CN105609752A - Preparation method for nano-granular Mn3O4/Super P lithium ion battery negative electrode material - Google Patents

Preparation method for nano-granular Mn3O4/Super P lithium ion battery negative electrode material Download PDF

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Publication number
CN105609752A
CN105609752A CN201610072507.7A CN201610072507A CN105609752A CN 105609752 A CN105609752 A CN 105609752A CN 201610072507 A CN201610072507 A CN 201610072507A CN 105609752 A CN105609752 A CN 105609752A
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Prior art keywords
lithium ion
ion battery
battery negative
superp
manganese dioxide
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CN201610072507.7A
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Inventor
曹丽云
王瑞谊
李瑞梓
许占位
黄剑锋
李嘉胤
康倩
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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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
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a nano-granular Mn3O4/Super P lithium ion battery negative electrode material and a preparation method therefor. Potassium permanganate, tetrahydrate manganese chloride and Super P are taken as raw materials; manganese dioxide is prepared by adopting a low temperature coprecipitation method firstly; then manganese dioxide is mixed with Super P to be subjected to thermal treatment to obtain a nano-granular Mn3O4/Super P (MS) compound; and the compound can be used as the high-performance lithium ion battery negative electrode material. The MS nanoparticles have relatively large specific surface areas and can be in full contact with an electrolyte, so that the activity injection site of the material can be greatly improved; meanwhile, the diffusion distance of lithium ions in the material is shortened, ion transport is accelerated, and the material obtains high specific capacity; and in addition, the granular nanostructure can effectively relieve structural expansion/shrinkage in ion intercalation/deintercalation, so that high cycling stability of the MS particles is realized.

