CN1562771A - Spherical shaped lithium manganate and preparation method - Google Patents
Spherical shaped lithium manganate and preparation method Download PDFInfo
- Publication number
- CN1562771A CN1562771A CN 200410009004 CN200410009004A CN1562771A CN 1562771 A CN1562771 A CN 1562771A CN 200410009004 CN200410009004 CN 200410009004 CN 200410009004 A CN200410009004 A CN 200410009004A CN 1562771 A CN1562771 A CN 1562771A
- Authority
- CN
- China
- Prior art keywords
- lithium manganate
- spherical
- manganese dioxide
- lithium
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 5
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 5
- 239000011565 manganese chloride Substances 0.000 claims abstract description 5
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 4
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 74
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 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 4
- 239000000126 substance Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- -1 sodium fluorosilicate Chemical group 0.000 claims 3
- 239000012935 ammoniumperoxodisulfate Substances 0.000 claims 1
- 229940104869 fluorosilicate Drugs 0.000 claims 1
- 125000005385 peroxodisulfate group Chemical group 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 239000011572 manganese Substances 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 abstract 1
- 235000002908 manganese Nutrition 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000010405 anode material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 150000002697 manganese compounds Chemical class 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Abstract
The characteristics are: at first, to make manganese sulfate or manganese chloride or manganese nitric reacting with perman-ganate or peroxydisulfate in liquid phase medium and to add edulcorating additive agent in, to control pH value, temp., feed speed to generate spherical manganese bioxide. then to uniform mix the spherical manganese bioxide, battery level lithium hydroxide or lithium nitric or lithium carbonate and zinc or aluminium or zirconium in organic solution the to dry them, finally to burn the dried material to create spherical lithium manganate.
Description
Technical Field
The invention relates to spherical lithium manganate used as a lithium ion battery anode material, belonging to the field of new energy materials.
The invention also relates to a preparation method of the spherical lithium manganate.
Background
Lithium manganate is a positive electrode material of lithium ion batteries, and has the advantages of low price, good safety, excellent rate discharge performance, no environmental pollution and the like, so that the lithium manganate is a popular subject of domestic and foreign research. At present, a lot of reports are made on the preparation method of lithium manganate, and two methods are mainly provided, wherein one method is a high-temperature solid phase method which is prepared by calcining a mixture of a lithium compound and a manganese compound at 2-3 temperature sections at 500-900 ℃; the other method is a liquid phase synthesis method, which is to dissolve lithium salt and manganese salt in a mixed solution of polybasic organic weak acid and polyhydric alcohol, form gel precipitate through the processes of sol and gelation, and heat treat the gel precipitate to prepare the lithium manganate. The chemical stability and long-term circulation stability of the lithium manganate prepared by the method are not solved, because the reactants are difficult to be uniformly mixed by the traditional solid phase method, a product with a single phase is difficult to obtain, the impurity content of the manganese compound serving as the raw material is high, particularly Na and K ions are difficult to remove, the shape is irregular, the particle size distribution range is wide, the activity is low, and a lithium manganate product with excellent performance cannot be prepared; the lithium manganate product prepared by the traditional liquid phase method has small granularity, large specific surface and small density, and influences the electrochemical performance of the lithium manganate product.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide spherical lithium manganate with excellent performance, which is an excellent lithium ion battery cathode material.
The invention also provides a preparation method of the lithium manganate.
The purpose of the invention is realized by the following technical scheme:
the spherical lithium manganate is characterized in that the lithium manganate is spherical, the average particle size is 5-30 mu m, and the tap density is 1.8-2.5 g/cm3The specific surface area is 0.5 to 1.5m2The total content of Na and K ions is less than 800ppm, and the content of other impurities is less than 200 ppm.
