CN104795566A - Battery negative electrode active material based on quinone structure and preparation method and application thereof - Google Patents
Battery negative electrode active material based on quinone structure and preparation method and application thereof Download PDFInfo
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- CN104795566A CN104795566A CN201410245029.6A CN201410245029A CN104795566A CN 104795566 A CN104795566 A CN 104795566A CN 201410245029 A CN201410245029 A CN 201410245029A CN 104795566 A CN104795566 A CN 104795566A
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- quinones
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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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
-
- 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
- H01M4/137—Electrodes based on electro-active polymers
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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
- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
- H01M2220/00—Batteries for particular applications
- H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
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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 battery negative electrode active material based on a quinone structure, and a preparation method and an application of the battery negative electrode active material. The battery negative electrode active material comprises a quinone compound taking the quinone structure as an electrochemical oxidation-reduction reaction site, wherein the quinone compound comprises any one of a benzoquinone sodium salt derivate, an anthraquinone sodium salt derivate, or a naphthoquinone sodium salt derivate. The benzoquinone sodium salt derivate, the anthraquinone sodium salt derivate, or the naphthoquinone sodium salt derivate comprises at least one of the following groups of -ONa, -SO3Na, or -COONa.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of battery cathode active material based on quinones structure and its production and use.
Background technology
The new forms of energy such as solar energy, wind energy have the advantages such as renewable, environmental friendliness, but due to its unsteadiness, need through power conversion and storage device to improve reliability and utilance when being connected to the grid.Chemical power source is one of energy-storage system having application prospect most, and wherein lithium ion battery is because of its advantage such as high-energy-density and high voltage, has been widely used in portable type electronic product and electric automobile.But lithium resource reserves are limited and cost for purification is high, limit it and use on a large scale.
Sodium and lithium of the same clan, have similar chemical property, and a rich reserves, cost for purification is cheap.But sodium ion radius is comparatively large, in conventional inorganic electrode material, is comparatively difficult to realize reversible embedding/deviate from, causes it to there is reversible specific capacity low, the problem of cycle performance difference.At present, the research of anticathode material mainly concentrates on Carbon anode, alloy anode and minority oxide and phosphate negative pole etc.
In carbon negative pole material, the carbon-coating degree of disorder of hard carbon is maximum, storage sodium effect is best, specific capacity can 200-300mAh/g (J Electrochem Soc, 2001,148, A803), but because its storage sodium current potential is too low and high rate performance is poor, in quick charge or when overcharging, sodium may form dendrite at surface deposition, causes potential safety hazard; Alloy material is as tin, phosphorus and lead etc., although have higher storage sodium capacity, first all efficiency is lower, cycle performance difference (J Power Sources, 2013,225,316-322), this is mainly because the volume deformation of alloy in deintercalation sodium process is larger, cause structural deterioration, and then storage sodium performance is declined (Angew Chem, 2013 rapidly, 125,4731-4734); Na
2ti
3o
7deng poorly conductive, the storage sodium hypopotenia of oxide cathode material, first all coulombic efficiencies are low, and cyclical stability also has much room for improvement (AdvEnergy Mater, 2013,3,1186-1194); And with NaTi
2(PO
4)
3for although the phosphate negative material cyclical stability of representative is higher, its higher storage sodium current potential causes energy density to reduce (JElectrochem Soc, 2011,158, A1067-1070); Organic cathode material, take para-phthalic sodium as Typical Representative (Adv Energy Mater, 2012,2,962-965), there is specific capacity high, the advantage that cyclical stability is high, but lower owing to storing up sodium current potential, and electrolyte is in a large amount of reduction decomposition of electrode surface, cause first all efficiency to be only about 60%, be difficult to practical application.
Summary of the invention
Embodiments provide a kind of battery cathode active material based on quinones structure and its production and use, the battery cathode active material preparation method based on quinones structure is simple, can apply in the preparation of sodium ion secondary battery.The sodium ion secondary battery prepared based on the battery cathode active material of quinones structure utilizing the embodiment of the present invention to provide, has higher operating voltage and head week coulombic efficiency, stable circulation, security performance is good.
First aspect, embodiments provides a kind of battery cathode active material based on quinones structure, it is characterized in that, described battery cathode active material comprises with the quinones of quinones structure for electrochemical redox reaction site;
Wherein, described quinones comprises any one in benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative; Described benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative have following group-ONa ,-SO respectively
3at least one in Na or-COONa.
Preferably, the structure of described benzoquinones sodium salt derivative is as shown in general formula (I):
General formula (I)
Wherein, radicals R
1, R
2, R
3, R
4in at least one group be-ONa ,-SO
3one in Na or-COONa, all the other groups comprise-ONa ,-SO
3na ,-COONa ,-H ,-CH
3,-NH
2,-OCH
3, one or more in-Cl ,-Br or-F.
