CN102010010A - Method for preparing lithium ion battery negative electrode material ZnMn2O4 - Google Patents
Method for preparing lithium ion battery negative electrode material ZnMn2O4 Download PDFInfo
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- CN102010010A CN102010010A CN 201010545470 CN201010545470A CN102010010A CN 102010010 A CN102010010 A CN 102010010A CN 201010545470 CN201010545470 CN 201010545470 CN 201010545470 A CN201010545470 A CN 201010545470A CN 102010010 A CN102010010 A CN 102010010A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title abstract description 10
- 229910007477 ZnMn2O4 Inorganic materials 0.000 title abstract 5
- 239000007773 negative electrode material Substances 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 235000014692 zinc oxide Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 4
- 235000014872 manganese citrate Nutrition 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical group [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 235000004416 zinc carbonate Nutrition 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 claims description 3
- 239000011564 manganese citrate Substances 0.000 claims description 3
- 229940097206 manganese citrate Drugs 0.000 claims description 3
- 239000011667 zinc carbonate Substances 0.000 claims description 3
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000000840 electrochemical analysis Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XMLHTAFIAXPIDG-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;manganese(3+) Chemical class [Mn+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XMLHTAFIAXPIDG-UHFFFAOYSA-K 0.000 description 1
- OKOYFIHZDKMHAM-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;manganese Chemical compound [Mn].OC(=O)CC(O)(C(O)=O)CC(O)=O OKOYFIHZDKMHAM-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention discloses a method for preparing a lithium ion battery negative electrode material ZnMn2O4. In the method, thermal decomposition of a monomolecular precursor [ZnMn2(C6H507)2].8H2O is utilized to prepare submicron sheet ZnMn2O4 with the particle size of 100-200nm, wherein the prepared ZnMn2O4 material has high purity and forms a cavitation structure after conglobation. Electrochemical tests prove that as for the ZnMn2O4 prepared by the method, the charging specific capacity in the first week is as high as 678mAh/g, and the good charging/discharging reversibility can be maintained under different charging/discharging current densities, and the charging/discharging specific capacity can still be maintained at about 650mAh/g after 150 cycles and has a slowly increased trend. The method in the invention has the advantages of simple process, cheap raw materials, short high temperature calcinating time and wide application prospect, is easy for industrialization, beneficial to energy conservation and environment protection, and conforms to actual production.
Description
Technical field
The present invention relates to a kind of preparation method of lithium storage materials, be specifically related to lithium ion battery negative material ZnMn
2O
4The preparation method.
Background technology
Lithium-ion secondary cell occupies the consumption market rapidly with its superior performance, and is considered to the major impetus energy of power vehicle of future generation and hybrid vehicle.At present, the negative material that lithium ion battery adopted generally all is a carbon materials, as graphite, soft carbon, hard carbon etc., though carbon negative pole material has some excellent characteristic, but also there is significant disadvantages, as soft carbon first charge-discharge irreversible capacity height, do not have tangible charge and discharge platform: the hard carbon first charge-discharge efficiency is low, does not have tangible first charge-discharge platform and the very big current potential hysteresis that causes because of impure H etc.
