CN103334012A - Method for preparing metal doped manganese dioxide powder by utilizing electrolytic manganese anode slime and application of manganese dioxide powder - Google Patents

Method for preparing metal doped manganese dioxide powder by utilizing electrolytic manganese anode slime and application of manganese dioxide powder Download PDF

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Publication number
CN103334012A
CN103334012A CN2013102221860A CN201310222186A CN103334012A CN 103334012 A CN103334012 A CN 103334012A CN 2013102221860 A CN2013102221860 A CN 2013102221860A CN 201310222186 A CN201310222186 A CN 201310222186A CN 103334012 A CN103334012 A CN 103334012A
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dioxide powder
doped
metal
manganse dioxide
electrolytic manganese
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CN103334012B (en
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卢周广
王慧硕
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Southwest University of Science and Technology
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Southwest University of Science and Technology
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention provides a method for preparing metal doped manganese dioxide powder by utilizing electrolytic manganese anode slime and an application of manganese dioxide powder. The method for preparing the metal doped manganese dioxide powder by utilizing the electrolytic manganese anode slime comprises the following steps of: preparing electrolytic manganese anode slime, screening, rinsing, drying, mixing electrolytic manganese anode slime pre-treatment products with water, steel balls and additive, and carrying out ball milling to obtain manganese-containing composite slurry, filtering the manganese-containing composite slurry by adopting a pressure filter, taking filter residue, and drying, thus the metal doped manganese dioxide powder used as an electrode material is obtained. According to the method for preparing the metal doped manganese dioxide powder by utilizing the electrolytic manganese anode slime, industrial waste electrolytic manganese anode slime is taken as a raw material and is recycled and used for preparing the electrode material, recycling of a manganese element is realized, and other compounds except manganese, existing in the metal doped manganese dioxide powder, can be directly recycled without a complex screening and separation process in the prior art, so that the whole method is easy and practical in process, energy is saved, environmental protection is realized, cost is low, the method for preparing the metal doped manganese dioxide powder by utilizing the electrolytic manganese anode slime is applicable to industrial production, and the prepared metal doped manganese dioxide powder has good electrochemical activity and can serve as the electrode material.

Description

A kind of method and application for preparing metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag
Technical field
The present invention relates to Industrial Metal and recycle the field, particularly relate to a kind of method and application for preparing metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag.
Background technology
Along with the development of China's iron and steel and non-ferrous metals industry, manganese and alloy thereof are indispensable raw materials as additive, reductor and the sweetening agent of iron and steel, non-ferrous metals industry, and its demand also constantly increases, and also spurs the electrolytic metal Mn industrial boom.Though it is lower to the requirement of ore that electrolytic process is produced manganese metal, and can access high purity metal, but it can produce considerable waste water, waste gas and waste residue in electrolytic process, as: just have a large amount of anode slag to produce in clear groove process, this anode slag is by part Mn in the electrolytic solution 2+Be oxidized to Mn in the positive column 4+Hydrous oxide.The main component of manganese anode slag is MnO 2, contain small amounts of Pb O simultaneously 2, Fe 2O 3, SiO 2, other compounds such as CuO, MnO 2Massfraction about 60%～80%, form complicatedly because of it, electrolytic process has seriously changed compound property, the recycling difficulty is big, so be used for the electrolytic manganese factory oxidation ferrous iron except a small amount of, the overwhelming majority becomes waste, can only store up at present or cheap selling as the raw material of ferromanganese smelting.In the production process of electrolytic manganese, the total amount of anode slag accounts for about 10% of electrolytic manganese output, and electrolytic manganese per ton produces 80～100 kilograms anode slag.Therefore, the electrolytic manganese anode slag is carried out resource utilization and be recycled into the focus of paying close attention to for people.
Publication number is that the Chinese patent application of CN1414140A is used the useless element in the extractant separaitng electrolytic tank anode slag, makes the anode slag clean Manganse Dioxide that is of quenching, but not in the antianode slag other objectionable impuritiess handle, environment has been caused secondary pollution.Publication number is that the Chinese patent application of CN102628106A adopts the reductive agent lixiviation process that tetravalence, sexavalence manganese are reduced to manganous sulfate to make the aqueous solution that contains manganous sulfate, handle by purifying successively subsequently and remove lead, iron, aluminium and other beavy metal impurities, finally make the electrolytic solution that can be used in the electrolytic manganese production, realized the recovery of valuable metals such as manganese and lead, but the complex process that it relates to, the cost height is difficult to industrial application.
Summary of the invention
In view of this, the invention provides a kind of method for preparing metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, be that raw material recycles and for the preparation of electrode materials with industrial waste electrolytic manganese anode slag, realized the recycling of manganese element, and exist in the metal-doped Manganse Dioxide powder demanganization outside other compounds carry out complicated screening and separating operation not needing in prior art and can realize directly that the existence of recycling and other compounds has improved the manganese bioxide electrode material performance, entire method technology is simple and easy to do, energy-conserving and environment-protective, cost is low, be suitable for suitability for industrialized production, the metal-doped Manganse Dioxide powder that makes has good electrochemical activity, as electrode materials.