Preferably, the structure of described anthraquinone sodium salt derivative is as shown in general formula (II):
General formula (II)
Wherein, radicals R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8in at least one group be-ONa ,-SO
3one in Na or-COONa, all the other groups comprise-ONa ,-SO
3na ,-COONa ,-H ,-CH
3,-NH
2,-OCH
3, one or more in-Cl ,-Br or-F.
Preferably, the structure of described naphthoquinones sodium salt derivative is as shown in general formula (III):
General formula (III)
Wherein, radicals R
1, R
2, R
3, R
4, R
5, R
6in at least one group be-ONa ,-SO
3one in Na or-COONa, all the other groups comprise-ONa ,-SO
3na ,-COONa ,-H ,-CH
3,-NH
2,-OCH
3, one or more in-Cl ,-Br or-F.
Second aspect, embodiments provide a kind of preparation method of the battery cathode active material based on quinones structure, described method is aqua-solution method, comprising:
The NaOH of required stoichiometry 101wt% ~ 110wt% and required stoichiometric quinones are dissolved in deionized water in proportion, form mixed solution; Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones;
By described mixed solution evaporate to dryness in the air atmosphere of 100 DEG C;
After excessive sodium hydrate is removed in EtOH Sonicate cleaning, dry, grinding obtains powder;
Described powder is placed in vacuum drying oven, dries 8 hours, grind again afterwards, obtain described battery cathode active material for 100 DEG C.
The third aspect, embodiments provide a kind of preparation method of the battery cathode active material based on quinones structure, described method is spray drying process, comprising:
The NaOH of required stoichiometry 101wt% ~ 110wt% and required stoichiometric quinones are dissolved in deionized water in proportion, form mixed solution; Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones;
Described mixed solution is carried out spraying dry;
After excessive sodium hydrate is removed in EtOH Sonicate cleaning, dry, grinding obtains powder;
Described powder is placed in vacuum drying oven, dries 8 hours, grind again afterwards, obtain described battery cathode active material for 100 DEG C.
Preferably, describedly described mixed solution carried out spraying dry be specially:
Add the aqueous dispersion carbon nano-tube of 1wt% ~ 10wt% at described mixed solution, after ultrasonic 3-5 hour mixes, carry out spraying dry.
Fourth aspect, embodiments provide a kind of preparation method of the battery cathode active material based on quinones structure, it is characterized in that, described method is organic solvent method, comprising:
Be dissolved in ethanolic solution by ultrasonic for the NaOH of required stoichiometry 101wt% ~ 110wt%, obtain the first solution;
Required stoichiometric quinones is dissolved in organic solvent in proportion, obtains the second solution; Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones; Described organic solvent comprises dimethyl sulfoxide (DMSO) or dimethyl formamide;
Under room temperature, described first solution is added in described second solution with certain speed, and carries out magnetic agitation simultaneously, generate sediment;
Centrifugal process is adopted to be separated described sediment;
After EtOH Sonicate cleaning is carried out to isolated sediment, dry at 50 DEG C and obtain powder;
Described powder is placed in vacuum drying oven, dries 8 hours, grind again afterwards, obtain described battery cathode active material for 100 DEG C.
5th aspect, embodiments provide a kind of preparation method of the battery cathode active material based on quinones structure, it is characterized in that, described method is Ethanol Method, comprising:
Be dissolved in ethanolic solution by ultrasonic for the NaOH of required stoichiometry 101wt% ~ 110wt%, obtain the first solution;
Required stoichiometric quinones is added in described first solution; Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones;
Stirred at ambient temperature, after 24 hours, adopts centrifugal process isolate sediment and dry;
Grinding is carried out to isolated sediment and obtains powder;
Described powder is placed in vacuum drying oven, dries 8 hours, grind again afterwards, obtain described battery cathode active material for 100 DEG C.
6th aspect, embodiments provides a kind of cathode pole piece of sodium ion secondary battery, comprising:
Collector, be coated on conductive additive on described collector and binding agent and the battery cathode active material based on quinones structure described in above-mentioned first aspect.
7th aspect, embodiments provides a kind of sodium ion secondary battery comprising the cathode pole piece of above-mentioned 6th aspect.
Eighth aspect, embodiments provide the purposes of the sodium ion secondary battery described in a kind of above-mentioned 7th aspect, described sodium ion secondary battery is used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
Embodiments provide a kind of battery cathode active material based on quinones structure and its production and use, the battery cathode active material preparation method based on quinones structure is simple, can apply in the preparation of sodium ion secondary battery.The sodium ion secondary battery prepared based on the battery cathode active material of quinones structure utilizing the embodiment of the present invention to provide, has higher operating voltage and head week coulombic efficiency, stable circulation, security performance is good.
