CN109638277A - A kind of preparation method of Magnesium ion battery manganous oxide negative electrode material - Google Patents
A kind of preparation method of Magnesium ion battery manganous oxide negative electrode material Download PDFInfo
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- CN109638277A CN109638277A CN201811506739.4A CN201811506739A CN109638277A CN 109638277 A CN109638277 A CN 109638277A CN 201811506739 A CN201811506739 A CN 201811506739A CN 109638277 A CN109638277 A CN 109638277A
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- Prior art keywords
- manganese
- negative electrode
- electrode material
- manganous oxide
- ion battery
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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 invention discloses a kind of preparation methods of the manganous oxide negative electrode material of Magnesium ion battery.The manganous oxide negative electrode material that there is electrochemical reversible to store up magnesium performance is prepared for by manganese oxalate pyrolysismethod, reaction equilibrium potential is about 0.87 V(vs.Mg/Mg2+), the granularity of thermal decomposition product is 30 ~ 50 nm at 400 DEG C, and first discharge specific capacity is 39.6 mAh/g, and fake capacitance capacity specific gravity is larger in specific capacity, slowly decline as cycle-index increases its redox peak current, as pyrolysis temperature increases its specific capacity in slow downward trend.The present invention shows advantage in the control of the granularity of manganous oxide negative electrode material and in terms of improving specific capacity, and future is possible to obtain practical application.
Description
Technical field
The present invention relates to a kind of Magnesium ion battery negative electrode materials, are especially used for the manganous oxide cathode material of Magnesium ion battery
Material.
Background technique
Magnesium ion battery has specific energy height, and (magnesium theory specific energy reaches 2205Ah/kg, 3832mAh/cm3), chemical property
Stablize, cheap, resourceful, advantages of environment protection, is the following contenders for being expected to replace lithium ion battery.But
It is that Magnesium ion battery research is still in the primary stage.Wherein, it is based on Mg (BuEtAlCl2)2, Grignard Reagent, amino magnesium halogen complexing
The series of electrolyte of object, ionic liquid, polymer gel etc., however it remains oxidizing potential is lower, magnesium deposit-dissolve out invertibity
Difference, ionic conductivity is low, electrode material interface impedance is larger, with positive electrode matching it is poor the problems such as；Positive electrode is main
Use for reference existing anode material for lithium-ion batteries, but by magnesium ion charge density is larger and electrolyte oxidation current potential it is more low because
Element restricts, and the invertibity that magnesium ion migrates in most positive electrodes is poor, and generally existing structural stability is poor, reaction electricity
The problems such as position is lower, specific energy is smaller；The research of Magnesium ion battery negative electrode material relatively lags behind, and is seen in being limited only to for report
Mg, Sn, Sb, Bi metal and its alloy and nanometer Li4Ti5O12.Mg and Mg alloy material of cathode surface is easy to generate magnesium ion hardly possible
With the fine and close passivating film passed through, magnesium deposition-dissolution efficiency is limited, and is possible to generate column crystallization and cause positive and negative extremely short
Road.
The theoretical specific capacity of manganous oxide reaches 755mAh/g, very concerned as lithium ion battery negative material, still
It has not been reported as the feasibility and chemical property of Magnesium ion battery negative electrode material.Manganous oxide is in Magnesium ion battery electricity
The reaction equilibrium potential solved in liquid is about 0.8V (vs.Mg/Mg2+), therefore can be avoided magnesium metal branch/cylindrulite precipitation and may cause
Security risk.Therefore, manganous oxide is expected to develop into a kind of high with theoretical specific capacity, has a safety feature, resourceful,
The novel magnesium ion cell negative electrode material of advantages of environment protection.
Summary of the invention
The purpose of the present invention is preparing the manganous oxide with electrochemistry storage magnesium performance, and it is living to be used as Magnesium ion battery cathode
Property material.
Specific steps are as follows:
(1) the pure manganous salt of 0.05~0.5moL soluble analysis is dissolved in 100~1000mL deionized water, in magnetic force
It is slowly added to the oxalic acid aqueous solution that 45~450L mass percent concentration is 15% under stirring and obtains manganese oxalate precipitating, continues to stir
30 minutes, filtering was washed with deionized to sulfate radical-free and detects, will be deposited at 60 DEG C and be dried to obtain oxalic acid Asia manganese forerunner
Body.
(2) oxalic acid Asia manganese presoma obtained by step (1) is warming up in the tube furnace of logical argon gas with 5 DEG C/min of rates
400~900 DEG C, 1 hour is kept the temperature, is then naturally cooling to room temperature, takes out grinding, obtains the oxidation with electrochemistry storage magnesium performance
Sub- manganese negative electrode material.
