CN112582601A - Method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide and lithium nickel manganese oxide - Google Patents
Method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide and lithium nickel manganese oxide Download PDFInfo
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- CN112582601A CN112582601A CN202011462674.5A CN202011462674A CN112582601A CN 112582601 A CN112582601 A CN 112582601A CN 202011462674 A CN202011462674 A CN 202011462674A CN 112582601 A CN112582601 A CN 112582601A
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- lithium
- manganese oxide
- nickel
- manganese
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- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002699 waste material Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 63
- 229910002102 lithium manganese oxide Inorganic materials 0.000 title claims abstract description 34
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 76
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011812 mixed powder Substances 0.000 claims abstract description 55
- 238000005245 sintering Methods 0.000 claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 42
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 40
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 29
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000007873 sieving Methods 0.000 claims abstract description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 65
- 229910052748 manganese Inorganic materials 0.000 claims description 50
- 239000011572 manganese Substances 0.000 claims description 50
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 34
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 12
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 11
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 11
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003345 natural gas Substances 0.000 claims description 8
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 7
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 6
- 239000005750 Copper hydroxide Substances 0.000 claims description 6
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 230000001351 cycling effect Effects 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 4
- 229960004887 ferric hydroxide Drugs 0.000 claims description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 54
- 238000011084 recovery Methods 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 12
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000010926 waste battery Substances 0.000 abstract description 3
- 239000007790 solid phase Substances 0.000 abstract description 2
- 229910052596 spinel Inorganic materials 0.000 description 17
- 239000011029 spinel Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 238000012216 screening Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- WLJDBAQOCCWKQY-UHFFFAOYSA-N [Mn].[Nb] Chemical compound [Mn].[Nb] WLJDBAQOCCWKQY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- KBMLJKBBKGNETC-UHFFFAOYSA-N magnesium manganese Chemical compound [Mg].[Mn] KBMLJKBBKGNETC-UHFFFAOYSA-N 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/54—Reclaiming serviceable parts of waste 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
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide and lithium nickel manganese oxide, and belongs to the field of waste battery anode recovery. Aiming at the problems of low recovery value and high cost of the existing lithium manganate material by a wet method, the invention provides a method for preparing lithium nickel manganate by using waste lithium manganate, which comprises the following steps: sintering waste lithium manganate powder in a reducing atmosphere to completely decompose the lithium manganate powder into mixed powder of manganese oxide and lithium carbonate; adding a nickel source, a lithium source and a doping element compound into the mixed powder, and fully mixing and ball-milling to obtain a mixture; and (4) sintering the mixture obtained in the step S2 in an air atmosphere, cooling, crushing and sieving to obtain the lithium nickel manganese oxide. According to the method, the pure solid phase is adopted for recycling the lithium manganate, the recycling rate is obviously improved, the problems of complex environment-friendly treatment and recycling process and high environment-friendly cost caused by the adoption of a large amount of acid-base and organic reagents in a wet method are solved, and the prepared lithium nickel manganese has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of recycling of waste battery positive electrode materials, and particularly relates to a method for preparing lithium nickel manganese oxide by using waste lithium manganese oxide and lithium nickel manganese oxide.
Background
Lithium manganate materials are widely used as battery positive electrode materials due to low cost, good safety and low temperature performance. Particularly, the rapid development of the new energy automobile industry, the output of lithium manganate batteries is continuously increased, and meanwhile, the recovery of valuable elements in waste lithium manganate materials and waste lithium manganate batteries generated in the production is necessary. The traditional waste lithium manganate battery material recovery technology mainly adopts a wet method, needs to consume a large amount of acid, alkali and organic reagents, and has the advantages of long reaction process, no environmental protection and low lithium and manganese recovery rate. In addition, compared with the recovery of metal elements such as nickel, cobalt and the like of the ternary material, the recovery value of manganese is low, and in addition, the medicament and the environmental protection cost are low, and the recovery economic benefit of lithium manganate is poor. In order to solve the problems, the method directly prepares a brand new battery anode material through simple treatment of the waste battery anode material and recycles the battery anode material, and the method greatly shortens the technical process and period of battery recovery, saves cost and improves high recovery value. At present, a plurality of groups develop new recovery methods, and certainly, the main method for recovering the waste lithium manganate material is to recover valuable metal elements of manganese and lithium by adopting a wet method, so that the wet method has low recovery value, is easy to generate pollution, and increases certain cost.