Accompanying drawing explanation
Below by drawings and Examples, the technical scheme of the embodiment of the present invention is described in further detail.
The aqua-solution method preparation that Fig. 1 provides for the embodiment of the present invention 2 is based on preparation method's flow chart of the battery cathode active material of quinones structure;
The spray drying process preparation that Fig. 2 provides for the embodiment of the present invention 3 is based on preparation method's flow chart of the battery cathode active material of quinones structure;
The organic solvent method preparation that Fig. 3 provides for the embodiment of the present invention 4 is based on preparation method's flow chart of the battery cathode active material of quinones structure;
The Ethanol Method preparation that Fig. 4 provides for the embodiment of the present invention 5 is based on preparation method's flow chart of the battery cathode active material of quinones structure;
The active material Na that Fig. 5 provides for the embodiment of the present invention 6
2c
6h
2o
4xRD collection of illustrative plates;
The active material Na that Fig. 6 provides for the embodiment of the present invention 6
2c
6h
2o
4sEM figure;
The charging and discharging curve figure of the sodium-ion battery that Fig. 7 provides for the embodiment of the present invention 6;
The active material NaC that Fig. 8 provides for the embodiment of the present invention
10h
6o
3and Na
2c
14h
6o
4xRD collection of illustrative plates;
The active material NaC that Fig. 9 provides for the embodiment of the present invention 7
10h
6o
3sEM figure;
The charging and discharging curve figure of the sodium-ion battery that Figure 10 provides for the embodiment of the present invention 7;
The Na that Figure 11 provides for the embodiment of the present invention 8
2c
14h
6o
4sEM figure;
The charging and discharging curve figure of the sodium-ion battery that Figure 12 provides for the embodiment of the present invention 8;
The charging and discharging curve figure of the sodium-ion battery that Figure 13 provides for the embodiment of the present invention 9;
The charging and discharging curve figure of the sodium-ion battery that Figure 14 provides for the embodiment of the present invention 10.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, should be understood to these embodiments and be only used for specifically describing more in detail, but be not intended to limit the scope of the invention.
Embodiment 1
The embodiment of the present invention 1 provides a kind of cell negative electrode material based on quinones structure, comprises with the quinones of quinones structure for electrochemical redox reaction site;
Wherein, quinones comprises any one in benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative; Benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative have following group-ONa ,-SO respectively
3at least one in Na or-COONa.
Concrete, the structure of benzoquinones sodium salt derivative is as shown in general formula (I):
General formula (I)
Wherein, radicals R
1, R
2, R
3, R
4in at least one group be-ONa ,-SO
3one in Na or-COONa, all the other groups comprise-ONa ,-SO
3na ,-COONa ,-H ,-CH
3,-NH
2,-OCH
3, one or more in-Cl ,-Br or-F.
The structure of anthraquinone sodium salt derivative is as shown in general formula (II):
General formula (II)
Wherein, radicals R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8in at least one group be-ONa ,-SO
3one in Na or-COONa, all the other groups comprise-ONa ,-SO
3na ,-COONa ,-H ,-CH
3,-NH
2,-OCH
3, one or more in-Cl ,-Br or-F.
The structure of naphthoquinones sodium salt derivative is as shown in general formula (III):
General formula (III)
Wherein, radicals R
1, R
2, R
3, R
4, R
5, R
6in at least one group be-ONa ,-SO
3one in Na or-COONa, all the other groups comprise-ONa ,-SO
3na ,-COONa ,-H ,-CH
3,-NH
2,-OCH
3, one or more in-Cl ,-Br or-F.
The quinones provided in the above embodiment of the present invention can as battery cathode active material, and preparation method is simple, can apply in the preparation of sodium ion secondary battery.Apply the sodium ion secondary battery prepared based on the battery cathode active material of quinones structure of the present invention, there is higher operating voltage and head week coulombic efficiency, stable circulation, security performance are good.
Embodiment 2
Present embodiments provide a kind of preparation method of the battery cathode active material based on quinones structure, be specially aqua-solution method, as shown in Figure 1, comprise:
Step 101, is dissolved in deionized water in proportion by the NaOH of required stoichiometry 101wt% ~ 110wt% and required stoichiometric quinones, forms mixed solution;
Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones.
Step 102, by described mixed solution evaporate to dryness in the air atmosphere of 100 DEG C;
Step 103, after excessive sodium hydrate is removed in EtOH Sonicate cleaning, dry, grinding obtains powder;
Step 104, is placed in vacuum drying oven by described powder, dries 8 hours, grinds afterwards again, obtain described battery cathode active material for 100 DEG C.
