CN107093731A - Many vanadium oxygen cluster compounds and its preparation method and application, and the lithium ion battery comprising it - Google Patents
Many vanadium oxygen cluster compounds and its preparation method and application, and the lithium ion battery comprising it Download PDFInfo
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- CN107093731A CN107093731A CN201710324146.5A CN201710324146A CN107093731A CN 107093731 A CN107093731 A CN 107093731A CN 201710324146 A CN201710324146 A CN 201710324146A CN 107093731 A CN107093731 A CN 107093731A
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- H—ELECTRICITY
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- 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
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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The invention provides many vanadium oxygen cluster compounds and its preparation method and application, and the lithium ion battery comprising it.Many vanadium oxygen cluster compound Stability Analysis of Structures provided by the present invention, there is higher capacity and fast charging and discharging performance simultaneously, and can be applied to as negative material in lithium ion battery, further obtained lithium ion battery equally also has excellent theoretical capacity and preferable cycle performance.In the inventive method, many vanadium oxygen cluster compounds, many vanadium oxygen cluster compound Stability Analysis of Structures convenient with preparation method, simple to operate and obtained, the features such as electric property is excellent are prepared by raw material mixing and solvent-thermal method.
Description
Technical field
The present invention relates to field of lithium ion battery material, in particular to many vanadium oxygen cluster compounds and preparation method thereof
And application, and the lithium ion battery comprising it.
Background technology
The energy and environment be the mankind enter faced in century two it is most severe the problem of, tap a new source of energy with it is renewable clear
The clean energy is also most one of technical field of decisive influence in World Economics.It is small-sized with the development of microelectric technique
Change equipment is increasing, and high performance electrochmical power source enters the large-scale application stage.
Lithium ion battery is ideal chargeable chemical cell in the world at present, compared to traditional nickel-cadmium cell or
For person's Ni-MH battery, lithium ion battery has that voltage is high, capacity is big, the low advantage of self-discharge rate.Due to its properties more
To be outstanding, lithium ion battery is also widely used in communication and automotive field at present, and promoting the use of for electric automobile also makes
The demand for obtaining lithium ion battery increasingly increases.
The performance that the performance of lithium ion battery depends primarily on electrode material is good and bad.To the electrode material in lithium ion battery
Basic demand mainly include it is following some：With high reversible capacity, good Structural flexibility and stability, quick lithium
Ion diffusion rates, long cycle life, preferable security, production cost is low and environmentally friendly.In commercial Li-ion electricity
Chi Zhong, positive pole is mainly such as LiCoO of material containing Li with higher oxygen reduction potential2, LiMn2O4, and developed make in recent years
LiFePO4.And graphite is the most frequently used business negative material because graphite has production cost low, operating voltage it is low and
Steadily, and the advantages of long lifespan.But, the composition of the lithium intercalation compound of Li ions insertion graphite generation is generally LiC6, this
The lithium carbide of stoichiometric proportion corresponds to less theoretical capacity (372mAhg-1) and less actual energy density.Meanwhile, Li
Transmission rate of the ion in graphite electrode is typically smaller than 10-6cm2s-1, and the electrochemistry diffusion coefficient of Li ions and battery
Power density is closely related, so the battery constituted using graphite as negative pole has relatively low power density.In order to improve lithium ion
The energy and power density of battery, it is to have very much to develop the negative material with larger capacity and higher li ion transmission speed
Necessary
Polyacid, also referred to as polyoxometallate (Polyoxometalates is abbreviated as POMs), be in skeleton structure by
One metalloid that transition elements is constructed before Mo, W, V, Nb and Ta etc.-oxygen cluster (Metal-Oxygen Clusters) compound.By
The various excellent properties showed in polyacid, such as fluorescence, catalytic activity and single molecular magnetses etc., POMs has drawn
The very big concern of people is played.In terms of the visual angle of structure and electronics, their molecular structure may be considered the gold of nano-scale
Belong to oxide, they are also the molecule base cluster compound of most species.In recent years, POMs is because of its unique structure and excellent electricity more
Sub- redox characteristic and studied as lithium ion cell positive or negative material.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of many vanadium oxygen cluster compounds, many vanadium oxygen cluster chemical combination provided by the present invention
Thing Stability Analysis of Structures, while having higher capacity and fast charging and discharging performance, and can be further used as negative material and apply
In lithium ion battery.
