CN103904316B - Manganese base sodium ultrafine powder preparation method - Google Patents
Manganese base sodium ultrafine powder preparation method Download PDFInfo
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- CN103904316B CN103904316B CN201210570474.0A CN201210570474A CN103904316B CN 103904316 B CN103904316 B CN 103904316B CN 201210570474 A CN201210570474 A CN 201210570474A CN 103904316 B CN103904316 B CN 103904316B
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- Prior art keywords
- sodium
- preparation
- manganese
- manganese base
- superfine powder
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- 239000011734 sodium Substances 0.000 title claims abstract description 96
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 78
- 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 title claims abstract description 65
- 239000011572 manganese Substances 0.000 title claims abstract description 45
- 239000000843 powder Substances 0.000 title claims abstract description 44
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 39
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract 2
- -1 sodium inorganic compound Chemical class 0.000 claims description 17
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 9
- 150000002697 manganese compounds Chemical class 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 229940077388 benzenesulfonate Drugs 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical group [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims 2
- 235000011152 sodium sulphate Nutrition 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 235000019800 disodium phosphate Nutrition 0.000 claims 1
- GTTYPHLDORACJW-UHFFFAOYSA-N nitric acid;sodium Chemical compound [Na].O[N+]([O-])=O GTTYPHLDORACJW-UHFFFAOYSA-N 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 17
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000003746 solid phase reaction Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 229910019338 NaMnO2 Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 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
- H01M4/48—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- 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
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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 relates to a manganese base sodium preparation method, particularly to a manganese base sodium ultrafine powder preparation method, which comprises: mixing a sodium-containing inorganic compound, a sodium-containing surfactant and a manganese-containing compound according to a Na/Mn molar ratio of 1, heating for 1-8 h at a temperature of 200-500 DEG C, sintering for 4-20 h at a temperature of 600-1000 DEG C, and cooling to a room temperature to obtain the product. According to the preparation method, the sodium-containing surfactant is adopted, and the sodium-containing surfactant and the sodium-containing inorganic compound provide sodium ions required by the solid phase reaction so as to reduce the use amount of the strong alkaline sodium-containing raw material and reduce the corrosion on the equipment; and the protection and activation effect of the organic functional groups is utilized so as to reduce the reaction temperature, reduce the particle size of the product manganese base sodium, and increase the specific surface area, such that the electrochemical activity and other properties are improved.
Description
Technical field
The present invention relates to a kind of preparation method of manganese base sodium is and in particular to a kind of preparation method of manganese base sodium superfine powder.
Background technology
Sodium-ion battery makes electrode material or electrolyte due to the sodium element using rich reserves, compares lithium ion battery
There is cost advantage, receive the extensive concern of researcher in recent years；Especially its inexpensive advantage especially caters to wind-powered electricity generation, light
The needs of the extensive energy storage of new forms of energy electrical network such as volt, contain huge market application foreground.
The principle of sodium-ion battery is similar to lithium ion battery, by " rocking chair " formula of sodium ion in charge and discharge process
Move back and forth and to realize the conversion between electric energy and chemical energy；It is also similar to that lithium ion battery, sodium-ion battery positive material
Property plays conclusive effect to the charge-discharge performance of battery with cycle life.At present, that is studying has embedding sodium function
Sodium-ion battery positive material mainly include NaxMO2(0<x≤1, M=Co, Mn, Ni)、 λ-MnO2、LixNayMn2- xAlzO4(0≤x<1.1, 0≤y<1, 0≤x+y<1.1 and 0≤z<0.1)、NaV(PO4) F and NaxMyFe(CN)6(M=Fe,
Co, Ni, 0<x≤1, 0<Y≤1) etc.；Wherein, the NaMnO of layer structure2Because stable chemical nature, preparation method are simple, former
The advantages of material abundance, recently receive much concern in the research of water system sodium-ion battery.A new cheap asymmetric
aqueous supercapacitor : Activated carbon // NaMnO2( Q.T.Qu et al. Journal
Of Power Sources, 194 (2009) P1222-1225) disclose one kind by activated carbon and NaMnO2Composition sodium from
Sub- hybrid battery, shows higher specific energy and cyclical stability.U.S. Patent application US20090253025A1 also discloses that
One kind is with activated carbon and NaMnO2As electrode, Na2SO4The sodium ion hybrid battery constituting as electrolyte.