The aqua-solution method preparation that the present embodiment provides, based on the preparation method of the battery cathode active material of quinones structure, can be used in the battery cathode active material prepared described in above-described embodiment 1.The method that the present embodiment provides is simple, with low cost, be applicable to the application that can manufacture on a large scale.
Embodiment 3
Present embodiments provide a kind of preparation method of the battery cathode active material based on quinones structure, be specially spray drying process, as shown in Figure 2, comprise:
Step 201, is dissolved in deionized water in proportion by the NaOH of required stoichiometry 101wt% ~ 110wt% and required stoichiometric quinones, forms mixed solution;
Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones.
Step 202, carries out spraying dry by described mixed solution;
Step 203, after excessive sodium hydrate is removed in EtOH Sonicate cleaning, dry, grinding obtains powder;
Step 204, is placed in vacuum drying oven by described powder, dries 8 hours, grinds afterwards again, obtain described battery cathode active material for 100 DEG C.
The spray drying process preparation that the present embodiment provides, based on the preparation method of the battery cathode active material of quinones structure, can be used in the battery cathode active material prepared described in above-described embodiment 1.The method that the present embodiment provides is simple, with low cost, be applicable to the application that can manufacture on a large scale.
Embodiment 4
Present embodiments provide a kind of preparation method of the battery cathode active material based on quinones structure, be specially organic solvent method, as shown in Figure 3, comprise:
Step 301, is dissolved in ethanolic solution by ultrasonic for the NaOH of required stoichiometry 101wt% ~ 110wt%, obtains the first solution;
Step 302, is dissolved in required stoichiometric quinones in proportion in organic solvent, obtains the second solution;
Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones; Described organic solvent comprises dimethyl sulfoxide (DMSO) or dimethyl formamide;
Step 303, under room temperature, adds described first solution in described second solution with certain speed, and carries out magnetic agitation simultaneously, generates sediment;
Step 304, adopts centrifugal process to be separated described sediment;
Step 305, after carrying out EtOH Sonicate cleaning, dries and obtains powder isolated sediment at 50 DEG C;
Step 306, is placed in vacuum drying oven by described powder, dries 8 hours, grinds afterwards again, obtain described battery cathode active material for 100 DEG C.
The organic solvent method preparation that the present embodiment provides, based on the preparation method of the battery cathode active material of quinones structure, can be used in the battery cathode active material prepared described in above-described embodiment 1.The method that the present embodiment provides is simple, with low cost, be applicable to the application that can manufacture on a large scale.
Embodiment 5
Present embodiments provide a kind of preparation method of the battery cathode active material based on quinones structure, be specially Ethanol Method, as shown in Figure 4, comprise:
Step 401, is dissolved in ethanolic solution by ultrasonic for the NaOH of required stoichiometry 101wt% ~ 110wt%, obtains the first solution;
Step 402, adds required stoichiometric quinones in described first solution;
Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones;
Step 403, stirred at ambient temperature, after 24 hours, adopts centrifugal process isolate sediment and dry;
Step 404, carries out grinding to isolated sediment and obtains powder;
Step 405, is placed in vacuum drying oven by described powder, dries 8 hours, grinds afterwards again, obtain described battery cathode active material for 100 DEG C.
The Ethanol Method preparation that the present embodiment provides, based on the preparation method of the battery cathode active material of quinones structure, can be used in the battery cathode active material prepared described in above-described embodiment 1.The method that the present embodiment provides is simple, with low cost, be applicable to the application that can manufacture on a large scale.
The following method provided with any embodiment in the multiple instantiation application embodiment of the present invention 2 to embodiment 5 prepares the detailed process based on the cell negative electrode material of quinones structure, and is applied to method and the battery behavior of secondary cell.
Embodiment 6
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
The present embodiment adopts aforementioned organic solvents legal system for battery cathode active material, concrete steps are: by 2,5-dihydroxy-1,4-benzoquinones is dissolved in dimethyl sulfoxide (DMSO), separately be dissolved in ethanolic solution by ultrasonic for the NaOH of 105wt%, under room temperature magnetic agitation, ethanolic solution is added dropwise in dimethyl sulphoxide solution and is precipitated.Sediment centrifugal process is separated, and with EtOH Sonicate cleaning several, by gained powder at 100 DEG C, dries under vacuum condition, gained red-brown powder.Red-brown powder is for subsequent use after grinding, be active material Na of the present invention
2c
6h
2o
4, its structural formula is as follows:
Fig. 5 is shown in by its X-ray diffraction (XRD) collection of illustrative plates, and from XRD, the crystallinity of this active material is good.Fig. 6 is the SEM figure of this material, and as can be seen from the figure, particle size distribution is mainly from 50 to 100 nanometers.
