CN102544472A - Spherical aluminum-doped manganous-manganic oxide and preparation method thereof - Google Patents
Spherical aluminum-doped manganous-manganic oxide and preparation method thereof Download PDFInfo
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- CN102544472A CN102544472A CN201110457933XA CN201110457933A CN102544472A CN 102544472 A CN102544472 A CN 102544472A CN 201110457933X A CN201110457933X A CN 201110457933XA CN 201110457933 A CN201110457933 A CN 201110457933A CN 102544472 A CN102544472 A CN 102544472A
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- aluminum
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- manganic oxide
- spherical aluminum
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 title abstract 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 123
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011572 manganese Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 12
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 39
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 12
- 229940099596 manganese sulfate Drugs 0.000 claims description 12
- 235000007079 manganese sulphate Nutrition 0.000 claims description 12
- 239000011702 manganese sulphate Substances 0.000 claims description 12
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 11
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 10
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229960001484 edetic acid Drugs 0.000 claims description 9
- 235000013024 sodium fluoride Nutrition 0.000 claims description 9
- 239000011775 sodium fluoride Substances 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 7
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 7
- 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 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 6
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 235000015424 sodium Nutrition 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 14
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 11
- 239000004411 aluminium Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- -1 sulfate radical Chemical class 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 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
- 238000005406 washing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QOMYXTKMJQKPQJ-UHFFFAOYSA-N alumane;manganese Chemical compound [AlH3].[Mn].[Mn].[Mn] QOMYXTKMJQKPQJ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses spherical aluminum-doped manganous-manganic oxide. The spherical aluminum-doped manganous-manganic oxide is a composite oxide, and the chemical formula of the spherical aluminum-doped manganous-manganic oxide is Mn3O4*xAl2O3, wherein x is within 0.01-0.5, the D50 granularity is 5-20 microns, and the tap density is not less than 2.0g/cm<3>. The invention also provides a preparation method of the spherical aluminum-doped manganous-manganic oxide. The preparation method of the spherical aluminum-doped manganous-manganic oxide comprises the following steps of: firstly weighting an aluminum salt and a manganese salt for preparing a mixed solution including trivalent aluminum and divalent manganese with water; preparing a sodium hydroxide solution, adding the mixed solution and the sodium hydroxide solution to a reactor according to the certain mol ratio to carry out a coprecipitation reaction, controlling the reaction temperature to be 40-80 DEG C and a pH value to be 7.5-13.5, and carrying out an oxidation treatment; finally separating, rinsing and drying reaction products to acquire the spherical aluminum-doped manganous-manganic oxide. The spherical aluminum-doped manganous-manganic oxide disclosed by the invention has the advantages of optimized microstructure, high tap density and realization on uniform aluminum doping on a molecular level, and the preparation method of the spherical aluminum-doped manganous-manganic oxide disclosed by the invention has the advantages of simple process step and small pollution.
Description
Technical field
The present invention relates to oxide of a kind of manganese of mixing aluminium and preparation method thereof, relate in particular to a kind of aluminium trimanganese tetroxide particle and preparation method thereof of mixing.
Background technology
LiMn2O4 is used for especially power-type lithium ion battery of lithium ion battery, have advantages such as aboundresources, low price, security performance are good, environmentally safe, but its storge quality, cycle performance and high-temperature behavior is the key that influences its use.
At present, make LiMn2O4 and mainly use electrolytic manganese dioxide, through mixing with lithium carbonate or lithium hydroxide as raw material; Roasting and making under 800 ℃ of left and right sides high temperature then, the quality of the LiMn2O4 product that obtains like this is good inadequately, and major defect is that the electrolytic manganese dioxide powder is made by mechanical disintegration; The bad control of its granule-morphology is generally the indefinite form particle, and specific area is big; The impurity content of electrolytic manganese dioxide itself is high in addition; Be generally more than 1.2% like sulfate radical, calcium, magnesium addition about 300ppm, the level of sodium impurity content 3000ppm; And in crushing process, bring iron tramp easily into because of the plant equipment problem, these factors all cause negative effect to the quality of LiMn2O4 product.Producing high-quality LiMn2O4 preferably uses spherical mangano-manganic oxide to be raw material; Make through mixing through high-temperature roasting equally with lithium carbonate or lithium hydroxide; Be that the production process of mangano-manganic oxide is a wet method on the other hand because its appearance, helps the processing of battery production process for sphere, specific area are little and reduces the capacity attenuation that the manganese dissolving is caused on the one hand; Can control impurity content well, help keeping the cycle performance of battery.