For example, the Chinese patent with the application number of CN201810104669.3 and the publication date of 2018, 8 and 14 discloses a method for preparing a lithium manganese phosphate/carbon anode material from a waste lithium manganate battery, wherein the method comprises the steps of supplementing required elements into the anode material of the waste lithium manganate battery according to the stoichiometric ratio of lithium manganese phosphate, adding a carbon source, and mechanically activating the mixture in a dispersion medium to form a nano-scale precursor slurry; and drying the obtained precursor slurry at 40-150 ℃, and sintering for 2-10 h at 400-800 ℃ in an inert atmosphere to obtain the lithium manganese phosphate/carbon anode material. The disadvantages of the patent are that: because the lithium manganate and the lithium manganese iron phosphate have different crystal structures, the lithium manganate is difficult to be completely converted into the lithium manganese iron phosphate under normal pressure, and the feasibility of the method is not high.
Also like Chinese patent application No. CN201410280343.8, which is published as 10/1/2014, the patent discloses a method for preparing lithium nickel manganese oxide by using waste lithium manganese oxide batteries, and belongs to the field of recycling of waste lithium manganese oxide batteries. According to the embodiment of the invention, the positive active substance comprising LiMn2O4 is obtained from waste lithium manganate batteries, the positive active substance is leached to obtain a solution containing Li + and Mn2+, then nickel salt, lithium salt and a precipitator are added into the solution containing Li + and Mn2+ to react to obtain a precipitate, and the precipitate is calcined to obtain spinel-type LiNi0.5Mn1.5O4, so that the recovery and utilization of manganese and lithium are realized. The disadvantages of the patent are that: the method is a wet route, the raw materials such as acid and alkali added in the reaction are more, the flow is more, the process control difficulty is high, the discharge of a large amount of three wastes cannot be avoided, the environment-friendly treatment cost is high, and the economic benefit is low.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of low recovery value and high cost of the existing lithium manganate material by a wet method, the invention provides a method for preparing lithium nickel manganate by using waste lithium manganate and lithium nickel manganate. The method for preparing the lithium nickel manganese oxide by utilizing the lithium manganese oxide avoids a leaching and recycling process, has the advantages of whole solid-phase reaction, simple process and environmental protection, can directly convert the waste lithium manganese oxide into the high-pressure lithium nickel manganese oxide, and can obtain the product with excellent electrical property. The recycling of the waste lithium manganate material is effectively realized. Meanwhile, the problems of complex environment-friendly treatment and recovery process and high environment-friendly cost due to the adoption of a large amount of acid-base and organic reagents in a wet method are avoided.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide comprises the following steps:
s1: sintering waste lithium manganate powder in a reducing atmosphere to completely decompose the lithium manganate powder into mixed powder of manganese oxide and lithium carbonate;
s2: adding a nickel source, a lithium source and a doping element compound for improving the cycling stability of the anode material into the mixed powder respectively, and performing full mixing and ball milling to obtain a mixture;
s3: sintering the mixture obtained in the step S2 in an air atmosphere, cooling, crushing and sieving to obtain the molecular formula LiMn3xNixM2-4xO4The lithium nickel manganese oxide.
Further, the reducing atmosphere in step S1 includes one or more of methane, natural gas, and carbon monoxide.
Furthermore, the sintering temperature of the lithium manganate powder is 400-800 ℃, and the sintering time is 2-5 h.
Further, in step S2, the doping element compound is a hydroxide of the doping element, the nickel source includes one or more of nickel oxide, nickel hydroxide, nickel sulfate, nickel carbonate, and nickel nitrate, and the lithium source includes one of lithium carbonate, lithium hydroxide, and lithium nitrate.
Furthermore, the hydroxide of the doping element is one of aluminum hydroxide, iron hydroxide, magnesium hydroxide, copper hydroxide and niobium hydroxide.
Furthermore, the molar ratio of the nickel source to the manganese element in the mixed powder is (0.8-1.2): 3; the molar ratio of the lithium source to the manganese element in the mixed powder is (0.15-0.4): 1; the molar ratio of the doping elements in the doping element compound to the manganese elements in the mixed powder is (1-4): 29.
furthermore, the molar ratio of the nickel source to the manganese element in the mixed powder is 1: 3; the molar ratio of the lithium source to the manganese element in the mixed powder is (0.18-0.30): 1; the mol ratio of the doping element in the doping element compound to the manganese element in the mixed powder is (1.5-2.5): 29.
furthermore, in the step S2, a ball mill is adopted for full mixing, the ball milling time is 1-5 h, and the rotating speed of the ball mill is 500-800 r/min.