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material Na prepared
2c
6h
2o
4powder mixes according to the mass ratio of 70:20:10 with acetylene black, binding agent Kynoar (PVDF), add appropriate 1-METHYLPYRROLIDONE (NMP) solution, in the environment of air drying, grinding forms slurry, then slurry is evenly coated in current collector aluminum foil, and dry under infrared baking lamp, be cut into 8 × 8mm
2pole piece.Under vacuum in 100 DEG C of dryings 10 hours, transfer to glove box immediately for subsequent use.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, with NaClO
4/ diethyl carbonate (EC:DEC) solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and be 0.9V when discharging by voltage, charge when voltage is 2V, test result is shown in Fig. 7.The charge and discharge cycles curve of first week and second week is shown in figure respectively.Found out by Fig. 7, its first all discharge capacity can reach 288mAh/g, and first all coulombic efficiencies are about 88.7%.
Embodiment 7
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
Adopt aqueous solution legal system for battery cathode active material in the present embodiment, concrete steps are: the 2-hydroxyl-1 weighing stoichiometric proportion, the NaOH of 4-naphthoquinones and 105wt% is dissolved in deionized water, evaporate to dryness at 100 DEG C, clean post-drying several times with EtOH Sonicate again, the reddish brown powder of gained is active material NaC of the present invention
10h
6o
3, its structural formula is as follows:
Fig. 8 a is shown in by its XRD collection of illustrative plates, and from XRD, the crystallinity of this active material is good.Fig. 9 is the SEM figure of this material, and as can be seen from the figure, its pattern is the elongated piece of ten a few to tens of microns.
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material Na prepared
2c
6h
2o
4powder mixes according to the mass ratio of 70:20:10 with Ketjen black (KB), polyfluortetraethylene of binding element (PTFE), makes the uniform sheet of thickness, then suppresses in collector aluminium online, and dry under infrared baking lamp, is cut into 8 × 8mm
2pole piece.Under 100 DEG C of vacuum conditions, drying 10 hours, transfers to glove box for subsequent use immediately.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, with NaPF
6/ EC:DEC: propene carbonate (PC) solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and test voltage scope is 1.5-3V, and test result is shown in Figure 10.First week is illustrated respectively and second week charging and discharging curve in figure.Found out by Figure 10, its first all charging capacity can reach 151mAh/g, and first all coulombic efficiencies are about 99%.
Embodiment 8
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
The present embodiment adopts aqueous solution method battery cathode active material, and concrete steps are with embodiment 7, and raw materials used is 2,6-dihydroxy anthraquinone.Gained powder is for subsequent use after grinding, is active material Na of the present invention
2c
14h
6o
4, its structural formula is as follows:
Fig. 8 b is shown in by its XRD collection of illustrative plates.Figure 11 is the SEM figure of this material, and as can be seen from the figure, particle size distribution is mainly from several microns to tens microns, and large particle is reunited by little rod-shpaed particle with forming.
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material Na prepared
2c
14h
6o
4powder mixes according to the mass ratio of 80:15:5 with carbon black Super P, binding agent PTFE, makes the uniform sheet of thickness, then suppresses in collector aluminium online, and dry under infrared baking lamp, is cut into 8 × 8mm
2pole piece.Under vacuum in 100 DEG C of dryings 10 hours, transfer to glove box immediately for subsequent use.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, with NaPF
6/ PC solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and test voltage scope is 0.9-3V, and test result is shown in Figure 12.Be respectively shown in figure first week and second week charging and discharging curve.Found out by Figure 12, its first all charging capacity can reach 185mAh/g, and first all coulombic efficiencies are about 81%.
Embodiment 9
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
The present embodiment adopts aforementioned spray drying process battery cathode active material, and concrete steps are: the weighing anthraquinone-1-sulfonic acid of stoichiometric proportion and the NaOH of 101wt% ~ 110wt% are dissolved in deionized water, add the aqueous dispersion carbon nano-tube of 10wt%.Ultrasonic mixing after 3 hours by mixed solution spraying dry at 120 DEG C.Gained powder is dried under vacuo at 100 DEG C, is active material NaC of the present invention
14h
7o
5s, its structural formula is as follows:
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material NaC prepared
14h
7o
5s powder mixes according to the mass ratio of 85:10:5 with acetylene black (AB), binding agent PVDF, add appropriate nmp solution, in the environment of air drying, grinding forms slurry, then slurry is evenly coated in current collector aluminum foil, and dry under infrared baking lamp, be cut into 8 × 8mm
2pole piece.Under 100 DEG C of vacuum conditions, drying 10 hours, transfers to glove box for subsequent use immediately.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, with NaClO
4/ EC:DMC solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and be 1V when discharging by voltage, charge when voltage is 3V, test result is shown in Figure 13.The charge and discharge cycles curve of first week and second week is shown in figure respectively.Found out by Figure 13, its first all discharge capacity can reach 144mAh/g, and first all coulombic efficiencies are about 82.3%.