For further improving the LiMn2O4 performance of products, avoiding the destruction of Jahn-Teller effect to lithium manganate material, more useful way is in lithium manganate material, to mix aluminium ion to improve stability of structure.The mode of mixing aluminium at present is when LiMn2O4 mixes with lithium source substance, to mix aluminium salt or aluminum oxide simultaneously; When high-temperature roasting, make aluminium ion infiltrate into lithium manganate material inside; But the effect of this mode is unsatisfactory; Might the inhomogeneous material that causes of batch mixing inhomogeneous, and the aluminising process mainly concentrates on the particle surface of material, and the aluminising effect of particle nexine can not get ensureing.
Summary of the invention
The technical problem that the present invention will solve is the deficiency that overcomes prior art; The spherical aluminum-doped mangano-manganic oxide that a kind of microstructure optimization, tap density are high, on molecular level, realize evenly mixing aluminium is provided, also corresponding provide a kind of can effectively control impurity content and scope, processing step simply, pollution less, spherical aluminum-doped METHODS OF MAKING MANGANIC MANGANOUS OXIDE that cost is low.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of spherical aluminum-doped mangano-manganic oxide, and said spherical aluminum-doped mangano-manganic oxide is a kind of composite oxides, and its chemical formula is Mn
3O
4 xAl
2O
3, wherein,
x=0.01～0.5, the D of said spherical aluminum-doped mangano-manganic oxide
50Granularity is 5 μ m～20 μ m, the tap density>=2.0g/cm of said spherical aluminum-doped mangano-manganic oxide
3(be preferably 2.2 g/cm
3～3.0 g/cm
3).
As a total technical conceive, the present invention also provides a kind of above-mentioned spherical aluminum-doped METHODS OF MAKING MANGANIC MANGANOUS OXIDE, may further comprise the steps:
(1) takes by weighing the soluble manganese salt of aluminum soluble salt and bivalent manganese by the stoichiometric proportion in the said chemical formula, be mixed with the mixed solution that contains trivalent aluminium ion and divalent manganesetion with pure water or deionized water;
(2) weighing sodium hydroxide is mixed with sodium hydroxide solution with pure water or deionized water;
(3) join the sodium hydroxide solution in mixed solution in the above-mentioned steps (1) and the step (2) in the reactor continuously; The total mole number of divalent manganesetion and trivalent aluminium ion is (0.5～1.5) with the ratio of the molal quantity of NaOH in the control reactor: 2; Carry out coprecipitation reaction then; Control reaction temperature is 40 ℃～80 ℃; The pH value of reactant liquor is 7.5～13.5, and the oxidant that in reactant liquor, adds capacity simultaneously carries out oxidation processes to the sediment that generates in the course of reaction;
(4) product after the above-mentioned steps (3) is separated, the sediment after separating with pure water or rinsed with deionized water then is again through being drying to obtain spherical aluminum-doped mangano-manganic oxide.
As further improvement to above-mentioned spherical aluminum-doped METHODS OF MAKING MANGANIC MANGANOUS OXIDE; Said step (1) join mixed solution in also be added with blender A, said blender A comprises at least a in department basis, OP-10, lauryl sodium sulfate, ammonium fluoride, ammonium chloride, ammonium sulfate, ammonium nitrate, sodium fluoride, ethanol, ethylene glycol, isopropyl alcohol, n-butanol, ethylenediamine tetra-acetic acid (EDTA), disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, carboxymethyl cellulose, sodium carboxymethylcellulose, the polyvinyl alcohol.
Above-mentioned spherical aluminum-doped METHODS OF MAKING MANGANIC MANGANOUS OXIDE; Said step (1) join mixed solution in; The total concentration of divalent manganesetion preferably is controlled at 20g/L～200g/L; The total concentration of trivalent aluminium ion preferably is controlled at 0.05g/L～50g/L, and the total concentration of said blender A preferably is controlled at 0.1g/L～20g/L.