The preparation method of spherical lithium manganate is characterized by comprising the following steps:
a) firstly, preparing 0.15-2.0M aqueous solution from industrial manganese sulfate, manganese chloride or manganese nitrate and 0.1-2.0M aqueous solution from isovolumetric industrial permanganate or peroxydisulfate;
b) adding the two isometric aqueous solutions prepared in the step a) into a reaction kettle at the flow rate of 15-20L/h, stirring and adding soluble fluosilicate, wherein the adding amount of the soluble fluosilicate is 2-2.5% of the weight of the generated manganese dioxide, heating to 20-90 ℃, adjusting and controlling the pH value of a reaction system to be 0.01-3.0 by using sulfuric acid or hydrochloric acid, stirring for 1-2 hours after the addition is finished, and separating manganese dioxide precipitate after the generation of spherical manganese dioxide;
c) washing the precipitate in the step (b) with water with the pH of 2-5 for 2-3 times, wherein the amount of the washing water is 10-12 times of the volume of the precipitate, washing with deionized water, filtering and drying to obtain spherical manganese dioxide;
d) uniformly mixing the dried manganese dioxide in the item (c) with a composition of battery-grade lithium hydroxide or lithium nitrate or lithium carbonate and one or two or more of zinc or aluminum or zirconium in any proportion in an alcohol or ether or ketone solvent, wherein the molar ratio of the lithium hydroxide or the lithium nitrate or the lithium carbonate to the manganese dioxide is 0.45-0.65, and the dosage of the composition of one or two or more of zinc or aluminum or zirconium in any proportion is 0.5-1.5% of the theoretical weight of the lithium manganate, and then drying the mixture;
e) and calcining the dried material in a calcining furnace at the temperature of 600-900 ℃ for 6-15 hours, cooling, grinding and screening, and obtaining the spherical lithium manganate product under the screen.
The permanganate is potassium permanganate or sodium permanganate, and can also be chlorate or hypochlorite; the peroxydisulfate is ammonium peroxydisulfate or sodium peroxydisulfate or potassium peroxydisulfate; the soluble fluosilicate is sodium fluosilicate or potassium fluosilicate or ammonium fluosilicate; the raw material manganese dioxide can also be electrolytic and chemical manganese dioxide; the zinc or aluminum or zirconium can also be cobalt, nickel, titanium, chromium or vanadium.
The spherical lithium manganate of the invention is prepared by carrying out the following redox reactions in a liquid phase according to the reaction of a manganese salt such as manganese sulfate or manganese chloride or manganese nitrate and a permanganate or hypochlorite or chlorate or peroxydisulfate of a strong oxidant:
the manganese dioxide generated by the reaction formulas (1), (2) and (3) is generated at the liquid phase medium pH of 0.01-3.0, the temperature of 20-90 ℃ and the feeding speed of 15-20L/h, and because harmful impurities K, Na exist in the raw materials, an impurity removing agent such as soluble fluosilicate is added in the reaction process, so that K, Na ions can be prevented from entering manganese dioxide crystals, and the extremely low impurities of the manganese dioxide are ensured.
High purity manganese dioxide is mixed with a battery grade lithium compound such as lithium hydroxide or lithium nitrate or lithium carbonate and calcined to produce spherical lithium manganate, which reacts as follows:
mixing high-purity manganese dioxide and a battery-grade lithium compound such as lithium hydroxide, lithium nitrate or lithium carbonate with an alcohol, ether or ketone solvent to uniformly mix reactants, calcining to generate spherical lithium manganate, controlling the temperature at 600-900 ℃ for 6-15 hours, and simultaneously adding a composition of one or two or more of zinc, aluminum or zirconium doped with elements in any proportion to improve the cycling stability of the lithium manganate material to prepare the high-quality lithium ion battery anode material.
The spherical lithium manganate prepared by the method of the invention is automatically monitored in the whole process, and the scanning electron micrograph of the generated manganese dioxide is shown in figure 1, and the manganese dioxide is spherical or approximately spherical, has uniform particles, narrow particle size distribution range and particlesThe crystal form is gamma type with high activity and low impurity content, the total content of Na and K elements is less than 500ppm, and the content of other impurities is below 100 ppm. The scanning electron micrograph of the prepared spherical lithium manganate is shown in figure 2, the particle size distribution range is narrow, as shown in figure 3, the specific gravity is large, the specific surface area is small, the charge-discharge cycle characteristic is stable, and the tap density is 1.8-2.5. g/cm3The specific surface area is 0.5 to 1.5m2(iv) g, an average particle diameter of 5 to 30 μm.
The lithium manganate provided by the invention is used as a lithium ion anode material, the initial capacity is 110-125 mAh/g, and the battery test is as follows: the positive electrode is coated by mixing lithium manganate, binder and conductive agent in a weight ratio of 90: 6: 4, the metal lithium is used as a negative electrode, and the electrolyte is 1M LiPF6DEC (1: 1)/EC, charging and discharging at room temperature at 1C, and capacity retention rate after 200 cycles is 90% -95%, as shown in FIG. 4.
