CN102010010B - 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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- CN102010010B CN102010010B CN2010105454708A CN201010545470A CN102010010B CN 102010010 B CN102010010 B CN 102010010B CN 2010105454708 A CN2010105454708 A CN 2010105454708A CN 201010545470 A CN201010545470 A CN 201010545470A CN 102010010 B CN102010010 B CN 102010010B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title abstract description 16
- 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 28
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [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 group [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical group OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 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
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 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
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000003860 storage 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
- 239000011572 manganese Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 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
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000000926 separation method 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
- 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
- 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
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 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
- 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 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
- 239000008151 electrolyte solution 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
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode 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; Like graphite, soft carbon, hard carbon etc.,, also there is significant disadvantages though carbon negative pole material has some excellent characteristic; High like soft carbon first charge-discharge irreversible capacity, 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 concern widely as lithium ion battery negative material.The crystalline structure of these MOXs itself can not can not form alloy with lithium for lithium ion provides the room, promptly its reaction mechanism be not lithium ion embedding with deviate from or form alloy, but react: M with metallic lithium generation reversible
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 storage.Like CoO, Co
3O
4In charge and discharge cycles, can all can keep 700mAh/g.At present, complex metal oxides is as the 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 be Zn follow metal M (M=Co, Fe, Mn) and Li
2Reversible reaction takes place in O, and metal Li can also form alloy at low potential with Zn simultaneously, improves lithium storage content.But because Co costs an arm and a leg 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 of forming battery with the positive electrode material of identical match is higher, thus energy density increases.Recently, the ZnFe of Y. Sharma and people such as Z.Y. Wang different-shape that two kinds of different preparing 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, professor Zhang Lizhi has reported the ZnMn of two kinds of different-shapes
2O
4The compound method of material and the application in lithium ion battery thereof think that the compound method of material has remarkably influenced to its chemical property.Just because of preparation methods has very big influence to the performance of material, develop featured compound method and study compound method necessary to the influence 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 compound 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 above-mentioned deficiency that prior art exists, a kind of lithium ion battery negative material ZnMn is provided
2O
4The preparation method.The present invention adopts the unit molecule precursor process to prepare ZnMn
2O
4, its cycle performance is highly stable, and high rate performance is better, the ZnMn of this 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 slow ascendant trend is arranged.This battery material has high rate performance preferably, and specific storage is high, and concrete technical scheme is following.
A kind of lithium ion battery negative material ZnMn
2O
4The preparation method, may further comprise the steps:
Step 3, the sedimentation and filtration with step 2 gained, washing and drying obtain presoma (SSPs);
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, said zinc salt is zinc oxide, zinc carbonate or zinc chloride.
Among the above-mentioned preparation method, said manganese salt is manganous carbonate, Manganous chloride tetrahydrate or manganese citrate [Mn (C
6H
6O
7) (H
2O)].
Among the above-mentioned preparation method, said complexing agent is Hydrocerol A, ammonium citrate, oxyacetic acid or oxalic acid.
Among the above-mentioned preparation method, said solvent is a water.
Among the above-mentioned preparation method, said 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 ir spectra, thermogravimetric analysis, ultimate analysis and EDS analysis and characterization (promptly using IR, TG, EA and EDS sign); Resulting ZnMn
2O
4Product is used XRD, and SEM and TEM (HTEM) characterize, and carries out the chemical property analysis to selecting presoma in 2 hours sample of 700 degree calcinings.
The present invention adopts simple unit molecule 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 slow ascendant trend is arranged.This battery material has high rate performance preferably, and specific storage is high.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, the synthetic material purity is high, and pattern is unique, the particle size range narrow distribution, and the calcination process required time is very short; Help energy-conservation;
3, this material has higher first charge-discharge specific storage as the negative material of lithium-ion secondary cell, and circulation 100 circle back capability retentions are high and slow ascendant trend is arranged, and high rate performance is better, is applicable to the big production of actual mass-producing.
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 view at A place among Fig. 4 d;
Fig. 5 is product ZnMn
2O
4The cyclic voltammetric test pattern;
Fig. 6 is product ZnMn
2O
4Discharge curve;
Fig. 7 is product ZnMn
2O
4The charge-discharge performance test pattern.