As further improvement to above-mentioned spherical aluminum-doped METHODS OF MAKING MANGANIC MANGANOUS OXIDE; Said step (2) join sodium hydroxide solution in also be added with blender B, said blender B comprises at least a in department basis, OP-10, lauryl sodium sulfate, ammoniacal liquor, ethylenediamine, ammonium fluoride, ammonium chloride, ammonium sulfate, ammonium nitrate, sodium fluoride, ethanol, ethylene glycol, isopropyl alcohol, n-butanol, EDTA, EDTA disodium, EDTA four sodium, carboxymethyl cellulose, sodium carboxymethylcellulose, the polyvinyl alcohol.
Above-mentioned spherical aluminum-doped METHODS OF MAKING MANGANIC MANGANOUS OXIDE, said step (2) join sodium hydroxide solution in, concentration sodium hydroxide preferably is controlled at 50g/L～500g/L, the total concentration of said blender B preferably is controlled at 0.1g/L～50g/L.
Above-mentioned blender A and/or the effect of blender B all are that the deposition of being convenient in the subsequent step (3) is grown to sphere; Can the direction of growth that change deposit seed through selective absorption on the mechanism; Also can be the speed of growth that can improve crystal grain through the interface wet ability that changes deposit seed and reactant liquor, can also be to influence the speed of growth that reaction speed is controlled deposit seed; No matter,, then all can heat and come accelerate dissolution if select for use the dissolution velocity of material slow for blender A and/or blender B.
Above-mentioned spherical aluminum-doped METHODS OF MAKING MANGANIC MANGANOUS OXIDE; Soluble manganese salt in the said step (1) preferably includes at least a in manganese sulfate, manganese nitrate, the manganese chloride; For example can be a kind of in the aforementioned soluble manganese salt; Also can be the mixing of the arbitrary proportion of wherein any two kinds of manganese salt, can also be wherein three kinds the mixing of arbitrary proportion.
Above-mentioned spherical aluminum-doped METHODS OF MAKING MANGANIC MANGANOUS OXIDE; Aluminum soluble salt in the said step (1) preferably includes at least a in aluminum sulfate, aluminum nitrate, the aluminium chloride; For example can be a kind of in the aforementioned aluminum soluble salt; Also can be the mixing of the arbitrary proportion of wherein any two kinds of aluminium salt, can also be wherein three kinds the mixing of arbitrary proportion.
Above-mentioned spherical aluminum-doped METHODS OF MAKING MANGANIC MANGANOUS OXIDE, the oxidant in the said step (3) preferably include at least a in hydrogen peroxide solution, oxygen, air, ammonium persulfate or the sodium thiosulfate.
Compared with prior art, the invention has the advantages that: preparation method's of the present invention technological process is simple, is easy to realize large-scale production; Main building-up process is a wet production, can be through controlling the impurity content that raw-material impurity level reduces product; Produce microstructure and be spherical powder particle, that has realized molecular level evenly mixes the aluminium effect.The tap density of the spherical aluminum-doped mangano-manganic oxide product that use the inventive method produces is up to 2.0g/cm
3More than, be the important raw and processed materials of synthetic high-quality LiMn2O4.Product of the present invention can significantly improve the cycle performance and the high-temperature behavior of LiMn2O4 product; And can strengthen the application of LiMn2O4 product in lithium ion compact battery and electrokinetic cell, the LiMn2O4 synthetic with product of the present invention is the ideal material of lithium-ion-power cell and high-end lithium ion compact battery.
Description of drawings
Fig. 1 is the electron micrograph of the spherical aluminum-doped mangano-manganic oxide that makes in the embodiment of the invention 1.
Fig. 2 is the electron micrograph of the spherical aluminum-doped mangano-manganic oxide that makes in the embodiment of the invention 2.
Embodiment
Below in conjunction with Figure of description and specific embodiment the present invention is further described.