Due to the adoption of the technical scheme, compared with the prior art, the technology has the advantages and effects that:
a) the product has excellent physical, chemical and electrochemical properties, and is an excellent lithium ion battery anode material.
b) The method has the advantages of simplicity, low energy consumption, high efficiency, short reaction time, automatic monitoring of the whole process,
c) the raw materials are easy to obtain, and the cost is low.
Drawings
FIG. 1 is a scanning electron micrograph of spherical manganese dioxide
FIG. 2 is a scanning electron micrograph of spherical lithium manganate
FIG. 3 is a particle size distribution diagram of spherical lithium manganate
FIG. 4 is a graph showing the cycle characteristics of spherical lithium manganate electrodes
Detailed Description
Example 1
Firstly, preparing 100L of 0.15M aqueous solution and equal volume of industrial-grade manganese sulfatePreparing 0.1M aqueous solution by potassium permanganate; adding the prepared two isometric aqueous solutions into a reaction kettle at the flow rate of 20L/h, stirring, adding 43.5g of soluble sodium fluosilicate, heating to 20 ℃, adjusting the pH value of a reaction system to 3 by using a sulfuric acid aqueous solution, stirring for 1 hour after the addition is finished, and separating manganese dioxide precipitate after spherical manganese dioxide is generated; washing the precipitate with water with pH of 5 for 2 times, washing with 20L of water, washing with deionized water, filtering, and drying to obtain spherical manganese dioxide; taking 2kg of manganese dioxide, 0.42kg of lithium hydroxide and 10.4g of zinc, adding organic alcohol solvent, uniformly mixing, drying, calcining the dried product in a high-temperature furnace at 600 ℃ for 15 hours, cooling, grinding and screening, and screening to obtain a spherical lithium manganate product. The detection shows that the tap density of the lithium manganate is 1.8g/cm3Average particle diameter of 5.0 μm and specific surface area of 1.5m2The total content of Na and K ions is less than 800ppm, the content of other impurities is less than 200ppm, the initial capacity is 125mAh/g, and the capacity retention rate is 95% after 200 times of circulation.
Example 2
Firstly, preparing 100L of 1.0M aqueous solution from industrial manganese chloride and preparing 1.0M aqueous solution from industrial sodium hypochlorite with the same volume; adding the two prepared isometric aqueous solutions into a reaction kettle at the flow rate of 18L/h, stirring, adding 194g of soluble potassium fluosilicate, heating to 70 ℃, adjusting the pH value of a reaction system to 0.1 by using a hydrochloric acid aqueous solution, stirring for 1.5 hours after the addition is finished, generating spherical manganese dioxide, and separating out manganese dioxide precipitate; washing the precipitate with water with pH of 3.5 for 2 times, washing with 45L of water, washing with deionized water, filtering, and drying to obtain spherical manganese dioxide; taking 2kg of manganese dioxide, 0.89kg of lithium nitrate and 10.4g of zinc and aluminum respectively, adding an organic ether solvent, uniformly mixing, drying, calcining the dried product in a high-temperature furnace at 750 ℃ for 10 hours, cooling, grinding and screening to obtain a spherical lithium manganate product. The detection shows that the tap density of the lithium manganate is 2.2g/cm3Average particle diameter of 18.7 μm and specific surface area of 1.02m2The total content of Na and K ions is less than 800ppm, the content of other impurities is less than 200ppm, the initial capacity is 118mAh/g, and the 200-time circulation capacity is maintainedThe ratio was 93%.
Example 3
Firstly, preparing 100L of 2.0M aqueous solution from industrial manganese nitrate and 2.0M aqueous solution from industrial sodium peroxodisulfate with the same volume; adding the two prepared isometric aqueous solutions into a reaction kettle at the flow rate of 15L/h, stirring, adding 435g of soluble sodium fluosilicate, heating to 90 ℃, adjusting the pH value of a reaction system to 0.01 by using a sulfuric acid aqueous solution, stirring for 2 hours after the addition is finished, and separating manganese dioxide precipitate after spherical manganese dioxide is generated; washing the precipitate with water with pH of 2.5 for 3 times, washing with 100L of water, washing with deionized water, filtering, and drying to obtain spherical manganese dioxide; taking 2kg of manganese dioxide, 0.556kg of lithium carbonate, 10g of zinc, 15g of aluminum and 6.2g of zirconium, adding an organic ketone solvent, uniformly mixing, drying, calcining the dried product in a high-temperature furnace at 900 ℃ for 6 hours, cooling, grinding and screening, and screening to obtain a spherical lithium manganate product. The detection shows that the tap density of the lithium manganate is 2.5g/cm3Average particle diameter of 35 μm and specific surface area of 0.5m2The total content of Na and K ions is less than 800ppm, the content of other impurities is less than 200ppm, the initial capacity is 110mAh/g, and the retention rate of the 200-time circulation capacity is 90%.