Furthermore, in step S3, the sintering temperature is 750-900 ℃ and the sintering time is 13-30 h.
The lithium nickel manganese oxide is prepared by the method for preparing the lithium nickel manganese oxide by utilizing the waste lithium manganese oxide.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, waste lithium manganate powder is fully sintered at high temperature in a reducing atmosphere, a molecular structure connected with lithium and manganese in lithium manganate is broken through, lithium is combined with carbon and oxygen to be converted into lithium carbonate, manganese is reduced into a low-valence manganese oxide from a valence state of +3 or +4, and the spinel structure of the manganese oxide is still maintained, so that the lithium manganate is beneficial to being converted into lithium nickel manganate with the spinel structure from the aspect of energy compared with other materials, and after a nickel source, a lithium source and a doping element compound are added and supplemented, the lithium nickel manganate is subjected to high-temperature sintering to obtain a lithium nickel manganate crystal with a complete and stable structure, a lithium ion diffusion channel is smooth, and the electrical property is good; the whole process adopts a pure solid phase preparation mode, compared with wet recovery, the recovery rate is obviously improved, the full recovery and reutilization of manganese-lithium valuable elements can be basically realized, and meanwhile, the whole process is simple and environment-friendly, the process cost is low, and the energy consumption is low; the problems of complex environment-friendly treatment and recovery process and high environment-friendly cost due to the adoption of a large amount of acid and alkali and organic reagents in the process of recovering lithium manganate by using a wet method are solved;
(2) one or more gases of methane, natural gas and carbon monoxide are used as reducing gas, the sources are wide, and the carbon element is sufficient, so that lithium in the lithium manganate powder can be fully combined with carbon to form lithium carbonate; meanwhile, the sintering temperature is controlled to be 400-800 ℃, the sintering time is controlled to be 2-5 h, the manganese-lithium bond in the lithium manganate powder is ensured to be broken, decomposed and converted fully and thoroughly, manganese oxide and lithium carbonate are favorably formed, and a good foundation is provided for the subsequent preparation of the lithium nickel manganese oxide;
(3) the invention limits the molar weight of the added nickel source, lithium source and doping elements, so that the lithium nickel manganese oxide can form a stable and uniform spinel crystal structure conveniently, and has good electrical property; the lithium source is added so that the molar ratio of manganese to lithium conforms to LiMn3xNixM2-4xO4The stoichiometric ratio in the process, and meanwhile, the gram capacity of the material can be improved by appropriate excess of lithium; the doping element compound is a hydroxide of a metal doping element, so that the high-temperature cycle performance is obviously improved by about 10-15%, the cycle retention rate of 100 times exceeds 95%, good conditions are improved for the subsequent formation of the lithium nickel manganese oxide, and the excellent electrochemical performance of the lithium nickel manganese oxide is ensured;
(4) according to the invention, in the sintering process of the last step, the temperature is controlled to be 750-900 ℃, the time is controlled to be 13-30 h, and the temperature is controlled to ensure that the formed lithium nickel manganese oxide product has high crystallinity, ordered crystal structure arrangement and good electrical property; the control of time ensures that the formed lithium nickel manganese oxide product has a complete structure, a moderate particle size, a high capacity and a good cycle performance;
(5) according to the invention, the waste lithium manganate material is derived from waste lithium manganate anode materials generated in the production process of the lithium manganate material and waste lithium manganate materials obtained by disassembling lithium manganate batteries, so that the waste lithium manganate material can be recycled in time, and the waste of resources is avoided; meanwhile, the nickel lithium manganate prepared by utilizing the waste lithium manganate material has a high voltage platform relative to lithium manganate, and is added with a doping element compound for improving the cycling stability of the anode material, so that the high-temperature cycling performance is further improved, the added value of the product is high, and the economic benefit is obvious.
Detailed Description
The invention is further described with reference to specific examples.
A method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide comprises the following steps:
s1: placing waste lithium manganate powder into a rotary kiln, and sintering in a reducing atmosphere to completely decompose the lithium manganate powder into mixed powder of manganese oxide and lithium carbonate; specifically, the waste lithium manganate powder is derived from waste lithium manganate anode materials generated in the production process of lithium manganate materials and waste lithium manganate materials obtained by disassembling lithium manganate batteries. When the lithium manganate powder is sintered in a reducing atmosphere, the molecular structure connected with manganese and lithium in the original lithium manganate powder is broken, the lithium is combined with carbon and oxygen to be converted into lithium carbonate, the manganese is reduced into a low-valence manganese oxide from a valence state of +3 or +4, and meanwhile, the spinel structure of the manganese oxide is still maintained.
