CN104795566B - GND active material based on quinones structure and its production and use - Google Patents
GND active material based on quinones structure and its production and use Download PDFInfo
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- CN104795566B CN104795566B CN201410245029.6A CN201410245029A CN104795566B CN 104795566 B CN104795566 B CN 104795566B CN 201410245029 A CN201410245029 A CN 201410245029A CN 104795566 B CN104795566 B CN 104795566B
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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
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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
- H01M4/137—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
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- 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 GND active material based on quinones structure and its production and use, wherein the GND active material includes the quinones using quinones structure as electrochemical redox reaction site；Wherein, the quinones includes any one in benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative；The benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative have following group ONa, SO respectively3At least one of Na or COONa.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of GND active material based on quinones structure and its
Preparation method and purposes.
Background technology
The new energy such as solar energy, wind energy have the advantage such as renewable, environment-friendly, but due to its unstability, are incorporated to electricity
Need to improve reliability and utilization rate by energy conversion and storage device during net.Electrochmical power source is the storage for most having application prospect
One of energy system, the advantages of wherein lithium ion battery is because of its high-energy-density and high voltage is widely used to portable electronic
In product and electric automobile.But lithium resource reserves are limited and cost for purification is high, its large-scale use is limited.
Sodium is of the same clan with lithium, with similar chemical property, and rich reserves, and cost for purification is cheap.But sodium ion radius
It is larger, reversible intercalation/deintercalation is relatively difficult in traditional inorganic electrode material, causes it to there is reversible specific capacity low, circulation
The problem of poor performance.At present, the research to negative material is concentrated mainly on Carbon anode, alloy anode and a small number of oxides and phosphorus
Hydrochlorate negative pole etc..
The carbon-coating degree of disorder of hard carbon is maximum in carbon negative pole material, and preferably, specific capacity can 200-300mAh/g (J for storage sodium effect
Electrochem Soc, 2001,148, A803), but sodium current potential is too low and high rate performance is poor because it is stored up, in quick charge or
When overcharging, sodium may deposit to form dendrite on surface, cause potential safety hazard；Alloy material such as tin, phosphorus and lead etc., although have
Higher storage sodium capacity, but first week is less efficient, cycle performance is poor (J Power Sources, 2013,225,316-322),
This volume deformation mainly due to alloy during deintercalation sodium is larger, causes structure to be destroyed, and then make storage sodium performance rapidly
Decline (Angew Chem, 2013,125,4731-4734)；Na2Ti3O7Poorly conductive, storage sodium electricity Deng oxide cathode material
Position is too low, and first week coulombic efficiency is low, and cyclical stability also has much room for improvement (Adv Energy Mater, 2013,3,1186-
1194)；And with NaTi2(PO4)3Although higher for the phosphate negative material cyclical stability of representative, its higher storage sodium electricity
Position causes energy density reduction (J Electrochem Soc, 2011,158, A1067-1070)；Organic cathode material, with to benzene
Sodium diformate is Typical Representative (Adv Energy Mater, 2012,2,962-965), high with specific capacity, and cyclical stability is high
Advantage, but because storage sodium current potential is relatively low, electrolyte is in a large amount of reduction decompositions of electrode surface, and it is only 60% left to cause first all efficiency
It is right, it is difficult to practical application.
The content of the invention
The embodiments of the invention provide a kind of GND active material based on quinones structure and preparation method thereof and use
On the way, the GND active material preparation method based on quinones structure is simple, can be using in the preparation of sodium ion secondary battery.
The sodium ion secondary battery prepared using the GND active material provided in an embodiment of the present invention based on quinones structure, is had
Higher operating voltage and first all coulombic efficiency, stable circulation, have a safety feature.
In a first aspect, the embodiments of the invention provide a kind of GND active material based on quinones structure, its feature
It is, the GND active material includes the quinones using quinones structure as electrochemical redox reaction site；
Wherein, the quinones includes benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative
In any one；The benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative have following base respectively
Group-ONa ,-SO3At least one of Na or-COONa.
It is preferred that, the structure of the benzoquinones sodium salt derivative is as shown in logical formula (I)：
Logical formula (I)
Wherein, group R1、R2、R3、R4In at least one group be-ONa ,-SO3One kind in Na or-COONa, remaining
Group includes-ONa ,-SO3Na、-COONa、-H、-CH3、-NH2、-OCH3,-Cl, the one or more in-Br or-F.
It is preferred that, shown in the structure such as formula (II) of the anthraquinone sodium salt derivative：
Formula (II)
Wherein, group R1、R2、R3、R4、R5、R6、R7、R8In at least one group be-ONa ,-SO3In Na or-COONa
One kind, remaining group include-ONa ,-SO3Na、-COONa、-H、-CH3、-NH2、-OCH3,-Cl ,-Br or one kind in-F or
It is several.