The invention provides and a kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, and oven dry makes electrolytic manganese anode slag pre-treatment product, and described electrolytic manganese anode slag contains MnO 2, and contain Fe 2O 3, Cr 2O 3, PbO 2, SiO 2With among the CuO one or more;
(2) getting described electrolytic manganese anode slag pre-treatment product mixes 1:0.4～0.8:2～4:1.2～4 by volume with water, steel ball, additive, by the rotating speed ball milling 1～12h of ball mill with 90～120r/min, make and contain the manganese composite mortar, described additive is selected from one or more in graphitized carbon black, electrically conductive graphite and the acetylene black;
(3) get the described manganese composite mortar that contains and filter with pressure filter, get filter residue, dry to water content be 0～3%, make the metal-doped Manganse Dioxide powder as electrode materials.
Wherein, the electrolytic manganese anode slag is that electrolytic process prepares the anode slag mixture of collecting in the production of manganese metal, contains MnO 2, and contain Fe 2O 3, Cr 2O 3, PbO 2, SiO 2With among the CuO one or more.MnO 2Massfraction about 60%～80%.
Step (1) is removed block impurity and soluble impurity for the electrolytic manganese anode slag is carried out pre-treatment, makes comparatively pure electrolytic manganese anode slag pre-treatment product.
Preferably, screening was the screenings of 150～300 mesh sieves, extracting screen underflow.
Preferably, rinsing is for using water rinse.
Preferably, bake out temperature is 100～110 ℃ described in the step (1).
Step (2) is for to carry out ball milling to electrolytic manganese anode slag pre-treatment product, the ball milling product that makes uniform particle diameter and good dispersity contains the manganese composite mortar, wherein Manganse Dioxide is amorphous structure, the adding of additive is used for improving the stability of ball milling product on the one hand, and the electrochemical activity that also can be the electrode materials of subsequent preparation on the other hand lays a good foundation.
Preferably, the product of electrolytic manganese anode slag pre-treatment described in the step (2) mixes 1:0.5～0.7:2.5～3.5:2～3 by volume with water, steel ball, additive.
Preferably, ball milling described in the step (2) is the rotating speed ball milling 3～9h with 100～110r/min.
Preferably, mechanical milling process is that per 30 minutes blowings return once.
Preferably, be cooled to normal temperature by recirculated water in the mechanical milling process.
Step (3) is with the solid-liquid separation in the ball milling product, and drying makes the less metal-doped Manganse Dioxide powder of water content.The Manganse Dioxide powder that can take a morsel metal-doped subsequently carries out sreen analysis and ultimate analysis.Metal-doped Manganse Dioxide powder self contains MnO 2And other compounds, the existence of other compounds has improved the manganese bioxide electrode material performance, simultaneously, carry out complicated screening and separating operation other compounds among the present invention do not need in prior art and can directly realize recycling, other compounds are selected from Fe 2O 3, Cr 2O 3, PbO 2, SiO 2With among the CuO one or more.
Preferably, the particle diameter of described metal-doped Manganse Dioxide powder is 1～10 μ m.
Preferably, contained Manganse Dioxide is indefinite kenel in the described metal-doped Manganse Dioxide powder.
Preferably, bake out temperature is 100～110 ℃ described in the step (3).
Preferably, the hot gas that kiln is passed through provides life hot water by heat exchanger.And preferably, the waste water that will produce in rinsing and ball milling obtains cleaning water and continues recycle by sewage disposal.
The present invention also provides a kind of and has prepared the application of metal-doped Manganse Dioxide powder in preparation electrode of super capacitor, lithium ion battery negative or gas battery electrode that the method for metal-doped Manganse Dioxide powder makes with the electrolytic manganese anode slag, and the described method for preparing metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag as previously mentioned.
Preferably, the described metal-doped application of Manganse Dioxide powder in the preparation electrode of super capacitor may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 75～100 weight parts and the conductive agent of 0～25 weight part mixes; Adding an amount of ethanol then grinds, under constantly grinding, be that the ratio of 90～95:5～10 adds binding agent in the weight ratio of the gross weight of described metal-doped Manganse Dioxide powder and conductive agent and weight of binder, continue to be ground to ethanol and volatilize fully, make super capacitor electrode paste; Described super capacitor electrode paste is rolled flakiness and cutting, make pole piece with the collector roll-in subsequently, drying makes electrode of super capacitor.More preferably, the add-on of ethanol is 1～5 weight part.Further preferably, the thickness of pole piece is 0.4～0.6mm.Further preferably, drying is dry 24h under 80～100 ℃ of temperature.
Preferably, the described metal-doped application of Manganse Dioxide powder in preparation lithium ion battery negative electrode may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 75～100 weight parts and the conductive agent of 0～25 weight part mixes; Under constantly grinding, be that the ratio of 90～95:5～10 adds binding agent in the weight ratio of the gross weight of described metal-doped Manganse Dioxide powder and conductive agent and weight of binder, continue to grind, make the lithium ion battery negative electrode slurry, and use scraper evenly to coat the lithium ion battery negative electrode slurry on the Copper Foil, dry, cutting makes the lithium ion battery negative electrode again.More preferably, drying is dry 24h under 80～100 ℃ of temperature.
