CN110336016A - A kind of preparation method for mixing aluminium LiMn2O4 - Google Patents
A kind of preparation method for mixing aluminium LiMn2O4 Download PDFInfo
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- CN110336016A CN110336016A CN201910638681.7A CN201910638681A CN110336016A CN 110336016 A CN110336016 A CN 110336016A CN 201910638681 A CN201910638681 A CN 201910638681A CN 110336016 A CN110336016 A CN 110336016A
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 53
- 239000004411 aluminium Substances 0.000 title claims abstract description 52
- 238000002156 mixing Methods 0.000 title claims abstract description 50
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 45
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 33
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 32
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 23
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 229910006330 Li—Mn—Al—O Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000004663 powder metallurgy Methods 0.000 claims abstract description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- 230000035484 reaction time Effects 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 4
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 238000005352 clarification Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052744 lithium Inorganic materials 0.000 abstract description 7
- 229910001947 lithium oxide Inorganic materials 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 aluminium manganese Chemical compound 0.000 description 1
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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 belongs to be passed through air after LiMn2O4 preparation and technical field of modification more particularly to a kind of preparation method for mixing aluminium LiMn2O4, including manganese powder addition water and ammonium chloride solution to be reacted；Ammonium hydroxide and ammonium chloride mixed solution are sequentially added in reaction process, liquor alumini chloridi, filtration washing is dried to obtain the mangano-manganic oxide powder for mixing aluminium after reaction；Obtained powder is added in clear lithia water and obtains amorphous Li-Mn-Al-O powder after heating reaction, obtains mixing aluminium LiMn2O4 after powder metallurgy roasting；This method reacts generation by the mangano-manganic oxide of Uniform Doped aluminium in lithia water and mixes aluminium LiMn2O4, it improves lithium carbonate and mangano-manganic oxide mixing and LiMn2O4 mixes the uniformity of aluminium, the capacity and cyclical stability of LiMn2O4 is greatly improved, and non-high-purity lithium carbonate can be used to generate high-purity lithium carbonate as lithium source by pyrolysis after hydrogenation, realize low cost, high performance target.
Description
Technical field
The invention belongs to LiMn2O4 preparation and technical field of modification, and in particular to a kind of preparation method for mixing aluminium LiMn2O4.
Background technique
With the fast development for applying the new-energy automobile electrical source of power field for representative with electric vehicle, in electric car
The advantages that utilization rate of lithium battery obviously rises, and lithium manganate battery is because its is at low cost, good rate capability is electronic in car
It is used widely in the fields such as bicycle.But there are capacity attenuations for LiMn2O4 fastly (especially under hot conditions), and cycle life is short
The shortcomings that, it is limited in the application in vehicle mounted dynamic battery high-end applications field.Studies have shown that the adulterated al in lithium manganate material
The stability of material structure can be improved in element, avoids the dissolution of manganese during high temperature circulation, so as to improve lithium manganate material height
Cycle performance under temperature.But the doping way of conventional solid method mixing is difficult to ensure the uniformity coefficient of mixing, the capacity of product
It is bad with cycle performance.
In recent years, Japan and Korea S and Chinese Enterprise by the way of mixing aluminium to front end doping and rear end doping is concentrated mainly on, such as
Patent application 201610152937.X provides a kind of method that a step is dual modified to mangaic acid lithium doping, cladding, specific steps
It is as follows: (1) it weighs spherical mangano-manganic oxide and is dissolved in distilled water or ethyl alcohol, 50-90 DEG C of water-bath stirring；(2) silicon source is added
Enter in step (1) acquired solution, is slowly dropped into after dilution with (1) described solution the step of the stirring of 300~600rmp/min revolving speed
In, 30-60min is persistently stirred, suspension is obtained；(3) dry, obtain powder；(4) powder and lithium salts for obtaining step (3)
Mixed grinding is heated up 600-650 DEG C of heat preservation 7-8h, 750-850 DEG C of heat preservation 10-15h with 2-4 DEG C/min, is adulterated, coated pair
Weight modified spinelle type LiMn2O4.Although this method synthetic method is relatively simple, this mangano-manganic oxide mix aluminium mode with
And the effect is unsatisfactory for back lithium source solid phase method ball milling mixing, properties of product are general.
