CN103337604A - Hollow spherical NiMn2O4 lithium ion battery cathode material and preparation method thereof - Google Patents

Hollow spherical NiMn2O4 lithium ion battery cathode material and preparation method thereof Download PDF

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CN103337604A
CN103337604A CN2013102829217A CN201310282921A CN103337604A CN 103337604 A CN103337604 A CN 103337604A CN 2013102829217 A CN2013102829217 A CN 2013102829217A CN 201310282921 A CN201310282921 A CN 201310282921A CN 103337604 A CN103337604 A CN 103337604A
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nimn
lithium ion
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CN103337604B (en
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杨文胜
冯玉龙
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a hollow spherical NiMn2O4 lithium ion battery cathode material and a preparation method thereof, and belongs to the field of lithium ion battery electrode material technology. Particle size of the hollow spherical material is 1 to 3 micrometers; the spherical shell is made of NiMn2O4 nanometer crystals, and has a porous structure. The porous spherical shell is in favor of penetration of electrolyte, is capable of shortening diffusion distance of lithium ions, and possesses excellent electrochemistry cycling stability and rate capability. The preparation method is based on ''Kirkendall effect'', and the hollow spherical NiMn2O4 can be obtained directly by performing high temperature solid phase reaction. The preparation method comprises following steps: taking solid spherical MnCO3 as a precursor; roasting at a low temperature to obtain porous solid spherical manganese dioxide; and then roasting the porous solid spherical manganese dioxide with a nickel salt to obtain the hollow spherical spinel-type NiMn2O4 cathode material. The preparation method is simple in technologies, do not need a template, and is suitable for large-scaled production.

Description

Hollow ball shape NiMn 2O 4Lithium ion battery negative material and preparation method
Technical field
The invention belongs to lithium ion battery electrode material and preparing technical field thereof, particularly relate to a kind of hollow ball shape NiMn 2O 4Lithium ion battery negative material and preparation method.
Background technology
The metal oxide lithium ionic cell negative material has specific discharge capacity and volume and capacity ratio advantages of higher, gets more and more people's extensive concerning in recent years.Spinel-type NiMn wherein 2O 4Have cheaper cost of material, the high theoretical specific capacity is a kind of lithium ion battery negative material with good development potentiality.At document (1) Journal of Materials Chemistry, among 2011, the 21:10206-10218, people such as Fabrice M. Courtel utilize coprecipitation method to prepare nanometer spinel type NiMn 2O 4, and studied its chemical property as lithium ion battery negative material.Though this material has higher initial specific capacity, the electrochemistry cyclical stability is poor.
For lithium ion battery electrode material, the material microscopic appearance has material impact to its performance.Adopt the simple process preparation to have the NiMn of special microscopic appearance 2O 4Electrode material is the work with significant application value and scientific meaning to promote its chemical property.The hollow ball shape electrode material is conducive to the infiltration of electrolyte, has shortened the diffusion distance of lithium ion, is conducive to the performance performance of electrode material.Adopt solid phase reaction method to prepare hollow ball shape spinel-type NiMn 2O 4Lithium ion battery negative material is not seen bibliographical information as yet.
Summary of the invention
The object of the present invention is to provide a kind of hollow ball shape NiMn 2O 4Lithium ion battery negative material and preparation method, this material has good electrochemistry cyclical stability and high rate performance; And preparation technology is simple, easy operating, is applicable to large-scale production.
Hollow ball shape NiMn of the present invention 2O 4The hollow ball particle diameter of lithium ion battery negative material is 1 ~ 3 micron; Spherical shell is by NiMn 2O 4Nanocrystalline formation is loose structure.The porous spherical shell is conducive to the infiltration of electrolyte, has shortened the diffusion distance of lithium ion, has good electrochemistry cyclical stability and high rate performance as lithium ion battery negative material.