Description

A kind of Nanoparticulate Mn3O4The preparation method of/Super P lithium ion battery negative material
Technical field
The invention belongs to lithium ion battery field, be specifically related to a kind of Nanoparticulate Mn3O4/ SuperP lithium ion batteryThe preparation method of negative material.
Background technology
Since 21 century, people for multipotency more and more the demand of cleaning ambient force many countries all in developmentA more eco-friendly energy storage system, with respect to lead-acid battery, nickel-cadmium cell, chargeable lithium-ion electricPond has high energy density, long cycle life, and the advantages such as memory-less effect, are expected to for electric automobile and mixingThe aspects such as power vehicle. Along with its range of application is more and more wider, people to the performance requirement of lithium ion battery also more and moreHeight, the capacity of lithium ion battery depends on its electrode material consumingly, especially negative material, traditional negative pole materialMaterial is material with carbon element, but because its theoretical specific capacity only has 372mAhg‐1, and in the time of over-charging of battery, also can go outExisting safety issue, so researchers just start to explore another and can substitute the negative material of material with carbon element.
Mangano-manganic oxide is due to its ABUNDANT NATUREAL RESOURSES, low toxicity, low cost, high theoretical specific capacity (936mAhg‐1)Etc. feature, be widely used in the research of lithium ion battery negative material. But because its electric conductivity is low by (10‐7～10‐8S/cm)And limited its capacity performance, and SuperP is the granular conductive black of a kind of armorphous nano, therefore withSuperP is compound is a kind of method of effective chemical property that improves it.
The method of preparing at present mangano-manganic oxide/carbon complex mainly contains hydro-thermal method and electrolysis. Zhao ?huiWang etc.As adopting hydro-thermal method, raw material prepares Mn taking four water manganese nitrates and multi-walled carbon nano-tubes3O4/ CNTs compound,100mAg‐1Under current density, first discharge specific capacity is 1380mAhg‐1, circulation 50 circle specific discharge capacities are only surplus592mAhg‐1。[WangZH,YuanLX,ShaoQG,etal.Mn3O4nanocrystalsanchoredonmulti‐walledcarbonnanotubesashigh‐performanceanodematerialsforlithium‐ionBatteries[J] .MaterialsLetters, 2012,80:110 ?113.]. The method preparation process complexity, the circulation of product is steadyQualitative poor. MingjunJing etc. are taking the aqueous solution of sodium chloride and carbon quantum dot as electrolyte, by constant voltageLower electrolytic manganese metal electrode 4h, washing and drying, processes 2h for 250 DEG C and obtains Mn3O4/CdotsCompound, at 100mAg‐1Under current density, first discharge specific capacity is 1124.8mAhg‐1, circulation 50 circle specific discharge capacities are 937mAhg‐1。[JingM,WangJ,HouH,etal.CarbonquantumdotcoatedMn3O4withenhancedperformancesforlithium‐ionbatteries[J].JournalofMaterialsChemistryA,2015,3(32):16824 ?16830.]. The cyclical stability that the method is prepared product increases, but the preparation process of carbon quantum dot stillMore complicated, is unwell to large-scale industrial production.
Summary of the invention
The object of this invention is to provide the Nanoparticulate that a kind of technique is simple, with low cost, can realize large-scale productionMn3O4The preparation method of/SuperP lithium ion battery negative material.
For achieving the above object, its concrete technical scheme is as follows:
1) getting potassium permanganate and tetrahydrate manganese chloride by the amount of substance ratio of 2:3 is added to the water respectively and is mixed with mass fractionFor the liquor potassic permanganate of 1.25%-2.5% and the tetrahydrate manganese chloride solution of 2.25%-4.5%, and mix, at room temperature stirMix, filter to obtain manganese dioxide precipitate;
2) manganese dioxide precipitate being washed to washing lotion is that neutral rear being dried to obtain manganese dioxide powder;
3) manganese dioxide powder is mixed to obtain to mixed material with SuperP with 3:1-1:2 mass ratio;
4) mixed material heat treatment in inert atmosphere is obtained to Nanoparticulate Mn3O4/ SuperP lithium ion battery is negativeUtmost point material.
Described step 1) stirring be magnetic agitation.
Described step 2) in washing lotion be deionized water.
Described step 4) in inert atmosphere be argon gas atmosphere.
Described step 4) in heat treatment temperature be 400-600 DEG C, the time is 2-5h.
The present invention, taking potassium permanganate, tetrahydrate manganese chloride and SuperP as raw material, first adopts low-temperature co-precipitation method to prepareManganese dioxide, after it is mixed and is heat-treated with SuperP, prepare Nanoparticulate Mn3O4/ SuperP lithium fromSub-cell negative electrode material, can be used as high performance lithium ion battery negative material. Have technique simple, with low cost,Can realize the advantages such as large-scale production. As lithium ion battery negative material, there is high capacity and good circulation steadyQualitative, these high performances all depend on the grain structure of its nanometer shape.
The Nanoparticulate Mn of synthesized of the present invention3O4/ SuperP lithium ion battery negative material has large specific surfaceLong-pending, can fully contact with electrolyte, the activity that has increased lithium ion is injected position, has improved the capacity of electrode material,The structure of Nanoparticulate can be accelerated lithium ion transport therein, and has effectively alleviated lithium ion in embedding and de-Go out the Volume Changes causing in process, thereby improved well its chemical property.
Brief description of the drawings
