CN107331837A - A kind of cyano group complex compound and its preparation method and application - Google Patents

A kind of cyano group complex compound and its preparation method and application Download PDF

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Publication number
CN107331837A
CN107331837A CN201710473337.8A CN201710473337A CN107331837A CN 107331837 A CN107331837 A CN 107331837A CN 201710473337 A CN201710473337 A CN 201710473337A CN 107331837 A CN107331837 A CN 107331837A
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cyano
solution
complex compound
sodium
mixed
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CN201710473337.8A
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CN107331837B (en
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谢健
沈志龙
孙云坡
曹高劭
赵新兵
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浙江大学
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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
    • 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
    • H01M4/364—Composites as mixtures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/08—Simple or complex cyanides of metals
    • C01C3/12—Simple or complex iron cyanides
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/58—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 cyano group complex compound, it is specially：Ferrous ammonium cyanide and deionized water are mixed to get solution A, by divalent transition metal ion M2+Soluble-salt and deionized water be mixed to get solution B, then solution A and solution B are mixed, intermediate product are obtained after hydro-thermal reaction；The in the mixed solvent that soluble sodium salt is dissolved in ethylene glycol/deionized water is obtained into solution C, intermediate product is mixed with solution C, cyano group complex compound is obtained after ion-exchange reactions.The invention discloses a kind of preparation method of cyano group complex compound, this method can regulate and control to the pattern and lattice structure of target product, the cyano group complex compound prepared has good crystallinity, it is applied in sodium-ion battery electrode, is remarkably improved the chemical property of sodium-ion battery.

Description

A kind of cyano group complex compound and its preparation method and application

Technical field

The present invention relates to the technical field of novel energy storage cell, and in particular to a kind of cyano group complex compound and its preparation side Method and application.

Background technology

Lithium ion battery is widely used as mobile electronic device, such as smart mobile phone, notebook computer, and in electricity now Net energy storage, electric automobile field have huge market.But, with the popularization of lithium ion battery, particularly in electric automobile Upper large-scale use, the consumption of lithium resource is also huge.And the reserves of lithium resource are limited, and at present to discarded lithium from The recovery of elemental lithium lacks effective, economic technology in sub- battery.By contrast, the reserves of sodium element on earth are much high In elemental lithium, price is also far below lithium.Therefore, in recent years, sodium-ion battery is noted extensively.It is generally believed that sodium ion is electric Pond has tempting prospect in power network energy storage field.

Traditional lithium ion battery uses LiCoO2、LiFePO4、LiMn2O4, ternary material as positive electrode, it is but this kind of The chemical property of the corresponding sodium compound of material is undesirable, show as capacity it is low even without activity, charging/discharging voltage is low, fill The shortcomings of discharge platform is not obvious.By contrast, some ferrocyanides due in structure containing the room that volume is larger, favorably In the insertion and abjection of the larger sodium ion of volume, therefore capacity is higher, and charging/discharging voltage is higher, be adapted as sodium from Sub- cell positive material.

Although ferrocyanide has high theoretical capacity, such material is easily decomposed at high temperature, typically at low temperature Prepare, it is general to use coprecipitation or hydro-thermal method.Wherein coprecipitation is that bivalent soluble salt is added in ferrocyanide, Precipitated, and hydro-thermal method uses single ferrocyanide as presoma, adds acid (generally hydrochloric acid) reaction precipitation, this The more difficult control of two methods reaction rate, and transition metal is limited only to iron in the latter's product.

But the general crystallinity of ferrocyanide also therefore, prepared is poor, causes it to be assembled as positive electrode To sodium-ion battery capacity is relatively low, cyclical stability is undesirable.

The content of the invention

The invention discloses a kind of preparation method of cyano group complex compound, this method can to the pattern of target product and Lattice structure is regulated and controled, and the cyano group complex compound prepared has good crystallinity, is applied to sodium ion electricity In the electrode of pond, the chemical property of sodium-ion battery, particularly capacity are remarkably improved.