Preferably, the described metal-doped application of Manganse Dioxide powder in preparation gas battery electrode may further comprise the steps:
The conductive agent of getting metal-doped Manganse Dioxide powder, 40～70 weight part gacs and 0～10 weight part of 0.1～10 weight part mixes; Adding an amount of ethanol then grinds, under constantly grinding, be that the ratio of 90～95:5～10 adds binding agent in the weight ratio of the gross weight of described metal-doped Manganse Dioxide powder, gac and conductive agent and weight of binder, continue to be ground to ethanol and volatilize fully, make the gas battery electrode slurry; Described gas battery electrode slurry is rolled flakiness and cutting, make pole piece with the collector roll-in subsequently, drying makes the gas battery electrode.More preferably, the add-on of ethanol is 1～5 weight part.More preferably, the thickness of pole piece is 0.4～0.6mm.More preferably, drying is dry 24h under 80～100 ℃ of temperature.
The invention provides a kind of method for preparing metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, be that raw material recycles and for the preparation of electrode materials with industrial waste electrolytic manganese anode slag, realized the recycling of manganese element, and exist in the metal-doped Manganse Dioxide powder demanganization outside other compounds carry out complicated screening and separating operation not needing in prior art and can realize directly that the existence of recycling and other compounds has improved the manganese bioxide electrode material performance, entire method technology is simple and easy to do, energy-conserving and environment-protective, cost is low, be suitable for suitability for industrialized production, the metal-doped Manganse Dioxide powder that makes has good electrochemical activity, as electrode materials.
Description of drawings
Fig. 1 is the cyclic voltammetry curve figure under the electrode of super capacitor sweep velocity 10mV/s that makes in the embodiment of the invention one for Fig. 1.
Fig. 2 is the constant current charge-discharge graphic representation of the electrode of super capacitor that makes in the embodiment of the invention one.
Fig. 3 is the XRD figure of the metal-doped Manganse Dioxide powder that makes in the embodiment of the invention one.
Fig. 4 is the sreen analysis figure of the metal-doped Manganse Dioxide powder that makes in the embodiment of the invention one.
Embodiment
The following stated is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also are considered as protection scope of the present invention.
Embodiment one
A kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, dries under 100 ℃ of temperature, makes electrolytic manganese anode slag pre-treatment product, and it is 76.38% MnO that described electrolytic manganese anode slag contains massfraction 2, and the Fe that contains 2.56% 2O 3, 0.023% Cr 2O 3With 7.08% PbO 2
(2) get electrolytic manganese anode slag pre-treatment product 0.005m 3, water 0.003m 3, steel ball 0.015m 3With graphitized carbon black 0.01m 3Mix, by the rotating speed ball milling 10h of ball mill with 90r/min, blowing returned once in per 30 minutes, and process recirculated water cools off to normal temperature, and the recycling circulating hot water is used for heat supply, made to contain the manganese composite mortar;
(3) get and contain the manganese composite mortar and filter with pressure filter, get filter residue, under 100 ℃ of temperature, dry to water content be 1%, make metal-doped Manganse Dioxide powder, metal-doped Manganse Dioxide powder is carried out sreen analysis, ultimate analysis, and the hot gas that kiln is passed through can provide life hot water by heat exchanger.
The application of the metal-doped Manganse Dioxide powder that the embodiment of the invention one makes in the preparation electrode of super capacitor may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 0.075g and the conductive agent KS-6 of 0.015g mixes; The ethanol that adds 5mL then fully grinds, and under constantly grinding, adds the massfraction that contains tetrafluoroethylene 0.005g and is 5% polytetrafluoroethylsolution solution and continue to be ground to ethanol and volatilize fully, makes super capacitor electrode paste; Described super capacitor electrode paste is rolled into cutting 10mm * 10mm size behind the thin slice that thickness is about 0.5mm, subsequently with collector nickel foam roll-in on roll squeezer of handling well in advance, make the pole piece that thickness is 0.4mm, 80 ℃ of vacuum-drying 12h make electrode of super capacitor.
Electrochemical property test
The electrode of super capacitor that makes among the embodiment one is carried out electro-chemical test: get two close above-mentioned electrode of super capacitor of quality and be assembled into as working electrode and counter electrode that two electrode systems carry out the cyclic voltammetric test and constant current charge-discharge is tested, wherein electrolytic solution is 6mol/L KOH solution.
Fig. 1 is the cyclic voltammetry curve figure under the electrode of super capacitor sweep velocity 10mV/s that makes in the embodiment of the invention one.As can be seen from Figure 1 under alkaline condition, electrode of super capacitor shows the electric double layer capacitance characteristic.
Fig. 2 is the constant current charge-discharge graphic representation of the electrode of super capacitor that makes in the embodiment of the invention one.As can be seen from Figure 2 metal-doped Manganse Dioxide powder has higher charge/discharge capacity.
Fig. 3 is the XRD figure of the metal-doped Manganse Dioxide powder that makes in the embodiment of the invention one.As can be seen from Figure 3 the Manganse Dioxide characteristic diffraction peak is broad peak, represents that contained Manganse Dioxide becomes indefinite kenel through a series of art breading in the metal-doped Manganse Dioxide powder.
