CN106229501A - A kind of nano strip magnesium Mn oxide and the preparation method of water system Magnesium ion battery electrode - Google Patents
A kind of nano strip magnesium Mn oxide and the preparation method of water system Magnesium ion battery electrode Download PDFInfo
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- CN106229501A CN106229501A CN201610821168.8A CN201610821168A CN106229501A CN 106229501 A CN106229501 A CN 106229501A CN 201610821168 A CN201610821168 A CN 201610821168A CN 106229501 A CN106229501 A CN 106229501A
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- 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
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- 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
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
- H01M4/466—Magnesium based
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention is to provide a kind of nano strip magnesium Mn oxide and the preparation method of water system Magnesium ion battery electrode.(1) potassium permanganate, ammonium salt aqueous solution than mixing, are leached solid by equimolar, drying at room temperature, obtain presoma；(2) described presoma is mixed according to mass ratio 1:86～91 with the mixed solution being made up of water and sec-butyl alcohol, carry out reduction reaction and obtain colloidal sol, and by described colloidal sol aging 24h at 60 DEG C, obtain gel；(3) described gel is carried out ion exchange under magnesium source compound aqueous solution, obtain layered magnesium Mn oxide；(4) it is transferred in reactor carry out hydro-thermal reaction by layered magnesium Mn oxide, by precipitate through filtering, wash, be dried to obtain end product Mg1.1Mn6O12·4.5H2O.Raw material sources of the present invention are quite varied, aqueous electrolyte advantage of lower cost, environment-protecting asepsis.
Description
Technical field
The present invention relates to a kind of preparation method for water system anode of magnesium ion battery material.
Background technology
In today of science and technology high speed development, energy storage and conversion always people pay close attention to and the problem of research.And all
In multi-energy storage and conversion devices, battery plays highly important role, such as modal battery of mobile phone, pen in life
Remembering this computer battery and power battery of electric vehicle, these have incorporated the life of people and closely related already.In field of batteries,
Lead-acid battery is the energy storage device being applied at first, but its service life is short, energy density is low；Subsequently, height is had
The lithium ion battery of energy density is used widely, and along with the development of lithium power technology, the demand of lithium is the most more come by people
The biggest, but tellurian lithium resource is limited, and its price is sufficiently expensive, and meanwhile, the organic electrolyte of lithium electricity more can cause
Safety problem during use, our environment also can be caused the biggest pollution by waste battery.Therefore, water system battery system
Appearance not only reduce cost, also solve environmental issue；And wherein, water system Magnesium ion battery especially by feat of magnesium ion with
Lithium ion has similar chemical property, close ionic radius, illustrates huge potential, and is expected in extensive energy storage
Application replaces lithium ion battery.
At present, the research to water system anode of magnesium ion battery material is little, prior art immediate with the present patent application
Can be found in document: J.Lee, J.B.Ju, W.I.Cho, et al.Todorokite-type MnO2 as a zinc-ion
intercalating material Electrochimica.Acta,112(2013),138-143。
Summary of the invention
It is an object of the invention to provide a kind of raw material sources extensive, technique is simple, the nano strip magnesium manganese of low cost
The preparation method of oxide.The present invention also aims to provide the preparation method of a kind of water system Magnesium ion battery electrode.
The preparation method of the nano strip magnesium Mn oxide of the present invention specifically includes following steps:
(1) potassium permanganate, ammonium salt aqueous solution than mixing, are leached solid by equimolar, drying at room temperature, obtain presoma；
(2) described presoma is mixed according to mass ratio 1:86～91 with the mixed solution being made up of water and sec-butyl alcohol, enter
Row reduction reaction obtains colloidal sol, and by described colloidal sol aging 24h at 60 DEG C, obtains gel；
(3) described gel is carried out ion exchange under magnesium source compound aqueous solution, obtain layered magnesium Mn oxide；
(4) it is transferred in reactor carry out hydro-thermal reaction by layered magnesium Mn oxide, by precipitate through filtering, washing
Wash, be dried to obtain end product Mg1.1Mn6O12·4.5H2O.Hydrothermal temperature is 200 DEG C, the time is 4h.
