CN103337604B - 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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CN103337604B
CN103337604B CN201310282921.7A CN201310282921A CN103337604B CN 103337604 B CN103337604 B CN 103337604B CN 201310282921 A CN201310282921 A CN 201310282921A CN 103337604 B CN103337604 B CN 103337604B
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spherical
lithium ion
nimn2o4
nimn
ion battery
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CN103337604A (en
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杨文胜
冯玉龙
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Beijing University of Chemical Technology
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    • 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
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.Wherein spinel-type NiMn 2o 4having cheaper cost of material, higher theoretical specific capacity, is a kind of lithium ion battery negative material with good development potentiality.At document (1) Journal of Materials Chemistry, in 2011,21:10206-10218, the people such as the Fabrice M. Courtel nanometer spinel type NiMn that utilized coprecipitation method to prepare 2o 4, and have studied its chemical property as lithium ion battery negative material.Though this material has higher initial specific capacities, electrochemical cycle stability is poor.
For lithium ion battery electrode material, material microscopic appearance has material impact to its performance.Simple process preparation is adopted to have the NiMn of special microscopic appearance 2o 4electrode material, to promote its chemical property, is a job with significant application value and scientific meaning.Hollow ball shape electrode material is conducive to the infiltration of electrolyte, shortens the diffusion path of lithium ion, is conducive to the performance of electrode material.Solid phase reaction method is adopted to prepare hollow ball shape spinel-type NiMn 2o 4lithium ion battery negative material there is not yet bibliographical information.
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 excellent electrochemical cycle stability and high rate performance; And preparation technology is simple, be easy to operation, 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.Porous spherical shell is conducive to the infiltration of electrolyte, shortens the diffusion path of lithium ion, has excellent electrochemical cycle stability and high rate performance as lithium ion battery negative material.
Of the present inventionly prepare hollow ball shape NiMn 2o 4the method of lithium ion battery negative material, without the need to template, just can directly obtain hollow ball shape NiMn based on " Kinkendal Effect " by high-temperature solid phase reaction method 2o 4, its process flow diagram as shown in Figure 1: with solid spherical MnCO 3for presoma, low-temperature bake obtains the solid spherical manganese dioxide of porous, and then roasting prepares hollow ball shape spinel-type NiMn together with nickel salt 2o 4negative material.Concrete technology 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; By absolute ethyl alcohol and NH in whipping process 4hCO 3solution joins MnSO simultaneously 4in solution, wherein MnSO 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; Keep agitation reaction 1 ~ 3 hour, obtains white precipitate, centrifugation, with deionized water and ethanol respectively washing precipitation 2 ~ 5 times to remove SO 4 2-; To 40 ~ 80 be deposited in oc vacuumize 10 ~ 24 hours, obtains spherical MnCO 3white powder.
(2) by MnCO prepared by step (1) 3powder in air atmosphere, with 1 ~ 5 oc minute -1ramp to 300 ~ 500 oc constant temperature 5 ~ 10 hours, then naturally cool to room temperature, obtain shaggy porous MnO 2black powder.
(3) by MnO prepared by step (2) 2powder and nickel salt are that 2:1 mixes and grinds 10 ~ 60 minutes, by mixture in air atmosphere, with 2 ~ 10 according to Mn/Ni atomic ratio oc minute -1ramp to 600 ~ 900 oc constant temperature calcining 5 ~ 15 hours, then naturally cool to room temperature, obtain hollow ball shape NiMn 2o 4black powder.Wherein, nickel salt is nickel acetate, the one in nickel nitrate.
Fig. 2 stereoscan photograph shows synthesized MnCO 3for spherical, 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 μm.Adopt x-ray diffractometer to characterize synthetic material structure, Fig. 5 test result shows prepared spinel-type NiMn 2o 4purity is high and have higher degree of crystallinity.