Fig. 1 is Nanoparticulate Mn prepared by the present invention3O4SEM (the scanning of/SuperP lithium ion battery negative materialElectronic Speculum) figure (50,000 times of multiplication factors).
Fig. 2 is Nanoparticulate Mn prepared by the present invention3O4(X penetrates the XRD of/SuperP lithium ion battery negative materialLine diffraction) figure.
Fig. 3 is Nanoparticulate Mn prepared by the present invention3O4The Raman of/SuperP lithium ion battery negative material(Raman spectrum) figure.
Fig. 4 is Nanoparticulate Mn prepared by the present invention3O4/ SuperP lithium ion battery negative material is as lithium-ion electricThe cyclical stability figure of pond negative material.
Detailed description of the invention
Embodiment 1:
1) getting potassium permanganate and tetrahydrate manganese chloride by the amount of substance ratio of 2:3 is added to the water respectively and is mixed with mass fractionBe 1.25% liquor potassic permanganate and 2.25% tetrahydrate manganese chloride solution, and mix at room temperature magnetic agitation, mistakeFilter to obtain manganese dioxide precipitate;
2) manganese dioxide precipitate being washed to washing lotion by deionized water is that neutral rear being dried to obtain manganese dioxide powder;
3) manganese dioxide powder is mixed to obtain to mixed material with SuperP with 3:1 mass ratio;
4) mixed material is obtained in argon gas atmosphere to the cell negative electrode material of solid with 400 DEG C of heat treatment 5h.
Embodiment 2:
1) getting potassium permanganate and tetrahydrate manganese chloride by the amount of substance ratio of 2:3 is added to the water respectively and is mixed with mass fractionBe 2.5% liquor potassic permanganate and 4% tetrahydrate manganese chloride solution, and mix, at room temperature magnetic agitation, filtersObtain manganese dioxide precipitate;
2) manganese dioxide precipitate being washed to washing lotion by deionized water is that neutral rear being dried to obtain manganese dioxide powder;
3) manganese dioxide powder is mixed to obtain to mixed material with SuperP with 2:1 mass ratio;
4) mixed material is obtained in argon gas atmosphere to the cell negative electrode material of solid with 600 DEG C of heat treatment 2h.
Embodiment 3:
1) getting potassium permanganate and tetrahydrate manganese chloride by the amount of substance ratio of 2:3 is added to the water respectively and is mixed with mass fractionBe 1.5% liquor potassic permanganate and 3% tetrahydrate manganese chloride solution, and mix, at room temperature magnetic agitation, filtersObtain manganese dioxide precipitate;
2) manganese dioxide precipitate being washed to washing lotion by deionized water is that neutral rear being dried to obtain manganese dioxide powder;
3) manganese dioxide powder is mixed to obtain to mixed material with SuperP with 1:1 mass ratio;
4) mixed material is obtained in argon gas atmosphere to the cell negative electrode material of solid with 500 DEG C of heat treatment 3.5h.
Embodiment 4:
1) getting potassium permanganate and tetrahydrate manganese chloride by the amount of substance ratio of 2:3 is added to the water respectively and is mixed with mass fractionBe 2% liquor potassic permanganate and 4.5% tetrahydrate manganese chloride solution, and mix, at room temperature magnetic agitation, filtersObtain manganese dioxide precipitate;
2) manganese dioxide precipitate being washed to washing lotion by deionized water is that neutral rear being dried to obtain manganese dioxide powder;
3) manganese dioxide powder is mixed to obtain to mixed material with SuperP with 1:2 mass ratio;
4) mixed material is obtained in argon gas atmosphere to the cell negative electrode material of solid with 450 DEG C of heat treatment 4.5h.
Embodiment 5:
1) getting potassium permanganate and tetrahydrate manganese chloride by the amount of substance ratio of 2:3 is added to the water respectively and is mixed with mass fractionBe 1.8% liquor potassic permanganate and 3.5% tetrahydrate manganese chloride solution, and mix, at room temperature magnetic agitation, filtersObtain manganese dioxide precipitate;
2) manganese dioxide precipitate being washed to washing lotion by deionized water is that neutral rear being dried to obtain manganese dioxide powder;
3) manganese dioxide powder is mixed to obtain to mixed material with SuperP with 1.5:1 mass ratio;
4) mixed material is obtained in argon gas atmosphere to the cell negative electrode material of solid with 550 DEG C of heat treatment 2.5h.
Embodiment 6:
1) getting potassium permanganate and tetrahydrate manganese chloride by the amount of substance ratio of 2:3 is added to the water respectively and is mixed with mass fractionBe 2.3% liquor potassic permanganate and 2.5% tetrahydrate manganese chloride solution, and mix, at room temperature magnetic agitation, filtersObtain manganese dioxide precipitate;
2) manganese dioxide precipitate being washed to washing lotion by deionized water is that neutral rear being dried to obtain manganese dioxide powder;
3) manganese dioxide powder is mixed to obtain to mixed material with SuperP with 2.5:1 mass ratio;
4) mixed material is obtained in argon gas atmosphere to the cell negative electrode material of solid with 600 DEG C of heat treatment 2h.
As can be seen from Figure 1, the Nanoparticulate Mn preparing3O4/ SuperP lithium ion battery negative material presents allEven ground graininess pattern, granular size is about 20-50nm.
As can be seen from Figure 2, successfully prepared the Mn of Tetragonal by preparation method of the present invention3O4, Qi ZhonghanThere is a small amount of MnO impurity.
As can be seen from Figure 3, certain carbon containing in prepared sample, has G peak and the appearance of D peak significantly, and 650cm-1The peak that the peak at place is Mn oxide.
From Fig. 4, can find out to have good chemical property, first discharge specific capacity is 1382mAhg-1，After 50 circles, reversible specific capacity rises to 1427mAhg-1。