In this step, preferably, the reducing atmosphere comprises one or more of methane, natural gas, carbon monoxide; the reducing gas has wide sources and sufficient carbon elements in the gas, and lithium in the lithium manganate powder can be fully combined with carbon to form lithium carbonate. And meanwhile, the sintering temperature in the rotary kiln is controlled to be 400-800 ℃, and under the temperature, the lithium manganate powder is combined with the reducing atmosphere of carbon, so that the lithium manganese bond can be broken and decomposed to form lithium carbonate and manganese oxide. The temperature is too low to provide enough energy to break the lithium manganese bond, and the temperature is too high, so that a small part of lithium carbonate is volatilized, thereby reducing the recovery rate. Controlling the sintering time to be 2-5 h, ensuring that the manganese-lithium bond is fully decomposed and converted, ensuring that the time is too low and the decomposition and conversion are not sufficient, and ensuring that the uniformity of the structure of the subsequently prepared lithium nickel manganese oxide is poor; too high time increases energy consumption and increases production cost.
S2: adding a nickel source, a lithium source and a doping element compound for improving the cycle stability of the anode material into the mixed powder respectively, and performing full mixing and ball milling in a ball mill for 1-5 hours at the rotating speed of 500-800 r/min to obtain a mixture, so as to ensure full reaction; in the step, the manganese oxide is converted to the lithium nickel manganese oxide which is also in a spinel structure under the action of a nickel source, a lithium source and a doping element compound. The doped element compound is a hydroxide of a doped element, and particularly refers to one of aluminum hydroxide, ferric hydroxide, magnesium hydroxide, copper hydroxide and niobium hydroxide. The nickel source comprises one or more of nickel oxide, nickel hydroxide, nickel sulfate, nickel carbonate and nickel nitrate, and the lithium source comprises one of lithium carbonate, lithium hydroxide and lithium nitrate.
In the step, preferably, the content of the manganese element in the mixed powder is measured, and the molar ratio of the nickel source to the manganese element in the mixed powder is (0.8-1.2): 3; the molar ratio of the lithium source to the manganese element in the mixed powder is (0.15-0.4): 1; the molar ratio of the doping elements in the doping element compound to the manganese elements in the mixed powder is (1-4): 29 a nickel source, a lithium source and a compound of a doping element are added. The selection is mainly based on the final lithium nickel manganese LiMn3xNixM2-4xO4The molecular formula (2) is added according to the proportion, so that a stable and uniform spinel crystal structure can be formed, and the electrical property is good. The gram capacity can be improved by supplementing a lithium source in a lithium passing mode, and the molar ratio of the lithium source to manganese is (0.15-0.4): the electrical property is good within the range of 1, and when the electrical property exceeds the range, ion mixing and discharging are generated, so that the gram capacity is reduced; below this range, some of the manganese and nickel may not form crystals and become a hetero-phase affecting electrical properties. And (3) the molar ratio of the doping element in the doping element compound to the manganese element in the mixed powder is (1-4): the high-temperature cycle performance is obviously improved in 29, the cycle retention rate is improved by about 10-15%, the retention rate of 100 cycles is over 95%, and the material capacity is slightly reduced. When the content is less than the range, the cycle performance is not remarkably improved; above this range, the gram capacity of the material is reduced too much and the loss is severe. The step is further optimized, and the molar ratio of the nickel source to the manganese element in the mixed powder is 1: 3; the molar ratio of the lithium source to the manganese element in the mixed powder is (0.18-0.30): 1; the molar ratio of the doping elements in the doping element compound to the manganese elements in the mixed powder is (1.5-2.5): 29, ensuring that the electrical property of the nickel lithium manganate formed subsequently is excellent.
S3: sintering the mixture obtained in the step S2 in an air atmosphere, cooling, crushing and sieving to obtain the molecular formula LiMn3xNixM2-4xO4The lithium nickel manganese oxide. Specifically, the sintering temperature in the step is 750-900 ℃ in the time rangeThe product in the enclosure has high crystallinity, ordered arrangement of crystal structures and good electrical property. The crystallization property is low below 750 ℃, the defects are many, and the structural distortion in the lithium ion de-intercalation process is easy to cause; oxygen defects increase above 900 ℃, the number of impure phases increases, and the cycle performance deteriorates. The sintering time is controlled to be 13-30 h, preferably 16-23 h. The nickel lithium manganate obtained in the time range has a complete structure, a moderate particle size, a high capacity and a good cycle performance. The crystal form of the material is not completely developed within 13 hours; the particle size of the material particles is more than 30h, which greatly influences the cycle performance.