Fig. 4 is the sreen analysis figure of the metal-doped Manganse Dioxide powder that makes in the embodiment of the invention one.As can be seen from Figure 4 the particle diameter of metal-doped Manganse Dioxide powder mainly is distributed in 1～10 mu m range, and particle is thinner.
To sum up, the metal-doped Manganse Dioxide powder that makes in the embodiment of the invention one has favorable charge-discharge reversibility and higher specific storage.
Embodiment two
A kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, dries under 110 ℃ of temperature, makes electrolytic manganese anode slag pre-treatment product, and it is 80.00% MnO that described electrolytic manganese anode slag contains massfraction 2, and the Fe that contains 3.09% 2O 3With 0.04% Cr 2O 3
(2) get electrolytic manganese anode slag pre-treatment product 0.005m 3, water 0.0020m 3, steel ball 0.0150m 3With graphitized carbon black 0.015m 3Mix, by the rotating speed ball milling 12h of ball mill with 120r/min, blowing returned once in per 30 minutes, and process recirculated water cools off to normal temperature, and the recycling circulating hot water is used for heat supply, made to contain the manganese composite mortar;
(3) get and contain the manganese composite mortar and filter with pressure filter, get filter residue, under 100 ℃ of temperature, dry to water content be 2%, make metal-doped Manganse Dioxide powder.The particle diameter of the metal-doped Manganse Dioxide powder that the embodiment of the invention two makes mainly is distributed in 1～10 mu m range, and particle is thinner, and contained Manganse Dioxide becomes indefinite kenel through a series of art breading in the metal-doped Manganse Dioxide powder.
The application of the metal-doped Manganse Dioxide powder that the embodiment of the invention two makes in the preparation electrode of super capacitor may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 0.1g and the conductive agent acetylene black of 0.025g mixes; The ethanol that adds 5mL then fully grinds, and under constantly grinding, adds the massfraction that contains tetrafluoroethylene 0.0125g and is 5% polytetrafluoroethylsolution solution and continue to be ground to ethanol and volatilize fully, makes super capacitor electrode paste; Described super capacitor electrode paste is rolled into cutting 10mm * 10mm size behind the thin slice that thickness is about 0.4mm, subsequently with collector nickel foam roll-in on roll squeezer of handling well in advance, make the pole piece that thickness is 0.4mm, 100 ℃ of vacuum-drying 12h make electrode of super capacitor.
Embodiment three
A kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, dries under 105 ℃ of temperature, makes electrolytic manganese anode slag pre-treatment product, and it is 60% MnO that described electrolytic manganese anode slag contains massfraction 2, and the Fe that contains 2.01% 2O 3, 0.023% Cr 2O 3, 6.5% PbO 2With 0.009% SiO 2
(2) get electrolytic manganese anode slag pre-treatment product 0.005m 3, water 0.0035m 3, steel ball 0.0150m 3With graphitized carbon black 0.006m 3Mix, by the rotating speed ball milling 9h of ball mill with 100r/min, blowing returned once in per 30 minutes, and process recirculated water cools off to normal temperature, and the recycling circulating hot water is used for heat supply, made to contain the manganese composite mortar;
(3) get and contain the manganese composite mortar and filter with pressure filter, get filter residue, under 100 ℃ of temperature, dry to water content be 1%, make metal-doped Manganse Dioxide powder.The particle diameter of the metal-doped Manganse Dioxide powder that the embodiment of the invention three makes mainly is distributed in 1～10 mu m range, and particle is thinner, and contained Manganse Dioxide becomes indefinite kenel through a series of art breading in the metal-doped Manganse Dioxide powder.
The application of the metal-doped Manganse Dioxide powder that the embodiment of the invention three makes in the preparation electrode of super capacitor may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 0.09g and the conductive agent Super P of 0.03g mixes; The ethanol that adds 5mL then fully grinds, and under constantly grinding, adds the massfraction that contains tetrafluoroethylene 0.006g and is 5% polytetrafluoroethylsolution solution and continue to be ground to ethanol and volatilize fully, makes super capacitor electrode paste; Described super capacitor electrode paste is rolled into cutting 10mm * 10mm size behind the thin slice that thickness is about 0.4mm, subsequently with collector nickel foam roll-in on roll squeezer of handling well in advance, make the pole piece that thickness is 0.4mm, 100 ℃ of vacuum-drying 12h make electrode of super capacitor.
Embodiment four
A kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, dries under 100 ℃ of temperature, makes electrolytic manganese anode slag pre-treatment product, and it is 75.23% MnO that described electrolytic manganese anode slag contains massfraction 2, and the Fe that contains 5.04% 2O 3With 12% PbO 2
(2) get electrolytic manganese anode slag pre-treatment product 0.005m 3, water 0.003m 3, steel ball 0.0125m 3With graphitized carbon black 0.010m 3Mix, by the rotating speed ball milling 3h of ball mill with 110r/min, blowing returned once in per 30 minutes, and process recirculated water cools off to normal temperature, and the recycling circulating hot water is used for heat supply, made to contain the manganese composite mortar;
(3) get and contain the manganese composite mortar and filter with pressure filter, get filter residue, under 100 ℃ of temperature, dry to water content be 1%, make metal-doped Manganse Dioxide powder.The particle diameter of the metal-doped Manganse Dioxide powder that the embodiment of the invention four makes mainly is distributed in 1～10 mu m range, and particle is thinner, and contained Manganse Dioxide becomes indefinite kenel through a series of art breading in the metal-doped Manganse Dioxide powder.