By the hollow ball shape spinel-type NiMn that the inventive method is synthesized 2o 4as lithium ion battery negative material, mix by the mass ratio of 70:20:10 with commercially available acetylene black conductor and Kynoar PVDF binding agent, be coated on copper foil of affluxion body, 80 oc is dried, and the thickness of compressing tablet to 30 ~ 70 μm, obtain the electrode slice that diameter is 1 cm, in 120 with sheet-punching machine odry 24 hours of C vacuum (<10 Pa).Using metal lithium sheet as to electrode, adopt Celgard 2400 barrier film, 1 molL -1liPF 6+ EC+DMC+DEC (EC/DMC/DEC volume ratio is 1:1:1) is electrolyte, at German M. Braun company Unlab type dry argon gas glove box (H 2o < 1 ppm, O 2< 1 ppm) in be assembled into experimental cell, adopt the blue electric CT2001A type cell tester in Wuhan to carry out electrochemical property test at ambient temperature, discharge and recharge cut-ff voltage scope is 0.01 ~ 3 V (vs. Li +/ Li), test result as Fig. 6 and Fig. 7, hollow ball shape spinel structure NiMn 2o 4electrode material has excellent electrochemical cycle stability and high rate performance.
Feature of the present invention and advantage are: hollow ball shape NiMn 2o 4the spherical shell of spinel is by NiMn 2o 4nanocrystalline formation, be loose structure, porous spherical shell is conducive to the infiltration of electrolyte, shortens the diffusion path of lithium ion, has excellent electrochemical cycle stability and high rate performance as lithium ion battery negative material.In addition, the inventive method, without the need to template, can directly obtain hollow ball shape NiMn by high temperature solid state reaction 2o 4spinel, has the advantages that technique is simple, be easy to operation, is applicable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the inventive method synthesis hollow ball shape spinel-type NiMn 2o 4process flow diagram.
Fig. 2 is the MnCO of preparation in example 1 3the stereoscan photograph of presoma.
Fig. 3 is the MnO of preparation in example 1 2stereoscan photograph.
Fig. 4 is the NiMn of preparation in example 1 2o 4stereoscan photograph.
Fig. 5 is the NiMn of preparation in example 1 of the present invention 2o 4x-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 NiMn prepared by example 1 2o 4electrochemistry cycle performance curve.Abscissa is circulating cycle number, and unit is: week; Ordinate is specific discharge capacity, and unit is: MAH gram -1(mAhg -1).
Fig. 7 is NiMn prepared by example 1 2o 4high rate performance curve.Abscissa is circulating cycle number, and unit is: week; Ordinate is specific discharge capacity, and unit is: MAH gram -1(mAhg -1).
Embodiment
Embodiment 1
By 1.69 g MnSO 4h 2o and 7.9 g NH 4hCO 3be dissolved in 200 mL deionized waters respectively and obtain respective solution; MnSO in stirring 4add 20 mL absolute ethyl alcohols in solution, add the NH prepared simultaneously 4hCO 3solution, reacts 1 hour, obtains white precipitate, with absolute ethyl alcohol and deionized water washing centrifugation each 3 times to remove SO 4 2-; The sample obtained is placed in 50 oin C baking oven, drying 20 hours, obtains spherical MnCO as shown in Figure 2 3powder.
By above-mentioned MnCO 3powder is placed in Muffle furnace, with 3 oc minute -1ramp to 400 oc constant temperature 5 hours, then naturally cool to room temperature, obtain the spherical MnO of black as shown in Figure 3 2powder.
Take 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 odispersed with stirring is heated to dry under C; The compound obtained is poured in agate mortar and grind mixing in 30 minutes, put into Muffle furnace, with 3 oc minute -1ramp to 750 oc 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.
By this hollow ball shape spinel-type NiMn 2o 4as lithium ion battery negative material, mix by the mass ratio of 70:20:10 with commercially available acetylene black conductor and Kynoar PVDF binding agent, be coated on copper foil of affluxion body, 80 oc is dried, and the thickness of compressing tablet to 50 μm, obtain the electrode slice that diameter is 1 cm, in 120 with sheet-punching machine odry 24 hours of C vacuum (<10 Pa).Using metal lithium sheet as to electrode, adopt Celgard 2400 barrier film, 1 molL -1liPF 6+ EC+DMC+DEC (EC/DMC/DEC volume ratio is 1:1:1) is electrolyte, at German M. Braun company Unlab type dry argon gas glove box (H 2o < 1 ppm, O 2< 1 ppm) in be assembled into experimental cell, adopt the blue electric CT2001A type cell tester in Wuhan to carry out electrochemical property test at ambient temperature, discharge and recharge cut-ff voltage scope is 0.01 ~ 3 V (vs. Li +/ Li), test result as Fig. 6 and Fig. 7, hollow ball shape spinel structure NiMn 2o 4electrode material has excellent electrochemical cycle stability, and after circulating 248 weeks, specific capacity also has 400 mAhg -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
By 1.69 g MnSO 4h 2o and 15.8 g NH 4hCO 3be dissolved in 500 mL deionized waters respectively and obtain respective solution; MnSO in stirring 4add 50 mL absolute ethyl alcohols in solution, add the NH prepared simultaneously 4hCO 3solution, reacts 2 hours, obtains white precipitate, with absolute ethyl alcohol and deionized water washing centrifugation each 3 times to remove SO 4 2-; The sample obtained is placed in 60 oin C baking oven, drying 15 hours, obtains spherical MnCO 3powder.