The second object of the present invention is to provide a kind of preparation method of described many vanadium oxygen cluster compounds, the inventive method
In, many vanadium oxygen cluster compounds are prepared by raw material mixing and solvent-thermal method, it is convenient with preparation method, simple to operate and made
The many vanadium oxygen cluster compound Stability Analysis of Structures obtained, the features such as electric property is excellent.
Third object of the present invention is to provide a kind of application of many vanadium oxygen cluster compounds, many vanadium oxygen clusters of the invention
Compound has the excellent electric properties such as higher capacity and fast charging and discharging performance, it is thus possible to should in lithium ion battery
With.
Fourth object of the present invention is to provide a kind of lithium ion battery, its using many vanadium oxygen cluster compounds of the invention be negative
Pole material.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of many vanadium oxygen cluster compounds, the structural formula of many vanadium oxygen cluster compounds is as follows：[Mx(H2O)y]a[V15O36
(NO3)z]b·cH2O；
Wherein, M is metal ion；
Wherein, X=1~3, y=6~10, z=1~3；
Wherein, a=1~3, b=1~2, c=12~15.
Optionally, in the present invention, in many vanadium oxygen cluster compounds, M is alkali metal or alkaline earth metal cation；
It is preferred that, M is alkali metal cation.
Optionally, in the present invention, in many vanadium oxygen cluster compounds：X=2~3, y=8~10, z=1~2；
And/or, a=2~3, b=1, c=13~15.
Optionally, in the present invention, the structural formula of many vanadium oxygen cluster compounds is as follows：[M2(H2O)9]2[V15O36
(NO3)]·15H2O；
Wherein, M is alkali metal cation.
Meanwhile, present invention also offers the preparation method of many vanadium oxygen cluster compounds, methods described comprises the following steps：
Vanadate and sulphite are dissolved in the mixed solvent, and stirred, then, by gained mixed system in reactor
Middle heating response, then cold filtration, i.e. much vanadium oxygen cluster compounds.
Optionally, in the present invention, the vanadate is metavanadate, and the sulphite is that alkali metal or alkaline-earth metal are sub-
Sulfate.
Optionally, in the present invention, the mixed solvent is water and the mixed solution of alkali organic solvent.
Optionally, in the present invention, the heating response in a kettle. is specially：It is 150~200 DEG C of conditions in temperature
Under, react 12~36h.
Likewise, the application present invention also offers many vanadium oxygen cluster compounds in photoelectric material.
Further, present invention provides the lithium ion battery for including many vanadium oxygen cluster compounds of the present invention.
Compared with prior art, beneficial effects of the present invention are：
(1) many vanadium oxygen cluster compounds of the invention have the excellent electrical property such as higher capacity and fast charging and discharging performance
Can, and the negative material of lithium ion battery can be further used as use；Meanwhile, the lithium ion battery further prepared is equally
With excellent theoretical capacity and preferable cycle performance；
(2) preparation method of the present invention is convenient, simple to operate, and obtained many vanadium oxygen cluster compound Stability Analysis of Structures, electricity
The features such as excellent performance.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described.
Fig. 1 is provided the molecule mono-crystalline structures figure and packed structures figure of vanadium metal oxygen cluster compound by the embodiment of the present invention 1；
Figure is a) molecule mono-crystalline structures figure, and figure is b) packed structures figure
Fig. 2 is provided the powder diffraction data (XRD) and theoretical modeling of vanadium metal oxygen cluster compound by the embodiment of the present invention 1
It is worth comparison diagram；
Fig. 3 is that the embodiment of the present invention 1 is synthesized and technology path；
Fig. 4 by experimental example 1 of the present invention offer lithium ion battery cycle performance test chart.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, be
The conventional products that can be obtained by commercially available purchase.