Claims (7)
1. The spherical lithium manganate is characterized in that the lithium manganate is spherical, the average particle size is 5-30 mu m,and the tap density is 1.8-2.5 g/cm3The specific surface area is 0.5 to 1.5m2The total content of Na and K ions is less than 800ppm, and the content of other impurities is less than 200 ppm.
2. The method for preparing spherical lithium manganate according to claim 1, characterized in that it is carried out by the following steps:
a) firstly, preparing 0.15-2.0M aqueous solution from industrial manganese sulfate, manganese chloride or manganese nitrate and 0.1-2.0M aqueous solution from isovolumetric industrial permanganate or peroxydisulfate;
b) adding the two isometric aqueous solutions prepared in the step a) into a reaction kettle at the flow rate of 15-20L/h, stirring and adding soluble fluosilicate, wherein the adding amount of the soluble fluosilicate is 2-2.5% of the weight of the generated manganese dioxide, heating to 20-90 ℃, adjusting and controlling the pH value of a reaction system to be 0.01-3.0 by using sulfuric acid or hydrochloric acid, stirring for 1-2 hours after the addition is finished, and separating manganese dioxide precipitate after the generation of spherical manganese dioxide;
c) washing the precipitate in the step (b) with water with the pH of 2-5 for 2-3 times, wherein the amount of the washing water is 10-12 times of the volume of the precipitate, washing with deionized water, filtering and drying to obtain spherical manganese dioxide;
d) uniformly mixing the dried manganese dioxide in the item (c) with a composition of battery-grade lithium hydroxide or lithium nitrate or lithium carbonate and one or two or more of zinc or aluminum or zirconium in any proportion in an alcohol or ether or ketone solvent, wherein the molar ratio of the lithium hydroxide or the lithium nitrate or the lithium carbonate to the manganese dioxide is 0.45-0.65, and the dosage of the composition of one or two or more of zinc or aluminum or zirconium in any proportion is 0.5-1.5% of the theoretical weight of the lithium manganate, and then drying the mixture;
e) and calcining the dried material in a calcining furnace at the temperature of 600-900 ℃ for 6-15 hours, cooling, grinding and screening, and obtaining the spherical lithium manganate product under the screen.
3. The method for preparing spherical lithium manganate as claimed in claim 1, wherein said permanganate is potassium permanganate or sodium permanganate, or chlorate or hypochlorite.
4. The method for preparing spherical lithium manganate as claimed in claim 1, wherein said peroxodisulfate is ammonium peroxodisulfate or sodium peroxodisulfate or potassium peroxodisulfate.
5. The method for preparing spherical lithium manganate according to claim 1, wherein said soluble fluorosilicate is sodium fluorosilicate, potassium fluorosilicate or ammonium fluorosilicate.
6. The method for preparing spherical lithium manganate as claimed in claim 1, wherein said manganese dioxide as raw material may be electrolytic manganese dioxide or chemical manganese dioxide.
