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 PDFInfo
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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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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 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 23
- 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 34
- 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 13
- 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
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 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
- 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
- 230000005518 electrochemistry 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
- 238000003756 stirring Methods 0.000 description 6
- 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
- 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
- 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
- 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
- 239000004020 conductor Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000010586 diagram 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Classifications
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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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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
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
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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Cited By (1)
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| CN111558379A (en) * | 2020-05-21 | 2020-08-21 | 苏州大学 | Preparation method of hollow spherical black lead copper ore phase metal oxide electrocatalyst, electrocatalyst and application thereof |
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| 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 |
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| CN104037402B (en) * | 2014-06-19 | 2016-05-18 | 合肥国轩高科动力能源有限公司 | Method for preparing hollow nickel-manganese composite oxide spheres |
| 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 |
| CN104466108B (en) * | 2014-12-03 | 2017-01-04 | 上海交通大学 | Used as negative electrode of Li-ion battery hollow porous spherical mixed oxide and preparation method thereof |
| 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 |
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| 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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| CN103094572B (en) * | 2013-01-31 | 2015-04-08 | 湘潭大学 | Lithium vanadate anode material and preparation method thereof |
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