Described ammonium salt is in 4 bromide, tetraethylammonium bromide, 4-propyl bromide or tetrabutyl ammonium bromide
A kind of.
Described water and the volume ratio of sec-butyl alcohol are 1:1,2:3 or 2:5.
Described magnesium source compound is magnesium chloride or magnesium nitrate.
Gel is 1:100 with the photograph mol ratio of magnesium source compound aqueous solution.
The preparation method of the water system Magnesium ion battery electrode of the present invention specifically includes:
According to Mg1.1Mn6O12·4.5H2O, Kynoar, the ratio that mass ratio is 80%:10%:10% of acetylene black
It is mixed and made into electrode pastes, described electrode pastes is coated on carbon cloth or flexible graphite paper and is dried at 70～100 DEG C
To water system Magnesium ion battery electrode.
With the water system Magnesium ion battery electrode of the present invention as positive pole, carbon-point is to electrode, and saturated calomel electrode is reference electricity
Pole, Mg (NO3)2Aqueous solution is electrolyte, is assembled into the water system battery of three-electrode system together.
The present invention has synthesized the magnesium Mn oxide Mg with nano strip pattern first1.1Mn6O12·4.5H2O also successfully should
Positive electrode for Magnesium ion battery.The magnesium Mn oxide of nano strip belongs to the one of manganese dioxide crystal formation, and it has eight
Face body caged molecular sieve pore passage structure, the size in cage hole is 0.69nm, and the radius of magnesium ion is only 0.072nm, this just explanation
The magnesium Mn oxide of nano strip has sufficiently large duct and allows magnesium ion to carry out deintercalation, provides as positive electrode for it
Theories integration.Meanwhile, the present invention has abandoned the organic electrolyte that traditional cost is high, toxic, security performance is low, adopts
It is electrolyte with lower-cost magnesium salt solution, while keeping considerable specific capacity, it is possible to real realization is contemporary to electricity
The requirement that pond low cost, environmental protection and safety are high.Therefore the magnesium Mn oxide Mg of nano strip is probed into1.1Mn6O12·
4.5H2O behavior in aqueous electrolyte seems particularly significant.
Advantages of the present invention:
(1) the magnesium Mn oxide prepared by sol-gal process can obtain the structure of nano strip, this nano-scale
Electrode material be not only advantageous to increase and the contact area of electrolyte, it is simple to the direct ion of electrolyte exchanges, but also subtracts
The little deintercalation path of magnesium ion, beneficially magnesium ion rapidly enters inside solid phase, and then improves capacity；
(2) to utilize cheap inorganic magnesium salt aqueous solution be electrolyte, it is to avoid organic electrolyte is inflammable and explosive, cost is high,
Pollute the shortcomings such as environment, reach the requirement of environmental protection, the safety coefficient that improve；
(3) ionic conductivity of aqueous electrolyte organic electrolyte to be significantly larger than, the impedance of electrolyte is less, more added with
It is beneficial to carry out high rate charge-discharge；
(4) relative to traditional lithium ion battery, the raw material resources of water system Magnesium ion battery is abundanter, and cost is more
Cheap.
Through electro-chemical test, the material of the present invention is at 20mA g-1Under electric current density, 0.5mol dm-3Mg(NO3)2Electrolysis
Liquid can reach 152.9mAh g-1；At 100mA g-1Under electric current density, 0.5mol dm-3Mg(NO3)2Warp in electrolyte
200 circles circulate its capability retention and reach 88.9%, and coulombic efficiency is close to 100%.
Accompanying drawing explanation
Fig. 1 is the Mg under embodiment 1 synthesis condition1.1Mn6O12·4.5H2The XRD figure of O；
Fig. 2 is the Mg under embodiment 1 synthesis condition1.1Mn6O12·4.5H2The shape appearance figure of O；
Fig. 3 is Mg1.1Mn6O12·4.5H2O is at 0.5mol dm-3Mg(NO3)21mVs in electrolyte-1Sweep the circulation volt under speed
Antu；
Fig. 4 is Mg1.1Mn6O12·4.5H2O at 0.5mol dm-3Mg(NO3)220mAg in electrolyte-1Under electric current density
Constant current charge-discharge curve chart；
Fig. 5 is Mg1.1Mn6O12·4.5H2O at 0.5mol dm-3Mg(NO3)2100mAg in electrolyte-1Under electric current density
Cycle efficieny figure.
