CN106044862A - Method for preparing nano-manganese oxide through low-temperature electrolysis - Google Patents

Method for preparing nano-manganese oxide through low-temperature electrolysis Download PDF

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CN106044862A
CN106044862A CN201610381874.5A CN201610381874A CN106044862A CN 106044862 A CN106044862 A CN 106044862A CN 201610381874 A CN201610381874 A CN 201610381874A CN 106044862 A CN106044862 A CN 106044862A
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manganese dioxide
electrolysis
low
temperature
manganese
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肖启振
曹珍
王艺蓉
李朝晖
雷钢铁
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Xiangtan University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/21—Manganese oxides
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention provides a method for preparing nano-manganese oxide through low-temperature electrolysis, and belongs to the technical field of manganese dioxide preparation. The method includes the steps that a copper plate is used as a cathode, a graphite plate is used as an anode, the electrolysis temperature is 5-30 DEG C, the cathode current density is 100-1000 A/m<2>, the concentration of H2SO4 in electrolyte is 30-60 g/L, the concentration of MnSO4 is 40-70 g/L, and standing, suction filtration (washing and alcohol washing), vacuum drying and grinding are carried out on the prepared electrolysis MnO2 to prepare the finished nano MnO2 product. The prepared nano MnO2 are spherical particles, and the particle size is 50-200 nm. Compared with other kinds of high-temperature electrolysis manganese oxide (usually the temperature is 98 DEG C), and the product is nano gamma MnO2 uniform in particle size. The method is mild in condition, simple in production equipment and lower in cost, an electrolysis system is stable and controllable, treatment is simple and safe and small in environment pollution, effluent can be electrolyzed circularly, and the method has more considerable current efficiency and maneuverability and allows large-scale industrial production.

Description

Low-temperature electrolytic prepares the method for nano-manganese dioxide
Technical field
The invention belongs to Preparation Technology of Electrolytic Manganese Dioxide field, specifically low-temperature electrolytic and prepare the side of nano-manganese dioxide Method.
Background technology
Since invention aneroid battery in 1888, manganese dioxide is as the main positive electrode of aneroid battery, and its performance is to zinc-manganese The performance of aneroid battery has decisive influence.At present, the preparation method of manganese dioxide mainly has chemical method, electrolysis etc..Chemistry Productivity and the purity of manganese dioxide are the highest, but chemical manganese bioxide exist mean diameter compared with big, operation is complicated, environmental pollution is tight Weigh, can not produce continuously, be unsuitable for the shortcomings such as industrialized production, and have that purity is high, discharge capacity is big, electro-chemical activity is strong, The electrolytic manganese dioxide of the advantages such as volume is little, life-span length, can be used not only as excellent battery depolarizing agent, it is possible to as super electricity Oxidant, lithium ion battery and the raw material of manganese-zinc ferrite soft magnetic materials in container material, Chemical Manufacture, is also excellent clean Water filtrate, and compare activated carbon, zeolite, its absorption property is more preferable.
The nanometer electrolytic manganese dioxide that this method produces, compared to chemical manganese bioxide, its chemical composition and crystal structure base This is consistent, and has the advantages such as particle diameter is little and uniform, volume is little, specific surface area is big, electro-chemical activity is good, and productivity is 92%, and 100 Purpose product index is 90%, and product purity is 95%.The nanometer electrolytic manganese dioxide that this method produces can be used as battery raw material, it is possible to It is widely used as the oxidation/reduction agent during fine chemistry industry produces, catalyst, water purification filtrate etc..Electrolysis titanium dioxide existing on market Manganese method mostly is the block micron order manganese bioxide material of high temperature preparation, and energy consumption is high, the most disposable.Control electrolytic condition, can reduce Manganese dioxide deposition on battery lead plate.In patent 201110171479.1, use ultrasonic electrolysis, utilize barrier film and interpolation simultaneously Agent, makes manganese dioxide disperse as far as possible in the electrolytic solution.This patent is under the conditions of aseptate, by controlling low temperature and dispersion Agent, controls manganese dioxide nucleation and growth mechanism so that it is being suspended in electrolyte, product is the nanometer γ-MnO of uniform particle sizes2。 The method mild condition, produces equipment simple, and productivity is high, and electrolysis system is stablized controlled, and liquid waste processing is simple, safety, environment Polluting little, waste liquid electrolysis capable of circulation, production cost is lower.By research proper temperature, suitable electric current density, high current efficiency Under, low-temperature electrolytic prepares the method for nano-manganese dioxide, can substantially reduce raw material and the grid electricity fee cost of enterprise, improves city of enterprise Field competitiveness, it is achieved energy-conserving and environment-protective.