It is preferred that, shown in the structure such as formula (III) of the naphthoquinones sodium salt derivative：
Formula (III)
Wherein, group R1、R2、R3、R4、R5、R6In at least one group be-ONa ,-SO3One in Na or-COONa
Kind, remaining group includes-ONa ,-SO3Na、-COONa、-H、-CH3、-NH2、-OCH3,-Cl ,-Br or one kind or several in-F
Kind.
Second aspect, the embodiments of the invention provide a kind of preparation side of the GND active material based on quinones structure
Method, methods described is aqua-solution method, including：
The quinones of required stoichiometry 101wt%~110wt% sodium hydroxide and required stoichiometry is pressed
Ratio is dissolved in deionized water, forms mixed solution；Wherein, the quinones is specially hydroxyl quinones, carboxylic acid
One kind in quinones or sulfonic acid quinones；
The mixed solution is evaporated in 100 DEG C of air atmosphere；
EtOH Sonicate cleaning is removed after excessive sodium hydrate, and drying, grinding obtains powder；
The powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtains the battery and bear
Pole active material.
The third aspect, the embodiments of the invention provide a kind of preparation side of the GND active material based on quinones structure
Method, methods described is spray drying process, including：
The quinones of required stoichiometry 101wt%~110wt% sodium hydroxide and required stoichiometry is pressed
Ratio is dissolved in deionized water, forms mixed solution；Wherein, the quinones is specially hydroxyl quinones, carboxylic acid
One kind in quinones or sulfonic acid quinones；
The mixed solution is spray-dried；
EtOH Sonicate cleaning is removed after excessive sodium hydrate, and drying, grinding obtains powder；
The powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtains the battery and bear
Pole active material.
It is preferred that, it is described to be spray-dried the mixed solution specially：
1wt%~10wt% aqueous dispersion CNT is added in the mixed solution, ultrasonic 3-5 hours is well mixed
It is spray-dried afterwards.
Fourth aspect, the embodiments of the invention provide a kind of preparation side of the GND active material based on quinones structure
Method, it is characterised in that methods described is organic solvent method, including：
Required stoichiometry 101wt%~110wt% sodium hydroxide ultrasound is dissolved in ethanol solution, first is obtained molten
Liquid；
The quinones of required stoichiometry is dissolved in organic solvent in proportion, the second solution is obtained；Wherein, it is described
Quinones is specially one kind in hydroxyl quinones, carboxylic acid quinones or sulfonic acid quinones；It is described to have
Machine solvent includes dimethyl sulfoxide (DMSO) or dimethylformamide；
At room temperature, first solution is added in second solution with certain speed, and carries out magnetic agitation simultaneously,
Generate sediment；
The sediment is separated using centrifugal process；
The sediment isolated is carried out after EtOH Sonicate cleaning, drying obtains powder at 50 DEG C；
The powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtains the battery and bear
Pole active material.
5th aspect, the embodiments of the invention provide a kind of preparation side of the GND active material based on quinones structure
Method, it is characterised in that methods described is Ethanol Method, including：
Required stoichiometry 101wt%~110wt% sodium hydroxide ultrasound is dissolved in ethanol solution, first is obtained molten
Liquid；
The quinones of stoichiometry needed for being added in first solution；Wherein, the quinones is specific
For one kind in hydroxyl quinones, carboxylic acid quinones or sulfonic acid quinones；
After stirring 24 hours at room temperature, sediment is isolated using centrifugal process and dried；
The sediment isolated is ground and obtains powder；
The powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtains the battery and bear
Pole active material.
6th aspect, the embodiments of the invention provide a kind of cathode pole piece of sodium ion secondary battery, including：
Base described in collector, the conductive additive being coated on the collector and binding agent and above-mentioned first aspect
In the GND active material of quinones structure.
7th aspect, the embodiments of the invention provide a kind of sodium ion of the cathode pole piece including the above-mentioned 6th aspect is secondary
Battery.
Eighth aspect, the embodiments of the invention provide a kind of use of the sodium ion secondary battery described in above-mentioned 7th aspect
On the way, the sodium ion secondary battery be used for solar power generation, wind-power electricity generation, intelligent grid peak regulation, distribution power station, back-up source or
The extensive energy storage device of communication base station.
The embodiments of the invention provide a kind of GND active material based on quinones structure and preparation method thereof and use
On the way, the GND active material preparation method based on quinones structure is simple, can be using in the preparation of sodium ion secondary battery.
The sodium ion secondary battery prepared using the GND active material provided in an embodiment of the present invention based on quinones structure, is had
Higher operating voltage and first all coulombic efficiency, stable circulation, have a safety feature.