Embodiment 10
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
Adopt aqua-solution method synthetic active substance in the present embodiment, raw material is 2-hydroxy-anthraquione, and method is with embodiment 7.The reddish brown powder of gained is active material NaC of the present invention
14h
7o
3, its structural formula is as follows:
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material NaC prepared
14h
7o
3powder mixes according to the mass ratio of 80:10:10 with acetylene black (AB), binding agent PTFE, makes the uniform sheet of thickness, is then compressed on stainless (steel) wire, and dry under infrared baking lamp, is cut into 8 × 8mm
2pole piece.Under 100 DEG C of vacuum conditions, drying 10 hours, transfers to glove box for subsequent use immediately.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, with NaClO
4/ PC solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and test voltage scope is 1-3V, and test result is shown in Figure 14.Found out by Figure 14, its first all discharge capacity can reach 189mAh/g, and first all coulombic efficiencies are about 88.7%.
Embodiment 11
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
The present embodiment adopts aforementioned spray drying process battery cathode active material, and concrete steps are with embodiment 9, and raw materials used is anthraquinone-2-sulfonic acid.Gained powder is for subsequent use after grinding, is active material NaC of the present invention
14h
7o
5s, its structural formula is as follows:
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material NaC prepared
14h
7o
5s powder mixes according to the mass ratio of 80:15:5 with Graphene, binding agent PTFE, makes the uniform sheet of thickness, then suppresses in collector aluminium online, and dry under infrared baking lamp, is cut into 8 × 8mm
2pole piece.Under 100 DEG C of vacuum conditions, drying 10 hours, transfers to glove box for subsequent use immediately.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, with NaPF
6/ EC:DEC solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and test voltage scope is 1-3V, and test result is in table 1.
Embodiment 12
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
Adopt aqueous solution method synthetic active substance in the present embodiment, raw material be 1,2-dihydroxy anthraquinone, method is with embodiment 6.Gained powder is active material Na of the present invention
2c
14h
6o
4, its structural formula is as follows:
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material Na prepared
2c
14h
6o
4powder mixes according to the mass ratio of 60:30:10 with Ketjen black (KB), binding agent sodium alginate, and in the environment of normal temperature, grinding forms slurry, then slurry is evenly coated on copper foil of affluxion body, and dry under infrared baking lamp, is cut into 8 × 8mm
2pole piece.Under 100 DEG C of vacuum conditions, drying 10 hours, transfers to glove box for subsequent use immediately.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, using NaFSI/PC solution as electrolyte, be assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and test voltage scope is 0.9-3V, and test result is in table 1.
Embodiment 13
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
Adopt aqueous solution method synthetic active substance in the present embodiment, concrete steps are: the tetrahydroxy quinone and the 105wt% NaOH that weigh required stoichiometric proportion are dissolved in deionized water.Add the aqueous dispersion carbon nano-tube of 5wt%.Ultrasonic mixing after 3 hours by mixed solution spraying dry at 150 DEG C.Gained powder is dried under vacuo at 100 DEG C, is active material Na of the present invention
4c
6h
2o
4, its structural formula is as follows:
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material Na prepared
2c
6h
2o
4powder mixes according to the mass ratio of 80:10:10 with Ketjen black (KB), binding agent PTFE, makes the uniform sheet of thickness, then suppresses in collector aluminium online, and dry under infrared baking lamp, is cut into 8 × 8mm
2pole piece.Under vacuum in 100 DEG C of dryings 10 hours, transfer to glove box immediately for subsequent use.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, with NaPF
6/ EC:DMC solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and test voltage scope is 0.8-3V, and test result is in table 1.
Embodiment 14
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
Adopt aqueous solution method synthetic active substance in the present embodiment, raw material be 5,8-dihydroxy naphthoquinones, method is with embodiment 13.Gained powder is active material Na of the present invention
2c
10h
4o
4, its structural formula is as follows:
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material Na prepared
2c
10h
4o
4powder mixes according to the mass ratio of 75:15:10 with acetylene black, binding agent sodium carboxymethylcellulose (CMC), in the environment of normal temperature, grinding forms slurry, then slurry is evenly coated in current collector aluminum foil, and dry under infrared baking lamp, be cut into 8 × 8mm
2pole piece.Under vacuum in 100 DEG C of dryings 10 hours, transfer to glove box immediately for subsequent use.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, with NaClO
4/ EC:DMC:PC solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and test voltage scope is 0.8-3V, and test result is in table 1.