In recent years, nano-metal-oxide (M
xO
y, M=Fe, Zn, Mn, Co, Cu ...) caused widely concern as lithium ion battery negative material.The crystal structure of these metal oxides itself can not can not form alloy with lithium for lithium ion provides the room, namely its reaction mechanism be not lithium ion embedding with deviate from or form alloy, but the reaction reversible with the lithium metal generation: M
xO
y+ 2ye
-+ 2yLi
+=xM
0+ yLi
2O, the metal that reaction forms is dispersed in amorphous amorphous Li
2Among the O, because reaction height is reversible, therefore metal oxide stability in the electrochemical window of battery can provide high reversible capacity and stable specific capacity.Such as CoO, Co
3O
4In charge and discharge cycles, can all can keep 700mAh/g.At present, composite metal oxide is as negative material such as the ZnCo of lithium ion battery
2O
4, ZnFe
2O
4, ZnMn
2O
4Be suggested Deng in succession, the mechanism of these materials mainly is that Zn follows metal M (M=Co, Fe, Mn) and Li
2Reversible reaction takes place in O, and metal Li can also form alloy at electronegative potential with Zn simultaneously, improves lithium storage content.But because Co is expensive and unfriendly to environment, so ZnFe
2O
4And ZnMn
2O
4Bigger actual application value is arranged, with ZnFe
2O
4Compare ZnMn
2O
4Discharge platform lower, the electromotive force that forms battery with the positive electrode of identical match is higher, thus energy density increases.Recently, the ZnFe of Y. Sharma and the people such as Z.Y. Wang different-shape that two kinds of different preparation methods are obtained
2O
4Negative material as lithium ion battery has carried out relevant report.The ZnFe of Y. Sharma report wherein
2O
4Material can keep 610 mAh/g after charge and discharge cycles 50 times, and the ZnFe of Z.Y. Wang report
2O
4Material can keep 900 mAh/g after charge and discharge cycles 50 times.Since 2008, Zhang Li knows that professor has reported the ZnMn of two kinds of different-shapes
2O
4The synthetic method of material and the application in lithium ion battery thereof think that the synthetic method of material has appreciable impact to its chemical property.Just because of the material preparation method has very big impact to the performance of material, develop featured synthetic method and study synthetic method necessary to the impact of the correlated performance of material.Based on the above fact and at present to having the ZnMn of application prospect
2O
4The relevant report of the synthetic method of material is few, the sheet ZnMn of a kind of synthesizing submicron of the present invention
2O
4The novel preparation method of material.
Summary of the invention
The objective of the invention is to overcome the prior art above shortcomings, a kind of lithium ion battery negative material ZnMn is provided
2O
4The preparation method.The present invention adopts the unimolecule precursor process to prepare ZnMn
2O
4, its cycle performance is highly stable, and high rate performance is better, the ZnMn of the method preparation
2O
4Its first all charge ratio capacity is up to 678 mAh/g, and capacity still keeps well stability after circulation 100 circles, and rising trend is arranged.This battery material has high rate performance preferably, the specific storage height, and concrete technical scheme is as follows.
A kind of lithium ion battery negative material ZnMn
2O
4The preparation method, may further comprise the steps:
Among the above-mentioned preparation method, zinc salt in the step 1: manganese salt: the mol ratio of complexing agent is that 1:2:2 is to 1:2:8.
Among the above-mentioned preparation method, described zinc salt is zinc oxide, zinc carbonate or zinc chloride.
Among the above-mentioned preparation method, described manganese salt is manganese carbonate, manganese chloride or manganese citrate [Mn (C
6H
6O
7) (H
2O)].
Among the above-mentioned preparation method, described complexing agent is citric acid, ammonium citrate, oxyacetic acid or oxalic acid.
Among the above-mentioned preparation method, described solvent is a water.
Among the above-mentioned preparation method, described precursor molecule formula is [ZnMn
2(C
6H
5O
7)
2] 8H
2O.
Among the above-mentioned preparation method, it is 2 hours with calcination time that described calcining temperature is 700 ℃.
The presoma of gained is with infrared spectrum, thermogravimetric analysis, elementary analysis and EDS analysis and characterization (namely use IR, TG, EA and EDS characterize); Resulting ZnMn
2O
4Product XRD, SEM and TEM (HTEM) characterize, and carry out the chemical property analysis to selecting presoma in 2 hours sample of 700 degree calcinings.
The present invention adopts simple unimolecule precursor process to synthesize lithium storage materials ZnMn
2O
4, this material has excellent chemical property, and its first all charge ratio capacity is up to 678 mAh/g, and capacity still keeps well stability (640 mAh/g) after circulation 100 circles, and rising trend is arranged.This battery material has high rate performance preferably, the specific storage height.Technology of the present invention is simple, and is easy to operate, and experimental situation is not had particular requirement, and environmental friendliness, is applicable to expanded reproduction.
Generally speaking, compared with prior art, the present invention has following advantage and positively effect:
1, whole technology is very simple, and is easy to operate, and cost is low, especially with water as solvent, environmentally friendly;
2, synthetic material purity height, the pattern uniqueness, the particle size range narrow distribution, the calcination process required time is very short; Help energy-conservation;
3, this material has higher first charge-discharge specific capacity as the negative material of lithium rechargeable battery, and the rear capability retention of circulation 100 circles is high and rising trend is arranged, and high rate performance is better, is applicable to the big production of actual scale.