The lithium nickel manganese oxide is prepared by the method for preparing the lithium nickel manganese oxide by utilizing the waste lithium manganese oxide. The lithium nickel manganese oxide prepared by the method has a high voltage platform relative to lithium manganese oxide, and the high-temperature cycle performance is further improved by adding the doping element compound, so that the lithium nickel manganese oxide has the advantages of complete and stable structure, smooth lithium ion diffusion channel, good electrical performance, high product added value and obvious economic benefit.
It is worth to be noted here that high-voltage lithium nickel manganese oxide is an attractive lithium ion battery positive electrode material in development, and the high-voltage lithium nickel manganese oxide material has a spinel structure and a three-dimensional lithium ion diffusion channel, and is more beneficial to diffusion of lithium ions. The working voltage platform of the high-voltage lithium nickel manganese oxide material is as high as 4.7V, and the material is the highest voltage material in the existing commercial anode materials. The reversible capacity reaches 146mAh/g, and compared with a 4V working voltage platform of a lithium manganate material, the lithium manganate material has great advantages. Particularly, compared with a lithium manganate material, the cycling stability of the high-pressure lithium nickel manganese oxide at high temperature is greatly improved. Some domestic and foreign companies such as SANYO, Korea LG Chemicals, etc. have started LiNi0.5Mn1.5O4The commercial development of the material. Along with the development of fluorine electrolyte specially used for high-voltage anode materials by electrolyte manufacturers such as the Japan Dajin industry and the like, 5V lithium nickel manganese will meet huge market demands. The waste lithium manganate is recycled, and the nickel lithium manganate is prepared by a pure fixation method, so that the complete recycling and reutilization of valuable elements of manganese lithium can be basically realized; avoid using wet process to retrieve lithium manganate and adopt a large amount of acid and alkaliAnd organic reagent, the environment-friendly treatment and recovery process is complicated, the environment-friendly cost is high, the invention basically does not produce three wastes, and is environment-friendly. Meanwhile, the waste lithium manganate is directly converted into high-voltage lithium nickel manganate with excellent electrical property, the added value of the product is high, and the economic benefit is obvious.
Example 1
A method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide comprises the following steps:
s1, placing the waste lithium manganate powder in a rotary kiln, sintering for 3h at 450 ℃ in a methane atmosphere, and fully reacting to completely decompose the lithium manganate into mixed powder of manganese oxide and lithium carbonate;
s2, screening the mixed powder, testing the content of manganese in the mixed powder, adding nickel oxide according to the molar ratio of nickel to manganese of 1:3, and adding nickel oxide according to the molar ratio of lithium to manganese of 0.2: 1 adding lithium carbonate; adding aluminum hydroxide according to the molar ratio of aluminum to manganese of 1.8:29, mixing and adding the aluminum hydroxide into a ball mill, and mixing and ball-milling for 2 hours at the rotating speed of 500r/min to obtain a mixture;
and S3, transferring the mixture into a tube furnace, sintering for 18h at 750 ℃ in an air atmosphere, slowly cooling, crushing and sieving to obtain the high-pressure lithium nickel manganese oxide material with the spinel structure.
The high-voltage lithium nickel manganese oxide material is subjected to a fastening electrical property test, the first discharge specific capacity of 0.2C reaches 122mAh/g, the circulation capacity retention rate of 100 times is 97.5%, and the high-voltage lithium nickel manganese oxide material has excellent electrochemical properties.
Example 2
A method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide comprises the following steps:
s1, placing the waste lithium manganate powder in a rotary kiln, sintering for 2h at 500 ℃ in the atmosphere of natural gas, and fully reacting to completely decompose the lithium manganate into mixed powder of manganese oxide and lithium carbonate;
s2, screening the mixed powder, testing the content of manganese in the mixed powder, adding nickel hydroxide according to the molar ratio of nickel to manganese of 1:3, and adding nickel hydroxide according to the molar ratio of lithium to manganese of 0.22: 1 adding lithium hydroxide; adding aluminum hydroxide according to the molar ratio of aluminum to manganese of 2.0:29, mixing and adding into a ball mill, and mixing and ball-milling for 3 hours at the rotating speed of 600r/min to obtain a mixture;
and S3, transferring the mixture into a tube furnace, sintering for 20h at 800 ℃ in the air atmosphere, slowly cooling, crushing and sieving to obtain the high-pressure lithium nickel manganese oxide material with the spinel structure.
