6
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
-
- 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
-
- 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
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for doping molybdenum into a lithium battery anode material, which comprises the following steps: (1) mixing lithium molybdate with a precursor and a lithium source, wherein water is required to be added in the mixing process to obtain a water-containing wet material with the water content of 1-5% by mass; (2) and (3) performing subsequent high-temperature sintering on the wet material containing water, cooling, crushing and sieving to obtain the molybdenum-doped anode material. The molybdenum doping method disclosed by the invention is uniform in doping and simple in process, can solve the problem of high energy consumption caused by the fact that a large amount of water needs to be dried by evaporating the mother liquor to dryness, and effectively improves the gram volume of the cathode material on the premise of keeping the cycle performance.
Description
Technical Field
The invention belongs to the field of metallurgical electrode materials, and particularly relates to a method for doping molybdenum in a lithium battery positive electrode material.
Background
The performance of lithium ion batteries, as a new generation of environmentally-friendly and high-energy batteries, has been improved as one of the hot spots in the research of the battery industry, and doping and coating of the lithium ion battery anode materials are the main methods for improving the comprehensive performance of the anode materials.
The existing research shows that the molybdenum doping is beneficial to improving the capacity, the conductivity and the cycle performance of the anode material, and a large number of Chinese patent documents disclose methods for doping molybdenum to lithium manganate, ternary materials (NCM and NCA), lithium-rich manganese-based materials, nickel-manganese binary materials and the like. The disclosed molybdenum doping method comprises a precursor precipitation molybdenum doping method, a mother liquor evaporation molybdenum doping method, a solid phase mixing molybdenum doping method and the like.
The precursor precipitation molybdenum-doping method is that a soluble molybdenum source is added into the precursor when the anode precursor is produced, molybdenum and other main metal ions (such as nickel, manganese and cobalt) are co-precipitated together through a precipitator to obtain the precursor, then the precursor is subjected to lithium mixing, and the molybdenum-doped anode material is obtained through high-temperature solid-phase synthesis. As molybdenum element is easy to form molybdate with high solubility, the method has reports, but the molybdenum content in the actual precipitate is very low, the target molybdenum doping proportion cannot be realized, and the aim of molybdenum doping modification cannot be achieved.
The method for evaporating the mother liquor to dryness and doping the molybdenum is divided into two cases, one of which is represented by a sol-gel method, a soluble molybdenum source and a main metal salt are added into a lithium source solution for mixing when a precursor is prepared, the mother liquor is evaporated to dryness after corresponding treatment to prepare the precursor doped with the molybdenum, and then high-temperature solid phase synthesis is carried out; and the other method is to add soluble molybdenum source solution and precursor into lithium source, mix and evaporate to dryness, and then carry out high-temperature solid phase synthesis. The methods all need to dry a large amount of mother liquor, have high energy consumption and complex process and are not beneficial to industrial production.
The solid phase mixing molybdenum-doping method is mainly characterized in that a molybdenum source, a precursor and a lithium source are subjected to solid mixing, and then high-temperature solid phase synthesis is carried out to obtain the anode material. The method has simple process, but is difficult to realize that molybdenum element diffuses and permeates into a large amount of particles to be doped from limited molybdenum source particles and is uniformly distributed, thereby restricting the performance of the material.
Disclosure of Invention
The invention aims to solve the technical problem that the existing molybdenum doping method cannot simultaneously meet the requirements of low energy consumption and uniform diffusion, and provides a molybdenum doping method for a lithium battery anode material, which has uniform doping and a simple process, in order to overcome the defects and shortcomings in the background technology.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for doping molybdenum in a lithium battery anode material comprises the following steps:
(1) mixing lithium molybdate with a precursor and a lithium source, wherein water is required to be added in the mixing process to obtain a water-containing wet material with the water content of 1-5% by mass;
(2) and (3) performing subsequent high-temperature sintering on the wet material containing water, cooling, crushing and sieving to obtain the molybdenum-doped anode material.
Preferably, in the step (1), a lithium molybdate solution is mixed with the precursor and the lithium source. The moisture content of the wet material in the step is small, and the lithium molybdate solution is favorable for ensuring that the lithium molybdate is completely dissolved.
Preferably, the concentration of the lithium molybdate solution is 1-3mol/L, and is determined according to the target molybdenum doping amount and the target water content of the subsequent wet material. The lithium molybdate can be directly purchased from the market, and can also be obtained by reacting molybdenum trioxide with lithium hydroxide.
Preferably, the lithium source material in the step (1) includes any one or more of lithium carbonate or lithium hydroxide.