Embodiment 15
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
Adopt aqueous solution method synthetic active substance in the present embodiment, raw material be 1,4-dihydroxy anthraquinone, method is with embodiment 7.Gained powder is active material Na of the present invention
2c
14h
6o
4, its structural formula is as follows:
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material Na prepared
2c
14h
6o
4powder mixes according to the mass ratio of 50:40:10 with Super P, binding agent PVDF, and in the environment of air drying, grinding forms slurry, then slurry is evenly coated on copper foil of affluxion body, and dry under infrared baking lamp, is cut into 8 × 8mm
2pole piece.Under 100 DEG C of vacuum conditions, drying 10 hours, transfers to glove box for subsequent use immediately.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, with NaClO
4/ EC:DEC:PC solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and test voltage scope is 0.9-3V, and test result is in table 1.
Embodiment 16
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
Adopt aqueous solution method synthetic active substance in the present embodiment, raw material is 2,5-bis-is chloro-3,6-dihydroxy benzoquinones, method is with embodiment 7.Gained powder is active material Na of the present invention
2c
6cl
2o
4, its structural formula is as follows:
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material Na prepared
2c
6cl
2o
4powder mixes according to the mass ratio of 80:10:10 with Ketjen black (KB), binding agent butadiene-styrene rubber (SBR), and grinding forms uniform sizing material, then slurry is evenly coated on copper foil of affluxion body, and dry under infrared baking lamp, is cut into 8 × 8mm
2pole piece.Under 100 DEG C of vacuum conditions, drying 10 hours, transfers to glove box for subsequent use immediately.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, with NaPF
6/ PC solution, as electrolyte, is assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and test voltage scope is 0.9-3V, and test result is in table 1.
Embodiment 17
The present embodiment is for illustration of the preparation of battery cathode active material of the present invention and application thereof.
Adopt aqueous solution method synthetic active substance in the present embodiment, raw material be 1,8-dihydroxy anthraquinone, method is with embodiment 13.Gained powder is active material Na of the present invention
2c
14h
6o
4, its structural formula is as follows:
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concrete steps are: by the active material Na prepared
2c
14h
6o
4powder mixes according to the mass ratio of 80:15:5 with Super P, binding agent CMC, and in the environment of normal temperature, grinding forms slurry, then slurry is evenly coated on copper foil of affluxion body, and dry under infrared baking lamp, is cut into 8 × 8mm
2pole piece.Under 100 DEG C of vacuum conditions, drying 10 hours, transfers to glove box for subsequent use immediately.Carry out in the glove box being assemblied in Ar atmosphere of simulated battery, using sodium metal as to electrode, using NaFSI/PC solution as electrolyte, be assembled into CR2032 button cell.Use constant current charge-discharge pattern to carry out charge-discharge test, all tests are all carried out under C/10 current density, and test voltage scope is 0.9-3V, and test result is in table 1.
Table 1
Can find out, in the above embodiment of the present invention, apply sodium ion secondary battery prepared by battery cathode active material, there is higher operating voltage and head week coulombic efficiency, stable circulation, security performance are good.
The sodium ion secondary battery adopting method provided by the invention to prepare, may be used for the extensive energy storage devices such as solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
It should be noted that, although present invention has been description to a certain degree, significantly, under the condition not departing from the spirit and scope of the present invention, can carry out the suitable change of each condition.Can be understood as and the invention is not restricted to described embodiment, and be attributed to the scope of claim, it comprises the equivalent replacement of described each factor.
Above-described embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only the specific embodiment of the present invention; the protection range be not intended to limit the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. based on a battery cathode active material for quinones structure, it is characterized in that, described battery cathode active material comprises with the quinones of quinones structure for electrochemical redox reaction site;
Wherein, described quinones comprises any one in benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative; Described benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative have following group-ONa ,-SO respectively
3at least one in Na or-COONa.
2. battery cathode active material according to claim 1, is characterized in that, the structure of described benzoquinones sodium salt derivative is as shown in general formula (I):
General formula (I)
Wherein, radicals R
1, R
2, R
3, R
4in at least one group be-ONa ,-SO
3one in Na or-COONa, all the other groups comprise-ONa ,-SO
3na ,-COONa ,-H ,-CH
3,-NH
2,-OCH
3, one or more in-Cl ,-Br or-F.