(3) manganous oxide negative electrode material prepared by step (2) is pressed with acetylene black, polyvinylidene fluoride (PVDF) binder
7 ︰, 2 ︰, 1 mass ratio is fully ground mixing in the agate mortar, and 0.5~5 times of mixture quality of the pure N- methylpyrrole of analysis is added dropwise
Alkanone (NMP) continues to be ground into uniform sizing material, 316 type stainless steel foil surfaces is coated on, then in vacuum drying oven at 60 DEG C
8 hours dry, taking-up, punching, weighing obtain manganous oxide electrode slice.
(3) using the preparatory magnesium sheet polished as to electrode and reference electrode, to make 0.25moL/L Mg by oneself
(AlCl2EtBu)2/ THF solution is electrolyte, and all-glass paper makees diaphragm, and CR2032 type knob is assembled in the glove box of applying argon gas
Battery is detained, its cyclic voltammetric and charge-discharge performance are then tested.
The solubility manganous salt is one of manganese sulfate, manganese chloride, manganese acetate and manganese citrate.
Manganous oxide negative electrode material theoretical specific capacity with higher, preferable security performance, at the same have it is resourceful,
Advantages of environment protection is a kind of preferable energy storage material of comprehensive performance.Manganese oxalate thermolysis process is simple and easy, in storage magnesium
Can manganous oxide negative electrode material granularity control and show advantage in terms of improving charging and discharging capacity, future be possible to obtain into
One step develops and obtains practical application.
Detailed description of the invention
The XRD spectrum of the manganous oxide sample prepared under 400~900 DEG C of maturing temperatures of Fig. 1.
The SEM photograph of the manganous oxide sample prepared under 400 DEG C of maturing temperatures of Fig. 2.
The cyclic voltammetric performance of the manganous oxide prepared under 400 DEG C of maturing temperatures of Fig. 3.
The charge and discharge curve for the first time of the manganous oxide prepared under 400~900 DEG C of maturing temperatures of Fig. 4.
The charge-discharge performance of the manganous oxide prepared under 400~900 DEG C of maturing temperatures of Fig. 5.
Specific embodiment
Embodiment 1:
(1) the pure manganese sulfate monohydrate of 17.246g soluble analysis is dissolved in 200mL deionized water, under magnetic stirring
It is slowly added to the oxalic acid aqueous solution that 90mL mass percent concentration is 15% and obtains manganese oxalate precipitating, continue stirring 30 minutes, mistake
Filter is washed with deionized to sulfate radical-free and detects, oxalic acid Asia manganese presoma is dried to obtain at 60 DEG C.
(2) oxalic acid Asia manganese presoma obtained by step (1) is warming up in the tube furnace of logical argon gas with 5 DEG C/min of rates
400 DEG C, 1 hour is kept the temperature, is naturally cooling to room temperature, grinding is taken out and obtains manganous oxide negative electrode material.It is prepared at a temperature of 400 DEG C
The XRD of manganous oxide compose referring to Fig. 1, search result shows that the manganous oxide of preparation is face-centred cubic structure (corresponding JCPDS
No.07-0230), there is no other impurities phase.Referring to fig. 2, observation finds one to the SEM photograph of the manganous oxide prepared at 400 DEG C
Secondary particle is spherical in shape, and partial size is 30~50nm, and second particle is loose block.
(3) manganous oxide negative electrode material prepared by step (2) is pressed with acetylene black, polyvinylidene fluoride (PVDF) binder
7 ︰, 2 ︰, 1 mass ratio is fully ground mixing in the agate mortar, and 2.5 times of mixture quality of the pure N-Methyl pyrrolidone of analysis is added dropwise
(NMP) continue to be ground into uniform sizing material, be coated on 316 type stainless steel foil surfaces, then in vacuum drying oven dry 8 at 60 DEG C
Hour, taking-up, punching, weighing obtain manganous oxide electrode slice.
(4) using the magnesium sheet polished as to electrode and reference electrode, to make 0.25moL/L Mg (AlCl by oneself2EtBu)2/
THF solution is electrolyte, and all-glass paper makees diaphragm, CR2032 type button cell is assembled in the glove box of applying argon gas, then
Test its cyclic voltammetric (referring to Fig. 3) and charge-discharge performance (referring to fig. 4, Fig. 5).It can from electrochemical property test result
Out, manganous oxide shows reversible storage magnesium performance, and fake capacitance characteristic is more significant, electrochemical reaction equilibrium potential about 0.87V
(vs.Mg/Mg2+), with the increase of electric potential scanning cycle-index, redox peak current reduces；The oxidation prepared at 400 DEG C
The discharge capacity for the first time of sub- manganese negative electrode material is 39.6mAh/g, and residual capacity is about 19mAh/g after 50 weeks circulations.