Preferably, the mass fraction of the water content of the wet material containing water in the step (1) is 2-3%. The wet material containing water can enhance the uniform mass transfer of the molybdenum element and the lithium element. The molybdenum element and the lithium element are both effectively transferred to the surface of precursor particles or micropores of the precursor particles or contact gaps among the precursor particles by means of moisture, so that the uniform doping of the molybdenum element and the uniform mixing of the lithium element are realized. If the water content is too low, the uniform mass transfer effect of the molybdenum element and the lithium element can be reduced, and if the water content is too high, the molybdenum element and the lithium element are segregated in the water evaporation process before subsequent high-temperature synthesis, and on the contrary, negative effects are taken to cause unevenness.
Preferably, in the high-temperature sintering in the step (2), the wet material is directly fed into the roasting furnace without being dried. When the anode material is synthesized, a continuous roller kiln or a continuous tunnel kiln is usually used, vibration inevitably exists in the moving process of the material, if the dried material enters the kiln, a material layer is more and more dense along with the propulsion of the material, the mass transfer of oxygen in the environment atmosphere to the oxidation of the material is hindered, the oxidation is not thorough, the material is hardened, and secondary roasting after crushing is needed. The invention adopts a mode of feeding wet materials into the furnace, on one hand, the fluidity of the materials can be reduced, and the material layer is prevented from becoming compact, on the other hand, a large number of micropore channels are generated in the material layer due to the evaporation of moisture, thereby being beneficial to the mass transfer of oxygen in the environment atmosphere.
Preferably, the molybdenum-doped positive electrode material obtained in the step (2) is at least one of a molybdenum-doped lithium manganate positive electrode material, a molybdenum-doped lithium cobaltate positive electrode material, a molybdenum-doped ternary positive electrode material, a molybdenum-doped nickel-manganese binary positive electrode material and a molybdenum-doped lithium-rich manganese-based positive electrode material, and correspondingly, the precursor is a precursor corresponding to the molybdenum-doped positive electrode material. When producing lithium manganate, the precursor material can be manganese dioxide, trimanganese tetroxide or manganese carbonate; in the production of ternary materials (NCM or NCA), the precursor material may be nickel cobalt manganese oxide or hydroxide (NCM), nickel cobalt aluminium oxide or hydroxide (NCA); when producing the nickel-manganese binary or lithium-rich manganese-based material, the precursor material can be a nickel-manganese binary precursor or a lithium-rich manganese-based precursor respectively.
Compared with the prior art, the invention has the beneficial effects that:
(1) the anode material prepared by the method can realize uniform doping of molybdenum, and the material synthesized at high temperature is not agglomerated and is easy to crush, so that the subsequent treatment is convenient;
(2) the processing performance and the electrical performance of the anode material are obviously improved, and the gram capacity of the anode material is obviously improved;
(3) the production process is simple, a large amount of mother liquor does not need to be dried and then mixed, only one-time high-temperature roasting is needed, secondary sintering is not needed, and industrial production is easy to realize.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Comparative example 1:
lithium manganate product comparative example 1: and synthesizing lithium manganate by using electrolytic manganese dioxide.
(1) Taking 800Kg of electrolytic manganese dioxide with the particle size D50 of 16 mu m, adding lithium carbonate according to the lithium-manganese ratio of 0.54, putting the mixture into an inclined mixer with the volume of 2.5 cubic meters for mixing for 2 hours, and detecting that the water content of the mixture is 0.6%;
(2) and (3) loading the mixture into a sagger, controlling the thickness of a material layer in the sagger to be 6 centimeters, enabling the material to enter a roller kiln along with the sagger, controlling the temperature rise speed of a temperature rise section of the roller kiln to be 5 ℃/min, roasting the material at 800 ℃ for 15 hours, cooling the material to about 100 ℃ after 6 hours, discharging the material out of the furnace, loosening the material in the sagger without caking, and crushing and sieving the material to obtain the lithium manganate product.
Example 1:
lithium manganate product example 1: electrolytic manganese dioxide is used to synthesize the lithium manganate doped with molybdenum of 0.5%.
(1) Preparing a lithium molybdate solution with the concentration of 1.8 mol/L; taking 800Kg of electrolytic manganese dioxide with the particle size D50 of 16 mu m, adding lithium carbonate according to the lithium-manganese ratio of 0.54, and putting the mixture into an inclined mixer with the volume of 2.5 cubic meters for mixing for 2 hours; adding 22.6L of prepared lithium molybdate solution, continuously mixing for 0.5 hour, and detecting to obtain a mixture with the water content of 2.8%.
