CN110137491A - A kind of preparation method of anode material for lithium-ion batteries and products thereof and application - Google Patents
A kind of preparation method of anode material for lithium-ion batteries and products thereof and application Download PDFInfo
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- CN110137491A CN110137491A CN201910486004.8A CN201910486004A CN110137491A CN 110137491 A CN110137491 A CN 110137491A CN 201910486004 A CN201910486004 A CN 201910486004A CN 110137491 A CN110137491 A CN 110137491A
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- lithium
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- ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Materials Engineering (AREA)
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of anode material for lithium-ion batteries FeIIIFeII(CN)5Preparation method and products thereof and application, Fe is prepared with non-aqueous system coprecipitationIIIFeII(CN)5, FeIIIFeII(CN)5In be free of the crystallization water, can effectively promote the capacity of lithium ion battery and high rate performance using the material as positive electrode.Measuring oxygen element content in the material in electro microscope energy spectrum (EDS) is 0, that is, is shown without H2O.The preparation process is relatively easy, easy to operate.
Description
Technical field
The present invention designs a kind of anode material for lithium-ion batteries FeIIIFeII(CN)5Preparation method and products thereof and application.
Background technique
Lithium ion battery is widely used in civilian, military domain as a kind of new energy.To cope with a variety of demands, such as
Unmanned plane and batteries of electric automobile need to have high rate capability, therefore need to develop associated batteries material.PBs be considered as it is a kind of very
Have potential high-rate lithium ion battery anode material, has proposed the theoretical discharge multiplying power of 50C in the industry.Positive active material
The preparation process of PBs has tremendous influence to the performance of entire battery.Usual PBs's is in water bodys such as coprecipitation, hydro-thermal methods
It is generated in system, can there is mass crystallization water in lattice.The presence in crystallization water vacancy can tie up Li ion activity site, and lattice is complete
Whole property reduces, and phenomena such as serious carrier scattering occurs.This can seriously affect the battery material high-multiplying-power discharge performance and
Capacity.
PBs decomposition temperature is lower, and crystal decomposition is likely to result in during removing the crystallization water, there are certain limitation,
It need to propose new method.Synthesized in anhydrous system the active material can evade from root in product have water vacancy this lack
Point.Fail in the PBs synthesized in ethanol detection water outlet presence, that is, show in PBs lattice without will lead to battery capacity and
The water vacancy of high rate performance decline.
Summary of the invention
In view of the deficiencies of the prior art, it is an object of the invention to: a kind of anode material for lithium-ion batteries Fe is providedIIIFeII
(CN)5Preparation method.
Another object of the present invention is: providing a kind of anode material for lithium-ion batteries product that the above method obtains.
Another object of the present invention is to: a kind of application of the said goods is provided.
The object of the invention is realized by following proposal: a kind of preparation method of anode material for lithium-ion batteries, lithium-ion electric
Pond positive electrode is FeIIIFeII(CN)5, it is characterised in that measuring oxygen element content in the material in electro microscope energy spectrum (EDS) is 0,
Show without H2O., include the following steps:
(1) 0.04molFe will be contained3+Trivalent iron salt be dissolved in 100ml ethyl alcohol, magnetic stirrer 10min;
(2) by 0.03mol sodium ferrocyanide (Na4Fe(CN)6Grinding is crossed 150 meshes, is dissolved in 100ml ethyl alcohol, magnetic agitation
60min;
(3) above two solution is mixed, magnetic agitation 60min at 50 DEG C;
(4) above-mentioned reactant is centrifuged, ethanol washing 4 ~ 5 times, is put into 80 DEG C of baking ovens and dries 3h, obtains final product.
It the use of the trivalent iron salt arrived is one of iron chloride, ferric sulfate or combinations thereof.
Ferrocyanide sodium crystal need to grind and cross 150 meshes.
The solvent is ethyl alcohol.
The present invention provides a kind of anode material for lithium-ion batteries, is prepared according to any of the above-described the method.
The present invention provides a kind of application of anode material for lithium-ion batteries in nonaqueous lithium ion battery.
The invention has the advantages that: the synthesis of anode material of lithium-ion battery Fe in non-aqueous system ethyl alcoholIIIFeII(CN)5, make
Water vacancy is not contained in product, and final finished lithium ion battery can be made to have higher capacity and high rate performance.At electro microscope energy spectrum (EDS)
Measuring oxygen element content in the material is 0, that is, is shown without H2O。
Detailed description of the invention
Fig. 1 is example FeIIIFeII(CN)5The finished figure of material;
Fig. 2 is example FeIIIFeII(CN)5The SEM of material schemes;
Fig. 3 is example FeIIIFeII(CN)5The power spectrum elemental analysis result of material.
Specific embodiment
The present invention is described in detail by following specific example, but protection scope of the present invention is not only restricted to these
Examples of implementation.
Embodiment 1
A kind of anode material for lithium-ion batteries, anode material for lithium-ion batteries FeIIIFeII(CN)5, it is co-precipitated with non-aqueous system
Method prepares FeIIIFeII(CN)5, and FeIIIFeII(CN)5In be free of the crystallization water, specific steps are as follows:
(1) by 0.04molFeCl3It is dissolved in 100ml ethyl alcohol, magnetic agitation 10min;
(2) by 0.03mol Na4Fe(CN)6Grinding is crossed 150 meshes, is dissolved in 100ml ethyl alcohol, magnetic agitation 60min;
(3) above two solution is mixed, magnetic agitation 60min at 50 DEG C;
(4) above-mentioned reactant is centrifuged, ethanol washing 4 ~ 5 times, is put into 80 DEG C of baking ovens and dries 3h, obtains final product.
Fig. 1 is example FeIIIFeII(CN)5The finished figure of material, Fig. 2 are example FeIIIFeII(CN)5Material SEM figure and
Fig. 3 is example FeIIIFeII(CN)5The power spectrum elemental analysis of material is as a result, as can be seen from Figure 3, measure the material in electro microscope energy spectrum (EDS)
Oxygen element content is 0 in material, that is, is shown without H2O.The preparation process is relatively easy, easy to operate.
Embodiment 2
A kind of anode material for lithium-ion batteries is prepared by following specific steps:
(1) by 0.02molFe2(SO4)3It is dissolved in 100ml ethyl alcohol, magnetic agitation 10min;
(2) by 0.03mol Na4Fe(CN)6Grinding is crossed 150 meshes, is dissolved in 100ml ethyl alcohol, magnetic agitation 60min;
(3) above two solution is mixed, magnetic agitation 60min at 50 DEG C;Above-mentioned reactant is centrifuged, ethanol washing 4 ~ 5
It is secondary, it is put into 80 DEG C of baking ovens and dries 3h, obtain final product.
Embodiment 3
A kind of anode material for lithium-ion batteries is prepared by following specific steps:
(1) by 0.04molFe (NO3)3It is dissolved in 100ml ethyl alcohol, magnetic agitation 10min;
(2) 0.03mol Na4Fe (CN) 6 is ground, crosses 150 meshes, is dissolved in 100ml ethyl alcohol, magnetic agitation 60min;
(3) above two solution is mixed, magnetic agitation 60min at 50 DEG C;Above-mentioned reactant is centrifuged, ethanol washing 4 ~ 5
It is secondary, it is put into 80 DEG C of baking ovens and dries 3h, obtain final product.
Specific data are as follows as can be seen from Figure 3:
Table 1
。
Claims (6)
1. a kind of preparation method of anode material for lithium-ion batteries, anode material for lithium-ion batteries FeIIIFeII(CN)5,
It is characterized in that preparing Fe with non-aqueous system coprecipitationIIIFeII(CN)5, FeIIIFeII(CN)5In be free of the crystallization water, this method tool
Body step are as follows:
(1) 0.04molFe will be contained3+Trivalent iron salt be dissolved in 100ml ethyl alcohol, magnetic stirrer 10min;
(2) by 0.03mol sodium ferrocyanide (Na4Fe(CN)6Grinding is crossed 150 meshes, is dissolved in 100ml ethyl alcohol, magnetic agitation
60min;
(3) above two solution is mixed, magnetic agitation 60min at 50 DEG C;
(4) above-mentioned reactant is centrifuged, ethanol washing 4 ~ 5 times, is put into 80 DEG C of baking ovens and dries 3h, obtains final product.
2. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that the ferric iron used
Salt is one of iron chloride, ferric sulfate or combinations thereof.
3. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that ferrocyanide sodium crystal
It need to grind and cross 150 meshes.
4. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterised in that solvent is ethyl alcohol.
5. a kind of anode material for lithium-ion batteries, it is characterised in that -4 any the methods are prepared according to claim 1.
6. a kind of application of the anode material for lithium-ion batteries in nonaqueous lithium ion battery according to claim 5.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110492077A (en) * | 2019-08-23 | 2019-11-22 | 河南工学院 | A kind of ferrocyanide carbon composite anode material and preparation method thereof, kalium ion battery, sodium-ion battery |
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CN102181176A (en) * | 2011-06-03 | 2011-09-14 | 杭州弗沃德精细化工有限公司 | Process for preparing iron blue with fantastic color effect |
CN105288668A (en) * | 2015-11-25 | 2016-02-03 | 中国科学院深圳先进技术研究院 | Zinc-doped prussian blue nanoparticle, preparation method and applications thereof |
CN106960956A (en) * | 2017-04-01 | 2017-07-18 | 上海中聚佳华电池科技有限公司 | Modified Prussian blue material, sodium-ion battery positive plate and preparation method |
CN109216674A (en) * | 2018-08-31 | 2019-01-15 | 华南理工大学 | Prussian blue@graphite lithium battery composite positive pole of high-performance and preparation method thereof |
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2019
- 2019-06-05 CN CN201910486004.8A patent/CN110137491A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102181176A (en) * | 2011-06-03 | 2011-09-14 | 杭州弗沃德精细化工有限公司 | Process for preparing iron blue with fantastic color effect |
CN105288668A (en) * | 2015-11-25 | 2016-02-03 | 中国科学院深圳先进技术研究院 | Zinc-doped prussian blue nanoparticle, preparation method and applications thereof |
CN106960956A (en) * | 2017-04-01 | 2017-07-18 | 上海中聚佳华电池科技有限公司 | Modified Prussian blue material, sodium-ion battery positive plate and preparation method |
CN109216674A (en) * | 2018-08-31 | 2019-01-15 | 华南理工大学 | Prussian blue@graphite lithium battery composite positive pole of high-performance and preparation method thereof |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110492077A (en) * | 2019-08-23 | 2019-11-22 | 河南工学院 | A kind of ferrocyanide carbon composite anode material and preparation method thereof, kalium ion battery, sodium-ion battery |
CN110492077B (en) * | 2019-08-23 | 2022-07-01 | 河南工学院 | Ferrocyanide-carbon composite cathode material, preparation method thereof, potassium ion battery and sodium ion battery |
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Application publication date: 20190816 |