Preparation hollow ball shape NiMn of the present invention 2O 4The method of lithium ion battery negative material need not the template agent, just can directly obtain hollow ball shape NiMn based on " Ke Kendaer effect " by high-temperature solid phase reaction method 2O 4, its process flow diagram as shown in Figure 1: with solid spherical MnCO 3Be presoma, low-temperature bake obtains the solid spherical manganese dioxide of porous, prepares hollow ball shape spinel-type NiMn with nickel salt roasting together then 2O 4Negative material.Concrete processing step is as follows:
(1) compound concentration is 0.01 ~ 0.05 molL respectively -1MnSO 4Solution and concentration are 0.1 ~ 1 molL -1NH 4HCO 3Solution; In whipping process with absolute ethyl alcohol and NH 4HCO 3Solution joins MnSO simultaneously 4In the solution, MnSO wherein 4And NH 4HCO 3The ratio of amount of substance be 1:10 ~ 1:20, the volume of absolute ethyl alcohol and MnSO 4And NH 4HCO 3The cumulative volume of mixed solution is than being 0.02:1 ~ 0.1:1; Continued stirring reaction 1 ~ 3 hour, and obtained white precipitate, centrifugation, with deionized water and ethanol respectively washing precipitation 2 ~ 5 times to remove SO 4 2-To be deposited in 40 ~ 80 oC vacuumize 10 ~ 24 hours obtains spherical MnCO 3White powder.
(2) MnCO that step (1) is prepared 3Powder is under air atmosphere, with 1 ~ 5 oC minute -1Speed be warming up to 300 ~ 500 oC and constant temperature 5 ~ 10 hours naturally cool to room temperature then, obtain shaggy porous MnO 2Black powder.
(3) MnO that step (2) is prepared 2Powder and nickel salt are that 2:1 mixes and ground 10 ~ 60 minutes according to the Mn/Ni atomic ratio, with mixture under air atmosphere, with 2 ~ 10 oC minute -1Speed be warming up to 600 ~ 900 oC and constant temperature calcining 5 ~ 15 hours naturally cool to room temperature then, obtain hollow ball shape NiMn 2O 4Black powder.Wherein, nickel salt is nickel acetate, a kind of in the nickel nitrate.
Fig. 2 stereoscan photograph shows the MnCO that is synthesized 3Be sphere, uniform particle diameter; Roasting MnCO 3Preparation MnO 2Stereoscan photograph as shown in Figure 3, MnO 2Still keep spherical, rough surface; Spinel-type NiMn 2O 4Stereoscan photograph as shown in Figure 4, be hollow ball shape, particle size is 1 ~ 3 μ m.Adopt x-ray diffractometer that the synthetic material structure is characterized, Fig. 5 test result shows prepared spinel-type NiMn 2O 4Purity is high and have higher degree of crystallinity.
The hollow ball shape spinel-type NiMn that the inventive method is synthetic 2O 4As lithium ion battery negative material, mix with commercially available acetylene black conductive agent and the Kynoar PVDF binding agent mass ratio by 70:20:10, be coated on the copper foil of affluxion body 80 oC oven dry, and the thickness of compressing tablet to 30 ~ 70 μ m make the electrode slice that diameter is 1 cm with sheet-punching machine, in 120 oDry 24 hours of C vacuum (<10 Pa).As to electrode, adopt Celgard 2400 barrier films, 1 molL with metal lithium sheet -1LiPF 6+ EC+DMC+DEC (the EC/DMC/DEC volume ratio is 1:1:1) is electrolyte, at the German M. Braun Unlab of company type dry argon gas glove box (H 2O<1 ppm, O 2<1 ppm) be assembled into Experimental cell in, adopt the blue electric CT2001A type cell tester in Wuhan to carry out electrochemical property test at ambient temperature, discharging and recharging the cut-ff voltage scope is 0.01 ~ 3 V (vs. Li +/ Li), test result such as Fig. 6 and Fig. 7, hollow ball shape spinel structure NiMn 2O 4Electrode material has good electrochemistry cyclical stability and high rate performance.
Characteristics of the present invention and advantage are: hollow ball shape NiMn 2O 4The spherical shell of spinel is by NiMn 2O 4Nanocrystalline formation is loose structure, and the porous spherical shell is conducive to the infiltration of electrolyte, has shortened the diffusion distance of lithium ion, has good electrochemistry cyclical stability and high rate performance as lithium ion battery negative material.In addition, the inventive method need not the template agent, can directly obtain hollow ball shape NiMn by high temperature solid state reaction 2O 4Spinel has that technology is simple, the characteristics of easy operating, is applicable to large-scale production.
Description of drawings
Fig. 1 is the synthetic hollow ball shape spinel-type NiMn of the inventive method 2O 4Process flow diagram.
Fig. 2 is the MnCO of preparation in the example 1 3The stereoscan photograph of presoma.
Fig. 3 is the MnO of preparation in the example 1 2Stereoscan photograph.
Fig. 4 is the NiMn of preparation in the example 1 2O 4Stereoscan photograph.