The application of the metal-doped Manganse Dioxide powder that the embodiment of the invention four makes in the preparation electrode of super capacitor may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 0.1g and the conductive agent KS-6 of 0.03g mixes; The ethanol that adds 5mL then fully grinds, and under constantly grinding, adds the massfraction that contains tetrafluoroethylene 0.013g and is 5% polytetrafluoroethylsolution solution and continue to be ground to ethanol and volatilize fully, makes super capacitor electrode paste; Described super capacitor electrode paste is rolled into cutting 10mm * 10mm size behind the thin slice that thickness is about 0.4mm, subsequently with collector nickel foam roll-in on roll squeezer of handling well in advance, make the pole piece that thickness is 0.4mm, 100 ℃ of vacuum-drying 12h make electrode of super capacitor.
Embodiment five
A kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, dries under 110 ℃ of temperature, makes electrolytic manganese anode slag pre-treatment product, and it is 79.61% MnO that described electrolytic manganese anode slag contains massfraction 2, and the Fe that contains 3.26% 2O 3, 11% PbO 2With 0.0042% SiO 2
(2) get electrolytic manganese anode slag pre-treatment product 0.005m 3, water 0.004m 3, steel ball 0.0175m 3With graphitized carbon black 0.01m 3Mix, by the rotating speed ball milling 1h of ball mill with 120r/min, make and contain the manganese composite mortar;
(3) get and contain the manganese composite mortar and filter with pressure filter, get filter residue, under 100 ℃ of temperature, dry to water content be 1%, make metal-doped Manganse Dioxide powder.The particle diameter of the metal-doped Manganse Dioxide powder that the embodiment of the invention five makes mainly is distributed in 1～10 mu m range, and particle is thinner, and contained Manganse Dioxide becomes indefinite kenel through a series of art breading in the metal-doped Manganse Dioxide powder.
The application of the metal-doped Manganse Dioxide powder that the embodiment of the invention five makes in the preparation electrode of super capacitor may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 0.1g and the conductive agent acetylene black of 0.03g mixes; The ethanol that adds 5mL then fully grinds, and under constantly grinding, adds the massfraction that contains tetrafluoroethylene 0.013g and is 5% polytetrafluoroethylsolution solution and continue to be ground to ethanol and volatilize fully, makes super capacitor electrode paste; Described super capacitor electrode paste is rolled into cutting 10mm * 10mm size behind the thin slice that thickness is about 0.4mm, subsequently with collector nickel foam roll-in on roll squeezer of handling well in advance, make the pole piece that thickness is 0.4mm, 100 ℃ of vacuum-drying 12h make electrode of super capacitor.
Embodiment six
A kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, dries under 110 ℃ of temperature, makes electrolytic manganese anode slag pre-treatment product, and it is 65.82% MnO that described electrolytic manganese anode slag contains massfraction 2, and the Fe that contains 2.96% 2O 3, 10% PbO 2With 0.01% SiO 2
(2) get electrolytic manganese anode slag pre-treatment product 0.005m 3, water 0.002m 3, steel ball 0.010m 3With graphitized carbon black 0.02m 3Mix, by the rotating speed ball milling 1h of ball mill with 90r/min, make and contain the manganese composite mortar;
(3) get and contain the manganese composite mortar and filter with pressure filter, get filter residue, under 100 ℃ of temperature, dry to water content be 2%, make metal-doped Manganse Dioxide powder.The particle diameter of the metal-doped Manganse Dioxide powder that the embodiment of the invention six makes mainly is distributed in 1～10 mu m range, and particle is thinner, and contained Manganse Dioxide becomes indefinite kenel through a series of art breading in the metal-doped Manganse Dioxide powder.
The application of the metal-doped Manganse Dioxide powder that the embodiment of the invention six makes in the preparation electrode of super capacitor may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 0.1g and the conductive agent Super P of 0.04g mixes; The ethanol that adds 5mL then fully grinds, and under constantly grinding, adds the massfraction that contains tetrafluoroethylene 0.014g and is 5% polytetrafluoroethylsolution solution and continue to be ground to ethanol and volatilize fully, makes super capacitor electrode paste; Described super capacitor electrode paste is rolled into cutting 10mm * 10mm size behind the thin slice that thickness is about 0.4mm, subsequently with collector nickel foam roll-in on roll squeezer of handling well in advance, make the pole piece that thickness is 0.4mm, 100 ℃ of vacuum-drying 12h make electrode of super capacitor.