There is the NaMnO of layer structure2It is typically with solid phase reaction method preparation, Electrochemical
Properties of Monoclinic NaMnO2( Xiaohua Ma et al. Journal of the
Electrochemical Society, 158 (12) A1307-1302 (2011)) disclose a kind of NaMnO2Preparation side
Method, is to have the Na of stoichiometric proportion2CO3And Mn2O3First carry out ground and mixed, then carry out at heat at a temperature of 700 DEG C
Reason, finally processes a period of time for removing unreacted oxide under Ar air-flow；Although using this solid phase reaction method
Can obtain the crystalline phase of higher degree, but higher heat treatment temperature be unfavorable for preparing small size, bigger serface super
Fine powder body.
In order to obtain the NaMnO of little crystal grain2Powder, United States Patent (USP) US 6511647B1 discloses a kind of sol-gel system
Preparation Method, by Na2CO3Solution is added to manganese acetylacetonate（II）Form brown precipitate in solution, removed using rotary evaporation afterwards
Remove solvent, then by the brown solid obtaining mill-drying, finally heat treatment obtained comparing solid phase reaction after 8 hours at 670 DEG C
The little NaMnO of crystallite dimension that method obtains2Powder.But, due to employing organic metal salt and organic molten in the method in a large number
Agent, and it is unfavorable for large-scale industrial production.
Content of the invention
It is an object of the invention to provide a kind of preparation method of manganese base sodium superfine powder, reduce NaMnO2The crystal grain of powder
Size, increases its specific surface area, thus obtaining high electro-chemical activity, meets the needs of scale industrial production simultaneously.
The purpose of the present invention is achieved through the following technical solutions：A kind of preparation method of manganese base sodium superfine powder, including such as
Lower step：
（1）According to Na:The ratio that Mn mol ratio is equal to 1 will contain sodium inorganic compound, containing natrium surfactant with containing manganese
Compound mixes and obtains raw mixture, wherein the molal quantity of Na be in inorganic compound containing sodium the molal quantity of Na with containing sodium
The molal quantity sum of Na in surfactant.
Mixing can be with using dry mixed mode, by the dry powder containing sodium inorganic compound, the dry powder containing natrium surfactant
Carry out the raw mixture that ball milling or stirring are uniformly mixed with the dry powder containing manganese compound.Wet-mixing side can also be adopted
Formula, a kind of wet blending process is in the dry powder containing sodium inorganic compound, the dry powder containing natrium surfactant and to contain manganese compound
Dry powder in add dispersant, carry out ball milling or stirring, form uniform slurry, then mixed after being dried 5-15 hour
Uniform raw mixture is it is preferable that described dispersant can be in water, ethanol, butanol, propyl alcohol, amylalcohol and acetone
Plant or several, described drying mode can be infrared forced air drying, spray drying, freeze-drying or vacuum drying；Another kind of
Wet blending process is first to sequentially add solution containing natrium surfactant, contain manganese compound, carries out ball milling or stirring, in ball milling
Or add, in whipping process, the solution containing sodium inorganic compound, and continue ball milling or stirring 4-10 hour, then it is dried 5-
Obtain raw mixture after 15 hours, so can reduce the particle size containing manganese compound, improve reactivity, simultaneously facilitate
Dissolving it is preferred that the solvent of the described solution containing natrium surfactant is the water containing defoamer containing natrium surfactant,
The generation of a large amount of bubbles in adition process containing natrium surfactant can be prevented, the temperature of preferred solvent is 50-80 DEG C, can
To promote the dissolving containing natrium surfactant further.
（2）Above-mentioned mixture of raw material is heated 1-8 hour at a temperature of 200-500 DEG C, surface containing sodium can be promoted to live
Property agent thermal decomposition, producing gas, that product powder can be made to become nature is fluffy；Then sinter 4- at a temperature of 600-1000 DEG C
20 hours, it is cooled to room temperature and obtains product.