Summary of the invention
It is an object of the invention to: for the problem of above-mentioned existence, it is provided that a kind of low-temperature electrolytic prepares nano-manganese dioxide Method, the method is for MnSO4+H2SO4Aqueous solution is electrolyte, and negative electrode made by copper coin, graphite cake makees anode, low-temperature electrolytic The method preparing nano-manganese dioxide, can substantially reduce the production cost of enterprise, improves market competitiveness of enterprises, it is achieved energy-conservation Environmental protection.
To achieve these goals, the present invention adopts the following technical scheme that
Low-temperature electrolytic prepares the method for nano-manganese dioxide, and the method comprises the following steps:
(1) preparation electrolyte: with industrial manganic sulfate as raw material, be dissolved in deionized water, according to certain mass ratio, add dense sulfur Acid, and a small amount of dispersant A, stirring forms homogeneous solution, the most static a period of time.
(2) pretreatment: utilize water bath heating device that electrolyte is heated, make solution temperature be maintained at 5～30 DEG C, to two Individual battery lead plate is carried out.
(3) electrolysis: put up electrolysis unit and liquid inlet and outlet pipe, be electrolysed electrolyte, separates out titanium dioxide on anode Manganese.
(4) post processing: after electrolysis, processes the manganese dioxide on graphite cake clean, and is stood by electrolyte, and sucking filtration (is used Water and ethanol rinse), collect filtrate, continue electrolysis, be finally vacuum dried, grind, obtain low-temperature electrolytic nano-manganese dioxide Product, filtrate continues electrolysis.
In electrolysis bath, using copper coin to make negative electrode, graphite cake is electrolysed as anode, and electrolysis temperature is 5～30 DEG C, anode Electric current density is 100～1000A/m2, H in electrolyte2SO4Concentration is 30～50g/L, MnSO4Concentration is 40～60g/ L。
Further preferably, using copper coin to make negative electrode, graphite cake is electrolysed as anode, and electrolysis temperature is 5～30 DEG C, sun Electrode current density is 300～800A/m2, H in electrolyte2SO4Concentration is 30～50g/L, MnSO4Concentration be 40～ 60g/L。
Further, selected liquid inlet and outlet pipe, all in positive plate side, by adjusting, control suitable flow velocity.
The dominant response producing electrolytic manganese dioxide is:
On anode, the reaction of main generation is: Mn2++2H2O→MnO2+4H++2e-(E1=1.23V)
On negative electrode, the reaction of main generation is: 2H++2e-→H2↑ (E2=0V)
The overall reaction occurred in electrolytic process is: MnSO4+2H2O→MnO2+H2SO4+H2↑
Theoretical decomposition voltage is: E=E1-E2=1.23V
In sum, owing to have employed technique scheme, the invention has the beneficial effects as follows: the present invention is by controlling anode current The technological means such as density, concentration of electrolyte, electrolysis temperature, battery lead plate type reach low-temperature electrolytic and prepare the mesh of nano-manganese dioxide 's.The method is while ensureing product quality, and low-temperature electrolytic reduces grid electricity fee cost, decreases manganese dioxide on positive plate Deposition, increases anode life, extends electrolysis time, reduces enterprise's production cost further, promotes its market competitiveness, it is achieved joint Can environmental protection.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph that low-temperature electrolytic prepares nano-manganese dioxide finished product；
Fig. 2 is the XRD figure that low-temperature electrolytic prepares nano-manganese dioxide finished product；
Fig. 3 is the discharge curve that low-temperature electrolytic prepares the lithium-manganese dioxide battery of nano-manganese dioxide finished product.