A kind of spherical aluminum-doped mangano-manganic oxide of the present invention, this spherical aluminum-doped mangano-manganic oxide is a kind of composite oxides, the chemical formula of this spherical aluminum-doped mangano-manganic oxide is Mn
3O
4 xAl
2O
3, wherein,
x=0.01～0.5, D
50Granularity is 5 μ m～20 μ m, the tap density>=2.0g/cm of this spherical aluminum-doped mangano-manganic oxide
3
The manufacturing approach of this spherical aluminum-doped mangano-manganic oxide dusty material specifically can may further comprise the steps:
(1) takes by weighing the soluble manganese salt of aluminum soluble salt and bivalent manganese by the stoichiometric proportion in the above-mentioned chemical formula, be mixed with the mixed solution that contains divalent manganesetion 20g/L～200g/L and contain trivalent aluminium ion 0.05g/L～50g/L with pure water or deionized water; Soluble manganese salt is at least a in manganese sulfate, manganese nitrate, the manganese chloride; Aluminum soluble salt is at least a in aluminum sulfate, aluminum nitrate, the aluminium chloride;
(2) take by weighing blender A, it is joined in the mixed solution that step (1) obtains, the back that stirs forms that to contain blender A concentration be the mixed solution of 0.1g/L～20g/L; Blender A is at least a (according to the operating position of blender B, blender A can not add) in department's basis, OP-10, lauryl sodium sulfate, ammonium fluoride, ammonium chloride, ammonium sulfate, ammonium nitrate, sodium fluoride, ethanol, ethylene glycol, isopropyl alcohol, n-butanol, EDTA, EDTA disodium, EDTA four sodium, carboxymethyl cellulose, sodium carboxymethylcellulose and the polyvinyl alcohol; In the manganese salt solution of preparation, if deposition or impurity are arranged, need filter earlier or the removal of impurities processing, be before preparation, raw material to be carried out removal of impurities to handle the preferably opportunity of removing impurity;
(3) weighing sodium hydroxide uses pure water or deionized water to be mixed with the sodium hydroxide solution (used NaOH can be commercially available solid piece alkali, also can directly with commercially available liquid caustic soda prepare) of concentration as 50g/L～500g/L;
(4) take by weighing blender B, it is joined in the sodium hydroxide solution that step (3) obtains, the back that stirs forms that to contain blender B concentration be the sodium hydroxide solution of 0.1g/L～50g/L; Blender B is at least a (can according to circumstances not with blender B) in department basis, OP-10, lauryl sodium sulfate, ammoniacal liquor, ethylenediamine, ammonium fluoride, ammonium chloride, ammonium sulfate, ammonium nitrate, sodium fluoride, ethanol, ethylene glycol, isopropyl alcohol, n-butanol, EDTA, EDTA disodium, EDTA four sodium, carboxymethyl cellulose, sodium carboxymethylcellulose and the polyvinyl alcohol; Sodium hydroxide solution behind the sodium hydroxide solution of preparation or the adding blender B if deposition or impurity are arranged, need filter after preparation or the removal of impurities processing, for the impurity content that makes final products is minimum, preferably before preparation, raw material is carried out removal of impurities and handles;
(5) be (0.5～1.5) with the mixed solution that obtains respectively in above-mentioned steps (2) and the step (4) and sodium hydroxide solution in the ratio of the molal quantity sum of divalent manganesetion and trivalent aluminium ion and the molal quantity of NaOH: 2 ratio joins in the reactor (while promptly react time add in proportion) continuously; Carry out coprecipitation reaction; Control reaction temperature is 40 ℃～80 ℃; Through regulating the relative charging rate of manganese salt solution and sodium hydroxide solution; The pH value of control reactant liquor is 7.5～13.5; Simultaneously, the oxidant that in reactant liquor, adds capacity carries out oxidation processes to sediment, makes the manganous compound deposition be converted into mangano-manganic oxide; Oxidant is at least a in hydrogen peroxide solution, oxygen, air, ammonium persulfate or the sodium thiosulfate, and the consumption of oxidant can not be lower than the theoretical requirement of reaction; When course of reaction was continuous charging, the overfall on the product autoreactor was discharged;
(6) the middle product of discharging of centrifugal or sedimentation separation step (5); Again with pure water or rinsed with deionized water sediment; For guaranteeing water washing effect, the pH value of the washing lotion after the final washing of may command is 7～7.5, and is dry then; Dry run can directly be carried out in air, promptly gets spherical aluminum-doped mangano-manganic oxide powder-product after the drying.
Below in conjunction with Figure of description and specific embodiment the present invention is done further description.
