CN106920922A - The preparation method of the positive electrodes of KTiFe (CN) 6 - Google Patents
The preparation method of the positive electrodes of KTiFe (CN) 6 Download PDFInfo
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- CN106920922A CN106920922A CN201710231793.1A CN201710231793A CN106920922A CN 106920922 A CN106920922 A CN 106920922A CN 201710231793 A CN201710231793 A CN 201710231793A CN 106920922 A CN106920922 A CN 106920922A
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- ktife
- positive electrode
- titanium
- potassium
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
Abstract
The invention discloses a kind of KTiFe (CN)6The preparation method of positive electrode and its application in kalium ion battery, positive electrode are, by potassium resource, source of iron, titanium source, to be prepared from by coprecipitation.The present invention utilizes Co deposited synthesis new KTiFe (CN)6Potassium electricity positive electrode, the preparation method is simple, efficient, low cost；KTiFe(CN)6There is excellent capacity and good cycle performance as kalium ion battery positive electrode.
Description
Technical field
The invention belongs to Material Field, and in particular to Potassium titanium hexacyanoferrate KTiFe (CN)6The preparation method of positive electrode and
Its application in kalium ion battery field.
Background technology
With the development and the rise of electric automobile of portable electric appts, demand of the world today to lithium ion battery
Constantly increase.But lithium resource reserves on earth are very few, the content in the earth's crust only 0.0065%, global lithium storage
Amount is only 39,780,000 tons, wherein only 13,500,000 tons with extraction value.But sent out within 2015 according to US Geological Survey
The data of cloth, global lithium yield is about 36000 tons within 2014, and with the rise of electric automobile, this numeral still can constantly increase
Plus, according to this development rate, lithium resource will much can not meet people in future to the demand in terms of energy storage, and lithium will turn into one
Plant the faster resource of exhausted speed.Content of the sodium in the earth's crust is 2.64%, is 400 times of lithium, and by contrast, sodium resource compares lithium
It is resourceful many, this also imply that sodium-ion battery cost will be lower than lithium ion battery it is many.In current market
Under situation, sodium in fixed energy storage field by many people think that have great prospect.At the same time the congeners potassium of lithium sodium also by
Gradually it is of concern.It not only possesses the reserves similar to sodium, possesses the electrode potential similar with lithium, and also with lithium ion one
Sample can carry out deintercalation in graphite cathode.
Most preferably the iron cyanide is serial for current sodium-ion battery positive material performance.The unique framework knot of iron cyanogen compound
Structure is conducive to the deintercalation of potassium ion, is the essential element for constituting framework additionally, due to carbon nitrification key, moreover it is possible to improve the energy of material
Metric density, reduces the loss of magnesium-yttrium-transition metal, therefore ferrocyanide kalium ion battery material grinds into current kalium ion battery
The hot topic studied carefully, is expected to turn into the battery material of a new generation.
As a kind of new kalium ion battery positive electrode, KTiFe (CN)6Its theoretical capacity be 134 mAh/g, with compared with
The cycle performance of big potassium ion migrating channels, the operating voltage with 3.6V and 1.8V, and stabilization, with studying and open
The value of hair.
The content of the invention
In view of this, an object of the present invention is to provide one kind to prepare KTiFe (CN)6The method of positive electrode, should
Method is easy to operate, cycle is short, low cost；The second purpose is to provide using KTiFe (CN) obtained in methods described6Positive pole material
Material has the advantages that unique bouquet structure, pattern be homogeneous, chemical property is good；The third purpose is to provide KTiFe (CN)6Just
Application of the pole material in terms of kalium ion battery.To achieve the above object, the present invention specifically provides following technical scheme.
1. KTiFe(CN)6The preparation method of positive electrode, coprecipitation is passed sequentially through successively by potassium by coprecipitation
Salt, ferrocyanide salt, dissolve in water stirring and be obtained precursor solution, then by titanium salt it is soluble in water and it is slow be at the uniform velocity added drop-wise to before
In driving liquid solution, and with being stirred vigorously until completion of dropping, then still aging two hours, last suction filtration cleaning, 60 take the photograph
Family name's degree one night of vacuum drying obtains KTiFe (CN)6Precipitation；Ferrous cyanide ion, titanium ion in the ferrocyanide salt and titanium salt
Mol ratio be 0.5 ~ 1；Total potassium concentration is 1.5M ~ 2M in the solution.The method is comprised the following steps：
1）Coprecipitation prepares KTiFe (CN)6：By ferrocyanide and sylvite it is soluble in water molar concentration 0.03M ~ 0.15M
A liquid；Titanium salt is soluble in water that molar concentration is the B liquid of 0.06M ~ 0.12M；It is B liquid is slow and be at the uniform velocity added drop-wise to middle A liquid,
And stir, obtain C liquid；The mol ratio of ferrous cyanide ion, titanium ion in the ferrocyanide salt and titanium salt is 0.5 ~ 1；It is described
Total potassium concentration is 1.5M ~ 2M in solution；
2）C liquid still aging two hours are obtained into KTiFe (CN)6；Suction filtration is simultaneously cleaned three to four times, last 60 degrees Celsius with H2O
Vacuum drying obtains yellow green KTiFe (CN)6Powder；
Further, in the ferrocyanide salt and titanium salt ferrous cyanide ion, the mol ratio of titanium ion are 0.5 ~ 1；It is described molten
Total potassium concentration is 1.5M ~ 2M in liquid.