Detailed description of the invention
The present invention is described in further detail below in conjunction with the accompanying drawings, and following example are explanation of the invention, this Invention is not limited to following example.
Embodiment 1:
With industrial manganic sulfate as raw material, beaker is electrolysis bath, in the beaker of 5L, prepares 40 ± 10g/L sulphuric acid with deionized water Manganese, is slowly added to concentrated sulphuric acid according to mass ratio 1:1, and stirring forms homogeneous solution, and the most static a period of time, by large beaker Being placed in water-bath, arranging temperature is 5～10 DEG C, controls electrolyte temperature.With graphite as positive plate, copper coin is minus plate, Yin, yang pole plate is immersed in the electrolyte of 5～10 DEG C.The manganese sulfate of 80 ± 10g/L is added liquid be loaded in transfusion bottle, when surely Pressure DC source is at 100 ± 10A/m2Electric current density under when starting to be electrolysed, add in positive plate side, simultaneously with transfusion Bank of tubes goes out the sulphuric acid produced in electrolytic process, it is ensured that system acidity is stable, observes manganese dioxide and separates out situation, is electrolysed 12h.By electricity Solve after the electrolyte after stopping stands a night, carry out sucking filtration with buchner funnel, collect filtrate, and with each drip washing of water and ethanol 2 times, 70 DEG C of vacuum drying, dried solid grinds in quartz mortar, obtains the black nano manganese dioxide powder of electrolytic preparation. Weighing, productivity is 30%, and product purity is 90%, and the product index of 100 mesh is 40%, is loaded in sealed bag.The filtrate collected is entered again Row electrolysis.
Embodiment 2:
With industrial manganic sulfate as raw material, beaker is electrolysis bath, in the beaker of 5L, prepares 40 ± 10g/L sulphuric acid with deionized water Manganese, is slowly added to concentrated sulphuric acid according to mass ratio 1:1, and stirring forms homogeneous solution, and the most static a period of time, by large beaker Being placed in water-bath, arranging temperature is 10～20 DEG C, controls electrolyte temperature.With graphite as positive plate, copper coin is minus plate, Yin, yang pole plate is immersed in the electrolyte of 10～20 DEG C.The manganese sulfate of 80 ± 10g/L is added liquid be loaded in transfusion bottle, when Constant voltage dc source is at 200 ± 10A/m2Electric current density under when starting to be electrolysed, add in positive plate side, simultaneously with defeated Liquid bank of tubes goes out the sulphuric acid produced in electrolytic process, it is ensured that system acidity is stable, observes manganese dioxide and separates out situation, is electrolysed 12h.Will Electrolysis stop after electrolyte stand a night after, carry out sucking filtration with buchner funnel, collect filtrate, and with each drip washing of water and ethanol 2 Secondary, 70 DEG C of vacuum drying, dried solid grinds in quartz mortar, obtains the black nano manganese dioxide powder of electrolytic preparation End.Weighing, productivity is 40%, and product purity is 90%, and the product index of 100 mesh is 50%, is loaded in sealed bag.The filtrate collected It is electrolysed again.