Embodiment seven
A kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, dries under 100 ℃ of temperature, makes electrolytic manganese anode slag pre-treatment product, and it is 60% MnO that described electrolytic manganese anode slag contains massfraction 2, and the Fe that contains 2.04% 2O 3, 0.024% Cr 2O 3With 0.0005% CuO;
(2) get electrolytic manganese anode slag pre-treatment product 0.005m 3, water 0.0025m 3, steel ball 0.015m 3With graphitized carbon black 0.01m 3Mix, by the rotating speed ball milling 9h of ball mill with 100r/min, blowing returned once in per 30 minutes, and process recirculated water cools off to normal temperature, and the recycling circulating hot water is used for heat supply, made to contain the manganese composite mortar;
(3) get and contain the manganese composite mortar and filter with pressure filter, get filter residue, under 100 ℃ of temperature, dry to water content be 1%, make metal-doped Manganse Dioxide powder.The particle diameter of the metal-doped Manganse Dioxide powder that the embodiment of the invention seven makes mainly is distributed in 1～10 mu m range, and particle is thinner, and contained Manganse Dioxide becomes indefinite kenel through a series of art breading in the metal-doped Manganse Dioxide powder.
The application of the metal-doped Manganse Dioxide powder that the embodiment of the invention seven makes in the preparation lithium ion battery negative may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 0.1g and 0.03g conductive agent KS-6 mixes; Under constantly grinding, add the massfraction contain polyvinylidene difluoride (PVDF) 0.013g and be 5% polyvinylidene difluoride (PVDF) solution and continue to be ground to uniform suspension liquid, and use scraper suspension liquid evenly to be coated on the Copper Foil cutting electrode slice, carry out 100 ℃ of dry 24h again, make lithium ion battery negative.
Embodiment eight
A kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, dries under 100 ℃ of temperature, makes electrolytic manganese anode slag pre-treatment product, and it is 77.45% MnO that described electrolytic manganese anode slag contains massfraction 2, and the Fe that contains 2.0% 2O 3, 0.030% Cr 2O 3With 0.0004% CuO;
(2) get electrolytic manganese anode slag pre-treatment product 0.005m 3, water 0.003m 3, steel ball 0.020m 3With graphitized carbon black 0.015m 3Mix, by the rotating speed ball milling 8h of ball mill with 120r/min, blowing returned once in per 30 minutes, and process recirculated water cools off to normal temperature, and the recycling circulating hot water is used for heat supply, made to contain the manganese composite mortar;
(3) get and contain the manganese composite mortar and filter with pressure filter, get filter residue, under 100 ℃ of temperature, dry to water content be 1%, make metal-doped Manganse Dioxide powder.The particle diameter of the metal-doped Manganse Dioxide powder that the embodiment of the invention eight makes mainly is distributed in 1～10 mu m range, and particle is thinner, and contained Manganse Dioxide becomes indefinite kenel through a series of art breading in the metal-doped Manganse Dioxide powder.
The application of the metal-doped Manganse Dioxide powder that the embodiment of the invention eight makes in the preparation lithium ion battery negative may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 0.1g and 0.04g conductive agent acetylene black mixes; Under constantly grinding, add the massfraction contain polyvinylidene difluoride (PVDF) 0.014g and be 5% polyvinylidene difluoride (PVDF) solution and continue to be ground to uniform suspension liquid, and use scraper that suspension liquid is evenly coated on the Copper Foil, carry out 100 ℃ of dry 24h again, the cutting electrode slice makes lithium ion battery negative.
Embodiment nine
A kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, dries under 110 ℃ of temperature, makes electrolytic manganese anode slag pre-treatment product, and it is 80.00% MnO that described electrolytic manganese anode slag contains massfraction 2, and the Fe that contains 2.96% 2O 3, 0.027% Cr 2O 3With 0.0005% CuO;
(2) get electrolytic manganese anode slag pre-treatment product 0.005m 3, water 0.0035m 3, steel ball 0.010m 3With graphitized carbon black 0.02m 3Mix, by the rotating speed ball milling 8h of ball mill with 100r/min, blowing returned once in per 30 minutes, and process recirculated water cools off to normal temperature, and the recycling circulating hot water is used for heat supply, made to contain the manganese composite mortar;
(3) get and contain the manganese composite mortar and filter with pressure filter, get filter residue, under 100 ℃ of temperature, dry to water content be 1%, make metal-doped Manganse Dioxide powder.The particle diameter of the metal-doped Manganse Dioxide powder that the embodiment of the invention nine makes mainly is distributed in 1～10 mu m range, and particle is thinner, and contained Manganse Dioxide becomes indefinite kenel through a series of art breading in the metal-doped Manganse Dioxide powder.
The application of the metal-doped Manganse Dioxide powder that the embodiment of the invention nine makes in the preparation lithium ion battery negative may further comprise the steps:
Get the metal-doped Manganse Dioxide powder of 0.1g and 0.04g conductive agent Super P mixes; Under constantly grinding, add the massfraction contain polyvinylidene difluoride (PVDF) 0.014g and be 5% polyvinylidene difluoride (PVDF) solution and continue to be ground to uniform suspension liquid, and use scraper that suspension liquid is evenly coated on the Copper Foil, carry out 100 ℃ of dry 24h again, the cutting electrode slice makes lithium ion battery negative.