In addition, patent 201310131342.2 is disclosing a kind of preheating synthesis metallic aluminium doped spinel LiMn2O4 just
The method of pole material, the specific steps are as follows: 1) by lithium carbonate, electrolytic manganese dioxide, ANN aluminium nitrate nonahydrate according to a certain percentage with
Dehydrated alcohol is dispersing agent, and reaction precursor is obtained after ball milling, drying；2) by presoma respectively in 400-500 DEG C of pre-burning 4-
6h, 750 DEG C of calcining 6-36h, then be placed in the tube furnace for be connected with oxygen and make annealing treatment, room temperature is naturally cooled to, is ground up, sieved i.e.
Obtain anode material for lithium-ion batteries.Although this method technique is very simple, dehydrated alcohol and aluminum nitrate are in later period high temperature
Pollution problem when roasting is difficult to solve, and the LiMn2O4 impurity content prepared is very high, and capacity is lower, is difficult practical metaplasia
It produces.
Therefore, it researchs and develops novel LiMn2O4 and mixes aluminium method, mangano-manganic oxide and lithium source mix uniform during raising
Property, silicon source is uniformly doped into the lattice of LiMn2O4 is high capacity, and high circulation performance LiMn2O4 prepares the significant challenge faced.
Summary of the invention
Product appearance caused by aluminium LiMn2O4 mixes unevenly because of various materials in the process is mixed in order to solve solid phase method preparation
Measure low, the bad problem of cycle performance.The present invention reacts Uniform Doped during generating mangano-manganic oxide using hydrolytic precipitation
Aluminium element, and mangano-manganic oxide presoma is uniformly combined into lithium source by way of precipitating in lithia water, greatly
Increase material mixing uniformity, improve the capacity and cycle performance for mixing aluminium LiMn2O4.
Specifically, the present invention provides a kind of preparation methods for mixing aluminium LiMn2O4, which comprises the following steps:
(1) manganese powder aoxidizes: by manganese piece ball milling at manganese powder, water is added and ammonium chloride uniformly mixes, is passed through sky under certain temperature
Gas agitating reaction；
(2) it mixes the preparation of aluminium mangano-manganic oxide powder: sequentially adding ammonium hydroxide to the solution of step (1) and ammonium chloride mixing is molten
Liquid, liquor alumini chloridi, filtration washing, which is dried to obtain, after reaction mixes aluminium mangano-manganic oxide powder；
(3) prepared by lithium bicarbonate: industrial level lithium carbonate being added to the water and is mixed and made into suspension solution, is passed through at room temperature
CO2It is clarified to solution；
(4) it mixes the preparation of aluminium LiMn2O4: aluminium mangano-manganic oxide powder will be mixed obtained in (2), (3) obtained solution is added
In, filtering spray drying obtains amorphous Li-Mn-Al-O powder after agitating and heating reaction, obtains mixing aluminium manganese after powder metallurgy is roasted
Sour lithium.
Preferably, in step (1) granularity of manganese powder in 200-400 mesh.
Preferably, manganese powder and water solid-to-liquid ratio are 150-300g/L in step (1).
Preferably, the mass ratio of ammonium chloride additional amount and manganese powder amount is 1:8-1:15 in step (1).
Preferably, step (1) the solution reaction temperature is 30-90 DEG C, reaction time 10-18h.
Preferably, step (1) water and ammonium chloride can be separately added into manganese powder and uniformly mix, and can also be made into ammonium chloride solution and add
Enter manganese powder uniformly to mix.
Preferably, the molar ratio of the additional amount and manganese powder amount of aluminium chloride is 0.01:1-0.04:1, aluminium chloride in step (2)
Aqueous solution mass percent is 10-30%；The molar ratio of ammonium hydroxide additional amount and aluminium chloride additional amount is 3:1-4:1.