Embodiment 3:
With industrial manganic sulfate as raw material, beaker is electrolysis bath, in the beaker of 5L, prepares 40 ± 10g/L sulphuric acid with deionized water Manganese, according to mass ratio 1:1:0.05, is slowly added to concentrated sulphuric acid, and a small amount of dispersant A, and stirring forms homogeneous solution, at room temperature Static a period of time, being placed in water-bath by large beaker, arranging temperature is 10～20 DEG C, controls electrolyte temperature.With graphite For positive plate, copper coin is minus plate, is immersed in the electrolyte of 10～20 DEG C by yin, yang pole plate.By the sulphuric acid of 80 ± 10g/L Manganese is added liquid and is loaded in transfusion bottle, when constant voltage dc source is at 200 ± 10A/m2Electric current density under when starting to be electrolysed, at positive plate Side is added, and discharges the sulphuric acid produced in electrolytic process with tube for transfusion simultaneously, it is ensured that system acidity is stable, observes titanium dioxide Manganese separates out situation, is electrolysed 12h.After electrolyte after electrolysis being stopped stands a night, carry out sucking filtration with buchner funnel, collect filter Liquid, and with each drip washing of water and ethanol 2 times, 70 DEG C of vacuum drying, the grinding in quartz mortar of dried solid, obtain low temp. electric The black nano manganese dioxide powder solved.Weighing, productivity is 70%, and product purity is 90%, and the product index of 100 mesh is 70%, dress In sealed bag.The filtrate collected is electrolysed again.
Embodiment 4:
With industrial manganic sulfate as raw material, beaker is electrolysis bath, in the beaker of 5L, prepares 40 ± 10g/L sulphuric acid with deionized water Manganese, is slowly added to concentrated sulphuric acid, and a small amount of dispersant A according to mass ratio 1:1:0.1, and stirring forms homogeneous solution, the most quiet Only a period of time, being placed in water-bath by large beaker, arranging temperature is 20～30 DEG C, and heating electrolyte is to design temperature.With Graphite is positive plate, and copper coin is minus plate, is immersed in the electrolyte of 20～30 DEG C by yin, yang pole plate.By 80 ± 10g/L's Manganese sulfate is added liquid and is loaded in transfusion bottle, when constant voltage dc source is at 200 ± 10A/m2Electric current density under when starting to be electrolysed, at sun Pole plate side is added, and discharges the sulphuric acid produced in electrolytic process with tube for transfusion in positive plate side simultaneously, it is ensured that system acid Degree is stable, observes manganese dioxide and separates out situation, is electrolysed 12h.After electrolyte after electrolysis being stopped stands a night, use buchner funnel Carry out sucking filtration, collect filtrate, and with each drip washing of water and ethanol 2 times, 70 DEG C of vacuum drying, dried solid is in quartzy mortar Grind, obtain the black nano manganese dioxide powder of electrolytic preparation.Weighing, productivity is 90%, and product purity is 95%, 100 purposes Product index is 85%, is loaded in sealed bag.The filtrate collected is electrolysed again.
Described above is the detailed description for possible embodiments of the present invention, but embodiment is not limited to the present invention's Patent claim, the equal change completed under the technical spirit suggested by all present invention or modification change, all should be belonged to this The scope of the claims that invention is contained.

Claims (10)

1. the method that low-temperature electrolytic prepares nano-manganese dioxide, it uses the following step:
With industrial manganic sulfate as raw material, according to certain mass ratio, adding concentrated sulphuric acid, and a small amount of dispersant A, stirring is formed uniformly Solution；At a certain temperature, it is electrolysed by electrolysis unit, prepares nano-manganese dioxide；After electrolysis terminates, process graphite cake The most a small amount of upper manganese dioxide, and suspension is carried out sucking filtration, washs, be dried, prepare nano-manganese dioxide.
The method that the most according to claim 1, low-temperature electrolytic prepares nano-manganese dioxide, it is characterised in that: manganese sulfate, sulphuric acid, The mass ratio of dispersant A is: 1:1～1.5:0.02～0.1.
The method that the most according to claim 1, low-temperature electrolytic prepares nano-manganese dioxide, it is characterised in that: dispersant A is poly- Vinyl pyrrolidone, dodecyl sodium sulfate and Dodecyl trimethyl ammonium chloride etc..