Further, the potassium resource is potassium chloride, potassium carbonate, saleratus, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, hydroxide
One or more in potassium.
Further, the source of iron is that the source of iron is one or more in potassium ferrocyanide or sodium ferrocyanide.
Further, the titanium source is titanium trichloride.
2. using KTiFe (CN) obtained in the method6Positive electrode.
3. KTiFe(CN)6Application of the positive electrode in terms of kalium ion battery.
The beneficial effects of the present invention are：The present invention utilizes Co deposited synthesis new KTiFe (CN)6Positive pole material
Material, by mineralizer potassium resource, ferrous cyanogen root source, titanium source is obtained by coprecipitation and formed.The preparation method is simple, quick, cost
It is low, KTiFe (CN)6As kalium ion battery positive electrode, with excellent capacity and good cycle performance.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below：
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1.
Fig. 2 is the thing phase XRD of embodiment 1.
Fig. 3 is the CV curves of embodiment 2.
Fig. 4 is the constant current charge-discharge curve of embodiment 2.
Fig. 5 is the cyclic curve figure of embodiment 2.
Fig. 6 is the high rate performance figure of embodiment 2.
Specific embodiment
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.It is unreceipted specific in embodiment
The experimental technique of condition, generally according to normal condition or according to the condition proposed by manufacturer.
Embodiment 1, KTiFe (CN)6The preparation synthesis of positive electrode
Weigh the hydration potassium ferrocyanides of 3mmol tri- and 17.8g potassium chloride is dissolved in 100ml deionized waters, obtain A liquid；Weigh
6mmol titanium trichlorides obtain B liquid in being dissolved in 50ml deionized waters；A liquid is slow and uniform dropwise addition enters in B liquid, and with acutely stirring
Mix until completion of dropping obtains C liquid, then suction filtration after C liquid still aging two hours, and clean three to four times with deionized water, most
Afterwards 60 degrees Celsius of one nights of vacuum drying, obtain yellow green KTiFe (CN)6Powder.Products therefrom pattern is as shown in figure 1, sample topography
It is homogeneous, flower ball-shaped is presented, it is made up of the sheet of Nano grade.The thing phase XRD of product is as shown in Figure 2.As shown in Figure 2, it is made
The sample for obtaining is consistent with pertinent literature card peak position and without miscellaneous peak, illustrates successfully be prepared by this kind of method
KTiFe(CN)6Positive electrode, and the pure free from admixture of the material synthesized by this kind of method.
Embodiment 2, KTiFe (CN)6Application and its electrochemical property test of the positive electrode in kalium ion battery
KTiFe (CN) obtained in Example 16Positive electrode is with acetylene black and PVDF binding agents according to 7:2:1 ratio mixing,
Take appropriate 1-Methyl-2-Pyrrolidone（NMP）As solvent, ground 20 minutes in agate mortar, obtain blackish green sticky
Anode sizing agent.Take anode sizing agent to be uniformly coated on aluminium foil, be cut into aluminium foil directly with tablet press machine then by 30 DEG C of drying 24h
Footpath is the circle of 19mm, obtains final product positive plate；The positive plate that will be made is transferred in glove box the assembling for carrying out button cell, uses
Button cell model be CR2032, barrier film model Celgard 2400, electrolyte for 0.8M KPF6Solution（Solvent is carbon
Vinyl acetate and dimethyl carbonate by volume 1:The mixed liquor of 1 composition）, negative pole is metallic potassium piece.After assembling is finished, by battery
Glove box is removed, the test of chemical property is carried out under normal temperature after standing 24h in Land test systems, test voltage scope is
1~4V.Gained constant current charge-discharge curve such as Fig. 4 shows that gained cyclic curve such as Fig. 5 shows, gained high rate performance such as Fig. 6 shows.
As can be seen from Figure 4：The material is in 50 mAh g-1The lower capacity of current density close to 100 mAh g-1, it is made
The KTiFe (CN) for obtaining6Positive electrode has two charge and discharge platforms, and one is that, in 3.8V or so, one is in 1.8V or so.For
The material voltage platform is substantially and gentle for kalium ion battery, there is commercialized value.
As can be seen from Figure 5：The material is in 50 mAh g-1Current density under by 130 circle circulations after material
Still can not decay, illustrate the KTiFe (CN) synthesized by the method6Positive electrode cycle performance is good.