7. The method for preparing spherical lithium manganate as claimed in claim 1, wherein said zinc, aluminum or zirconium may be cobalt, nickel, titanium, chromium, vanadium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410009004 CN1283556C (en) | 2004-04-07 | 2004-04-07 | Spherical shaped lithium manganate and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410009004 CN1283556C (en) | 2004-04-07 | 2004-04-07 | Spherical shaped lithium manganate and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1562771A true CN1562771A (en) | 2005-01-12 |
| CN1283556C CN1283556C (en) | 2006-11-08 |
Family
ID=34477765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410009004 Expired - Fee Related CN1283556C (en) | 2004-04-07 | 2004-04-07 | Spherical shaped lithium manganate and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1283556C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101335348B (en) * | 2008-07-18 | 2010-06-02 | 清华大学 | Preparing method of lithium ionic cell 5V anode material spherical LiNi0.5Mn1.5O4 |
| CN101786666A (en) * | 2010-02-10 | 2010-07-28 | 彭天剑 | High-purity manganese dioxide and preparation method thereof as well as lithium manganese oxide anode material and preparation method thereof |
| CN102070199A (en) * | 2010-11-18 | 2011-05-25 | 清华大学 | Method for preparing micron frame-shaped manganese series lithium ion battery cathode material |
| CN102169990A (en) * | 2011-04-07 | 2011-08-31 | 先进储能材料国家工程研究中心有限责任公司 | Ternary cathode material and production method thereof |
| CN102820462A (en) * | 2012-08-24 | 2012-12-12 | 安徽亚兰德新能源材料股份有限公司 | Preparation process of anode material lithium manganate of spherical structure for lithium ion battery |
| CN103199236A (en) * | 2013-04-11 | 2013-07-10 | 武汉市弘阳科技发展有限公司 | Doped lithium manganate precursor, modified lithium manganate positive electrode material and preparation method thereof |
| CN103560242A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Device for processing electrolytic manganese dioxide of lithium ion battery |
| CN103715415A (en) * | 2013-12-17 | 2014-04-09 | 天津巴莫科技股份有限公司 | Lithium manganate anode material and preparation method thereof |
| US8895187B2 (en) | 2005-08-16 | 2014-11-25 | Lg Chem, Ltd. | Cathode active material and lithium secondary battery containing the same |
| CN106207158A (en) * | 2016-07-22 | 2016-12-07 | 湖南海利锂电科技股份有限公司 | The preparation method of rich lithium manganate cathode material for lithium |
| CN110171850A (en) * | 2019-04-24 | 2019-08-27 | 浙江浙能技术研究院有限公司 | Liquid-phase mass production device and preparation method of manganese oxide material for energy storage battery |
-
2004
- 2004-04-07 CN CN 200410009004 patent/CN1283556C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8895187B2 (en) | 2005-08-16 | 2014-11-25 | Lg Chem, Ltd. | Cathode active material and lithium secondary battery containing the same |
| US9263738B2 (en) | 2005-08-16 | 2016-02-16 | Lg Chem, Ltd. | Cathode active material and lithium secondary battery containing the same |
| CN101335348B (en) * | 2008-07-18 | 2010-06-02 | 清华大学 | Preparing method of lithium ionic cell 5V anode material spherical LiNi0.5Mn1.5O4 |
| CN101786666A (en) * | 2010-02-10 | 2010-07-28 | 彭天剑 | High-purity manganese dioxide and preparation method thereof as well as lithium manganese oxide anode material and preparation method thereof |
| CN101786666B (en) * | 2010-02-10 | 2012-02-22 | 彭天剑 | lithium manganate anode material and preparation method thereof |
| CN102070199A (en) * | 2010-11-18 | 2011-05-25 | 清华大学 | Method for preparing micron frame-shaped manganese series lithium ion battery cathode material |
| CN102070199B (en) * | 2010-11-18 | 2012-09-05 | 清华大学 | Method for preparing micron frame-shaped manganese series lithium ion battery cathode material |
| CN102169990A (en) * | 2011-04-07 | 2011-08-31 | 先进储能材料国家工程研究中心有限责任公司 | Ternary cathode material and production method thereof |
| CN102169990B (en) * | 2011-04-07 | 2013-06-26 | 先进储能材料国家工程研究中心有限责任公司 | Ternary cathode material and production method thereof |
| CN102820462A (en) * | 2012-08-24 | 2012-12-12 | 安徽亚兰德新能源材料股份有限公司 | Preparation process of anode material lithium manganate of spherical structure for lithium ion battery |
| CN103199236A (en) * | 2013-04-11 | 2013-07-10 | 武汉市弘阳科技发展有限公司 | Doped lithium manganate precursor, modified lithium manganate positive electrode material and preparation method thereof |
| CN103199236B (en) * | 2013-04-11 | 2016-02-03 | 武汉市弘阳科技发展有限公司 | Adulterated lithium manganate presoma, modified lithium manganate cathode material and preparation method thereof |
| CN103560242A (en) * | 2013-11-07 | 2014-02-05 | 广西桂柳化工有限责任公司 | Device for processing electrolytic manganese dioxide of lithium ion battery |