Many vanadium oxygen cluster compounds provided by the present invention, are a kind of using 15 core vanadium metal oxygen clusters as core, and with anti-
The new vanadium oxygen cluster compound of counter cation and the crystallization water, its cellular construction molecular formula is specific as follows：[Mx(H2O)y]a[V15O36
(NO3)z]b·cH2O；
Wherein, in many vanadium oxygen cluster compounds, its central metal V has two kinds of valence states, and one kind is tetravalence vanadium, and one kind is pentavalent
Vanadium；
Wherein, M is metal ion；
It is preferred that, the metal ion is alkali metal or alkaline earth metal cation, for example, can be Li+、Na+、K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+, or Ba2+Deng metal cation；
It is furthermore preferred that the metal ion is alkali metal cation, for example can be Li+、Na+、K+、Rb+、Cs+Deng metal
Cation；
It is further preferred that the metal ion is Na+Or K+Ion；
Wherein, X=1~3, y=6~10, z=1~3；
It is preferred that, X, Y, Z are respectively 1~3,6~10, and 1~3 integer, for example：X can be 1,2, or 3；Y can
Think 6,7,8,9, or 10；Z can be 1,2, or 3；
Wherein, a=1~3, b=1~2, c=12~15；
It is preferred that, a, b, c are respectively 1~3,1~2 and 12~15 integer, for example：A can be 1,2, or 3；B can
Think 1 or 2；C can be 12,13,14, or 15,
Precondition is that the selection of each parameter ensure that the charge balance of compound.
It is further preferred that the structural formula of many vanadium oxygen cluster compounds provided by the present invention is as follows：[M2(H2O)9]2[V15O36
(NO3)]·15H2O；
Wherein, the M is alkali metal cation, for example, can be Li+、Na+、K+、Rb+、Cs+Deng alkali metal cation；
It is further preferred that the alkali metal ion is Na+Or K+Ion, i.e. M are Na or K；
Meanwhile, present invention preferably provides many vanadium oxygen cluster compounds in, its central metal V equally includes two kinds of valence states, one
It is tetravalence vanadium to plant, and one kind is pentavalent vanadium；
Thus, the principle based on charge balance, the structural formula of many vanadium oxygen cluster compounds provided by the present invention further should
This is as follows：[M2(H2O)9]2[VIV 6VV 9O36(NO3)]·15H2O。
The preparation method of many vanadium oxygen cluster compounds of the present invention comprises the following steps：Vanadate and sulphite are dissolved in mixed
In bonding solvent, and stir, then, by gained mixed system heating response in a kettle., then cold filtration, i.e. much vanadium oxygen
Cluster compound.
In preparation method of the present invention：
It is preferred that, the vanadate is metavanadate；
It is further preferred that the vanadate is ammonium metavanadate, potassium metavanadate, or sodium metavanadate etc.；
It is furthermore preferred that the vanadate is ammonium metavanadate.
It is preferred that, the sulphite is metal sulphite, and molecular formula is Mx(SO3)y；
It is further preferred that the sulphite is alkali metal or alkaline-earth metal sulfite；
It is furthermore preferred that the sulphite is alkali metal sulfite, for example can be lithium sulfite, sodium sulfite, Asia
Potassium sulfate, or sulfurous acid rubidium；
Most preferably, the sulphite is sodium sulfite or potassium sulfite.
Still more preferably, the mol ratio of raw material metavanadate and metal sulphite is (1~15) in the present invention：1,
It for example can be, but be not limited to 3:1、5:1、8:1、10:1, or 12:1 etc..
It is preferred that, the mixed solvent is water and the mixed solution of alkali organic solvent；
It is further preferred that the alkali organic solvent is fatty amine, aromatic amine or nitrogen heterocyclic, such as it is described
Basic solvent can be the amine compounds such as ethamine, propylamine, butylamine, ethylenediamine, triethylamine, or be aniline, phenylenediamine etc.