Fig. 5 is the NiMn of preparation in the example 1 of the present invention 2O 4The X-ray diffraction spectrogram.Abscissa is angle 2 θ, and unit is: degree ( o); Ordinate is diffracted intensity, and unit is: absolute unit (a.u.).
Fig. 6 is the NiMn of example 1 preparation 2O 4Electrochemistry cycle performance curve.Abscissa is the circulating cycle number, and unit is: week; Ordinate is specific discharge capacity, and unit is: the MAH gram -1(mAhg -1).
Fig. 7 is the NiMn of example 1 preparation 2O 4The high rate performance curve.Abscissa is the circulating cycle number, and unit is: week; Ordinate is specific discharge capacity, and unit is: the MAH gram -1(mAhg -1).
Embodiment
Embodiment 1
With 1.69 g MnSO 4H 2O and 7.9 g NH 4HCO 3Be dissolved in 200 mL deionized waters respectively and obtain separately solution; MnSO in stir 4Add 20 mL absolute ethyl alcohols in the solution, add the NH for preparing simultaneously 4HCO 3Solution reacted 1 hour, obtained white precipitate, with absolute ethyl alcohol and deionized water washing centrifugation each 3 times to remove SO 4 2-The sample that obtains is placed 50 oDrying is 20 hours in the C baking oven, obtains spherical MnCO as shown in Figure 2 3Powder.
With above-mentioned MnCO 3Powder places Muffle furnace, with 3 oC minute -1Speed be warming up to 400 oC and constant temperature 5 hours naturally cool to room temperature then, obtain the spherical MnO of black as shown in Figure 3 2Powder.
Take by weighing the above-mentioned MnO of 1 g 2With 1.431 g Ni (Ac) 24H 2O puts into beaker, adds the absolute ethyl alcohol of 80 mL, 50 oThe heating dispersed with stirring is to dry under the C; Pour the compound that obtains in the agate mortar 30 minutes mixings of grinding, put into Muffle furnace, with 3 oC minute -1Speed be warming up to 750 oC and constant temperature 12 hours naturally cool to room temperature, obtain hollow ball shape NiMn as shown in Figure 4 2O 4Spinel, the XRD test result of Fig. 5 shows prepared spinel-type NiMn 2O 4Purity is high and have higher degree of crystallinity.
With this hollow ball shape spinel-type NiMn 2O 4As lithium ion battery negative material, mix with commercially available acetylene black conductive agent and the Kynoar PVDF binding agent mass ratio by 70:20:10, be coated on the copper foil of affluxion body 80 oC oven dry, and the thickness of compressing tablet to 50 μ m make the electrode slice that diameter is 1 cm with sheet-punching machine, in 120 oDry 24 hours of C vacuum (<10 Pa).As to electrode, adopt Celgard 2400 barrier films, 1 molL with metal lithium sheet -1LiPF 6+ EC+DMC+DEC (the EC/DMC/DEC volume ratio is 1:1:1) is electrolyte, at the German M. Braun Unlab of company type dry argon gas glove box (H 2O<1 ppm, O 2<1 ppm) be assembled into Experimental cell in, adopt the blue electric CT2001A type cell tester in Wuhan to carry out electrochemical property test at ambient temperature, discharging and recharging the cut-ff voltage scope is 0.01 ~ 3 V (vs. Li +/ Li), test result such as Fig. 6 and Fig. 7, hollow ball shape spinel structure NiMn 2O 4Electrode material has good electrochemistry cyclical stability, and specific capacity also has 400 mAhg after 248 weeks of circulation -1, this material also has excellent high rate performance, at 1 Ag -1Current density under, specific capacity still can reach 330 mAhg -1
Embodiment 2
With 1.69 g MnSO 4H 2O and 15.8 g NH 4HCO 3Be dissolved in 500 mL deionized waters respectively and obtain separately solution; MnSO in stir 4Add 50 mL absolute ethyl alcohols in the solution, add the NH for preparing simultaneously 4HCO 3Solution reacted 2 hours, obtained white precipitate, with absolute ethyl alcohol and deionized water washing centrifugation each 3 times to remove SO 4 2-The sample that obtains is placed 60 oDrying is 15 hours in the C baking oven, obtains spherical MnCO 3Powder.
With above-mentioned MnCO 3Powder places Muffle furnace, with 5 oC minute -1Speed be warming up to 400 oC and constant temperature 8 hours naturally cool to room temperature then, obtain the spherical MnO of black 2Powder.