Embodiment 1:
A kind of of the present invention spherical aluminum-doped mangano-manganic oxide as shown in Figure 1, the chemical formula of this spherical aluminum-doped mangano-manganic oxide is Mn
3O
40.052Al
2O
3, D
50Granularity is 9.7 μ m, and tap density is 2.4g/cm
3
Use pure water preparation divalent manganesetion concentration to be 58g/L and trivalent aluminium ion concentration manganese sulfate and aluminum sulfate mixed solution 20L, take by weighing 60g isopropyl alcohol and 70g sodium fluoride and join in the above-mentioned solution and stir as 1.0g/L; Use the sodium hydroxide solution 20L of pure water compound concentration as 200g/L; It in the ratio of the flow of manganese sulfate and aluminum sulfate mixed solution 500mL/h, manganese ion and aluminum ions molal quantity sum and the molal quantity of NaOH 1: 2 ratio; Use measuring pump that manganese sulfate and aluminum sulfate mixed solution and sodium hydroxide solution are added in the reactor of volume as 8L; The temperature of control reaction is 70 ℃, and the pH value of reactant liquor is 10.0, and the air of logical capacity carries out oxidation to deposition simultaneously; The overfall on product autoreactor top is discharged, and reaction is carried out stopping behind the 30h.Get the overflow product of 10h～20h, use after the sedimentation separation pure water wash several times to the pH value be 7.2, dry sediment must be mixed aluminium mangano-manganic oxide 310g in 120 ℃ baking oven then.
Product mangano-manganic oxide to present embodiment makes is tested, test result show its Mn element percentage composition be 69.6%, the percentage composition of Al element is 1.2%, size indicator D
50Be 9.7 μ m, tap density is 2.4g/cm
3, the photo of doing after ESEM (SEM) is observed is as shown in Figure 1, is spherical by visible its granule-morphology of Fig. 1.
Embodiment 2:
A kind of of the present invention spherical aluminum-doped mangano-manganic oxide as shown in Figure 2, the chemical formula of this spherical aluminum-doped mangano-manganic oxide is Mn
3O
40.075Al
2O
3, D
50Granularity is 11.7 μ m, and tap density is 2.2g/cm
3
Use pure water preparation divalent manganesetion concentration to be 58g/L and trivalent aluminium ion concentration manganese sulfate and aluminum sulfate mixed solution 200L, take by weighing 600g isopropyl alcohol and 700g sodium fluoride and join in the above-mentioned solution and stir as 1.5g/L; Use the sodium hydroxide solution 200L of pure water compound concentration as 120g/L; It in the mol ratio of flow, manganese ion and aluminum ions molal quantity sum and the NaOH of manganese sulfate and aluminum sulfate mixed solution 8L/h 1: 2 ratio; Use measuring pump that manganese sulfate and aluminum sulfate mixed solution and sodium hydroxide solution are added in the reactor of volume as 100L, the temperature of control reaction is 60 ℃, and the pH value of reactant liquor is 9.2; The air of logical capacity carries out oxidation to deposition simultaneously; The overfall on product autoreactor top is discharged, and reaction is carried out stopping behind the 19h, then the overflow product is mixed with product in the agitated reactor; Use after the sedimentation separation pure water wash several times to the pH value be 7.5, dry sediment must be mixed aluminium mangano-manganic oxide 11.4kg in 120 ℃ baking oven then.
The product that present embodiment is made is mixed the aluminium mangano-manganic oxide and is tested, test result show its Mn element percentage composition be 69.2%, the percentage composition of Al element is 1.7%, size indicator D
50Be 11.7 μ m, tap density is 2.2g/cm
3, it is as shown in Figure 2 to be ESEM (SEM) observation its result of back, is spherical by visible its granule-morphology of Fig. 2.
Embodiment 3:
A kind of spherical aluminum-doped mangano-manganic oxide of the present invention, the chemical formula of this spherical aluminum-doped mangano-manganic oxide is Mn
3O
40.25Al
2O
3, D
50Granularity is 17.2 μ m, and tap density is 2.2g/cm
3
Use pure water preparation to contain divalent manganesetion concentration and be 145g/L, trivalent aluminium ion concentration manganese nitrate and aluminum nitrate mixed solution 200L, take by weighing the 1080g ammonium fluoride and join in the above-mentioned mixed solution and stir as 12g/L; Use the sodium hydroxide solution 200L of pure water compound concentration, take by weighing the 1200g isopropyl alcohol and the 100g sodium carboxymethylcellulose joins in the sodium hydroxide solution, filter after the stirring and dissolving as 400g/L; It in the ratio of the flow of manganese nitrate and aluminum nitrate mixed solution 10L/h and manganese ion and aluminum ions molal quantity sum and the mole of NaOH 1: 2 ratio; Use measuring pump that aforesaid manganese nitrate and aluminum nitrate mixed solution and sodium hydroxide solution are added in the reactor that volume stirs as the band of 100L; The temperature of control reaction is 60 ℃; The pH value of reactant liquor is 9.2, and the hydrogen peroxide solution and the blowing air that add capacity simultaneously carry out oxidation to deposition, and the overfall on product autoreactor top is discharged; Reaction is carried out stopping behind the 20h; Then the product in the reactor is emitted and mixes with the product that overflows, use after the sedimentation separation pure water wash to the pH value be about 7.5, dry sediment must be mixed aluminium mangano-manganic oxide 38.6kg in 120 ℃ baking oven then.