Cyano group complex compound is prepared using ion-exchange, due to Na+Radius be less than NH4 +, in ion exchange process Middle Na+It is more easy to enter NH4 +In lattice, M2+Ion also easily enters in the lattice of sodium ferrocyanide, further increases the knot of product Brilliant degree.In ion-exchange, the NH in solid phase4 +By the Na in liquid phase+Substitution reaction speed is slow, and its reaction rate can Reaction rate can be effectively reduced by controlling reaction temperature, therefore using this method, the crystallinity of product is improved, so as to carry Its high capacity.

Concrete technical scheme is as follows：

A kind of preparation method of cyano group complex compound, comprises the following steps：

1) ferrous ammonium cyanide and deionized water are mixed to get solution A, by divalent transition metal ion M2+Soluble-salt Solution B is mixed to get with deionized water, then described solution A and solution B are mixed, intermediate product is obtained after hydro-thermal reaction；

2) in the mixed solvent that soluble sodium salt is dissolved in ethylene glycol/deionized water is obtained into solution C, by step 1) obtain Intermediate product is mixed with the solution C, and described cyano group complex compound is obtained after ion-exchange reactions.

Step 1) in：

Preferably, the concentration of the solution A is 0.1~0.5mol/L.The concentration of solution A is ferrous cyanogen in solution A Radical ion (Fe (CN)6 4-) concentration.

Raw material, which is removed, is selected from ferrous ammonium cyanide, is further selected from the hydrate of ferrous ammonium cyanide.

Preferably, described M2+Selected from Mn2+、Fe2+、Ni2+、Co2+In one or more, described soluble-salt choosing From chloride, sulfate, nitrate one or more；

The concentration of described solution B is 0.2~2.0mol/L, and the concentration of solution B is M in solution B2+Concentration.

Preferably, described divalent transition metal ion M2+Soluble-salt and ferrous ammonium cyanide mol ratio be 2.5 ~5.

Preferably, the temperature of the hydro-thermal reaction is 60~100 DEG C, the time is 1~5h.

Step 2) in：

Preferably, described soluble sodium salt is selected from sodium chloride, sodium acetate, sodium nitrate or sodium sulphate；

The volume ratio of described in the mixed solvent, ethylene glycol and deionized water is 90:10~95:5；

The concentration of described solution C is 0.2~2.0mol/L.

Preferably, described soluble sodium salt and step 1) described in the mol ratio of ferrous ammonium cyanide be 2.5~5.

Preferably, described ion-exchange reactions is carried out in a nitrogen atmosphere, reaction temperature is 130~180 DEG C, time For 0.5~5h.Further preferably, reaction temperature is 140~160 DEG C, and the reaction time is 1~2h.Reaction temperature is too low or the time Too short, ion exchange is not thorough, and the crystallization of cyano group complex compound is imperfect；Reaction temperature is too high or overlong time, in product Divalent metal is oxidizable, and reaction temperature is too high or overlong time, little on product crystallization influence, and can reduce the effect of synthesis Rate.

Preferably, the product after hydro-thermal reaction and ion-exchange reactions be both needed to it is post-treated including cooling, washing, dry Dry processing.

The temperature of described cooling does not have strict restriction, based on adequate operation, can typically be cooled to 15~30 DEG C Environment temperature.

The invention also discloses the cyano group complex compound prepared according to the above method, chemical formula is NaxM[Fe(CN)6]y, In formula, x=1.6~2, y=0.7~1, it is known that, product has high sodium and ferrous cyanogen root content, and high sodium and ferrous cyanogen root contain Amount can improve the crystallinity and capacity of product；Lattice structure is rhombohedral phase.It is generally believed that the ferrocyanogen of the lattice structure The chemical property of positive electrode is better than the material of Emission in Cubic, particularly capacity.It therefore, it can apply in sodium-ion battery neck Domain.

Is the particle of irregular shape is presented in the cyano group complex compound prepared, and size is submicron order.As excellent Choosing, the size of the cyano group complex compound is 200~400nm.Particle is unfavorable for greatly very much the diffusion of sodium ion, too small to be unfavorable for Electrode is coated with and reduces the volume energy density of battery.