Description of drawings
Fig. 1 is the infrared spectrogram of presoma SSPs in the embodiment;
Fig. 2 is thermogravimetric analysis and the differential thermal analysis curve of presoma SSPs in the embodiment;
Fig. 3 is product ZnMn
2O
4Powder diagram figure;
Fig. 4 a ~ Fig. 4 b is product ZnMn
2O
4Sem photograph;
Fig. 4 c ~ Fig. 4 g is product ZnMn
2O
4Transmission electron microscope picture, wherein Fig. 4 e is the enlarged drawing at A place among Fig. 4 d;
Fig. 5 is product ZnMn
2O
4Cyclic voltammetry figure;
Fig. 6 is product ZnMn
2O
4Discharge curve;
Fig. 7 is product ZnMn
2O
4The charge-discharge performance resolution chart.
Embodiment
Take by weighing 22.90 gram manganous carbonates, join in the 150 mL aqueous solution that contain 42.03 gram citric acids, mix by magnetic agitation, be warmed up to 60 ℃ of constant temperature 30 min, add 8.19 gram zinc oxide (wherein zinc oxide: manganous carbonate: the mol ratio of citric acid is 1:2:2) then, after continuing to stir 1 hour under this temperature, cool to room temperature with the sedimentation and filtration separation of gained, is used deionized water wash, vacuum-drying is 4 hours under 60 degree, obtains almost colourless presoma SSPs.The presoma SSPs that obtains is made respectively infrared spectrum (shown in Figure 1), thermogravimetric analysis (shown in Figure 2), elementary analysis and EDS analyze, its molecular formula is [ZnMn
2(C
6H
5O
7)
2] 8H
2O.Presoma in the lower calcining of 700 degree 2 hours, is obtained flaxen ZnMn
2O
4Product.
Take by weighing 22.90 gram manganous carbonates, join in the 150 mL aqueous solution that contain 42.03 gram citric acids, mix by magnetic agitation, be warmed up to 60 ℃ of constant temperature 30 min, add 10.81 gram zinc carbonates (wherein zinc carbonate: manganous carbonate: the mol ratio of citric acid is 1:6:6) then, after continuing to stir 2 hours under this temperature, cool to room temperature with the sedimentation and filtration separation of gained, is used deionized water wash, vacuum-drying is 4 hours under 60 degree, obtains almost colourless presoma.The presoma that obtains is made respectively infrared spectrum, thermogravimetric analysis, elementary analysis and EDS analyze, its molecular formula is [ZnMn
2(C
6H
5O
7)
2] 8H
2O.Presoma in the lower calcining of 700 degree 2 hours, is obtained flaxen ZnMn
2O
4Product.
According to document synthesizing citric acid manganese [Mn (C
6H
6O
7) (H
2O)].Take by weighing 52.62 gram manganese citrates, join in the 150 mL water, add 8.19 gram zinc oxide (wherein zinc oxide: the mol ratio of manganese citrate is 1:2), after stirring 1 hour under 60 degree, cool to room temperature with the sedimentation and filtration separation of gained, is used deionized water wash, vacuum-drying is 4 hours under 60 degree, obtains almost colourless presoma.The presoma that obtains is made respectively infrared spectrum, thermogravimetric analysis, elementary analysis and EDS analyze, its molecular formula is [ZnMn
2(C
6H
5O
7)
2] 8H
2O.Presoma in the lower calcining of 700 degree 2 hours, is obtained flaxen ZnMn
2O
4Product.
The product of presoma calcining gained after 2 hours under 700 degree is through the XRD analysis (see figure 3), diffraction peak intensity among the figure is very strong, the position at peak and standard spectrogram (JCPDS file No.24-1133) coincide fine, illustrate that the product after the calcining is the very high ZnMn of purity
2O
4The gained sample is through ESEM and transmission electron microscope analysis (seeing Fig. 4 a ~ Fig. 4 g), ZnMn
2O
4The particle of product forms pore space structure after material is reunited between the 100-200 nanometer.