Embodiment
Take by weighing 22.90 gram manganous carbonates, join in the 150 mL aqueous solution that contain 42.03 gram Hydrocerol As, mix through 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 Hydrocerol A 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 ir spectra (shown in Figure 1), thermogravimetric analysis (shown in Figure 2), ultimate analysis and EDS respectively analyze, its molecular formula is [ZnMn
2(C
6H
5O
7)
2] 8H
2O.Presoma was calcined 2 hours down in 700 degree, 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 Hydrocerol As, mix through 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 Hydrocerol A 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 ir spectra, thermogravimetric analysis, ultimate analysis and EDS respectively analyze, its molecular formula is [ZnMn
2(C
6H
5O
7)
2] 8H
2O.Presoma was calcined 2 hours down in 700 degree, obtained flaxen ZnMn
2O
4Product.
Embodiment 3
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 ir spectra, thermogravimetric analysis, ultimate analysis and EDS respectively analyze, its molecular formula is [ZnMn
2(C
6H
5O
7)
2] 8H
2O.Presoma was calcined 2 hours down in 700 degree, obtained flaxen ZnMn
2O
4Product.
The product of presoma gained after 700 degree are calcined 2 hours down 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, explain that the product after the calcining is the very high ZnMn of purity
2O
4The gained sample is through ESEM and TEM 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, static eliminator acetylene black and pvdf (PVDF) are the mixed of 8:1:1 ~ 5:3:2 according to mass ratio, add an amount of N-Methyl pyrrolidone solvent, to contain the LiPF of 1 mol/L
6EC-DEC-DMC (volume ratio is 1:1:1) be electrolytic solution, polypropylene porous film is a barrier film, metal lithium sheet is a counter electrode, in the argon gas glove box, forms button cell.Carry out charge-discharge test on the appearance discharging and recharging.Fig. 5, Fig. 6 and Fig. 7 are respectively the ZnMn of embodiment 1
2O
4Material, static eliminator acetylene black and pvdf (PVDF) are cyclic voltammogram, discharge curve and the charge-discharge performance test pattern 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 (4)
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; Said complexing agent is Hydrocerol A, ammonium citrate, oxyacetic acid or oxalic acid; Said zinc salt is zinc carbonate or zinc chloride or is replaced by zinc oxide; Said manganese salt is manganous carbonate, Manganous chloride tetrahydrate or manganese citrate;
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, and said precursor molecule formula is [ZnMn
2(C
6H
5O
7)
2] 8H
2O;
Step 4, with the said presoma of step 3 in the calcining 1 ~ 4 hour down of 500 ~ 800 ℃ of differing tempss, obtain product ZnMn
2O
4, product ZnMn
2O
4Submicron order sheet for the 90-200 nanometer.
2. preparation method as claimed in claim 1 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 said solvent is a water.
4. like each described preparation method of claim 1 ~ 3, it is characterized in that it is 2 hours with calcination time that described calcining temperature is 700 ℃.
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| CN103094558B (en) * | 2012-12-18 | 2016-03-02 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of zinc ferrite based nano composite material, preparation method and its usage |
| CN103545507B (en) * | 2013-10-31 | 2016-08-17 | 华南师范大学 | A kind of lithium ion battery negative material porous cobalt acid zinc and preparation method and application |
| CN103985858B (en) * | 2014-05-23 | 2016-05-25 | 北京理工大学 | A kind of preparation method of lithium ion battery negative material cobalt acid zinc nanometer sheet |
| 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 |
| CN109390564B (en) * | 2017-08-03 | 2020-08-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Ternary metal oxide based on zinc ion doping, preparation method and application thereof |
| CN107720829B (en) * | 2017-09-25 | 2019-09-13 | 南京理工大学 | The preparation method of lithium ion battery negative material zinc manganate |
| CN108400324B (en) * | 2018-03-07 | 2020-07-10 | 华南师范大学 | Lithium ion battery cathode material zinc manganate nanorod and preparation method thereof |
| CN109755526B (en) * | 2019-01-04 | 2021-05-11 | 中南大学 | Preparation method and application of manganese-chromium-zinc ternary metal oxide energy storage material |
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|---|---|---|---|---|
| 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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