The method that the most according to claim 1, low-temperature electrolytic prepares nano-manganese dioxide, it is characterised in that: copper coin is negative electrode, Graphite cake is anode, and electrolysis temperature is 5～30 DEG C, and anodic current density is 100～1000A/m2, H in electrolyte2SO4Dense Degree is 40～60g/L, MnSO4Concentration is 40～60g/L, MnSO4Adding liquid concentration is MnSO in electrolyte4The 2 of concentration Times, tank voltage is 2.0～8.0V, and electrolysing period is 2～10 days.
The method that the most according to claim 2, low-temperature electrolytic prepares nano-manganese dioxide, it is characterised in that: minus plate and anode The spacing of plate is 8～15cm.
The method that the most according to claim 2, low-temperature electrolytic prepares nano-manganese dioxide, it is characterised in that: selected enter, Drain pipe, all in positive plate side.
The method that the most according to claim 2, low-temperature electrolytic prepares nano-manganese dioxide, it is characterised in that: pass through liquid inlet and outlet Pipe, can control sulphuric acid and manganese sulfate concentration in solution, carry out continuous electrolysis, and electrolysis time can extend to 280h.
The method that the most according to claim 2, low-temperature electrolytic prepares nano-manganese dioxide, it is characterised in that: electrolysis terminates, and Time process graphite cake and copper coin.
The method that the most according to claim 2, low-temperature electrolytic prepares nano-manganese dioxide, it is characterised in that: the titanium dioxide of preparation Manganese is nanoscale manganese dioxide, and dispersion effect is good in the electrolytic solution, and particle diameter is 50-200nm.
The method that the most according to claim 2, low-temperature electrolytic prepares nano-manganese dioxide, it is characterised in that: the dioxy of preparation Changing manganese is γ-MnO2。
CN201610381874.5A 2016-06-02 2016-06-02 Method for preparing nano-manganese oxide through low-temperature electrolysis Pending CN106044862A (en)

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CN106784791A (en) * 2016-12-30 2017-05-31 湘潭大学 The preparation method of power type nanometer lithium manganate
CN108033521A (en) * 2017-12-19 2018-05-15 北京科技大学 Load gamma MnO2Active carbon particle electrode preparation method and application
CN108793256A (en) * 2018-06-26 2018-11-13 普瑞斯伊诺康有限公司 A kind of electrolytic manganese dioxide powder and preparation method thereof
RU2677095C1 (en) * 2018-02-05 2019-01-15 Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) Method of manufacturing a chemoresistor based on nanostructures of manganese oxide by electrochemical method
CN113061910A (en) * 2021-03-22 2021-07-02 长沙学院 Electrolytic manganese dioxide and preparation method and application thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784791A (en) * 2016-12-30 2017-05-31 湘潭大学 The preparation method of power type nanometer lithium manganate
CN108033521A (en) * 2017-12-19 2018-05-15 北京科技大学 Load gamma MnO2Active carbon particle electrode preparation method and application
CN108033521B (en) * 2017-12-19 2020-11-10 北京科技大学 Load gamma MnO2Preparation method and application of active carbon particle electrode
RU2677095C1 (en) * 2018-02-05 2019-01-15 Федеральное государственное бюджетное образовательное учреждение высшего образования "Саратовский государственный технический университет имени Гагарина Ю.А." (СГТУ имени Гагарина Ю.А.) Method of manufacturing a chemoresistor based on nanostructures of manganese oxide by electrochemical method
CN108793256A (en) * 2018-06-26 2018-11-13 普瑞斯伊诺康有限公司 A kind of electrolytic manganese dioxide powder and preparation method thereof
CN113061910A (en) * 2021-03-22 2021-07-02 长沙学院 Electrolytic manganese dioxide and preparation method and application thereof
CN113061910B (en) * 2021-03-22 2021-11-12 长沙学院 Electrolytic manganese dioxide and preparation method and application thereof

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Application publication date: 20161026