By above-mentioned MnCO 3powder is placed in Muffle furnace, with 5 oc minute -1ramp to 400 oc constant temperature 8 hours, then naturally cool to room temperature, obtain the spherical MnO of black 2powder.
Take 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 odispersed with stirring is heated to dry under C; The compound obtained is poured in agate mortar and grind mixing in 30 minutes, put into Muffle furnace, with 5 oc minute -1ramp to 800 oc constant temperature 10 hours, naturally cool to room temperature, obtain hollow ball shape NiMn 2o 4spinel.
Case study on implementation 3
By 1.69 g MnSO 4h 2o and 11.85 g NH 4hCO 3be dissolved in 300 mL deionized waters respectively and obtain respective solution; MnSO in stirring 4add 60 mL absolute ethyl alcohols in solution, add the NH prepared simultaneously 4hCO 3solution, reacts 3 hours, obtains white precipitate, with absolute ethyl alcohol and deionized water washing centrifugation each 3 times to remove SO 4 2-; The sample obtained is placed in 80 oin C baking oven, drying 10 hours, obtains spherical MnCO 3powder.
By above-mentioned MnCO 3powder is placed in Muffle furnace, with 1 oc minute -1ramp to 450 oc constant temperature 10 hours, then naturally cool to room temperature, obtain the spherical MnO of black 2powder.
Take 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 odispersed with stirring is heated to dry under C; The compound obtained is poured in agate mortar and grind mixing in 60 minutes, put into Muffle furnace, with 5 oc minute -1ramp to 700 oc constant temperature 15 hours, naturally cool to room temperature, obtain hollow ball shape NiMn 2o 4spinel.

Claims (2)

1. a hollow ball shape NiMn 2o 4the preparation method of lithium ion battery negative material, this described hollow ball particle diameter is 1 ~ 3 micron; Spherical shell is by NiMn 2o 4nanocrystalline formation is loose structure; It is characterized in that, comprise the following steps:
(1) compound concentration is 0.01 ~ 0.05molL respectively -1mnSO 4solution and concentration are 0.1 ~ 1molL -1nH 4hCO 3solution; By absolute ethyl alcohol and NH in whipping process 4hCO 3solution joins MnSO simultaneously 4in solution, wherein MnSO 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; Keep agitation reaction 1 ~ 3 hour, obtains white precipitate, centrifugation, with deionized water and ethanol respectively washing precipitation 2 ~ 5 times to remove SO 4 2-; 40 ~ 80 DEG C of vacuumizes 10 ~ 24 hours will be deposited in, obtain spherical MnCO 3white powder;
(2) by MnCO prepared by step (1) 3powder in air atmosphere, with 1 ~ 5 DEG C minute -1ramp to 300 ~ 500 DEG C and constant temperature 5 ~ 10 hours, then naturally cool to room temperature, obtain shaggy porous MnO 2black powder;
(3) by MnO prepared by step (2) 2powder and nickel salt are that 2:1 mixes and grinds 10 ~ 60 minutes, by mixture in air atmosphere, with 2 ~ 10 DEG C minutes according to Mn/Ni atomic ratio -1ramp to 600 ~ 900 DEG C and constant temperature calcining 5 ~ 15 hours, then naturally cool to room temperature, obtain hollow ball shape NiMn 2o 4black powder.
2. preparation method according to claim 1, is characterized in that, in step (3), nickel salt is nickel acetate, the one in nickel nitrate.
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