Compared with prior art, the invention has the advantages that：

1st, the present invention prepares cyano group complex compound using ion-exchange, can be to the pattern and lattice structure of target product Regulated and controled, there is high sodium and ferrous cyanogen root content in the cyano group complex compound prepared, and with good crystallization Property, obtained sodium-ion battery is assembled using it as positive electrode has high power capacity.

2nd, preparation method of the invention, with technique is simple, cost is low, the cycle is short, energy consumption is low and suitable industrialized production The advantages of.

Brief description of the drawings

Fig. 1 is the X ray diffracting spectrum of cyano group complex compound prepared by embodiment 1；

Fig. 2 is the charging and discharging curve for the sodium-ion battery that the cyano group complex compound assembling prepared with embodiment 1 is obtained.

Embodiment

Embodiment 1

Ferrous ammonium cyanide is dissolved in deionized water, is uniformly mixing to obtain with ferrous cyanide ion (Fe (CN)6 4-) count dense Spend the solution A for 0.1mol/L；By MnCl2It is dissolved in deionized water and obtains with Mn2+Count the solution B that concentration is 0.2mol/L (MnCl22.5) mol ratio with ferrous ammonium cyanide is；Solution A and solution B are mixed, through 60 DEG C of hydro-thermal reaction 2h, through filtering, After washing, drying, (NH is obtained4)xMn[Fe(CN)]yPrecipitation；NaCl is dissolved in ethylene glycol and the mixed solvent (two of deionized water The volume ratio of person is 90：10) solution C (mol ratio of NaCl and ferrous ammonium cyanide is 2.5) that concentration is 0.2mol/L is obtained in, By (NH4)xMn[Fe(CN)]yIt is added in solution C, after ultrasonic disperse, under nitrogen atmosphere, is reacted at 150 DEG C after 1.5h, Again after cooling down, filtering, wash, dry, cyano group complex compound Na is obtainedxMn[Fe(CN)]y.By icp analysis, x in product It is 0.85 to be worth for 1.75, y values, and lattice structure is rhombohedral phase, and particle size is 200~400nm.

Fig. 1 is the X-ray diffraction spectrum of cyano group complex compound prepared by this implementation, and the material can be attributed to ferromanganic cyaniding Sodium.

Using cyano group complex compound manufactured in the present embodiment as positive pole, using metallic sodium as negative pole, the glass fibre (trade mark Whatman GF/D) it is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte, full of Battery is assembled in the glove box of argon gas, charge-discharge test is carried out, charging and discharging curve is as shown in Figure 2.Constant current charge-discharge test (electricity Current density 30mA/g, voltage range 2V~4V.It was found from figure, capacity is up to 151mAh/g.

Comparative example 1

Do not use ion-exchange to prepare cyano group complex compound, and use direct reaction method to prepare.It is specific as follows, by Asia The sodium ferricyanide is dissolved in deionized water, is uniformly mixing to obtain with ferrous cyanide ion (Fe (CN)6 4-) meter concentration be 0.1mol/L Solution A；By MnCl2It is dissolved in deionized water and obtains with Mn2+Count the solution B (MnCl that concentration is 0.2mol/L2With ferrocyanide 2.5) sodium mol ratio is；Solution A and solution B are mixed, through 60 DEG C of hydro-thermal reaction 2h, after filtering, washing, drying, obtained NaxMn[Fe(CN)]yPrecipitation.As a result show, because reaction rate is very fast, product crystallization is bad, and particle size is smaller.

Positive pole, using metallic sodium as negative pole, the glass fibre (trade mark are used as using cyano group complex compound prepared by this comparative example Whatman GF/D) it is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte, full of Battery is assembled in the glove box of argon gas, charge-discharge test is carried out.Constant current charge-discharge tests (current density 30mA/g, voltage model Enclose 2V~4V to show, capacity is only 95mAh/g.

Comparative example 2

The preparation technology of cyano group complex compound and embodiment 1 are similar, except that ion-exchange reaction temperature is low In 120 DEG C, the reaction time is more than 5 hours, and other conditions keep constant.As a result show, because reaction temperature is too low, even if extension Reaction, ion exchange is not also thorough, and product sodium content is relatively low, causes Capacity Ratio relatively low.