The high-voltage lithium nickel manganese oxide material is subjected to a fastening electrical property test, the first discharge specific capacity of 0.2C reaches 123mAh/g, the cycle capacity retention rate of 100 times is 98.2%, and the high-voltage lithium nickel manganese oxide material has excellent electrochemical properties.
Example 3
A method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide comprises the following steps:
s1, placing the waste lithium manganate powder in a rotary kiln, sintering for 4 hours at 600 ℃ in the atmosphere of natural gas, and fully reacting to completely decompose the lithium manganate into mixed powder of manganese oxide and lithium carbonate;
s2, screening the mixed powder, testing the content of manganese in the mixed powder, adding nickel carbonate according to the molar ratio of nickel to manganese of 1:3, and adding nickel carbonate according to the molar ratio of lithium to manganese of 0.24: 1 adding lithium nitrate; adding ferric hydroxide according to the molar ratio of iron to manganese of 2.0:29, mixing and adding into a ball mill, and mixing and ball-milling for 4 hours at the rotating speed of 700r/min to obtain a mixture;
and S3, transferring the mixture into a tube furnace, sintering for 22h at 800 ℃ in the air atmosphere, slowly cooling, crushing and sieving to obtain the high-pressure lithium nickel manganese oxide material with the spinel structure.
The high-voltage lithium nickel manganese oxide material is subjected to a fastening electrical property test, the first discharge specific capacity of 0.2C reaches 124mAh/g, the circulation capacity retention rate of 100 times is 97.3%, and the high-voltage lithium nickel manganese oxide material has excellent electrochemical properties.
Example 4
A method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide comprises the following steps:
s1, placing the waste lithium manganate powder in a rotary kiln, sintering for 2h at 800 ℃ in the atmosphere of natural gas, and fully reacting to completely decompose the lithium manganate into mixed powder of manganese oxide and lithium carbonate;
s2, screening the mixed powder, testing the content of manganese in the mixed powder, adding nickel sulfate according to the molar ratio of nickel to manganese of 1:3, and adding nickel sulfate according to the molar ratio of lithium to manganese of 0.26: 1 adding lithium carbonate; adding magnesium hydroxide according to the magnesium-manganese molar ratio of 2.2:29, mixing and adding into a ball mill, and mixing and ball-milling for 3 hours at the rotating speed of 800r/min to obtain a mixture;
and S3, transferring the mixture into a tube furnace, sintering for 20h at 850 ℃ in the air atmosphere, slowly cooling, crushing and sieving to obtain the high-pressure lithium nickel manganese oxide material with the spinel structure.
The high-voltage lithium nickel manganese oxide material is subjected to a fastening electrical property test, the first discharge specific capacity of 0.2C reaches 128mAh/g, the retention rate of the 100-time circulation capacity is 96.9%, and the high-voltage lithium nickel manganese oxide material has excellent electrochemical properties.
Example 5
A method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide comprises the following steps:
s1, placing the waste lithium manganate powder in a rotary kiln, sintering for 3h at 600 ℃ in a methane atmosphere, and fully reacting to completely decompose the lithium manganate into mixed powder of manganese oxide and lithium carbonate;
s2, screening the mixed powder, testing the content of manganese in the mixed powder, adding nickel nitrate according to the molar ratio of nickel to manganese of 1:3, and adding nickel nitrate according to the molar ratio of lithium to manganese of 0.28: 1 adding lithium hydroxide; adding copper hydroxide according to the copper-manganese molar ratio of 2.3:29, mixing and adding the copper hydroxide and the copper hydroxide into a ball mill, and carrying out mixed ball milling for 5 hours at the rotating speed of 500r/min to obtain a mixture;
and S3, transferring the mixture into a tube furnace, sintering for 23h at 900 ℃ in the air atmosphere, slowly cooling, crushing and sieving to obtain the high-pressure lithium nickel manganese oxide material with the spinel structure.
The high-voltage lithium nickel manganese oxide material is subjected to a fastening electrical property test, the first discharge specific capacity of 0.2C reaches 127mAh/g, the circulation capacity retention rate of 100 times is 97.8%, and the high-voltage lithium nickel manganese oxide material has excellent electrochemical properties.