Preferably, ammonium chloride is for maintaining adition process solution ph constant in 6.0-8.0.
Preferably, ammonium hydroxide is commercially available ammonium hydroxide.
Preferably, ammonium hydroxide and ammonium chloride mixed solution addition time are that manganese powder is completely oxidized to four oxidations three in step (2)
2h before and after manganese, mixed solution can add liquor alumini chloridi after adding.
Preferably, the reaction was continued after aluminium chloride and ammonium hydroxide are added in step (2) 2-4h.
Preferably, in step (3) water and lithium carbonate according to liquid solid product mass ratio 18:1-25:1L/g.
Preferably, the molar ratio of lithium carbonate additional amount and manganese powder amount is 1:2-1:4 in step (3).
Preferably, reaction temperature is 40-90 DEG C in step (4), reaction time 2-6h.
Preferably, step (4) high-temperature roasting temperature is 700-850 DEG C, reaction time 10-20h.
The invention adopts the above technical scheme, the advantage is that:
(1) present invention passes through hydrolytic precipitation reaction adulterated al during generating mangano-manganic oxide with aluminium salt in the solution
Element adulterates addition time and additional amount more uniform, and that pass through control aluminium salt, can be on the body phase of mangano-manganic oxide and surface
Selectivity carries out quantitative doping, and product applicability is wider；
(2) make lithium bicarbonate is quantitative to gradate by the concentration and temperature that adjust lithia water in the present invention
It at lithium carbonate Precipitation, is uniformly adhered to mix the surface of aluminium mangano-manganic oxide, than lithium carbonate, mangano-manganic oxide solid phase method machine
Tool mixing is more uniform, and product mixes that aluminium LiMn2O4 capacity is higher, and cycle performance is more preferably；
(3) process for generating lithium carbonate again after the lithium carbonate dissolution being added in the present invention has good impurity-eliminating effect,
Therefore it can use non-pure Lithium Carbonate preparation pure Lithium Carbonate to prepare high-purity LiMn2O4, the production of LiMn2O4 can be reduced
Cost.
Detailed description of the invention
The following further describes the present invention with reference to the drawings.
Fig. 1 is a kind of process flow chart for mixing aluminium LiMn2O4 of the present invention.
Specific embodiment
The present invention will be further described with reference to the examples below.Described embodiment and its result are merely to illustrate
The present invention, without the present invention described in detail in claims should will not be limited.
Embodiment 1
(1) 400g manganese piece is taken, with zirconia ball ball milling to partial size less than 200 mesh, the mixing that water and 50g ammonium chloride is added is molten
Liquid 2.60L, solution temperature control at 30 DEG C, are passed through air with air pump under stiring and are reacted；
(2) when manganese powder oxidation reaction (entire oxidation reaction is 18 hours time-consuming) carries out 16h, ammonium hydroxide and chlorination are sequentially added
The amount of the mixed solution of ammonium, liquor alumini chloridi, liquor alumini chloridi and ammonium hydroxide is respectively 0.073mol and 0.22mol, and aluminium chloride is molten
The mass fraction of liquid is 10%, and the mass fraction of ammonium hydroxide is 30%, the reaction was continued after oxidation reaction 4h, after reaction mistake
It obtains mixing aluminium mangano-manganic oxide powder after the filtration cakes torrefaction that filter washing obtains；
(3) 269g industry level lithium carbonate is added in water 4.84L water, and it is clear to solution to be passed through carbon dioxide gas under stiring
Clearly；
(4) by mixing of obtaining of step (2) after step (3) obtained solution is added in aluminium mangano-manganic oxide, solution is begun to warm up,
Temperature maintains 40 DEG C, reaction time 6h, empty at 700 DEG C to burn after the filtration cakes torrefaction that filtration washing obtains after reaction
20h obtains mixing aluminium LiMn2O4, and properties of product analysis is shown in Table 1.