Aromatic amine, or be the nitrogen heterocyclics such as pyridine, substituted pyridines, imidazoles, substituted imidazole, pyrroles, substituted azole；
It is furthermore preferred that the alkali organic solvent be nitrogen heterocyclic, for example can be, but be not limited to pyridine, pyrroles,
Imidazoles, N- methylimidazoles, N- ethyl imidazol(e)s etc..
Still more preferably, the volume ratio of the alkaline organic solvent is (1~10)：(1~5)；For example can be,
But it is not limited to 2:1、3:1、5:1、7:1、7:2、8:3、8:5、1:2、2:5, or 3：4 etc..
It is preferred that, the temperature of the stirring is room temperature, and the time is 1~5h, such as can be 2,3 or 4h.
It is preferred that, the temperature heated in a kettle. is 150~200 DEG C, for example, can be, but be not limited to 160,
170th, 180, or 190 DEG C etc.；The time of heating is 12~36h, for example, can be, but be not limited to 18,24 or 32h etc..
It is preferred that, after many vanadium oxygen cluster compounds of product are filtrated to get, the step for drying product is still further comprised,
Dry temperature can be controlled at 120~180 DEG C, and the dry time can be 12~24h.
The preparation method of many vanadium oxygen cluster compounds of the present invention can be summarized as follows：
It is (1~15) by mol ratio：1 vanadate and sulphite is dissolved in volume ratio for (1~10)：The water of (1~5)
In the mixed solution of alkali organic solvent, and 1~5h is stirred at room temperature, then, by gained mixed system 150~200
12~36h of heating response in reactor under the conditions of DEG C, then cold filtration, i.e. much vanadium oxygen cluster compounds, then by product
12~24h is dried under the conditions of 120~180 DEG C.
Many vanadium oxygen cluster compounds provided by the present invention have polyelectron reduction reaction and quick lithium ion diffusion, because
And with higher capacity and fast charging and discharging performance, and functional material can be further used as and lithium ion battery etc. is applied to
Photoelectric device.
The negative material of lithium ion battery provided by the present invention is many vanadium oxygen cluster compounds of the invention, because the present invention is more
Vanadium oxygen cluster compound has excellent electric property, thus also causes lithium ion battery of the present invention to have high theoretical capacity and preferable
Cycle performance.
Embodiment 1
The ammonium metavanadate and 1 mM of anhydrous sodium sulfite of 10 mMs (mmol) are dissolved in 70 milliliters of water and 20 milliliters
The in the mixed solvent of N- ethyl imidazol(e)s, stirring at normal temperature 3 hours is then placed in 100 milliliters of reactors of body small in 180 DEG C of reactions 24
When, black crystals are filtrated to get, the crystal is shown as novel counter cation after being parsed through mono-crystalline structures be the 15 of sodium ion
Core vanadium metal oxygen cluster, its molecular formula is as follows：[Na2(H2O)9]2[VIV 6VV 9O36(NO3)]·15H2O。
The molecule mono-crystalline structures figure and packed structures figure of vanadium metal oxygen cluster are respectively such as Fig. 1 a) and Fig. 1 b) shown in, powder diffraction
Data (XRD) and theoretical modeling value comparison diagram are as shown in Figure 2；
Crystallographic data is as shown in table 1 below：
[the Na of table 12(H2O)9]2[VIV 6VV 9O36(NO3)]·15H2O crystallographic datas
Further, the vanadium oxygen cluster is dried into 12h in 120 DEG C of vacuum drying chambers, and is used as lithium ion battery negative material.
Embodiment 1 is synthesized and technology path is as shown in Figure 3.
Experimental example 1
Dried vanadium oxygen cluster is negative material using in embodiment 1, and with binding agent Kynoar, conductive agent acetylene black
In mass ratio 75:15:10 add in grinding container, and add 1-METHYLPYRROLIDONE and sized mixing as solvent, fully mill
It is even；Then, it is uniformly scratched on copper foil with scraper, then dries 12 hours, then cut in 100 DEG C of vacuum drying chamber
A diameter of 8mm disk is segmented into, cathode pole piece is made；
Simultaneously using lithium piece as polyethylene to electrode, is used for diaphragm material, 1mol/L lithium hexafluoro phosphate is used for electrolysis
Matter, using volume ratio 1:1:1 ethylene carbonate, methyl ethyl carbonate and diethyl carbonate is as electrolyte, the group in glove box
Dress up button-type lithium ion battery.