Embodiment 2:
Using 1 step of embodiment (1) preparation oxalic acid Asia manganese as raw material, respectively 500 DEG C, 600 DEG C and 700 DEG C, 800 DEG C,
Manganous oxide negative electrode material is prepared under 900 DEG C of maturing temperatures, by 1 step of embodiment (2) assembled battery, charge-discharge performance test knot
Fruit referring to fig. 4, Fig. 5.The result shows that as oxalic acid Asia manganese maturing temperature increases, the first charge-discharge of manganous oxide negative electrode material
Capacity and circulation volume slowly decline, this may have with manganous oxide as the raising of maturing temperature its crystal grain is gradually grown up
It closes, manganese poor electric conductivity in simultaneous oxidation Asia is unfavorable to the performance of its chemical property.Therefore, particle size nanosizing and raising
Electric conductivity is the prerequisite that manganous oxide negative electrode material performance improves.
Claims (1)
1. a kind of preparation method of Magnesium ion battery manganous oxide negative electrode material, it is characterised in that specific steps are as follows:
(1) 0.05 ~ 0.5 pure manganous salt of moL soluble analysis is dissolved in 100 ~ 1000 mL deionized waters, in magnetic
It is slowly added to the oxalic acid aqueous solution that 45 ~ 450 mL mass percent concentrations are 15 % under power stirring and obtains manganese oxalate precipitating, after
Continuous stirring 30 minutes, filtering are washed with deionized to sulfate radical-free and detect, and will be deposited at 60 DEG C and are dried to obtain oxalic acid Asia
Manganese presoma；
(2) oxalic acid Asia manganese presoma obtained by step (1) is warming up to 400 in the tube furnace of logical argon gas with 5 DEG C/min of rates
~ 900 DEG C, 1 hour is kept the temperature, is then naturally cooling to room temperature, takes out grinding, obtains having the oxidation of electrochemistry storage magnesium performance sub-
Manganese negative electrode material；
The solubility manganous salt is one of manganese sulfate, manganese chloride, manganese acetate and manganese citrate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116231085A (en) * | 2023-05-05 | 2023-06-06 | 宁德时代新能源科技股份有限公司 | Electrolyte, lithium metal battery, preparation method of lithium metal battery and power utilization device |
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| CN102070197A (en) * | 2011-01-26 | 2011-05-25 | 江苏方舟新能源股份有限公司 | Preparation method of spherical manganous oxide |
| CN104355334A (en) * | 2014-10-22 | 2015-02-18 | 太原理工大学 | Birnessite manganese oxide powder with ultrahigh specific capacitance characteristic as well as preparation method and application thereof |
| CN107369565A (en) * | 2017-07-17 | 2017-11-21 | 深圳中科瑞能实业有限公司 | Magnesium ion hybrid super capacitor and preparation method thereof |
| US9991508B2 (en) * | 2013-04-18 | 2018-06-05 | Changs Ascending Enterprise Co., Ltd | Chemical synthesis route for lithium ion battery applications |
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2018
- 2018-12-10 CN CN201811506739.4A patent/CN109638277A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070197A (en) * | 2011-01-26 | 2011-05-25 | 江苏方舟新能源股份有限公司 | Preparation method of spherical manganous oxide |
| US9991508B2 (en) * | 2013-04-18 | 2018-06-05 | Changs Ascending Enterprise Co., Ltd | Chemical synthesis route for lithium ion battery applications |
| CN104355334A (en) * | 2014-10-22 | 2015-02-18 | 太原理工大学 | Birnessite manganese oxide powder with ultrahigh specific capacitance characteristic as well as preparation method and application thereof |
| CN107369565A (en) * | 2017-07-17 | 2017-11-21 | 深圳中科瑞能实业有限公司 | Magnesium ion hybrid super capacitor and preparation method thereof |
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| CN116231085A (en) * | 2023-05-05 | 2023-06-06 | 宁德时代新能源科技股份有限公司 | Electrolyte, lithium metal battery, preparation method of lithium metal battery and power utilization device |
| CN116231085B (en) * | 2023-05-05 | 2023-09-22 | 宁德时代新能源科技股份有限公司 | Electrolyte, lithium metal battery, preparation method of lithium metal battery and power utilization device |
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