Embodiment 2
(1) 400g manganese piece is taken, with zirconia ball ball milling to partial size less than 400 mesh, the mixing that water and 27g ammonium chloride is added is molten
Liquid 1.33L, solution temperature control at 90 DEG C, are passed through air with air pump under stiring and are reacted；
(2) when manganese powder oxidation reaction (entire oxidation reaction is 10 hours time-consuming) carries out 12h, ammonium hydroxide and chlorination are sequentially added
The amount of the mixed solution of ammonium, liquor alumini chloridi, liquor alumini chloridi and ammonium hydroxide is respectively 0.29mol and 1.16mol, liquor alumini chloridi
Mass fraction be 30%, the mass fraction of ammonium hydroxide is 30%, the reaction was continued after oxidation reaction 2h, is washed after reaction
It obtains mixing aluminium mangano-manganic oxide powder after the filtration cakes torrefaction being obtained by filtration；
(3) 135g industry level lithium carbonate is added in water 3.38L water, and it is clear to solution to be passed through carbon dioxide gas under stiring
Clearly；
(4) by mixing of obtaining of step (2) after step (3) obtained solution is added in aluminium mangano-manganic oxide, solution is begun to warm up,
Temperature maintains 90 DEG C, reaction time 2h, after washing the filtration cakes torrefaction being obtained by filtration after reaction, empty at 850 DEG C to burn
10h obtains mixing aluminium LiMn2O4, and properties of product analysis is shown in Table 1.
Embodiment 3
(1) 400g manganese piece is taken, with zirconia ball ball milling to partial size less than 300 mesh, the mixing that water and 40g ammonium chloride is added is molten
Liquid 2L, solution temperature control at 60 DEG C, are passed through air with air pump under stiring and are reacted；
(2) when manganese powder oxidation reaction (entire oxidation reaction is 16 hours time-consuming) carries out 14h, ammonium hydroxide and chlorination are sequentially added
The amount of the mixed solution of ammonium, liquor alumini chloridi, liquor alumini chloridi and ammonium hydroxide is respectively 0.22mol and 0.77mol, liquor alumini chloridi
Mass fraction be 26%, the mass fraction of ammonium hydroxide is 30%, the reaction was continued after oxidation reaction 4h, is washed after reaction
It obtains mixing aluminium mangano-manganic oxide powder after the filtration cakes torrefaction being obtained by filtration；
(3) 202g industry level lithium carbonate is added in water 4.04L water, and it is clear to solution to be passed through carbon dioxide gas under stiring
Clearly；
(4) by mixing of obtaining of step (2) after step (3) obtained solution is added in aluminium mangano-manganic oxide, solution is begun to warm up,
Temperature maintains 70 DEG C, reaction time 4h, after washing the filtration cakes torrefaction being obtained by filtration after reaction, empty at 750 DEG C to burn
15h obtains mixing aluminium LiMn2O4, and properties of product analysis is shown in Table 1.
Embodiment 4
(1) 400g manganese piece is taken, with zirconia ball ball milling to partial size less than 350 mesh, the mixing that water and 35g ammonium chloride is added is molten
Liquid 1.60L, solution temperature control at 70 DEG C, are passed through air with air pump under stiring and are reacted；
(2) when manganese powder oxidation reaction (entire oxidation reaction is 14 hours time-consuming) carries out 12h, ammonium hydroxide and chlorination are sequentially added
The amount of the mixed solution of ammonium, liquor alumini chloridi, liquor alumini chloridi and ammonium hydroxide is respectively 0.15mol and 0.54mol, liquor alumini chloridi
Mass fraction be 20%, the mass fraction of ammonium hydroxide is 30%, the reaction was continued after oxidation reaction 3h, is washed after reaction
It obtains mixing aluminium mangano-manganic oxide powder after the filtration cakes torrefaction being obtained by filtration；
(3) 215g industry level lithium carbonate is added in water 4.30L water, and it is clear to solution to be passed through carbon dioxide gas under stiring
Clearly；
(4) by mixing of obtaining of step (2) after step (3) obtained solution is added in aluminium mangano-manganic oxide, solution is begun to warm up,
Temperature maintains 65 DEG C, reaction time 4.5h, after washing the filtration cakes torrefaction being obtained by filtration after reaction, empty at 820 DEG C
It burns 12h to obtain mixing aluminium LiMn2O4, properties of product analysis is shown in Table 1.