Take by weighing the above-mentioned MnO of 1 g 2With 1.431 g Ni (Ac) 24H 2O puts into beaker, adds the absolute ethyl alcohol of 80 mL, 50 oThe heating dispersed with stirring is to dry under the C; Pour the compound that obtains in the agate mortar 30 minutes mixings of grinding, put into Muffle furnace, with 5 oC minute -1Speed be warming up to 800 oC and constant temperature 10 hours naturally cool to room temperature, obtain hollow ball shape NiMn 2O 4Spinel.
Case study on implementation 3
With 1.69 g MnSO 4H 2O and 11.85 g NH 4HCO 3Be dissolved in 300 mL deionized waters respectively and obtain separately solution; MnSO in stir 4Add 60 mL absolute ethyl alcohols in the solution, add the NH for preparing simultaneously 4HCO 3Solution reacted 3 hours, obtained white precipitate, with absolute ethyl alcohol and deionized water washing centrifugation each 3 times to remove SO 4 2-The sample that obtains is placed 80 oDrying is 10 hours in the C baking oven, obtains spherical MnCO 3Powder.
With above-mentioned MnCO 3Powder places Muffle furnace, with 1 oC minute -1Speed be warming up to 450 oC and constant temperature 10 hours naturally cool to room temperature then, obtain the spherical MnO of black 2Powder.
Take by weighing the above-mentioned MnO of 1 g 2With 1.672 g Ni (NO 3) 26H 2O puts into beaker, adds 80 mL absolute ethyl alcohols, 50 oThe heating dispersed with stirring is to dry under the C; Pour the compound that obtains in the agate mortar 60 minutes mixings of grinding, put into Muffle furnace, with 5 oC minute -1Speed be warming up to 700 oC and constant temperature 15 hours naturally cool to room temperature, obtain hollow ball shape NiMn 2O 4Spinel.

Claims (3)

1. hollow ball shape NiMn 2O 4Lithium ion battery negative material is characterized in that: this hollow ball particle diameter is 1 ~ 3 micron; Spherical shell is by NiMn 2O 4Nanocrystalline formation is loose structure.
2. hollow ball shape NiMn according to claim 1 2O 4The preparation method of lithium ion battery negative material is characterized in that, may further comprise the steps:
(1) compound concentration is 0.01 ~ 0.05 molL respectively -1MnSO 4Solution and concentration are 0.1 ~ 1 molL -1NH 4HCO 3Solution; In whipping process with absolute ethyl alcohol and NH 4HCO 3Solution joins MnSO simultaneously 4In the solution, MnSO wherein 4And NH 4HCO 3The ratio of amount of substance be 1:10 ~ 1:20, the volume of absolute ethyl alcohol and MnSO 4And NH 4HCO 3The cumulative volume of mixed solution is than being 0.02:1 ~ 0.1:1; Continued stirring reaction 1 ~ 3 hour, and obtained white precipitate, centrifugation, with deionized water and ethanol respectively washing precipitation 2 ~ 5 times to remove SO 4 2-To be deposited in 40 ~ 80 oC vacuumize 10 ~ 24 hours obtains spherical MnCO 3White powder;
(2) MnCO that step (1) is prepared 3Powder is under air atmosphere, with 1 ~ 5 oC minute -1Speed be warming up to 300 ~ 500 oC and constant temperature 5 ~ 10 hours naturally cool to room temperature then, obtain shaggy porous MnO 2Black powder.
(3) MnO that step (2) is prepared 2Powder and nickel salt are that 2:1 mixes and ground 10 ~ 60 minutes according to the Mn/Ni atomic ratio, with mixture under air atmosphere, with 2 ~ 10 oC minute -1Speed be warming up to 600 ~ 900 oC and constant temperature calcining 5 ~ 15 hours naturally cool to room temperature then, obtain hollow ball shape NiMn 2O 4Black powder.