Claims (5)

1. a Nanoparticulate Mn3O4The preparation method of/SuperP lithium ion battery negative material, is characterized in that:
1) be added to the water respectively and be mixed with liquor potassic permanganate that mass fraction is 1.25%-2.5% and the tetrahydrate manganese chloride solution of 2.25%-4.5% than getting potassium permanganate and tetrahydrate manganese chloride by the amount of substance of 2:3, and mix, at room temperature stir, filter to obtain manganese dioxide precipitate;
2) manganese dioxide precipitate being washed to washing lotion is that neutral rear being dried to obtain manganese dioxide powder;
3) manganese dioxide powder is mixed to obtain to mixed material with SuperP with 3:1-1:2 mass ratio;
4) mixed material heat treatment in inert atmosphere is obtained to Nanoparticulate Mn3O4/ SuperP lithium ion battery negative material.
2. Nanoparticulate Mn according to claim 13O4The preparation method of/SuperP lithium ion battery negative material, is characterized in that: described step 1) stirring be magnetic agitation.
3. Nanoparticulate Mn according to claim 13O4The preparation method of/SuperP lithium ion battery negative material, is characterized in that: described step 2) in washing lotion be deionized water.
4. according to the Nanoparticulate Mn described in claim3O4The preparation method of/SuperP lithium ion battery negative material, is characterized in that: described step 4) in inert atmosphere be argon gas atmosphere.
5. according to the Nanoparticulate Mn described in claim3O4The preparation method of/SuperP lithium ion battery negative material, is characterized in that: described step 4) in heat treatment temperature be 400-600 DEG C, the time is 2-5h.
CN201610072507.7A 2016-02-02 2016-02-02 Preparation method for nano-granular Mn3O4/Super P lithium ion battery negative electrode material Pending CN105609752A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106252633A (en) * 2016-09-18 2016-12-21 陕西科技大学 A kind of preparation method of lithium ion battery negative material
CN109148894A (en) * 2018-09-05 2019-01-04 天津瑞晟晖能科技有限公司 Lithium ion cell positive, all-solid lithium-ion battery and preparation method thereof and electricity consumption device
CN109942024A (en) * 2019-03-07 2019-06-28 澳门大学 A kind of mangano-manganic oxide-graphene film nano-complex and the preparation method and application thereof
CN111640926A (en) * 2020-06-17 2020-09-08 郑州轻工业大学 Carbon nano tube/Mn of core-sheath nano cable structure3O4Composite material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104167532A (en) * 2014-04-03 2014-11-26 杭州电子科技大学 Graphite flake /trimanganese tetroxide composite nano-material with sandwich structure, its preparation method, and lithium ion battery using it

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104167532A (en) * 2014-04-03 2014-11-26 杭州电子科技大学 Graphite flake /trimanganese tetroxide composite nano-material with sandwich structure, its preparation method, and lithium ion battery using it

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
RUNG-CHUAN LEE等: "Synthesis of high-performance MnOx/carbon composite as lithium-ion battery anode by a facile co-precipitation method: Effects of oxygen stoichiometry and carbon morphology", 《JOURNAL OF POWER SOURCES》 *
YUFENG ZHAO等: "Synthesis of Sn-doped Mn3O4/C nanocomposites as super capacitor", 《MATERIALS LETTERS》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106252633A (en) * 2016-09-18 2016-12-21 陕西科技大学 A kind of preparation method of lithium ion battery negative material
CN109148894A (en) * 2018-09-05 2019-01-04 天津瑞晟晖能科技有限公司 Lithium ion cell positive, all-solid lithium-ion battery and preparation method thereof and electricity consumption device
CN109942024A (en) * 2019-03-07 2019-06-28 澳门大学 A kind of mangano-manganic oxide-graphene film nano-complex and the preparation method and application thereof
CN111640926A (en) * 2020-06-17 2020-09-08 郑州轻工业大学 Carbon nano tube/Mn of core-sheath nano cable structure3O4Composite material and preparation method thereof

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Application publication date: 20160525