Embodiment 5
(1) 400g manganese piece is taken, with zirconia ball ball milling to partial size less than 280 mesh, the mixing that water and 40g ammonium chloride is added is molten
Liquid 1.43L, solution temperature control at 80 DEG C, are passed through air with air pump under stiring and are reacted；
(2) when manganese powder oxidation reaction (entire oxidation reaction is 12 hours time-consuming) carries out 14h, ammonium hydroxide and chlorination are sequentially added
The amount of the mixed solution of ammonium, liquor alumini chloridi, liquor alumini chloridi and ammonium hydroxide is respectively 0.25mol and 0.88mol, liquor alumini chloridi
Mass fraction be 26%, the mass fraction of ammonium hydroxide is 30%, the reaction was continued after oxidation reaction 2.5h, is washed after reaction
It obtains mixing aluminium mangano-manganic oxide powder after washing the filtration cakes torrefaction being obtained by filtration；
(3) 250g industry level lithium carbonate is added in water 5.30L water, and it is clear to solution to be passed through carbon dioxide gas under stiring
Clearly；
(4) by mixing of obtaining of step (2) after step (3) obtained solution is added in aluminium mangano-manganic oxide, solution is begun to warm up,
Temperature maintains 50 DEG C, reaction time 3.5h, after washing the filtration cakes torrefaction being obtained by filtration after reaction, empty at 780 DEG C
It burns 14h to obtain mixing aluminium LiMn2O4, properties of product analysis is shown in Table 1.
Comparative example 1
(1) 400g manganese piece is taken, with zirconia ball ball milling to partial size less than 50 mesh, the mixing that water and 40g ammonium chloride is added is molten
Liquid 2L, solution temperature control at 60 DEG C, are passed through air with air pump under stiring and are reacted；
(2) when manganese powder oxidation reaction (entire oxidation reaction is 16 hours time-consuming) carries out 14h, ammonium hydroxide and chlorination are sequentially added
The amount of the mixed solution of ammonium, liquor alumini chloridi, liquor alumini chloridi and ammonium hydroxide is respectively 0.22mol and 0.77mol, liquor alumini chloridi
Mass fraction be 26%, the mass fraction of ammonium hydroxide is 30%, the reaction was continued after oxidation reaction 4h, is washed after reaction
It obtains mixing aluminium mangano-manganic oxide powder after the filtration cakes torrefaction being obtained by filtration；
(3) 202g industry level lithium carbonate is added in water 4.04L water, and it is clear to solution to be passed through carbon dioxide gas under stiring
Clearly；
(4) by mixing of obtaining of step (2) after step (3) obtained solution is added in aluminium mangano-manganic oxide, solution is begun to warm up,
Temperature maintains 70 DEG C, reaction time 4h, after washing the filtration cakes torrefaction being obtained by filtration after reaction, empty at 750 DEG C to burn
15h obtains mixing aluminium LiMn2O4, and properties of product analysis is shown in Table 1.