3. preparation method according to claim 2 is characterized in that, in step (3), nickel salt is nickel acetate, a kind of in the nickel nitrate.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103490059A (en) * 2013-10-11 2014-01-01 哈尔滨工业大学 Preparation method of high-voltage nickel lithium manganate cathode material with porous morphology
CN103579638A (en) * 2013-11-11 2014-02-12 上海中聚佳华电池科技有限公司 Air electrode catalyst of lithium air battery and preparation method of air electrode catalyst
CN104037402A (en) * 2014-06-19 2014-09-10 合肥国轩高科动力能源股份公司 Method for preparing hollow nickle-manganese composite oxide balls
CN104466108A (en) * 2014-12-03 2015-03-25 上海交通大学 Hollow porous spherical mixed oxide for lithium ion battery negative electrode and preparation method of hollow porous spherical mixed oxide
CN104362291B (en) * 2014-10-17 2016-06-08 安徽理工大学 A kind of lithium-enriched cathodic material of lithium ion battery and preparation method thereof and lithium ion battery
CN105742624A (en) * 2016-04-14 2016-07-06 河北工业大学 Preparation method of spherical lithium nickel manganese oxide material with hollow porous micro-nano level structure
CN109534412A (en) * 2018-11-14 2019-03-29 龙岩学院 A kind of three-dimensional porous NiMn2O4Preparation method and the application in super capacitor anode material
CN110783568A (en) * 2019-11-04 2020-02-11 陕西科技大学 Preparation method and application of hollow carbon-coated molybdenum selenide nanostructure
US10854395B1 (en) 2020-07-12 2020-12-01 United Arab Emirates University Asymmetric supercapacitor with hierarchical electrodes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102969505A (en) * 2012-12-12 2013-03-13 南京大学 LiFePO4 precursor hollow sphere and preparation method thereof
CN103094572A (en) * 2013-01-31 2013-05-08 湘潭大学 Lithium vanadate anode material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102969505A (en) * 2012-12-12 2013-03-13 南京大学 LiFePO4 precursor hollow sphere and preparation method thereof
CN103094572A (en) * 2013-01-31 2013-05-08 湘潭大学 Lithium vanadate anode material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FABRICE M. ET AL: ""High capacity anode materials for Li-ion batteries based on spinel metal oxides AMn2O4 (A=Co,Ni,and Zn)"", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 21, 26 May 2011 (2011-05-26), pages 10208 - 2 *
XUE-FA CHEN ET AL: ""Self-templated synthesis of hollow porous submicron ZnMn2O4 sphere as anode for lithium-ion batteries"", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 559, 15 May 2013 (2013-05-15) *

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CN103490059A (en) * 2013-10-11 2014-01-01 哈尔滨工业大学 Preparation method of high-voltage nickel lithium manganate cathode material with porous morphology
CN103490059B (en) * 2013-10-11 2016-01-27 哈尔滨工业大学 The preparation method of porous pattern high-voltage lithium nickel manganate anode material
CN103579638A (en) * 2013-11-11 2014-02-12 上海中聚佳华电池科技有限公司 Air electrode catalyst of lithium air battery and preparation method of air electrode catalyst
CN103579638B (en) * 2013-11-11 2016-04-27 上海中聚佳华电池科技有限公司 Air electrode catalyst of lithium-air battery and preparation method thereof
CN104037402A (en) * 2014-06-19 2014-09-10 合肥国轩高科动力能源股份公司 Method for preparing hollow nickle-manganese composite oxide balls
CN104037402B (en) * 2014-06-19 2016-05-18 合肥国轩高科动力能源有限公司 A kind of method of preparing nickel manganese composite oxide hollow ball
CN104362291B (en) * 2014-10-17 2016-06-08 安徽理工大学 A kind of lithium-enriched cathodic material of lithium ion battery and preparation method thereof and lithium ion battery
CN104466108A (en) * 2014-12-03 2015-03-25 上海交通大学 Hollow porous spherical mixed oxide for lithium ion battery negative electrode and preparation method of hollow porous spherical mixed oxide
CN105742624A (en) * 2016-04-14 2016-07-06 河北工业大学 Preparation method of spherical lithium nickel manganese oxide material with hollow porous micro-nano level structure
CN109534412A (en) * 2018-11-14 2019-03-29 龙岩学院 A kind of three-dimensional porous NiMn2O4Preparation method and the application in super capacitor anode material
CN110783568A (en) * 2019-11-04 2020-02-11 陕西科技大学 Preparation method and application of hollow carbon-coated molybdenum selenide nanostructure
CN110783568B (en) * 2019-11-04 2021-05-04 陕西科技大学 Preparation method and application of hollow carbon-coated molybdenum selenide nanostructure
US10854395B1 (en) 2020-07-12 2020-12-01 United Arab Emirates University Asymmetric supercapacitor with hierarchical electrodes

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