Preferably, step（2）In be cooled to room temperature after be ground.
Preferably, step（1）In inorganic compound containing sodium can be sodium carbonate（Na2CO3）, sodium acid carbonate（NaHCO3）, sulphur
Sour sodium（Na2SO4）, niter cake（NaHSO4）, sodium nitrate (NaNO3), sodium oxalate（Na2C2O4), sodium acetate (CH3COONa), phosphorus
Sour sodium（Na3PO4）, disodium hydrogen phosphate（Na2HPO4）, sodium dihydrogen phosphate（NaH2PO4）And NaOH（NaOH）One of or
Several.
Step（1）In can be trisodium citrate, sodium soap and its derivative, unsaturated fat containing natrium surfactant
Sour sodium and its derivative, sodium alkyl sulfate, sodium alkyl sulfonate, one kind of sodium alkyl benzene sulfonate, alkyl phosphoric acid sodium and amino acid sodium
Or it is several.
Step（1）In can be manganese dioxide containing manganese compound（MnO2）, manganese sesquioxide managnic oxide（Mn2O3）And mangano-manganic oxide
（Mn3O4）One or more of.
Preferably, the quality containing natrium surfactant accounts for the quality containing sodium inorganic compound and the matter containing natrium surfactant
The percentage of amount sum is less than 50%.
Compared with prior art, the preparation method of the manganese base sodium superfine powder of the present invention has advantages below：
（1）The preparation method of the present invention is passed through using containing natrium surfactant, on the one hand together with inorganic compound containing sodium
Sodium ion needed for solid phase reaction is provided, decreases the stronger usage amount containing sodium raw materials of alkalescence, reduce the corrosion to equipment and make
With；On the other hand protection and activation by its organo-functional group reduce reaction temperature, reduce the crystalline substance of product manganese base sodium
Particle size, increases specific surface area, and then improves the performances such as its electro-chemical activity；
（2）NaMnO using method of the present invention preparation2Superfine powder is as the positive electrode of water system sodium-ion battery
When, it is favorably improved the charge-discharge performance of battery；
（3）The preparation method of the present invention has the characteristics that low cost, simple to operate, non-environmental-pollution, is suitable for scale
Industrial production.
Brief description
Fig. 1 is the XRD of the manganese base sodium superfine powder of embodiments of the invention 1 preparation；
Fig. 2 is the SEM figure of the manganese base sodium superfine powder of embodiments of the invention 1 preparation；
Fig. 3 is the cyclic voltammetry curve contrast of the manganese base sodium superfine powder of embodiments of the invention 1 and comparative example 1 preparation
Figure；
Fig. 4 be embodiments of the invention 1 and comparative example 1 preparation manganese base sodium superfine powder as positive pole sodium-ion battery
In specific discharge capacity comparison diagram；
Fig. 5 be embodiments of the invention 1 and comparative example 1 preparation manganese base sodium superfine powder as positive pole sodium-ion battery
In charge and discharge efficiency comparative figure.
Specific embodiment
Below by embodiment, and combine accompanying drawing, technical scheme is described in further detail, but do not limit
Content in the present embodiment.
Embodiment 1
According to Na：Mn mol ratio 1：1 ratio adds in the stainless steel reaction tank containing 5 L of agate ball and contains
The aqueous solution 1000mL of 115.4 g lauryl sodium sulfate, adds 260.8 g MnO2, it is stirred, to above two
During raw material is stirred, it is added thereto to containing 137.8 g Na2CO3Aqueous solution 1000mL, be further continued for being stirred
3 h, put into infrared air dry oven afterwards and are dried 6 hours, and drying obtains raw mixture after completing to be ground.
Above-mentioned raw materials mixture is transferred in corundum crucible, puts into Muffle furnace, by temperature with 3 DEG C/minute of heating rate
It is heated to 350 DEG C from room temperature, and be incubated 4 hours；Then again with 5 DEG C/minute of ramp to 870 DEG C, and be incubated 10 hours,
After naturally cool to room temperature.