Embodiment ten
A kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, dries under 100 ℃ of temperature, makes electrolytic manganese anode slag pre-treatment product, and it is 60.00% MnO that described electrolytic manganese anode slag contains massfraction 2, and the Fe that contains 3.58% 2O 3, 0.01% Cr 2O 3, 0.005% SiO 2With 0.00043% CuO;
(2) get electrolytic manganese anode slag pre-treatment product 0.005m 3, water 0.003m 3, steel ball 0.015m 3With graphitized carbon black 0.01m 3Mix, by the rotating speed ball milling 8h of ball mill with 100r/min, blowing returned once in per 30 minutes, and process recirculated water cools off to normal temperature, and the recycling circulating hot water is used for heat supply, made to contain the manganese composite mortar;
(3) get and contain the manganese composite mortar and filter with pressure filter, get filter residue, under 100 ℃ of temperature, dry to water content be 1%, make metal-doped Manganse Dioxide powder.The particle diameter of the metal-doped Manganse Dioxide powder that the embodiment of the invention ten makes mainly is distributed in 1～10 mu m range, and particle is thinner, and contained Manganse Dioxide becomes indefinite kenel through a series of art breading in the metal-doped Manganse Dioxide powder.
The application of the metal-doped Manganse Dioxide powder that the embodiment of the invention ten makes in preparation gas battery electrode may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 0.1g, 0.4g gac and 0.5g conductive agent KS-6 mixes; Add 8ml ethanol then and grind, under constantly grinding, add the massfraction that contains tetrafluoroethylene 0.05g and be 5% polyvinylidene difluoride (PVDF) solution, continue to be ground to ethanol and volatilize fully, make gas battery electrode electrode materials slurry; Described gas battery electrode slurry is rolled flakiness and cutting, make the pole piece that thickness is 0.4mm with the collector roll-in subsequently, 100 ℃ of dryings make the gas battery electrode.
Embodiment 11
A kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, dries under 110 ℃ of temperature, makes electrolytic manganese anode slag pre-treatment product, and it is 80.00% MnO that described electrolytic manganese anode slag contains massfraction 2, and the Fe that contains 3.08% 2O 3, 13.80% PbO 2With 0.0004% CuO;
(2) get electrolytic manganese anode slag pre-treatment product 0.005m 3, water 0.0035m 3, steel ball 0.020m 3With graphitized carbon black 0.015m 3Mix, by the rotating speed ball milling 8h of ball mill with 100r/min, blowing returned once in per 30 minutes, and process recirculated water cools off to normal temperature, and the recycling circulating hot water is used for heat supply, made to contain the manganese composite mortar;
(3) get and contain the manganese composite mortar and filter with pressure filter, get filter residue, under 100 ℃ of temperature, dry to water content be 1%, make metal-doped Manganse Dioxide powder.The particle diameter of the metal-doped Manganse Dioxide powder that the embodiment of the invention 11 makes mainly is distributed in 1～10 mu m range, and particle is thinner, and contained Manganse Dioxide becomes indefinite kenel through a series of art breading in the metal-doped Manganse Dioxide powder.
The application of the metal-doped Manganse Dioxide powder that the embodiment of the invention 11 makes in preparation gas battery electrode may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 0.1g, 40g gac and 10g conductive agent acetylene black mixes; Add 8ml ethanol then and grind, under constantly grinding, add the massfraction that contains tetrafluoroethylene 8.01g and be 5% polyvinylidene difluoride (PVDF) solution, continue to be ground to ethanol and volatilize fully, make gas battery electrode electrode materials slurry; Described gas battery electrode slurry is rolled flakiness and cutting, make the pole piece that thickness is 0.4mm with the collector roll-in subsequently, 100 ℃ of dryings make the gas battery electrode.
To sum up, the invention provides a kind of method for preparing metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, be that raw material recycles and for the preparation of electrode materials with industrial waste electrolytic manganese anode slag, realized the recycling of manganese element, and exist in the metal-doped Manganse Dioxide powder demanganization outside other compounds carry out complicated screening and separating operation not needing in prior art and can realize directly that the existence of recycling and other compounds has improved the manganese bioxide electrode material performance, entire method technology is simple and easy to do, energy-conserving and environment-protective, cost is low, be suitable for suitability for industrialized production, the metal-doped Manganse Dioxide powder that makes has good electrochemical activity, as electrode materials.

Claims (10)

1. one kind prepares the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, it is characterized in that, may further comprise the steps:
(1) get the electrolytic manganese anode slag, block impurity is removed in screening, and soluble impurity is removed in rinsing, and oven dry makes electrolytic manganese anode slag pre-treatment product, and described electrolytic manganese anode slag contains MnO 2, and contain Fe 2O 3, Cr 2O 3, PbO 2, SiO 2With among the CuO one or more;
(2) getting described electrolytic manganese anode slag pre-treatment product mixes 1:0.4～0.8:2～4:1.2～4 by volume with water, steel ball, additive, by the rotating speed ball milling 1～12h of ball mill with 90～120r/min, make and contain the manganese composite mortar, described additive is selected from one or more in graphitized carbon black, electrically conductive graphite and the acetylene black;
(3) get the described manganese composite mortar that contains and filter with pressure filter, get filter residue, dry to water content be 0～3%, make the metal-doped Manganse Dioxide powder as electrode materials.