ZnMn with embodiment 1 ~ 3 preparation
2O
4Material, conductive agent acetylene black and Kynoar (PVDF) are the ratio mixing of 8:1:1 ~ 5:3:2 according to mass ratio, add an amount of 1-METHYLPYRROLIDONE solvent, to contain the LiPF of 1 mol/L
6EC-DEC-DMC (volume ratio is 1:1:1) be electrolyte, polypropylene porous film is barrier film, metal lithium sheet is to electrode, forms button cell in the argon gas glove box.Carry out charge-discharge test on the instrument discharging and recharging.Fig. 5, Fig. 6 and Fig. 7 are respectively the ZnMn of embodiment 1
2O
4Material, conductive agent acetylene black and Kynoar (PVDF) are cyclic voltammogram, discharge curve and the charge-discharge performance resolution chart of the battery assembled under the condition of 7.5:1.5:1 according to mass ratio.
Above-mentioned concrete embodiment is optimum embodiment, especially a calcining temperature of the present invention, but can not limit claim of the present invention, and other is any not to deviate from technical scheme of the present invention and be included within protection scope of the present invention.
Claims (9)
1. lithium ion battery negative material ZnMn
2O
4The preparation method, it is characterized in that may further comprise the steps:
Step 1, zinc salt, manganese salt, complexing agent and solvent is even, wherein zinc salt: manganese salt: the mol ratio of complexing agent is 1:2:2 ~ 1:2:8;
Step 2, the solution that step 1 is mixed at room temperature stir earlier, are warmed up to 60 ℃ ~ 100 ℃ constant temperature then and stir 0.5 ~ 5 hour, then cool to room temperature;
Step 3, the sedimentation and filtration with step 2 gained, washing and drying obtain presoma;
Step 4, with the described presoma of step 3 in the lower calcining of 500 ~ 800 ℃ of different temperatures 1 ~ 4 hour, obtain product ZnMn
2O
4
2. preparation method as claimed in claim 2 is characterized in that in the step 1 zinc salt: manganese salt: the mol ratio of complexing agent is 1:2:2,1:2:3 and 1:2:4.
3. preparation method as claimed in claim 1 is characterized in that described zinc salt is zinc oxide, zinc carbonate or zinc chloride.
4. preparation method as claimed in claim 1 is characterized in that described manganese salt is manganous carbonate, Manganous chloride tetrahydrate or manganese citrate.
5. preparation method as claimed in claim 1 is characterized in that described complexing agent is citric acid, ammonium citrate, oxyacetic acid or oxalic acid.
6. preparation method as claimed in claim 1 is characterized in that described solvent is a water.
7. preparation method as claimed in claim 1 is characterized in that described precursor molecule formula is [ZnMn
2(C
6H
5O
7)
2] 8H
2O.
8. as each described preparation method of claim 1 ~ 7, it is characterized in that it is 2 hours with calcination time that described calcining temperature is 700 ℃.
9. preparation method as claimed in claim 8 is characterized in that product ZnMn
2O
4Submicron order sheet for the 90-200 nanometer.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094558A (en) * | 2012-12-18 | 2013-05-08 | 深圳市贝特瑞新能源材料股份有限公司 | Zinc-ferrite-based nanometer composite as well as preparation method and application thereof |
| CN103545507A (en) * | 2013-10-31 | 2014-01-29 | 华南师范大学 | Negative material, namely porous zinc cobalt oxide, of lithium ion battery, as well as preparation method and applications of porous zinc cobalt oxide |
| CN103985858A (en) * | 2014-05-23 | 2014-08-13 | 北京理工大学 | Preparation method of ZnCo2O4 nano-plate serving as lithium ion battery negative electrode material |
| CN104355330A (en) * | 2014-09-19 | 2015-02-18 | 中国科学院宁波材料技术与工程研究所 | Preparation method of metal oxide and application of metal oxide in lithium ion battery |
| CN107720829A (en) * | 2017-09-25 | 2018-02-23 | 南京理工大学 | The preparation method of lithium ion battery negative material zinc manganate |
| CN108400324A (en) * | 2018-03-07 | 2018-08-14 | 华南师范大学 | A kind of lithium ion battery negative material zinc manganate nanometer rods and preparation method thereof |
| CN109390564A (en) * | 2017-08-03 | 2019-02-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Ternary metal oxide, preparation method and application based on zinc ion doping |
| CN109755526A (en) * | 2019-01-04 | 2019-05-14 | 中南大学 | A kind of preparation method and applications of manganese chromium zinc ternary metal oxide energy storage material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274779A (en) * | 2008-05-14 | 2008-10-01 | 华中师范大学 | Nano-scaled materials ZnMn2O4 for lithium storage and preparation thereof |
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