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 PDFInfo
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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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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910005802 NiMn2O4 Inorganic materials 0.000 title abstract 5
- 239000010406 cathode material Substances 0.000 title abstract 3
- 239000000463 material Substances 0.000 claims abstract description 24
- 150000002815 nickel Chemical class 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 229910003289 NiMn Inorganic materials 0.000 claims description 35
- 239000000843 powder Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 8
- 230000005518 electrochemistry Effects 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 238000003746 solid phase reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000011656 manganese carbonate Substances 0.000 abstract 1
- 235000006748 manganese carbonate Nutrition 0.000 abstract 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000035515 penetration Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000004904 shortening Methods 0.000 abstract 1
- 229910052596 spinel Inorganic materials 0.000 description 8
- 239000011029 spinel Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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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
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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
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
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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| 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 |
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Citations (2)
| 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 |
-
2013
- 2013-07-06 CN CN201310282921.7A patent/CN103337604B/en not_active Expired - Fee Related
Patent Citations (2)
| 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)
| 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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