Brief description of the drawings
Below by drawings and examples, the technical scheme to the embodiment of the present invention is described in further detail.
Fig. 1 is that the aqua-solution method that the embodiment of the present invention 2 is provided prepares the GND active material based on quinones structure
Preparation method flow chart；
Fig. 2 is that the spray drying process that the embodiment of the present invention 3 is provided prepares the GND active material based on quinones structure
Preparation method flow chart；
Fig. 3 is that the organic solvent method that the embodiment of the present invention 4 is provided prepares the GND active material based on quinones structure
Preparation method flow chart；
Fig. 4 is the system that the Ethanol Method that the embodiment of the present invention 5 is provided prepares the GND active material based on quinones structure
Preparation Method flow chart；
Fig. 5 is the active material Na that the embodiment of the present invention 6 is provided2C6H2O4XRD spectrum；
Fig. 6 is the active material Na that the embodiment of the present invention 6 is provided2C6H2O4SEM figure；
Fig. 7 is the charging and discharging curve figure for the sodium-ion battery that the embodiment of the present invention 6 is provided；
Fig. 8 is active material NaC provided in an embodiment of the present invention10H6O3And Na2C14H6O4XRD spectrum；
Fig. 9 is the active material NaC that the embodiment of the present invention 7 is provided10H6O3SEM figure；
Figure 10 is the charging and discharging curve figure for the sodium-ion battery that the embodiment of the present invention 7 is provided；
Figure 11 is the Na that the embodiment of the present invention 8 is provided2C14H6O4SEM figure；
Figure 12 is the charging and discharging curve figure for the sodium-ion battery that the embodiment of the present invention 8 is provided；
Figure 13 is the charging and discharging curve figure for the sodium-ion battery that the embodiment of the present invention 9 is provided；
Figure 14 is the charging and discharging curve figure for the sodium-ion battery that the embodiment of the present invention 10 is provided.
Embodiment
With reference to embodiment, the present invention is described in further detail, it should be understood that these embodiments are only
It is to be used to specifically describe in more detail, but is 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, including using quinones structure as electricity
The quinones of chemistry redox reaction site；
Wherein, quinones is included in benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative
Any one；Benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative respectively have following group-ONa ,-
SO3At least one of Na or-COONa.
Specifically, the structure of benzoquinones sodium salt derivative is as shown in logical formula (I)：
Logical formula (I)
Wherein, group R1、R2、R3、R4In at least one group be-ONa ,-SO3One kind in Na or-COONa, remaining
Group includes-ONa ,-SO3Na、-COONa、-H、-CH3、-NH2、-OCH3,-Cl, the one or more in-Br or-F.
Shown in the structure of anthraquinone sodium salt derivative such as formula (II)：
Formula (II)
Wherein, group R1、R2、R3、R4、R5、R6、R7、R8In at least one group be-ONa ,-SO3In Na or-COONa
One kind, remaining group include-ONa ,-SO3Na、-COONa、-H、-CH3、-NH2、-OCH3,-Cl ,-Br or one kind in-F or
It is several.
Shown in the structure of naphthoquinones sodium salt derivative such as formula (III)：
Formula (III)
Wherein, group R1、R2、R3、R4、R5、R6In at least one group be-ONa ,-SO3One in Na or-COONa
Kind, remaining group includes-ONa ,-SO3Na、-COONa、-H、-CH3、-NH2、-OCH3,-Cl ,-Br or one kind or several in-F
Kind.
The quinones provided in the above embodiment of the present invention can be used as GND active material, preparation method letter
It is single, can be using in the preparation of sodium ion secondary battery.Using the GND active material based on quinones structure of the present invention
The sodium ion secondary battery of preparation, with higher operating voltage and first all coulombic efficiency, stable circulation, has a safety feature.
Embodiment 2
A kind of preparation method of the GND active material based on quinones structure is present embodiments provided, it is specially water-soluble
Liquid method, as shown in figure 1, including：
Step 101, by required stoichiometry 101wt%~110wt% sodium hydroxide and the quinones of required stoichiometry
Compound is dissolved in deionized water in proportion, forms mixed solution；
Wherein, the quinones is specially hydroxyl quinones, carboxylic acid quinones or sulfonic acid quinones chemical combination
One kind in thing.
Step 102, the mixed solution is evaporated in 100 DEG C of air atmosphere；
Step 103, EtOH Sonicate cleaning is removed after excessive sodium hydrate, and drying, grinding obtains powder；
Step 104, the powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtain institute
State GND active material.