Referring to Fig. 1, analyze XRD spectrum and understand, the diffraction maximum shown in figure is matched with JCPDF card 25-0845, table
Bright products therefrom is α-NaMnO2；Referring to Fig. 2, products therefrom can be seen by the ball shaped nano flocking together from SEM spectrum
Brilliant and a small amount of nanometer bar construction.
Embodiment 2
According to Na：Mn mol ratio 1：1 ratio adds 19.1 g in the polytetrafluoroethylene (PTFE) ball grinder of 250 ml
Na2CO3, 13.9 g neopelexes and 17.4 g MnO2, and add 10 ml isopropanols and 50 ml deionized waters one
Rise and carry out ball milling 16 h, transfer to the slurry in spheroidal graphite tank in stainless steel pallet afterwards, put into infrared air dry oven 85
It is dried at DEG C, drying completes simply to be ground the raw mixture being uniformly mixed.
Above-mentioned raw materials mixture is transferred in the corundum crucible of 300 mL, puts into Muffle furnace, by temperature from room temperature with 5
DEG C/minute heating rate be heated to 300 DEG C, and be incubated 4 hours, then again with 5 DEG C/minute of ramp to 850 DEG C, and
Insulation 16 hours, finally naturally cools to room temperature.
Comparative example 1
According to Na：Mn mol ratio 1：1 ratio adds 260.8 in the stainless steel reaction tank containing 2 L of agate ball
g MnO2Solid and contain 159.0 g Na2CO3Aqueous solution 1000mL, be further continued for being stirred 3 h, put into infrared drum afterwards
Wind drying box is dried 6 hours, and drying obtains raw mixture after completing to be ground.Above-mentioned raw materials mixture is transferred to
In corundum crucible, put into Muffle furnace, temperature is heated to 350 DEG C with 3 DEG C/minute of heating rate from room temperature, and is incubated 4 hours；
Then again with 5 DEG C/minute of ramp to 870 DEG C, and be incubated 10 hours, finally naturally cool to room temperature.
Cyclic voltammetric performance test：Na with 0.5 mol/L2SO4The aqueous solution, is satisfied as to electrode as electrolyte, nickel sheet
With calomel electrode as reference electrode, tested respectively using the electrode being coated with product manganese base sodium powder body as working electrode,
As shown in figure 3, obtaining the manganese base sodium powder body of embodiment 1 preparation and the cyclic voltammetry curve of the manganese base sodium powder body of comparative example 1 preparation.
It can be seen that the manganese base sodium powder body phase of embodiment 1 preparation has higher electricity compared with manganese base sodium powder body prepared by comparative example 1
Chemism and specific capacity.
Product is used for the performance test of sodium-ion battery：Product manganese base sodium powder body is mixed by a certain percentage with acetylene carbon black
Close, be added to polytetrafluoroethylene (PTFE)（PTFE）Ethanol solution in, be sufficiently stirred for uniformly pasty state, after heating demulsification type, with manual
Milling train is rolled into film and is covered on nickel screen, is dried 4 hours afterwards, is then washed into the cathode film of a diameter of 12mm at 110 DEG C
Piece；Using activated carbon as negative electrode active material, cathode membrane is obtained according to the above-mentioned method preparing positive pole diaphragm；Then by positive pole
Diaphragm, cathode membrane are put in button cell shell together with barrier film, the Na of dropping 0.5mol/L2SO4After electrolyte, button is made in sealing
Formula sodium-ion battery.Charging-discharging performances are carried out to prepared sodium-ion battery using new prestige CT-3008W type battery test system
Test, as shown in Figure 4 and Figure 5, obtains respectively with the manganese base sodium powder of the manganese base sodium powder body of embodiment 1 preparation and comparative example 1 preparation
Body is as the specific discharge capacity of the sodium-ion battery of positive active material and efficiency for charge-discharge.It can be seen that embodiment 1
The manganese base sodium powder body phase of preparation has more as the sodium-ion battery of positive active material compared with manganese base sodium powder body prepared by comparative example 1
High specific discharge capacity and efficiency for charge-discharge.