3. battery cathode active material according to claim 1, is characterized in that, the structure of described anthraquinone sodium salt derivative is as shown in general formula (II):
General formula (II)
Wherein, radicals R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8in at least one group be-ONa ,-SO
3one in Na or-COONa, all the other groups comprise-ONa ,-SO
3na ,-COONa ,-H ,-CH
3,-NH
2,-OCH
3, one or more in-Cl ,-Br or-F.
4. battery cathode active material according to claim 1, is characterized in that, the structure of described naphthoquinones sodium salt derivative is as shown in general formula (III):
General formula (III)
Wherein, radicals R
1, R
2, R
3, R
4, R
5, R
6in at least one group be-ONa ,-SO
3one in Na or-COONa, all the other groups comprise-ONa ,-SO
3na ,-COONa ,-H ,-CH
3,-NH
2,-OCH
3, one or more in-Cl ,-Br or-F.
5. a preparation method for the battery cathode active material based on quinones structure as described in claim as arbitrary in the claims 1-4, it is characterized in that, described method is aqua-solution method, comprising:
The NaOH of required stoichiometry 101wt% ~ 110wt% and required stoichiometric quinones are dissolved in deionized water in proportion, form mixed solution; Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones;
By described mixed solution evaporate to dryness in the air atmosphere of 100 DEG C;
After excessive sodium hydrate is removed in EtOH Sonicate cleaning, dry, grinding obtains powder;
Described powder is placed in vacuum drying oven, dries 8 hours, grind again afterwards, obtain described battery cathode active material for 100 DEG C.
6. a preparation method for the battery cathode active material based on quinones structure as described in claim as arbitrary in the claims 1-4, it is characterized in that, described method is spray drying process, comprising:
The NaOH of required stoichiometry 101wt% ~ 110wt% and required stoichiometric quinones are dissolved in deionized water in proportion, form mixed solution; Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones;
Described mixed solution is carried out spraying dry;
After excessive sodium hydrate is removed in EtOH Sonicate cleaning, dry, grinding obtains powder;
Described powder is placed in vacuum drying oven, dries 8 hours, grind again afterwards, obtain described battery cathode active material for 100 DEG C.
7. preparation method according to claim 6, is characterized in that, describedly described mixed solution is carried out spraying dry is specially:
Add aqueous dispersion carbon nano-tube or the Graphene of 1wt% ~ 10wt% at described mixed solution, after within ultrasonic 3 ~ 5 hours, mixing, carry out spraying dry.
8. a preparation method for the battery cathode active material based on quinones structure as described in claim as arbitrary in the claims 1-4, it is characterized in that, described method is organic solvent method, comprising:
Be dissolved in ethanolic solution by ultrasonic for the NaOH of required stoichiometry 101wt% ~ 110wt%, obtain the first solution;
Required stoichiometric quinones is dissolved in organic solvent in proportion, obtains the second solution; Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones; Described organic solvent comprises dimethyl sulfoxide (DMSO) or dimethyl formamide;
Under room temperature, described first solution is added in described second solution with certain speed, and carries out magnetic agitation simultaneously, generate sediment;
Centrifugal process is adopted to be separated described sediment;
After EtOH Sonicate cleaning is carried out to isolated sediment, dry at 50 DEG C and obtain powder;
Described powder is placed in vacuum drying oven, dries 8 hours, grind again afterwards, obtain described battery cathode active material for 100 DEG C.
9. a preparation method for the battery cathode active material based on quinones structure as described in claim as arbitrary in the claims 1-4, it is characterized in that, described method is Ethanol Method, comprising:
Be dissolved in ethanolic solution by ultrasonic for the NaOH of required stoichiometry 101wt% ~ 110wt%, obtain the first solution;
Required stoichiometric quinones is added in described first solution; Wherein, described quinones is specially the one in hydroxyquinone compounds, carboxylic acid quinones or sulfonic acid quinones;
Stirred at ambient temperature, after 24 hours, adopts centrifugal process isolate sediment and dry;
Grinding is carried out to isolated sediment and obtains powder;
Described powder is placed in vacuum drying oven, dries 8 hours, grind again afterwards, obtain described battery cathode active material for 100 DEG C.
10. a cathode pole piece for sodium ion secondary battery, is characterized in that, described cathode pole piece comprises:
Collector, be coated on conductive additive on described collector and binding agent and the battery cathode active material based on quinones structure as described in claim as arbitrary in the claims 1-4.
11. 1 kinds of sodium ion secondary batteries comprising the cathode pole piece described in the claims 10.
12. 1 kinds of purposes as above-mentioned sodium ion secondary battery according to claim 11, it is characterized in that, described sodium ion secondary battery is used for the extensive energy storage device of solar power generation, wind power generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station.
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