The product that present embodiment is made is mixed the aluminium mangano-manganic oxide and is tested, test result show its Mn element percentage composition be 65.4%, the percentage composition of Al element is 5.3%, size indicator D
50Be 17.2 μ m, tap density is 2.2g/cm
3, do ESEM (SEM) and observe visible its granule-morphology in back for spherical.
Embodiment 4:
A kind of spherical aluminum-doped mangano-manganic oxide of the present invention, the chemical formula of this spherical aluminum-doped mangano-manganic oxide is Mn
3O
40.034Al
2O
3, D
50Granularity is 14.1 μ m, and tap density is 2.5g/cm
3
Use pure water preparation to contain divalent manganesetion concentration and be 73g/L and trivalent aluminium ion concentration manganese sulfate and aluminum sulfate mixed solution 30L as 0.9g/L; Use the sodium hydroxide solution 30L of pure water compound concentration, take by weighing that 180g ammonium chloride and 120g sodium fluoride join in the sodium hydroxide solution and stirring and dissolving is complete as 200g/L; It in the ratio of the flow of manganese sulfate and aluminum sulfate mixed solution 700mL/h and manganese ion and aluminum ions molal quantity sum and the mole of NaOH 1: 2 ratio; Use measuring pump that aforesaid manganese sulfate and aluminum sulfate mixed solution and sodium hydroxide solution are added in the reactor that volume stirs as the band of 8L; The temperature of control reaction is 70 ℃; The pH value of reactant liquor is 9.5; The air that feeds capacity simultaneously carries out oxidation to deposition, and the overfall on product autoreactor top is discharged, and reaction is carried out stopping behind the 40h; Get the product of overflow 30h～40h then, use after the sedimentation separation pure water wash to the pH value be about 7.5, dry sediment must be mixed aluminium mangano-manganic oxide 896g in 120 ℃ baking oven.
The product that present embodiment is made is mixed the aluminium mangano-manganic oxide and is tested, test result show its Mn element percentage composition be 70.0%, the percentage composition of Al element is 0.79%, size indicator D
50Be 14.1 μ m, tap density is 2.5g/cm
3, do ESEM (SEM) and observe visible its granule-morphology in back for spherical.
Claims (9)
1. spherical aluminum-doped mangano-manganic oxide, it is characterized in that: said spherical aluminum-doped mangano-manganic oxide is a kind of composite oxides, its chemical formula is Mn
3O
4 xAl
2O
3, wherein,
x=0.01～0.5, the D of said spherical aluminum-doped mangano-manganic oxide
50Granularity is 5 μ m～20 μ m, the tap density>=2.0g/cm of said spherical aluminum-doped mangano-manganic oxide
3
2. spherical aluminum-doped METHODS OF MAKING MANGANIC MANGANOUS OXIDE as claimed in claim 1 may further comprise the steps:
(1) takes by weighing the soluble manganese salt of aluminum soluble salt and bivalent manganese by the stoichiometric proportion in the said chemical formula, be mixed with the mixed solution that contains trivalent aluminium ion and divalent manganesetion with pure water or deionized water;
(2) weighing sodium hydroxide is mixed with sodium hydroxide solution with pure water or deionized water;
(3) join the sodium hydroxide solution in mixed solution in the above-mentioned steps (1) and the step (2) in the reactor continuously; The total mole number of divalent manganesetion and trivalent aluminium ion is (0.5～1.5) with the ratio of the molal quantity of NaOH in the control reactor: 2; Carry out coprecipitation reaction then; Control reaction temperature is 40 ℃～80 ℃; The pH value of reactant liquor is 7.5～13.5, and the oxidant that in reactant liquor, adds capacity simultaneously carries out oxidation processes to the sediment that generates in the course of reaction;
(4) product after the above-mentioned steps (3) is separated, the sediment after separating with pure water or rinsed with deionized water then is again through being drying to obtain spherical aluminum-doped mangano-manganic oxide.