Positive pole, using metallic sodium as negative pole, the glass fibre (trade mark are used as using cyano group complex compound prepared by this comparative example Whatman GF/D) it is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte, full of Battery is assembled in the glove box of argon gas, charge-discharge test is carried out.Constant current charge-discharge tests (current density 30mA/g, voltage model Enclose 2V~4V to show, capacity is only 115mAh/g.

Embodiment 2

Ferrous ammonium cyanide is dissolved in deionized water, is uniformly mixing to obtain with ferrous cyanide ion (Fe (CN)6 4-) count dense Spend the solution A for 0.2mol/L；It is 1 by mol ratio：1 MnCl2And FeSO4It is dissolved in deionized water and obtains with Mn2+And Fe2+Always Count the solution B (MnCl that concentration is 0.4mol/L2With FeSO4The ratio between total mole number and ferrous ammonium cyanide molal quantity for 3)；Will be molten Liquid A and solution B mixing, through 60 DEG C of hydro-thermal reaction 2h, after filtering, washing, drying, obtain (NH4)xMn0.5Fe0.5[Fe(CN)]y Precipitation；NaCl is dissolved in into the mixed solvent of ethylene glycol and deionized water, and (both volume ratios are 90：10) concentration is obtained in is 0.4mol/L solution C (mol ratio of NaCl and ferrous ammonium cyanide is 3), by (NH4)xMn0.5Fe0.5[Fe(CN)]yIt is added to molten In liquid C, after ultrasonic disperse, under nitrogen atmosphere, reacted at 140 DEG C after 2h, then after cooling down, filtering, wash, dry, obtain To cyano group complex compound NaxMn0.5Fe0.5[Fe(CN)]y, in formula, x=1.61, y=0.77；Lattice structure is rhombohedral phase, Particle size is 200~400nm.

Using cyano group complex compound manufactured in the present embodiment as positive pole, using metallic sodium as negative pole, the glass fibre (trade mark Whatman GF/D) it is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte, full of Battery is assembled in the glove box of argon gas, charge-discharge test is carried out.Constant current charge-discharge tests (current density 30mA/g, voltage model 2V~4V is enclosed, is shown, capacity is up to 142mAh/g.

Embodiment 3

Ferrous ammonium cyanide is dissolved in deionized water, is uniformly mixing to obtain with ferrous cyanide ion (Fe (CN)6 4-) count dense Spend the solution A for 0.1mol/L；By FeCl2It is dissolved in deionized water and obtains with Fe2+Count the solution B that concentration is 0.2mol/L (FeCl2With the ratio between ferrous ammonium cyanide molal quantity for 3)；Solution A and solution B are mixed, through 60 DEG C of hydro-thermal reaction 2h, through filtering, After washing, drying, (NH is obtained4)xFe[Fe(CN)]yPrecipitation；NaCl is dissolved in ethylene glycol and the mixed solvent (two of deionized water The volume ratio of person is 90：10) solution C (N that concentration is 0.2mol/L is obtained inaThe mol ratio of Cl and ferrous ammonium cyanide for 2.5), By (NH4)xFe[Fe(CN)]yIt is added in solution C, after ultrasonic disperse, under nitrogen atmosphere, is reacted at 160 DEG C after 1h, then After cooling down, filtering, wash, dry, cyano group complex compound Na is obtainedxFe[Fe(CN)]y, in formula, x=1.72, y=0.83； Lattice structure is rhombohedral phase, and particle size is 200~400nm.

Using ferrocyanogen positive electrode manufactured in the present embodiment as positive pole, using metallic sodium as negative pole, the glass fibre (trade mark Whatman GF/D) it is barrier film, NaPF6Ethylene carbonate (EC)/diethyl carbonate (DEC) solution be electrolyte, full of Battery is assembled in the glove box of argon gas, charge-discharge test is carried out.Constant current charge-discharge tests (current density 30mA/g, voltage model 2V~4V is enclosed, is shown, capacity is up to 148mAh/g.