(2) And (3) putting the wet material into a sagger, controlling the thickness of the material layer in the sagger to be 6 centimeters, enabling the material to enter a roller kiln along with the sagger, controlling the temperature rise speed of a temperature rise section of the roller kiln to be 5 ℃/min, roasting the material at 800 ℃ for 15 hours, cooling the material to about 100 ℃ after 6 hours, discharging the material out of the furnace, loosening the material in the sagger without caking, and crushing and sieving the material to obtain the lithium manganate product.
Comparative example 2:
lithium manganate product comparative example 2: synthesizing lithium manganate by using spherical mangano-manganic oxide.
(1) Taking 800Kg of spherical manganous-manganic oxide with the granularity D50 of 10 mu m, adding lithium carbonate according to the lithium-manganese ratio of 0.54, putting the mixture into an inclined mixer with the volume of 2.5 cubic meters for mixing for 2 hours, and detecting that the water content of the mixture is 0.2%;
(2) and (3) loading the mixture into a sagger, controlling the thickness of a material layer in the sagger to be 5 cm, enabling the material to enter a roller kiln along with the sagger, controlling the temperature rise speed of a temperature rise section of the roller kiln to be 5 ℃/min, roasting the material at 770 ℃ for 12 hours, cooling the material to about 100 ℃ for 6 hours, discharging the material out of the furnace, caking the material in the sagger, crushing the material, and sieving the crushed material to obtain the lithium manganate product.
Example 2:
lithium manganate product example 2: spherical mangano-manganic oxide is used for synthesizing the lithium manganate doped with molybdenum by 0.5 percent.
(1) And preparing a lithium molybdate solution with the concentration of 1.8 mol/L. Taking 800Kg of spherical manganous-manganic oxide with the particle size D50 of 10 mu m, adding industrial-grade lithium carbonate according to the lithium-manganese ratio of 0.54, and putting the mixture into an inclined mixer with the volume of 2.5 cubic meters for mixing for 2 hours; adding 26.7L of prepared lithium molybdate solution, continuously mixing for 0.5 hour, and detecting to obtain a mixture with the water content of 2.5%;
(2) and (3) putting the wet material into a sagger, controlling the thickness of a material layer in the sagger by 5 cm, enabling the material to enter a roller kiln along with the sagger, controlling the temperature rise speed of a temperature rise section of the roller kiln to be 5 ℃/min, roasting the material at 770 ℃ for 12 hours, cooling the material to about 100 ℃ after 6 hours, discharging the material out of the furnace, loosening the material in the sagger without caking, and crushing and sieving the material to obtain the lithium manganate product.
Comparative example 3:
523 ternary product comparative example 3: and synthesizing the 523 ternary cathode material by using the 523 ternary precursor.
(1) Taking 90g of 523 ternary precursor with the granularity D50 of 10 mu M, adding industrial-grade lithium carbonate according to the proportion of Li to M being 1.02, putting the mixture into a ball milling tank, mixing for 2 hours, and detecting that the water content of the mixture is 0.1%;
(2) and (2) loading the mixture into a sagger, feeding the material into an atmosphere furnace along with the sagger, controlling the temperature rise speed of a temperature rise section to be 5 ℃/min, roasting the material at 830 ℃ for 12 hours, cooling the material to about 100 ℃ for 6 hours, discharging the material out of the furnace, enabling the material in the sagger to be hard and hard, crushing the material, and then crushing and sieving the material to obtain a 523 ternary cathode material product.
Example 3:
523 ternary product example 3: and synthesizing the 523 ternary positive electrode material doped with 0.5% of molybdenum by using the 523 ternary precursor.
(1) And preparing a lithium molybdate solution with the concentration of 1.8 mol/L. Taking 90g of 523 ternary precursor with the granularity D50 of 10 mu M, adding lithium carbonate according to the proportion of Li to M being 1.02, and putting the mixture into a ball milling tank for mixing for 2 hours; adding 2.74ml of prepared lithium molybdate solution, continuously mixing for 0.5 hour, and detecting to obtain a mixture with the water content of 2.0%;
(2) and (2) putting the wet material into a sagger, feeding the material into an atmosphere furnace along with the sagger, controlling the temperature rise speed of a temperature rise section to be 5 ℃/min, roasting the material at 830 ℃ for 12 hours, cooling the material to about 100 ℃ after 6 hours, discharging the material out of the furnace, enabling the material in the sagger to be agglomerated but easy to crush, crushing and sieving the material to obtain a 523 ternary cathode material product.
Comparative example 4:
811 ternary product comparative example 4: and synthesizing 811 ternary cathode material by using 811 ternary precursor.