Claims (10)
1. a kind of preparation method of manganese base sodium superfine powder is it is characterised in that comprise the steps：
(1) according to Na:The ratio that Mn mol ratio is equal to 1 will contain sodium inorganic compound, containing natrium surfactant with containing manganese compound
Mix and obtain raw mixture, wherein the molal quantity of Na is that in inorganic compound containing sodium, live in the molal quantity of Na and surface containing sodium
The molal quantity sum of Na in property agent；
(2) above-mentioned raw materials mixture is heated 18 hours at a temperature of 200 500 DEG C, then in 600-1000 DEG C of temperature
Lower sintering 4 20 hours, is cooled to room temperature and obtains product.
2. manganese base sodium superfine powder according to claim 1 preparation method it is characterised in that in step (1) contain sodium inorganic
Compound is sodium carbonate (Na2CO3), sodium acid carbonate (NaHCO3), sodium sulphate (Na2SO4), niter cake (NaHSO4), nitric acid
Sodium (NaNO3), sodium oxalate (Na2C2O4), sodium acetate (CH3COONa), sodium phosphate (Na3PO4), disodium hydrogen phosphate
(Na2HPO4), one or more of sodium dihydrogen phosphate (NaH2PO4) and NaOH (NaOH).
3. the preparation method of manganese base sodium superfine powder according to claim 1 is it is characterised in that surface containing sodium in step (1)
Activating agent is trisodium citrate, sodium soap and its derivative, unrighted acid sodium and its derivative, sodium alkyl sulfate, alkane
One or more of base sodium sulfonate, sodium alkyl benzene sulfonate, alkyl phosphoric acid sodium and amino acid sodium.
4. the preparation method of manganese base sodium superfine powder according to claim 1 is closed it is characterised in that containing manganese in step (1)
Thing is one or more of manganese dioxide (MnO2), manganese sesquioxide managnic oxide (Mn2O3) and mangano-manganic oxide (Mn3O4).
5. the preparation method of manganese base sodium superfine powder according to claim 1 is it is characterised in that be cooled to room in step (2)
It is ground after temperature.
6. the preparation method of the manganese base sodium superfine powder according to any one in claim 15 is it is characterised in that contain sodium
The quality that the quality of surfactant accounts for containing sodium inorganic compound with the percentage of the quality sum containing natrium surfactant is
Less than 50%.
7. the preparation method of manganese base sodium superfine powder according to claim 1 is it is characterised in that the mixing in step (1) is adopted
Mode with dry mixed or wet-mixing.
8. manganese base sodium superfine powder according to claim 7 preparation method it is characterised in that in wet-mixing adopt water,
One or more of ethanol, butanol, propyl alcohol, amylalcohol and acetone, as dispersant, are lived with inorganic compound containing sodium, surface containing sodium
Property agent with containing carrying out ball milling together with manganese compound or stirring forms uniform slurry；It is uniformly mixed after described slurry drying
Described raw mixture.
9. the preparation method of manganese base sodium superfine powder according to claim 7 it is characterised in that in wet blending process first
Sequentially add the solution containing natrium surfactant, contain manganese compound, carry out ball milling or stirring, then in ball milling and whipping process
Add the solution containing sodium inorganic compound.
10. the preparation method of manganese base sodium superfine powder according to claim 9 is it is characterised in that contain natrium surfactant
The solvent of solution is the water containing defoamer.
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| CN1792820A (en) * | 2005-12-05 | 2006-06-28 | 华东理工大学 | Process for preparing nano manganese dioxide uniforming dispersing in water phate |
| CN102299313A (en) * | 2011-08-10 | 2011-12-28 | 东莞市迈科科技有限公司 | Preparation method of spinel-type lithium titanate |
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| US6511647B1 (en) * | 1998-09-11 | 2003-01-28 | Accentus Plc | Method of making a manganese oxide-based materials |
| CN1792820A (en) * | 2005-12-05 | 2006-06-28 | 华东理工大学 | Process for preparing nano manganese dioxide uniforming dispersing in water phate |
| CN102299313A (en) * | 2011-08-10 | 2011-12-28 | 东莞市迈科科技有限公司 | Preparation method of spinel-type lithium titanate |
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