As can be seen from Figure 6：Even if the material circulation performance remains unchanged steadily when charging and discharging currents change, this is illustrated
The high rate performance of material is good, and in 300mAhg-1Current density under still possess capacity；And different current densities
After circulation, remain to reply, the material remains unchanged and possesses good invertibity.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment to be described in detail the present invention, it is to be understood by those skilled in the art that can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (8)
1.KTiFe(CN)6The preparation method of positive electrode, it is characterised in that by coprecipitation successively by sylvite, ferrocyanide
Salt, dissolve stirring in water precursor solution is obtained, then it is titanium salt is soluble in water and be slowly at the uniform velocity added drop-wise in precursor solution,
And suction filtration and cleaned three to four times with H2O with being stirred vigorously until completion of dropping, after then standing two hours, last 60 take the photograph
Family name's degree vacuum drying obtains yellow green KTiFe (CN)6Powder；Ferrous cyanide ion, titanium in the ferrocyanide salt and titanium salt
The mol ratio of ion is 0.5 ~ 1；Total potassium concentration is 1.5M ~ 2M in the solution.
2. KTiFe (CN) according to claim 16 The preparation method of positive electrode, it is characterised in that including following step
Suddenly：
Coprecipitation prepares KTiFe (CN)6：By ferrocyanide and the sylvite A for obtaining molar concentration 0.03M ~ 0.15M soluble in water
Liquid；Titanium salt is soluble in water that molar concentration is the B liquid of 0.06M ~ 0.12M；It is B liquid is slow and be at the uniform velocity added drop-wise to middle A liquid, and stir
Mix, obtain C liquid；
2）C liquid still aging two hours are obtained into KTiFe (CN)6；Suction filtration is simultaneously cleaned three to four times with H2O, and last 60 degrees Celsius true
Sky drying obtains yellow green KTiFe (CN)6Powder；Ferrous cyanide ion, titanium ion in the ferrocyanide salt and titanium salt
Mol ratio is 0.5 ~ 1；Total potassium concentration is 1.5M ~ 2M in the solution.
3. KTiFe (CN) according to claim 16The preparation method of positive electrode, it is characterised in that the ferrocyanide
The mol ratio of ferrous cyanide ion, titanium ion in salt and titanium salt is 0.5 ~ 1；Total potassium concentration is 1.5M in the solution
~2M。
4. KTiFe (CN) according to claim 16The preparation method of positive electrode, it is characterised in that：The potassium resource is chlorine
Change one or more in potassium, potassium carbonate, saleratus, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium hydroxide.
5. KTiFe (CN) according to claim 16The preparation method of positive electrode, it is characterised in that：The ferrous cyanogen source
It is one or more in potassium ferrocyanide or sodium ferrocyanide.
6. KTiFe (CN) according to claim 16The preparation method of positive electrode, it is characterised in that：The titanium source is three
Titanium chloride.
7. using KTiFe (CN) obtained in claim 1 to 6 any one methods described6Positive electrode.
8. KTiFe (CN) described in claim 76Application of the positive electrode in terms of kalium ion battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107369846A (en) * | 2017-07-14 | 2017-11-21 | 北京理工大学 | Electrode slice and preparation method thereof and aluminium ion battery |
| CN109437240A (en) * | 2018-10-22 | 2019-03-08 | 清华大学深圳研究生院 | A kind of preparation method of kalium ion battery high potential positive electrode |
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| CN105789690A (en) * | 2014-12-23 | 2016-07-20 | 宁德时代新能源科技股份有限公司 | Rechargeable magnesium battery and preparation method thereof |
| CN105990567A (en) * | 2015-02-09 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | Preparation method of prussian blue analogue nano-material and use of prussian blue analogue in sodium-ion battery |
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2017
- 2017-04-11 CN CN201710231793.1A patent/CN106920922A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789690A (en) * | 2014-12-23 | 2016-07-20 | 宁德时代新能源科技股份有限公司 | Rechargeable magnesium battery and preparation method thereof |
| CN105990567A (en) * | 2015-02-09 | 2016-10-05 | 中国科学院宁波材料技术与工程研究所 | Preparation method of prussian blue analogue nano-material and use of prussian blue analogue in sodium-ion battery |
Non-Patent Citations (1)
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| J.N.GAUR: ""Ferrocyanide Complex of Titanium(III)"", 《ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107369846A (en) * | 2017-07-14 | 2017-11-21 | 北京理工大学 | Electrode slice and preparation method thereof and aluminium ion battery |
| CN107369846B (en) * | 2017-07-14 | 2020-10-27 | 北京理工大学 | Electrode plate, preparation method thereof and aluminum ion battery |
| CN109437240A (en) * | 2018-10-22 | 2019-03-08 | 清华大学深圳研究生院 | A kind of preparation method of kalium ion battery high potential positive electrode |
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Application publication date: 20170704 |