(1) Taking 90g of 811 ternary precursor with the particle size D50 of 10 mu M, adding lithium hydroxide according to the proportion of Li to M being 1.02, putting the mixture into a ball milling tank, mixing for 2 hours, and detecting that the water content of the mixture is 0.4%;
(2) and (2) loading the mixture into a sagger, feeding the material into an atmosphere furnace along with the sagger, controlling the temperature rise speed of a temperature rise section to be 5 ℃/min, introducing oxygen into the atmosphere furnace, roasting the material at 890 ℃ for 12 hours, cooling the material to about 100 ℃ after 6 hours, discharging the material out of the furnace, enabling the material in the sagger to be hard, crushing the material, and then crushing and sieving the material to obtain the 811 ternary cathode material product.
Example 4:
811 ternary product example 4: 811 ternary precursor is used to synthesize 811 ternary anode material with 0.5% molybdenum.
(1) And preparing a lithium molybdate solution with the concentration of 1.8 mol/L. Taking 90g of 811 ternary precursor with the particle size D50 of 10 mu M, adding lithium hydroxide according to the proportion of Li to M being 1.02, and putting the mixture into a ball milling pot for mixing for 2 hours; adding 2.7ml of prepared lithium molybdate solution, continuously mixing for 0.5 hour, and detecting to obtain a mixture with the water content of 2.2%;
(2) and (2) putting the wet material into a sagger, putting the material into an atmosphere furnace along with the sagger, controlling the temperature rise speed of a temperature rise section to be 5 ℃/min, introducing oxygen into the atmosphere furnace, roasting the material at 890 ℃ for 12 hours, cooling the material to about 100 ℃ for 6 hours, discharging the material out of the furnace, enabling the material in the sagger to be agglomerated but easy to crush, and crushing and sieving the material to obtain a 811 ternary cathode material product.
The positive electrode material obtained in each of the above examples and comparative examples, lithium manganate material, were as follows: the positive electrode material comprises PVDF, graphite and acetylene black, wherein the proportion is 9:0.6:0.2: 0.2; the ternary material is as follows: the positive electrode material is PVDF, wherein the proportion of super-p is 9:0.5: 0.5; a metal lithium sheet is used as a negative electrode to manufacture a CR2016 button cell, an electrical property test is carried out in a charging and discharging interval of 3.0V-4.3V in a temperature environment of 25 ℃, 0.2C is firstly detected, and then 1C (lithium manganate material 1C is 120mA/g, ternary material 1C is 200mA/g) circulation is carried out, and the detection results are shown in a table 1:
TABLE 1 relevant Properties of the positive electrode materials of the examples and comparative examples
According to the caking degree of the discharged materials of the comparative example and the embodiment, the caking degree of the materials is effectively reduced, and the subsequent processing is convenient. According to the data, the method effectively improves the gram volume of the anode material on the premise of maintaining the cycle performance.
Claims (7)
1. A method for doping molybdenum into a lithium battery anode material is characterized by comprising the following steps:
(1) mixing lithium molybdate with a precursor and a lithium source, wherein water is required to be added in the mixing process to obtain a water-containing wet material with the water content of 1-5% by mass;
(2) and (3) performing subsequent high-temperature sintering on the wet material containing water, cooling, crushing and sieving to obtain the molybdenum-doped anode material.
2. The method for doping molybdenum into the lithium battery positive electrode material according to claim 1, wherein the step (1) comprises mixing a lithium molybdate solution with the precursor and a lithium source.
3. The method for doping molybdenum into the lithium battery positive electrode material as claimed in claim 2, wherein the concentration of the lithium molybdate solution is 1 to 3 mol/L.
4. The method for doping molybdenum in the positive electrode material of a lithium battery as claimed in claim 1, wherein the lithium source in the step (1) comprises at least one of lithium carbonate or lithium hydroxide.
5. The method for doping molybdenum into the lithium battery positive electrode material as claimed in claim 1, wherein the moisture content of the moisture-containing wet material in the step (1) is 2-3% by mass.
6. The method for adding molybdenum to the positive electrode material for lithium battery as claimed in claim 1, wherein the high-temperature sintering in step (2) is carried out by feeding the wet aqueous material directly into the firing furnace without drying.
7. The method for doping molybdenum in the positive electrode material of the lithium battery as claimed in any one of claims 1 to 6, wherein the obtained molybdenum-doped positive electrode material is at least one of a molybdenum-doped lithium manganate positive electrode material, a molybdenum-doped lithium cobaltate positive electrode material, a molybdenum-doped ternary positive electrode material, a molybdenum-doped nickel-manganese binary positive electrode material and a molybdenum-doped lithium-rich manganese-based positive electrode material; correspondingly, the precursor is a precursor corresponding to the molybdenum-doped anode material.
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