Example 6
A method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide comprises the following steps:
s1, placing the waste lithium manganate powder in a rotary kiln, sintering for 4 hours at 500 ℃ in the atmosphere of natural gas, and fully reacting to completely decompose the lithium manganate into mixed powder of manganese oxide and lithium carbonate;
s2, screening the mixed powder, testing the content of manganese in the mixed powder, adding nickel hydroxide according to the molar ratio of nickel to manganese of 1:3, and adding nickel hydroxide according to the molar ratio of lithium to manganese of 0.25: 1 adding lithium nitrate; adding niobium hydroxide according to the niobium-manganese molar ratio of 1.9:29, mixing and adding into a ball mill, and mixing and ball milling for 4 hours at the rotating speed of 600r/min to obtain a mixture;
and S3, transferring the mixture into a tube furnace, sintering for 20h at 850 ℃ in the air atmosphere, slowly cooling, crushing and sieving to obtain the high-pressure lithium nickel manganese oxide material with the spinel structure.
The high-voltage lithium nickel manganese oxide material is subjected to a fastening electrical property test, the first discharge specific capacity of 0.2C reaches 125mAh/g, the cycle capacity retention rate of 100 times is 98.5%, and the high-voltage lithium nickel manganese oxide material has excellent electrochemical properties.
Comparative example 1
Compared with the embodiment 1, the method for preparing the lithium nickel manganese oxide by using the waste lithium manganese oxide comprises the following steps:
s1, placing the waste lithium manganate powder in a rotary kiln, sintering for 3h at 350 ℃ in a methane atmosphere, and fully reacting to completely decompose the lithium manganate into mixed powder of manganese oxide and lithium carbonate;
s2, screening the mixed powder, testing the content of manganese in the mixed powder, adding nickel oxide according to the molar ratio of nickel to manganese of 1:3, and adding nickel oxide according to the molar ratio of lithium to manganese of 0.2: 1 adding lithium carbonate; adding aluminum hydroxide according to the molar ratio of aluminum to manganese of 1.8:29, mixing and adding the aluminum hydroxide into a ball mill, and mixing and ball-milling for 2 hours at the rotating speed of 500r/min to obtain a mixture;
and S3, transferring the mixture into a tube furnace, sintering for 18h at 750 ℃ in an air atmosphere, slowly cooling, crushing and sieving to obtain the high-pressure lithium nickel manganese oxide material with the spinel structure.
The high-voltage lithium nickel manganese oxide material is subjected to a fastening electricity performance test, the first discharge specific capacity of 0.2C reaches 111mAh/g, and the cycle capacity retention rate of 100 times is 82.6%. Conditions changed compared to example 1: this comparative example had too low a sintering temperature in step S1, which was too low to decompose the lithium manganate into lithium carbonate and manganese oxide or incompletely decomposed, resulting in poor homogeneity or a large amount of impure phases in the material sintered in step S3, affecting the electrical properties.
Comparative example 2
Compared with the embodiment 1, the method for preparing the lithium nickel manganese oxide by using the waste lithium manganese oxide comprises the following steps:
s1, placing the waste lithium manganate powder in a rotary kiln, sintering for 3h at 450 ℃ in a methane atmosphere, and fully reacting to completely decompose the lithium manganate into mixed powder of manganese oxide and lithium carbonate;
s2, screening the mixed powder, testing the content of manganese in the mixed powder, adding nickel oxide according to the molar ratio of nickel to manganese of 1:3, and adding nickel oxide according to the molar ratio of lithium to manganese of 0.13: 1 adding lithium carbonate; adding aluminum hydroxide according to the molar ratio of aluminum to manganese of 1.8:29, mixing and adding the aluminum hydroxide into a ball mill, and mixing and ball-milling for 2 hours at the rotating speed of 500r/min to obtain a mixture;
and S3, transferring the mixture into a tube furnace, sintering for 18h at 750 ℃ in an air atmosphere, slowly cooling, crushing and sieving to obtain the high-pressure lithium nickel manganese oxide material with the spinel structure.
The high-voltage lithium nickel manganese oxide material is subjected to a fastening electricity performance test, the first discharge specific capacity of 0.2C reaches 108mAh/g, and the cycle capacity retention rate of 100 times is 79.5%. Conditions changed compared to example 1: this comparative example is too low in the molar ratio of lithium to manganese at step S2, and part of manganese ions and nickel ions do not pair with lithium ions to form a crystal form of spinel, becoming a hetero phase affecting electrical properties.