Then electro-chemical test is carried out to obtained lithium ion battery, with the performance of detecting electrode, specifically tests content
It is as follows with method：
Loop test：Button-type lithium battery is placed at room temperature and carries out electrochemical property test after 12 hours again：Circulation
Voltage range 0.01V-3V during performance test, current density is 100mA/g, and cycle-index is after 100 times, capacity is still up to
569mAh/g；In 300mA/g, circulation has reached 300 circles, and battery capacity still reaches 332mAh/g, and battery is at present still in circulation
In.The cycle performance test chart of lithium ion battery is as shown in Figure 4.
The many vanadium oxygen cluster compound Stability Analysis of Structures of the present invention simultaneously have higher capacity and good cyclical stability, Neng Goujin
One step is applied to as functional material in the devices such as lithium ion battery.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of many vanadium oxygen cluster compounds, it is characterised in that the structural formula of many vanadium oxygen cluster compounds is as follows：[Mx(H2O)y]a
[V15O36(NO3)z]b·cH2O；
Wherein, M is metal ion；
Wherein, X=1~3, y=6~10, z=1~3；
Wherein, a=1~3, b=1~2, c=12~15.
2. many vanadium oxygen cluster compounds according to claim 1, it is characterised in that in many vanadium oxygen cluster compounds, M is alkali
Metal or alkaline earth metal cation；
It is preferred that, M is alkali metal cation.
3. many vanadium oxygen cluster compounds according to claim 1, it is characterised in that in many vanadium oxygen cluster compounds：X=2
~3, y=8~10, z=1~2；
And/or, a=2~3, b=1, c=13~15.
4. many vanadium oxygen cluster compounds according to any one of claim 1-3, it is characterised in that many vanadium oxygen cluster chemical combination
The structural formula of thing is as follows：[M2(H2O)9]2[V15O36(NO3)]·15H2O；
Wherein, M is alkali metal cation.
5. the preparation method of many vanadium oxygen cluster compounds any one of claim 1-4, it is characterised in that methods described includes
Following steps：
Vanadate and sulphite are dissolved in the mixed solvent, and stirred, then, gained mixed system is added in a kettle.
Thermal response, then cold filtration, i.e. much vanadium oxygen cluster compounds.
6. preparation method according to claim 5, it is characterised in that the vanadate is metavanadate, the sulfurous acid
Salt is alkali metal or alkaline-earth metal sulfite.
7. preparation method according to claim 5, it is characterised in that the mixed solvent is water and alkali organic solvent
Mixed solution.
8. preparation method according to claim 5, it is characterised in that the heating response in a kettle. is specially：
Temperature be 150~200 DEG C under the conditions of, react 12~36h.
9. application of many vanadium oxygen cluster compounds in photoelectric material any one of claim 1-4.
10. include the lithium ion battery of many vanadium oxygen cluster compounds any one of claim 1-4.
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| CN109225333A (en) * | 2018-11-07 | 2019-01-18 | 聊城大学 | A kind of preparation method and its usage of three core nickel-vanadium oxygen cluster catalyst |
| CN113659288A (en) * | 2020-04-29 | 2021-11-16 | 北京小米移动软件有限公司 | Battery diaphragm and manufacturing method thereof, ion battery and terminal |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225333A (en) * | 2018-11-07 | 2019-01-18 | 聊城大学 | A kind of preparation method and its usage of three core nickel-vanadium oxygen cluster catalyst |
| CN109225333B (en) * | 2018-11-07 | 2021-05-25 | 聊城大学 | Preparation method and application of trinuclear nickel-vanadium oxygen cluster catalyst |
| CN113659288A (en) * | 2020-04-29 | 2021-11-16 | 北京小米移动软件有限公司 | Battery diaphragm and manufacturing method thereof, ion battery and terminal |
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| CN107093731B (en) | 2020-01-10 |
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