Detailed description of the invention
The present invention is described in more detail by distance below.
Embodiment 1
(1) potassium permanganate, tetraethylammonium bromide are mixed according to 15mmol equal proportion wiring solution-forming, leach solid, room temperature
It is dried, obtains presoma；
(2) by presoma at water and sec-butyl alcohol according under the equal-volume reduction than mixed solution, prepare colloidal sol, and
By colloidal sol aging 24h at 60 DEG C, obtain gel；
(3) by gel at 1mol dm-3Magnesium chloride brine under carry out ion exchange, strong agitation 1h, obtain layered magnesium
Mn oxide；
(4) layered magnesium Mn oxide is transferred in reactor 200 DEG C, 4h carry out hydro-thermal reaction, by precipitate through filtering,
Wash, be dried to obtain end product Mg1.1Mn6O12·4.5H2O。
Can be seen that from XRD figure feature peak-to-peak type is sharp-pointed, without obvious impurity peaks, embodiment 1 is optimum synthesis condition.
Embodiment 2
Change the volume ratio of the water in embodiment 1 step (2) and sec-butyl alcohol into 2:3 or 2:5.Remaining synthesis condition is constant.
Embodiment 3
Change magnesium chloride in embodiment 1 step (3) into magnesium nitrate.Remaining synthesis condition is constant.
Embodiment 4
Change hydrothermal condition in embodiment 1 step (4) into 150 DEG C, 40h.Remaining synthesis condition is constant.
Embodiment 5
By the magnesium Mn oxide Mg under embodiment 1 synthesis condition1.1Mn6O12·4.5H2O electrode slice, binding agent polyvinylidene fluoride
Alkene, the mass ratio of conductive agent acetylene black are that 80%:10%:10% is mixed and made into electrode pastes, are coated in the carbon cloth of 1cm × 1cm
Upper and dry at 80 DEG C, with carbon-point for electrode, saturated calomel electrode is that reference electrode is assembled into three-electrode system together
Water system battery.By this battery at 0.5mol dm-3MgCl2Aqueous solution carries out EIS impedance analysis, cyclic voltammetry and perseverance
Stream charge-discharge test.
Embodiment 6
By the magnesium Mn oxide Mg under embodiment 1 synthesis condition1.1Mn6O12·4.5H2O electrode slice, binding agent polyvinylidene fluoride
Alkene, the mass ratio of conductive agent acetylene black are that 80%:10%:10% is mixed and made into electrode pastes, are coated in the carbon cloth of 1cm × 1cm
Upper and dry at 80 DEG C, with carbon-point for electrode, saturated calomel electrode is that reference electrode is assembled into three-electrode system together
Water system battery.By this battery at 0.5mol dm-3Mg(NO3)2Aqueous solution is carried out EIS impedance analysis, cyclic voltammetry and
Constant current charge-discharge is tested.
Embodiment 7
By the magnesium Mn oxide Mg under embodiment 1 synthesis condition1.1Mn6O12·4.5H2O electrode slice, binding agent polyvinylidene fluoride
Alkene, the mass ratio of conductive agent acetylene black are that 80%:10%:10% is mixed and made into electrode pastes, are coated in the carbon cloth of 1cm × 1cm
Upper and dry at 80 DEG C, with carbon-point for electrode, saturated calomel electrode is that reference electrode is assembled into three-electrode system together
Water system battery.By this battery at 0.5mol dm-3MgSO4Aqueous solution carries out EIS impedance analysis, cyclic voltammetry and perseverance
Stream charge-discharge test.
Claims (10)
1. a preparation method for nano strip magnesium Mn oxide, is characterized in that comprising the steps:
(1) potassium permanganate, ammonium salt aqueous solution than mixing, are leached solid by equimolar, drying at room temperature, obtain presoma；
(2) described presoma is mixed according to mass ratio 1:86～91 with the mixed solution being made up of water and sec-butyl alcohol, carry out also
Former reaction obtains colloidal sol, and by described colloidal sol aging 24h at 60 DEG C, obtains gel；
(3) described gel is carried out ion exchange under magnesium source compound aqueous solution, obtain layered magnesium Mn oxide；
(4) be transferred in reactor carry out hydro-thermal reaction by layered magnesium Mn oxide, by precipitate through filtering, washing, dry
Dry obtain end product Mg1.1Mn6O12·4.5H2O。
The preparation method of nano strip magnesium Mn oxide the most according to claim 1, is characterized in that: described ammonium salt is four
One in methyl bromide ammonium, tetraethylammonium bromide, 4-propyl bromide or tetrabutyl ammonium bromide.