Claims (10)

1. a kind of preparation method of cyano group complex compound, it is characterised in that comprise the following steps：
1) ferrous ammonium cyanide and deionized water are mixed to get solution A, by divalent transition metal ion M2+Soluble-salt with going Ionized water is mixed to get solution B, then described solution A and solution B are mixed, and intermediate product is obtained after hydro-thermal reaction；
2) in the mixed solvent that soluble sodium salt is dissolved in ethylene glycol/deionized water is obtained into solution C, by step 1) obtained centre Product is mixed with the solution C, and described cyano group complex compound is obtained after ion-exchange reactions.
2. the preparation method of cyano group complex compound according to claim 1, it is characterised in that step 1) in, it is described The concentration of solution A is 0.1~0.5mol/L.
3. the preparation method of cyano group complex compound according to claim 1, it is characterised in that step 1) in, described M2 +Selected from Mn2+、Fe2+、Ni2+、Co2+In one or more, the one kind of soluble-salt in chloride, sulfate, nitrate Or it is a variety of；
The concentration of described solution B is 0.2~2.0mol/L；
Described divalent transition metal ion M2+Soluble-salt and ferrous ammonium cyanide mol ratio be 2.5~5.
4. the preparation method of cyano group complex compound according to claim 1, it is characterised in that step 1) in, the water The temperature of thermal response is 60~100 DEG C, and the time is 1~5h.
5. the preparation method of cyano group complex compound according to claim 1, it is characterised in that step 2) in, it is described Soluble sodium salt is selected from sodium chloride, sodium acetate, sodium nitrate or sodium sulphate；
The volume ratio of described in the mixed solvent, ethylene glycol and deionized water is 90:10~95:5；
The concentration of described solution C is 0.2~2.0mol/L.
6. the preparation method of cyano group complex compound according to claim 1, it is characterised in that step 2) in, it is described Soluble sodium salt and step 1) described in the mol ratio of ferrous ammonium cyanide be 2.5~5.
7. the preparation method of cyano group complex compound according to claim 1, it is characterised in that step 2) in, it is described Ion-exchange reactions is carried out in a nitrogen atmosphere, and reaction temperature is 130~180 DEG C, and the time is 0.5~5h.
8. a kind of cyano group complex compound prepared by method according to claim 1~7 any claim, its feature exists In chemical formula is NaxM[Fe(CN)6]y, in formula, x=1.6~2, y=0.7~1；Lattice structure is rhombohedral phase.
9. cyano group complex compound according to claim 8, it is characterised in that nothing is presented in described cyano group complex compound Regular shape, size is 200~400nm.
10. a kind of application of the cyano group complex compound in sodium-ion battery according to claim 8 or claim 9.
CN201710473337.8A 2017-06-21 2017-06-21 A kind of cyano complex compound and its preparation method and application CN107331837B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4192912A (en) * 1979-03-01 1980-03-11 Exxon Research & Engineering Co. Cells having cathodes with thiocyanogen-containing cathode-active materials
CN103441241A (en) * 2013-04-12 2013-12-11 中国科学院化学研究所 Preparation method and application of prussian blue complex/carbon composite material
CN104282908A (en) * 2014-09-24 2015-01-14 张五星 Method for synthesizing high-sodium iron-based Prussian blue electrode material
CN104716314A (en) * 2015-03-18 2015-06-17 上海中聚佳华电池科技有限公司 Prussian blue/reduced graphene oxide composite material as well as preparation method and application thereof
CN106549155A (en) * 2016-10-20 2017-03-29 河南师范大学 A kind of potassium sodium ferromanganese base prussian blue electrode material and its preparation method and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4192912A (en) * 1979-03-01 1980-03-11 Exxon Research & Engineering Co. Cells having cathodes with thiocyanogen-containing cathode-active materials
CN103441241A (en) * 2013-04-12 2013-12-11 中国科学院化学研究所 Preparation method and application of prussian blue complex/carbon composite material
CN104282908A (en) * 2014-09-24 2015-01-14 张五星 Method for synthesizing high-sodium iron-based Prussian blue electrode material
CN104716314A (en) * 2015-03-18 2015-06-17 上海中聚佳华电池科技有限公司 Prussian blue/reduced graphene oxide composite material as well as preparation method and application thereof
CN106549155A (en) * 2016-10-20 2017-03-29 河南师范大学 A kind of potassium sodium ferromanganese base prussian blue electrode material and its preparation method and application

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