2. a kind of method for preparing metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag as claimed in claim 1, it is characterized in that the product of electrolytic manganese anode slag pre-treatment described in the step (2) mixes 1:0.5～0.7:2.5～3.5:2～3 by volume with water, steel ball, additive.
3. as claimed in claim 1ly a kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, it is characterized in that ball milling described in the step (2) is the rotating speed ball milling 3～9h with 100～110r/min.
4. as claimed in claim 1ly a kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, it is characterized in that, the particle diameter of described metal-doped Manganse Dioxide powder is 1～10 μ m.
5. as claimed in claim 1ly a kind ofly prepare the method for metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag, it is characterized in that contained Manganse Dioxide is indefinite kenel in the described metal-doped Manganse Dioxide powder.
6. a kind of method for preparing metal-doped Manganse Dioxide powder with the electrolytic manganese anode slag as claimed in claim 1, it is characterized in that, mechanical milling process described in the step (2) is that per 30 minutes blowings return once, is cooled to normal temperature by recirculated water in the described mechanical milling process.
7. as claimed in claim 1ly a kind ofly prepare the application of metal-doped Manganse Dioxide powder in preparation electrode of super capacitor, lithium ion battery negative or gas battery electrode that the method for metal-doped Manganse Dioxide powder makes with the electrolytic manganese anode slag.
8. the metal-doped application of Manganse Dioxide powder in the preparation electrode of super capacitor as claimed in claim 7 is characterized in that, may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 75～100 weight parts and the conductive agent of 0～25 weight part mixes; Adding an amount of ethanol then grinds, under constantly grinding, be that the ratio of 90～95:5～10 adds binding agent in the weight ratio of the gross weight of described metal-doped Manganse Dioxide powder and conductive agent and weight of binder, continue to be ground to ethanol and volatilize fully, make super capacitor electrode paste; Described super capacitor electrode paste is rolled flakiness and cutting, make pole piece with the collector roll-in subsequently, drying makes electrode of super capacitor.
9. the metal-doped application of Manganse Dioxide powder in preparation lithium ion battery negative electrode as claimed in claim 7 is characterized in that, may further comprise the steps:
Getting the metal-doped Manganse Dioxide powder of 75～100 weight parts and the conductive agent of 0～25 weight part mixes; Under constantly grinding, be that the ratio of 90～95:5～10 adds binding agent in the weight ratio of the gross weight of described metal-doped Manganse Dioxide powder and conductive agent and weight of binder, continue to grind, make the lithium ion battery negative electrode slurry, and use scraper evenly to coat the lithium ion battery negative electrode slurry on the Copper Foil, dry, cutting makes the lithium ion battery negative electrode again.
10. the metal-doped application of Manganse Dioxide powder in preparation gas battery electrode as claimed in claim 7 is characterized in that, may further comprise the steps:
The conductive agent of getting metal-doped Manganse Dioxide powder, 40～70 weight part gacs and 0～10 weight part of 0.1～10 weight part mixes; Adding an amount of ethanol then grinds, under constantly grinding, be that the ratio of 90～95:5～10 adds binding agent in the weight ratio of the gross weight of described metal-doped Manganse Dioxide powder, gac and conductive agent and weight of binder, continue to be ground to ethanol and volatilize fully, make the gas battery electrode slurry; Described gas battery electrode slurry is rolled flakiness and cutting, make pole piece with the collector roll-in subsequently, drying makes the gas battery electrode.
CN201310222186.0A 2013-06-05 2013-06-05 Method for preparing metal doped manganese dioxide powder by utilizing electrolytic manganese anode slime and application of manganese dioxide powder Expired - Fee Related CN103334012B (en)

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CN104701524A (en) * 2015-03-03 2015-06-10 中南大学 Method for directly preparing nickel-cobalt-manganese ternary cathode material precursor from nickel electrolyte
CN106410119A (en) * 2015-07-31 2017-02-15 罗伯特·博世有限公司 Method for producing an electrode of a lithium-ion battery
CN109192540A (en) * 2018-09-18 2019-01-11 中联西北工程设计研究院有限公司 A kind of biomass carbonization product and manganese dioxide composite electrode material and preparation method thereof
CN110289410A (en) * 2019-06-28 2019-09-27 陕西科技大学 A kind of MnO with height ratio capacity2The preparation method of/Ag composite material
CN110299524A (en) * 2019-06-28 2019-10-01 陕西科技大学 It is a kind of to prepare lithium ion battery negative material MnO2The method of/Ag
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CN111250163A (en) * 2020-03-04 2020-06-09 中南大学 Solid waste based catalyst and preparation method and application thereof
CN115448368A (en) * 2022-10-17 2022-12-09 燕山大学 Preparation method and application of layered manganese dioxide capable of storing sodium by virtue of charge transfer
CN115448368B (en) * 2022-10-17 2023-09-05 燕山大学 Preparation method and application of layered manganese dioxide capable of storing sodium by means of charge transfer
CN116375093A (en) * 2023-05-09 2023-07-04 吉首大学 Method for preparing manganese oxide anode material of water-based zinc ion battery by utilizing electrolytic manganese anode slime

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