Comparative example 2
(1) 400g manganese piece is taken, with zirconia ball ball milling to partial size less than 300 mesh, the mixing that water and 40g ammonium chloride is added is molten
Liquid 2L, solution temperature control at 60 DEG C, are passed through air with air pump under stiring and are reacted；
(2) when manganese powder oxidation reaction (entire oxidation reaction is 16 hours time-consuming) carries out 14h, ammonium hydroxide and chlorination are sequentially added
The amount of the mixed solution of ammonium, liquor alumini chloridi, liquor alumini chloridi and ammonium hydroxide is respectively 0.22mol and 0.77mol, liquor alumini chloridi
Mass fraction be 26%, the mass fraction of ammonium hydroxide is 30%, the reaction was continued after oxidation reaction 4h, is washed after reaction
It obtains mixing aluminium mangano-manganic oxide powder after the filtration cakes torrefaction being obtained by filtration；
(3) 202g industry level lithium carbonate is added in water 4.04L water, and it is clear to solution to be passed through carbon dioxide gas under stiring
Clearly；
(4) by mixing of obtaining of step (2) after step (3) obtained solution is added in aluminium mangano-manganic oxide, solution is begun to warm up,
Temperature maintains 30 DEG C, reaction time 4h, after washing the filtration cakes torrefaction being obtained by filtration after reaction, empty at 750 DEG C to burn
15h obtains mixing aluminium LiMn2O4, and properties of product analysis is shown in Table 1.
1 solwution method of table synthesizes the performance evaluation for mixing aluminium LiMn2O4
The above is only to the specific implementation method applied for a patent, it is noted that for the common of the art
For technical staff, under conditions of not departing from the application patent principle, several modification and supplement can also be carried out, these are repaired
Changing and supplementing also should be within the scope of protection of this application.
Claims (10)
1. a kind of preparation method for mixing aluminium LiMn2O4, which comprises the following steps:
(1) manganese powder aoxidizes: by manganese piece ball milling at manganese powder, water is added and ammonium chloride uniformly mixes, is passed through air under certain temperature and stirs
Mix reaction；
(2) it mixes the preparation of aluminium mangano-manganic oxide powder: sequentially adding ammonium hydroxide and ammonium chloride mixed solution, chlorine to the solution of step (1)
Change aluminum solutions, filtration washing, which is dried to obtain, after reaction mixes aluminium mangano-manganic oxide powder；
(3) prepared by lithium bicarbonate: industrial level lithium carbonate being added to the water and is mixed and made into suspension solution, is passed through CO at room temperature2Extremely
Solution clarification；
(4) it mixes the preparation of aluminium LiMn2O4: aluminium mangano-manganic oxide powder will be mixed obtained in (2) and be added in (3) obtained solution, stirred
Filtering spray drying obtains amorphous Li-Mn-Al-O powder after mixing heating reaction, obtains mixing aluminium LiMn2O4 after powder metallurgy is roasted.
2. preparation method according to claim 1, which is characterized in that the granularity of manganese powder is in 200-400 mesh in step (1).
3. preparation method according to claim 1, which is characterized in that manganese powder and water solid-to-liquid ratio are 150- in step (1)
300g/L。
4. preparation method according to claim 1, which is characterized in that ammonium chloride additional amount and manganese powder amount in step (1)
Mass ratio is 1:8-1:15.
5. preparation method according to claim 1, which is characterized in that step (1) the solution reaction temperature is 30-90
DEG C, reaction time 10-18h.
6. preparation method according to claim 1, which is characterized in that the additional amount and manganese powder amount of aluminium chloride in step (2)
Molar ratio be 0.01:1-0.04:1, aluminum chloride aqueous solution mass percent be 10-30%；Ammonium hydroxide additional amount and aluminium chloride add
The molar ratio for entering amount is 3:1-4:1.
7. preparation method according to claim 1, which is characterized in that ammonium hydroxide and ammonium chloride mixed solution add in step (2)
The angle of incidence is that manganese powder is completely oxidized to 2h before and after mangano-manganic oxide, and mixed solution can add liquor alumini chloridi after adding.
8. preparation method according to claim 1, which is characterized in that aluminium chloride and ammonium hydroxide continue after being added in step (2)
React 2-4h.
9. preparation method according to claim 1, which is characterized in that water and lithium carbonate are according to liquid solid product in step (3)
Mass ratio 18:1-25:1L/g；The molar ratio of the lithium carbonate additional amount and manganese powder amount is 1:2-1:4.
10. preparation method according to claim 1, which is characterized in that reaction temperature is 40-90 DEG C in step (4), reaction
Time is 2-6h；The high-temperature roasting temperature is 700-850 DEG C, reaction time 10-20h.
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