Comparative example 3
Compared with the embodiment 1, the method for preparing the lithium nickel manganese oxide by using the waste lithium manganese oxide comprises the following steps:
s1, placing the waste lithium manganate powder in a rotary kiln, sintering for 3h at 450 ℃ in a methane atmosphere, and fully reacting to completely decompose the lithium manganate into mixed powder of manganese oxide and lithium carbonate;
s2, screening the mixed powder, testing the content of manganese in the mixed powder, adding nickel oxide according to the molar ratio of nickel to manganese of 1:3, and adding nickel oxide according to the molar ratio of lithium to manganese of 0.2: 1 adding lithium carbonate; adding aluminum hydroxide according to the molar ratio of aluminum to manganese of 1.8:29, mixing and adding the aluminum hydroxide into a ball mill, and mixing and ball-milling for 2 hours at the rotating speed of 500r/min to obtain a mixture;
and S3, transferring the mixture into a tube furnace, sintering for 18h at 1100 ℃ in the air atmosphere, slowly cooling, crushing and sieving to obtain the high-pressure lithium nickel manganese oxide material with the spinel structure.
The high-voltage lithium nickel manganese oxide material is subjected to a fastening electricity performance test, the first discharge specific capacity of 0.2C reaches 116mAh/g, and the cycle capacity retention rate of 100 times is 75.3%. Conditions changed compared to example 1: in this comparative example, the sintering temperature was too high in step S3, resulting in increased lithium nickel manganese oxide defects, increased impurity phases, and deteriorated cycle performance.
The examples described herein are merely illustrative of the preferred embodiments of the present invention and do not limit the spirit and scope of the present invention, and various modifications and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide is characterized by comprising the following steps: the method comprises the following steps:
s1: sintering waste lithium manganate powder in a reducing atmosphere to completely decompose the lithium manganate powder into mixed powder of manganese oxide and lithium carbonate;
s2: adding a nickel source, a lithium source and a doping element compound for improving the cycling stability of the anode material into the mixed powder respectively, and performing full mixing and ball milling to obtain a mixture;
s3: sintering the mixture obtained in the step S2 in an air atmosphere, cooling, crushing and sieving to obtain the molecular formula LiMn3xNixM2-4xO4The lithium nickel manganese oxide.
2. The method for preparing lithium nickel manganese oxide by using waste lithium manganese oxide according to claim 1, which is characterized in that: the reducing atmosphere in step S1 includes one or more of methane, natural gas, and carbon monoxide.
3. The method for preparing lithium nickel manganese oxide by using waste lithium manganese oxide according to claim 2, characterized in that: the sintering temperature of the lithium manganate powder is 400-800 ℃, and the sintering time is 2-5 h.
4. The method for preparing lithium nickel manganese oxide by using waste lithium manganese oxide according to claim 1, which is characterized in that: in the step S2, the doping element compound is a doping element hydroxide, the nickel source includes one or more of nickel oxide, nickel hydroxide, nickel sulfate, nickel carbonate, and nickel nitrate, and the lithium source includes one of lithium carbonate, lithium hydroxide, and lithium nitrate.
5. The method for preparing lithium nickel manganese oxide by using waste lithium manganese oxide according to claim 4, characterized in that: the hydroxide of the doping element is one of aluminum hydroxide, ferric hydroxide, magnesium hydroxide, copper hydroxide and niobium hydroxide.
6. The method for preparing lithium nickel manganese oxide by using waste lithium manganese oxide according to claim 1 or 5, characterized in that: the molar ratio of the nickel source to the manganese element in the mixed powder is (0.8-1.2): 3; the molar ratio of the lithium source to the manganese element in the mixed powder is (0.15-0.4): 1; the molar ratio of the doping elements in the doping element compound to the manganese elements in the mixed powder is (1-4): 29.
7. the method for preparing lithium nickel manganese oxide by using waste lithium manganese oxide according to claim 5, characterized in that: the molar ratio of the nickel source to the manganese element in the mixed powder is 1: 3; the molar ratio of the lithium source to the manganese element in the mixed powder is (0.18-0.30): 1; the molar ratio of the doping elements in the doping element compound to the manganese elements in the mixed powder is (1.5-2.5): 29.
8. the method for preparing lithium nickel manganese oxide by using waste lithium manganese oxide according to claim 6, characterized in that: and step S2, fully mixing the raw materials by using a ball mill, wherein the ball milling time is 1-5 h, and the rotating speed of the ball mill is 500-800 r/min.
9. The method for preparing lithium nickel manganese oxide by using waste lithium manganese oxide according to claim 1, which is characterized in that: in the step S3, the sintering temperature is 750-900 ℃, and the sintering time is 13-30 h.
10. A lithium nickel manganese oxide is characterized in that: the method for preparing the lithium nickel manganese oxide by using the waste lithium manganese oxide as claimed in any one of claims 1 to 9.
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