3. preparation method according to claim 2; It is characterized in that; Said step (1) join mixed solution in also be added with blender A, said blender A comprises at least a in department basis, OP-10, lauryl sodium sulfate, ammonium fluoride, ammonium chloride, ammonium sulfate, ammonium nitrate, sodium fluoride, ethanol, ethylene glycol, isopropyl alcohol, n-butanol, ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, carboxymethyl cellulose, sodium carboxymethylcellulose, the polyvinyl alcohol.
4. preparation method according to claim 3; It is characterized in that; Said step (1) join mixed solution in; The total concentration of divalent manganesetion is controlled at 20g/L～200g/L, and the total concentration of trivalent aluminium ion is controlled at 0.05g/L～50g/L, and the total concentration of said blender A is controlled at 0.1g/L～20g/L.
5. preparation method according to claim 2; It is characterized in that; Said step (2) join sodium hydroxide solution in also be added with blender B, said blender B comprises at least a in department basis, OP-10, lauryl sodium sulfate, ammoniacal liquor, ethylenediamine, ammonium fluoride, ammonium chloride, ammonium sulfate, ammonium nitrate, sodium fluoride, ethanol, ethylene glycol, isopropyl alcohol, n-butanol, EDTA, EDTA disodium, EDTA four sodium, carboxymethyl cellulose, sodium carboxymethylcellulose, the polyvinyl alcohol.
6. preparation method according to claim 5 is characterized in that, said step (2) join sodium hydroxide solution in, concentration sodium hydroxide is controlled at 50g/L～500g/L, the total concentration of said blender B is controlled at 0.1g/L～50g/L.
7. according to each described preparation method in the claim 2～6, it is characterized in that the soluble manganese salt in the said step (1) comprises at least a in manganese sulfate, manganese nitrate, the manganese chloride.
8. according to each described preparation method in the claim 2～6, it is characterized in that the aluminum soluble salt in the said step (1) comprises at least a in aluminum sulfate, aluminum nitrate, the aluminium chloride.
9. according to each described preparation method in the claim 2～6, it is characterized in that the oxidant in the said step (3) comprises at least a in hydrogen peroxide solution, oxygen, air, ammonium persulfate or the sodium thiosulfate.
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| CN103050680A (en) * | 2012-12-19 | 2013-04-17 | 中钢集团安徽天源科技股份有限公司 | High-density doped trimanganese tetroxide and preparation method thereof |
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Address after: 410013 Hunan province Changsha High-tech Development Zone torch City Jingxin Residential District 4 Building 101 Patentee after: Hunan Huitong high energy storage materials Refco Group Ltd. Address before: 410016 Hunan province Changsha Yuhua District People's Road No. 46 Ming Cheng International Building 26 floor Patentee before: HUNAN HUITONG SCIENCE & TECHNOLOGY Co.,Ltd. |
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Effective date of registration: 20170120 Address after: 554300 Guizhou Province Yang Tongren City Dalong Economic Development Zone Wan Patentee after: GUIZHOU DALONG HUICHENG NEW MATERIAL Co.,Ltd. Address before: 410013 Hunan province Changsha High-tech Development Zone torch City Jingxin Residential District 4 Building 101 Patentee before: Hunan Huitong high energy storage materials Refco Group Ltd. |
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Denomination of invention: A spherical Al doped manganous oxide and its preparation method Effective date of registration: 20201027 Granted publication date: 20140917 Pledgee: Tongren branch of China Construction Bank Corp. Pledgor: GUIZHOU DALONG HUICHENG NEW MATERIAL Co.,Ltd. Registration number: Y2020980007234 |
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Date of cancellation: 20221104 Granted publication date: 20140917 Pledgee: Tongren branch of China Construction Bank Corp. Pledgor: GUIZHOU DALONG HUICHENG NEW MATERIAL Co.,Ltd. Registration number: Y2020980007234 |
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Denomination of invention: A spherical aluminum doped manganese tetroxide and its preparation method Granted publication date: 20140917 Pledgee: Tongren branch of China Construction Bank Corp. Pledgor: GUIZHOU DALONG HUICHENG NEW MATERIAL Co.,Ltd. Registration number: Y2024980006908 |