| CN103715415A (en) * | 2013-12-17 | 2014-04-09 | 天津巴莫科技股份有限公司 | Lithium manganate anode material and preparation method thereof |
| CN103715415B (en) * | 2013-12-17 | 2016-03-23 | 天津巴莫科技股份有限公司 | The preparation method of manganate cathode material for lithium |
| CN106207158A (en) * | 2016-07-22 | 2016-12-07 | 湖南海利锂电科技股份有限公司 | The preparation method of rich lithium manganate cathode material for lithium |
| CN106207158B (en) * | 2016-07-22 | 2018-09-25 | 湖南海利锂电科技股份有限公司 | The preparation method of rich lithium manganate cathode material for lithium |
| CN110171850A (en) * | 2019-04-24 | 2019-08-27 | 浙江浙能技术研究院有限公司 | Liquid-phase mass production device and preparation method of manganese oxide material for energy storage battery |
| CN110171850B (en) * | 2019-04-24 | 2022-03-29 | 浙江浙能中科储能科技有限公司 | Liquid-phase mass production device and preparation method of manganese oxide material for energy storage battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1283556C (en) | 2006-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110048118B (en) | High-nickel cobalt lithium manganate single crystal precursor, preparation method thereof and high-nickel cobalt lithium manganate single crystal positive electrode material | |
| CN110642236B (en) | Zinc-based aqueous battery negative electrode material and preparation method thereof | |
| CN102344356B (en) | Preparation method of battery grade nano ferrous oxalate | |
| CN111785960B (en) | Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof | |
| CN103972497B (en) | Lithium ion battery Co2snO4/ C nano composite negative pole material and preparation and application thereof | |
| CN104900861B (en) | A kind of lithium hydrogentitanate Li H Ti O material and preparation method thereof | |
| CN101764223A (en) | Doped spherical LiMn2O4 (manganese acid lithium) and preparation method thereof | |
| CN1635648A (en) | Method for preparing high-density spherical ferric lithium phosphate as anode material of lithium-ion battery | |
| CN101704681B (en) | Method for preparing lithium titanate with spinel structure | |
| CN107394178B (en) | Cobalt carbonate/graphene composite material for sodium-ion battery cathode and preparation method and application thereof | |
| CN111785942A (en) | Water-based zinc ion battery positive electrode material and preparation method and application thereof | |
| CN104292100B (en) | Terephthalic acid calcium is as the application of lithium ion battery negative material | |
| CN102107906B (en) | Method for preparing lithium titanate material | |
| CN114864896A (en) | In-situ carbon-coated nano lithium iron phosphate cathode material and preparation method thereof | |
| CN102916170B (en) | Method for preparing carbon-coated nano-particle lithium titanate electrode material | |
| CN104409723A (en) | Electrochemical preparation method of ternary anode material | |
| CN105206815A (en) | Carbon-coated Li4Ti5O12-TiO2/Sn nanocomposite and preparation and application thereof | |
| CN1562771A (en) | Spherical shaped lithium manganate and preparation method | |
| CN102311109A (en) | Method for preparing LiFePO4/C composite cathode material by continuous reaction | |
| CN110911652B (en) | Nano spherical alpha-MnO 2 /Bi 2 O 3 Material, preparation method and application thereof | |
| WO2019104948A1 (en) | Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery | |
| CN107317019B (en) | Ferrous carbonate/graphene composite material for sodium ion battery cathode and preparation method and application thereof | |
| CN100411994C (en) | Process for preparing carbon-doped spherical Li4Ti5O12 | |
| CN101209859A (en) | λ－MnO 2 Preparation method of (2) | |
| CN114864932A (en) | Preparation method of sodium ion battery positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: QI LU Free format text: FORMER OWNER: ZHONGXINGUOAN MENGGULI ELECTRIC SOURCE TECHNOLOGY CO., LTD. Effective date: 20061215 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20061215 Address after: 102200 Beijing City, Changping District science and Technology Park of Changping Bai Fu Road 18 Patentee after: Qi Lu Address before: 102200 Beijing City, Changping District science and Technology Park of Changping Bai Fu Road 18 Patentee before: Zhongxinguoan Mengguli Power Supply Technology Co., Ltd. |
|
| CI01 | Correction of invention patent gazette |
Correction item: The transfer of tenth patents Correct: Qi Lu False: Qi Lu Number: 04 Page: 1177 Volume: 23 |
|
| ERR | Gazette correction |
Free format text: CORRECT: NO. 10 ¬ TRANSFER OF PATENT RIGHT; FROM: QI LU TO: QILU |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061108 Termination date: 20190407 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |