CN107492679A - A kind of preparation method of the Prussian blue electrode material of oxide coated by zinc - Google Patents

A kind of preparation method of the Prussian blue electrode material of oxide coated by zinc Download PDF

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Publication number
CN107492679A
CN107492679A CN201710667824.8A CN201710667824A CN107492679A CN 107492679 A CN107492679 A CN 107492679A CN 201710667824 A CN201710667824 A CN 201710667824A CN 107492679 A CN107492679 A CN 107492679A
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China
Prior art keywords
zinc
prussian blue
electrode
oxide coated
iron
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CN201710667824.8A
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Chinese (zh)
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CN107492679B (en
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刘阳
位港亚
乔芸
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河南师范大学
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    • H—ELECTRICITY
    • H01—BASIC 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
    • H—ELECTRICITY
    • H01—BASIC 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—BASIC 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H—ELECTRICITY
    • H01—BASIC 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
    • H01—BASIC 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
    • 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

Abstract

The invention discloses a kind of preparation method of the Prussian blue electrode material of oxide coated by zinc, belong to the synthesis technical field of electrode material.Technical scheme main points are：Zinc salt, carbonate are well mixed with Prussian blue material, 1 24h is calcined in 100 400 DEG C under inert gas shielding, the Prussian blue electrode material of oxide coated by zinc is cleaned and dried to obtain after being down to room temperature.Present invention process is simple, cost is cheap and safe and reliable, the obtained Prussian blue electrode material of oxide coated by zinc effectively reduces the generation of electrolyte and electrode material side reaction, so that electrode material has higher stability in charge and discharge process, so that the cyclical stability and high rate performance of battery are improved significantly, be advantageous to industrialized production.

Description

A kind of preparation method of the Prussian blue electrode material of oxide coated by zinc

Technical field

The invention belongs to the synthesis technical field of electrode material, and in particular to a kind of Prussian blue electrode material of oxide coated by zinc The preparation method of material.

Background technology

With the development of society, energy problem receives much concern always, the shortage of traditional fossil energy and getting worse Problem of environmental pollution makes the sight of people turn to wind energy, solar energy these renewable and clean energy resources.But wind energy, solar energy etc. Regenerative resource have the characteristics that it is discontinuous, unstable and uncontrollable, its store and grid-connected use seems particularly critical, therefore need Develop corresponding energy storage device to store it, and then guarantee the supply energy source of steady and continuous.With other energy storage sides Formula is compared, and electrochemical energy storage has the spies such as energy efficiency is high, have extended cycle life, maintenance cost is low, power and energy response are flexible Point, application advantage is obvious in terms of the integrated power network such as wind-powered electricity generation, photoelectricity.In electrochemical energy storage technology, rechargeable battery system System need strided forward to the battery system with high voltage and high-energy, and be use cost it is low, stably, the pollution-free, long-life Battery system.

Although lead-acid battery and Ni-Cr battery cost are low, the problem of concentrated sulfuric acid and heavy metal pollution be present.Lithium ion Battery turns into the important technology of energy storage technology with high-energy-density, high power density, high voltage, long-life and high security feature One of.However, as lithium ion battery is gradually applied to electric automobile, the demand of lithium will greatly increase, and the reserves of lithium are Limited, and skewness, this is stored up for development and application in the long-life of intelligent grid and the extensive energy storage of regenerative resource For energy battery, cost and price are difficult to fully meet demand.In consideration of it, there is an urgent need to develop the new long-life and price is low The honest and clean secondary cell for energy storage.Sodium rich reserves in the earth's crust, account for 2.74%, enrich element for the 6th, and widely distributed, together When, sodium has the physicochemical properties similar with lithium.Summary feature, the battery of sodium base have been increasingly becoming lithium ion battery Alternative.Therefore before developing the room temperature sodium-ion battery technology for being directed to extensive stored energy application with obvious application Scape.

Prussian blue material is the complex that a major class contains the transition metal that appraises at the current rate, and this kind of compound has complete vertical A large amount of coordination spaces be present, be advantageous to alkali metal ion insertion and abjection, electrode material can be used as in prismatic crystal type, its three-dimensional structure Use.And this kind of compound synthesis method is simple, cost is cheap, capacity is higher and pollution-free, has broad application prospects, But the chemical property of such compound needs to be optimized raising.Be advantageous to material in one layer of Zinc oxide film of its Surface coating The stability of material, the generation of side reaction is reduced, so as to improve the cyclical stability of battery and high rate performance.

The content of the invention

Present invention solves the technical problem that there is provided, a kind of technique is simple, cost is cheap and safe and reliable zinc oxide bag The preparation method of Prussian blue electrode material is covered, the Prussian blue electrode material of oxide coated by zinc made from this method effectively reduces Electrolyte and the generation of electrode material side reaction so that electrode material has higher stability in charge and discharge process, so as to So that the cyclical stability and high rate performance of battery are improved significantly, be advantageous to industrialized production.

The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, a kind of Prussian blue electrode material of oxide coated by zinc The preparation method of material, it is characterised in that concretely comprise the following steps：Zinc salt, carbonate are well mixed with Prussian blue material, in inertia 1-24h is calcined in 100-400 DEG C under gas shield, the Prussian blue electrode material of oxide coated by zinc is cleaned and dried to obtain after being down to room temperature Material, wherein zinc salt are the one or more in zinc nitrate, zinc acetate, zinc sulfate or zinc chloride, and carbonate is sodium acid carbonate, carbonic acid One or more in sodium, saleratus or potassium carbonate, the chemical general formula of Prussian blue material is AxM[N(CN)6]y·zH2O, Wherein A is the one or more in sodium, potassium, magnesium or calcium, and M be chromium, iron, cobalt, nickel, manganese or copper, N be chromium, iron, cobalt, nickel, manganese or Copper, 0<x<2,0<y<2,0<z<10。

Further preferably, the preparation method of the Prussian blue electrode material of described oxide coated by zinc, it is characterised in that specific Step is：By 0.015g zinc acetates, 0.012g sodium acid carbonates and the Prussian blue material Na of 0.1g iron iron x FeFe(CN)6Ground and mixed Uniformly it is put into atmosphere furnace, is heated to 200 DEG C of calcining 3h under nitrogen protection, is down to room temperature, it is then clear with water and ethanol Wash, solid product is dried again handles the Prussian blue electrode material for producing coating zinc oxide.

The present invention has the advantages that compared with prior art：

1st, the Prussian blue electrode material of oxide coated by zinc obtained by the present invention has high power capacity, high circulation stability and high coulomb The many merits such as efficiency, it is a kind of cheap and environment-friendly novel energy-storing electrode material；

2nd, the raw material used in preparation process of the present invention is thing widely distributed, cheap and environment-friendly in nature Matter, compared with conventional electrode material, its preparation method is simple and easily controllable, the obtained Prussian blue electrode of oxide coated by zinc Material property is more stable.

Brief description of the drawings

Fig. 1 is the XRD of Prussian blue material before and after oxide coated by zinc in embodiment 1；

Fig. 2 is the SEM figures of Prussian blue material before and after oxide coated by zinc in embodiment 1；

Fig. 3 is that Prussian blue material is used as the cycle performance curve of sodium ion positive electrode before and after oxide coated by zinc in embodiment 1；

Fig. 4 is that Prussian blue material is used as the CV curves of sodium ion positive electrode before and after oxide coated by zinc in embodiment 1.

Embodiment

The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair Bright scope.

Embodiment 1

By 0.015g zinc acetates, 0.012g sodium acid carbonates and the Prussian blue material Na of 0.1g iron iron x FeFe(CN)6Ground and mixed is equal It is even to be put into atmosphere furnace, 200 DEG C of calcining 3h are heated under nitrogen protection, are down to room temperature, are then cleaned with water and ethanol, Solid product is dried again handles the Prussian blue composite for producing coating zinc oxide.

Prussian blue material before and after obtained coating zinc oxide is subjected to XRD（Such as Fig. 1）And SEM（Such as Fig. 2）Test.Will Electrode material, conductive carbon black and the binding agent of preparation are according to mass ratio 7:2:1 ratio mixing, using deionized water as solvent, It is coated on aluminium foil, is dried in vacuo 12h, then using sodium perchlorate, PC, EC, FEC as electrolyte, sodium piece is to carry out perseverance to electrode Stream（200mA g–1）Performance test（Such as Fig. 3）, CV test, it is 0.2mV s to sweep speed–1（Such as Fig. 4）.

Embodiment 2

By 0.375g zinc acetates, 0.3g sodium acid carbonates and the Prussian blue material Na of 10g ferrimanganics x MnFe(CN)6Ground and mixed is uniform It is put into atmosphere furnace, is heated to 150 DEG C of calcining 4h under nitrogen protection, is down to room temperature, is then cleaned with water and ethanol, Gu Body product is dried again handles the Prussian blue composite for producing coating zinc oxide.

Embodiment 3

By 0.015g zinc nitrates, 0.012g sodium carbonate and the Prussian blue material Na of 0.1g iron iron x FeFe(CN)6Ground and mixed is uniform It is put into atmosphere furnace, is heated to 100 DEG C of calcining 3h under nitrogen protection, is down to room temperature, is then cleaned with water and ethanol, Gu Body product is dried again handles the Prussian blue composite for producing coating zinc oxide.

Embodiment 4

By 0.016g zinc chloride, 0.012g sodium acid carbonates and the Prussian blue material Na of 0.1g iron cobalts x CoFe(CN)6Ground and mixed is equal It is even to be put into atmosphere furnace, 200 DEG C of calcining 3h are heated under argon gas protection, room temperature is down to, is then cleaned with water and ethanol, Solid product is dried again handles the Prussian blue composite for producing coating zinc oxide.

Embodiment 5

By 0.3g zinc sulfate, 0.24g potassium carbonate and the Prussian blue material K of 20g iron nickel x NiFe(CN)6Ground and mixed is uniformly put into In atmosphere furnace, 400 DEG C of calcining 1h are heated under nitrogen protection, room temperature is down to, is then cleaned with water and ethanol, solid production Thing is dried again handles the Prussian blue composite for producing coating zinc oxide.

Embodiment 6

By 30g zinc acetates, 24g saleratus and the Prussian blue material K of 2kg iron nickel x NiFe(CN)6Ground and mixed is uniformly put into gas In atmosphere stove, 300 DEG C of calcining 24h are heated under nitrogen protection, room temperature is down to, is then cleaned with water and ethanol, solid production Thing is dried again handles the Prussian blue composite for producing coating zinc oxide.

Embodiment above describes the general principle of the present invention, main features and advantages, the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (2)

1. a kind of preparation method of the Prussian blue electrode material of oxide coated by zinc, it is characterised in that concretely comprise the following steps：By zinc salt, carbon Hydrochlorate is well mixed with Prussian blue material, and 1-24h is calcined in 100-400 DEG C under inert gas shielding, is down to after room temperature clearly Wash and be dried to obtain the Prussian blue electrode material of oxide coated by zinc, wherein zinc salt is in zinc nitrate, zinc acetate, zinc sulfate or zinc chloride One or more, carbonate be sodium acid carbonate, sodium carbonate, saleratus or potassium carbonate in one or more, it is Prussian blue The chemical general formula of material is AxM[N(CN)6]y·zH2O, wherein A be sodium, potassium, magnesium or calcium in one or more, M be chromium, iron, Cobalt, nickel, manganese or copper, N are chromium, iron, cobalt, nickel, manganese or copper, 0<x<2,0<y<2,0<z<10。
2. the preparation method of the Prussian blue electrode material of oxide coated by zinc according to claim 1, it is characterised in that specific Step is：By 0.015g zinc acetates, 0.012g sodium acid carbonates and the Prussian blue material Na of 0.1g iron iron x FeFe(CN)6Ground and mixed Uniformly it is put into atmosphere furnace, is heated to 200 DEG C of calcining 3h under nitrogen protection, is down to room temperature, it is then clear with water and ethanol Wash, solid product is dried again handles the Prussian blue electrode material for producing coating zinc oxide.
CN201710667824.8A 2017-08-07 2017-08-07 A kind of preparation method of the Prussian blue electrode material of oxide coated by zinc CN107492679B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109742358A (en) * 2019-01-03 2019-05-10 清远佳致新材料研究院有限公司 Application and anode material for lithium-ion batteries of the gallium/indium doping zinc oxide in anode material for lithium-ion batteries clad

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CN104716314B (en) * 2015-03-18 2017-12-19 上海中聚佳华电池科技有限公司 Prussian blue/redox graphene composite and its preparation method and application
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109742358A (en) * 2019-01-03 2019-05-10 清远佳致新材料研究院有限公司 Application and anode material for lithium-ion batteries of the gallium/indium doping zinc oxide in anode material for lithium-ion batteries clad

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