The preparation method of nano strip magnesium Mn oxide the most according to claim 1 and 2, is characterized in that: described water and
The volume ratio of sec-butyl alcohol is 1:1,2:3 or 2:5.
The preparation method of nano strip magnesium Mn oxide the most according to claim 1 and 2, is characterized in that: described magnesium source
Compound is magnesium chloride or magnesium nitrate.
The preparation method of nano strip magnesium Mn oxide the most according to claim 3, is characterized in that: described magnesium source chemical combination
Thing is magnesium chloride or magnesium nitrate.
The preparation method of nano strip magnesium Mn oxide the most according to claim 1 and 2, is characterized in that: gel and magnesium source
The photograph mol ratio of compound water solution is 1:100.
The preparation method of nano strip magnesium Mn oxide the most according to claim 3, is characterized in that: gel and magnesium source chemical combination
The photograph mol ratio of thing aqueous solution is 1:100.
The preparation method of nano strip magnesium Mn oxide the most according to claim 4, is characterized in that: gel and magnesium source chemical combination
The photograph mol ratio of thing aqueous solution is 1:100.
The preparation method of nano strip magnesium Mn oxide the most according to claim 5, is characterized in that: gel and magnesium source chemical combination
The photograph mol ratio of thing aqueous solution is 1:100.
10. a preparation method for water system Magnesium ion battery electrode, is characterized in that:
According to Mg1.1Mn6O12·4.5H2O, Kynoar, the ratio that mass ratio the is 80%:10%:10% mixing of acetylene black
Make electrode pastes, described electrode pastes is coated on carbon cloth or flexible graphite paper and is dried to obtain water at 70～100 DEG C
It it is Magnesium ion battery electrode；
Described Mg1.1Mn6O12·4.5H2O is prepared as follows:
(1) potassium permanganate, ammonium salt aqueous solution than mixing, are leached solid by equimolar, drying at room temperature, obtain presoma；
(2) by described presoma and the mixed solution being made up of water and sec-butyl alcohol different volumes, according to mass ratio 1:86's～91
Prepare colloidal sol under effect, and by described colloidal sol aging 24h at 60 DEG C, obtain gel；
(3) described gel is obtained stratiform with magnesium source compound aqueous solution according to carrying out ion exchange under the effect of mol ratio 1:100
Magnesium Mn oxide；
(4) be transferred in reactor carry out hydro-thermal reaction by layered magnesium Mn oxide, by precipitate through filtering, washing, dry
Dry obtain end product Mg1.1Mn6O12·4.5H2O。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107082453A (en) * | 2017-03-24 | 2017-08-22 | 哈尔滨工程大学 | Preparation and application process as the hydrated iron barium oxide of water system Magnesium ion battery negative material |
| CN109701547A (en) * | 2018-12-26 | 2019-05-03 | 华中科技大学 | A kind of high methyl hydride catalyzed active manganese cerium catalyst preparation method and product |
| CN110391392A (en) * | 2018-04-19 | 2019-10-29 | 北京金羽新能科技有限公司 | Water system ion battery flexible electrode and preparation method thereof and water system ion battery |
| CN114300277A (en) * | 2021-12-28 | 2022-04-08 | 辽宁大学 | Aluminum manganese oxide and application thereof as anode material in water system magnesium ion capacitor |
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| CN109701547A (en) * | 2018-12-26 | 2019-05-03 | 华中科技大学 | A kind of high methyl hydride catalyzed active manganese cerium catalyst preparation method and product |
| CN114300277A (en) * | 2021-12-28 | 2022-04-08 | 辽宁大学 | Aluminum manganese oxide and application thereof as anode material in water system magnesium ion capacitor |
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