The aqua-solution method that the present embodiment is provided prepares the preparation method of the GND active material based on quinones structure, energy
It is enough in and prepares GND active material described in above-described embodiment 1.The present embodiment provide method is simple and easy to apply, cost
Application cheap, suitable for that can manufacture on a large scale.
Embodiment 3
A kind of preparation method of the GND active material based on quinones structure is present embodiments provided, is specially sprayed
Seasoning, as shown in Fig. 2 including：
Step 201, by required stoichiometry 101wt%~110wt% sodium hydroxide and the quinones of required stoichiometry
Compound is dissolved in deionized water in proportion, forms mixed solution；
Wherein, the quinones is specially hydroxyl quinones, carboxylic acid quinones or sulfonic acid quinones chemical combination
One kind in thing.
Step 202, the mixed solution is spray-dried；
Step 203, EtOH Sonicate cleaning is removed after excessive sodium hydrate, and drying, grinding obtains powder；
Step 204, the powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtain institute
State GND active material.
The spray drying process that the present embodiment is provided prepares the preparation method of the GND active material based on quinones structure,
It can be used in preparing the GND active material described in above-described embodiment 1.The present embodiment provide method it is simple and easy to apply, into
This application cheap, suitable for that can manufacture on a large scale.
Embodiment 4
A kind of preparation method of the GND active material based on quinones structure is present embodiments provided, it is specially organic
Solvent method, as shown in figure 3, including：
Step 301, required stoichiometry 101wt%~110wt% sodium hydroxide ultrasound is dissolved in ethanol solution, obtained
To the first solution；
Step 302, the quinones of required stoichiometry is dissolved in organic solvent in proportion, obtains the second solution；
Wherein, the quinones is specially hydroxyl quinones, carboxylic acid quinones or sulfonic acid quinones chemical combination
One kind in thing；The organic solvent includes dimethyl sulfoxide (DMSO) or dimethylformamide；
Step 303, at room temperature, first solution is added in second solution with certain speed, and carried out simultaneously
Magnetic agitation, generates sediment；
Step 304, the sediment is separated using centrifugal process；
Step 305, the sediment isolated is carried out after EtOH Sonicate cleaning, drying obtains powder at 50 DEG C；
Step 306, the powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtain institute
State GND active material.
The organic solvent method that the present embodiment is provided prepares the preparation method of the GND active material based on quinones structure,
It can be used in preparing the GND active material described in above-described embodiment 1.The present embodiment provide method it is simple and easy to apply, into
This application cheap, suitable for that can manufacture on a large scale.
Embodiment 5
Present embodiments provide a kind of preparation method of the GND active material based on quinones structure, specially ethanol
Method, as shown in figure 4, including：
Step 401, required stoichiometry 101wt%~110wt% sodium hydroxide ultrasound is dissolved in ethanol solution, obtained
To the first solution；
Step 402, the quinones of stoichiometry needed for being added in first solution；
Wherein, the quinones is specially hydroxyl quinones, carboxylic acid quinones or sulfonic acid quinones chemical combination
One kind in thing；
Step 403, after stirring 24 hours at room temperature, sediment is isolated using centrifugal process and dried；
Step 404, the sediment isolated is ground and obtains powder；
Step 405, the powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtain institute
State GND active material.
The Ethanol Method that the present embodiment is provided prepares the preparation method of the GND active material based on quinones structure, can
For preparing the GND active material described in above-described embodiment 1.The present embodiment provide method is simple and easy to apply, cost is low
Application honest and clean, suitable for that can manufacture on a large scale.
It is following to illustrate what is provided using any embodiment into embodiment 5 of the embodiment of the present invention 2 with multiple instantiations
Method prepares the detailed process of the cell negative electrode material based on quinones structure, and is applied to the method and electricity of secondary cell
Pond characteristic.
Embodiment 6
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
The present embodiment prepares GND active material using aforementioned organic solvents method, concretely comprises the following steps：By 2,5- dihydroxies
Base-Isosorbide-5-Nitrae-benzoquinones is dissolved in dimethyl sulfoxide (DMSO), separately 105wt% sodium hydroxide ultrasound is dissolved in ethanol solution, in room temperature magnetic
Under power stirring, ethanol solution is added dropwise in dimethyl sulphoxide solution and precipitated.Sediment is separated with centrifugal process, and uses second
Alcohol is cleaned by ultrasonic for several times, by gained powder at 100 DEG C, is dried under vacuum condition, gained red-brown powder.Red-brown powder is passed through
It is standby after grinding, it is the active material Na of the present invention2C6H2O4, its structural formula is as follows：
Its X-ray diffraction (XRD) collection of illustrative plates is shown in Fig. 5, and from XRD, the crystallinity of the active material is good.Fig. 6 is the thing
The SEM figures of matter, it can be seen that particle size distribution is main from 50 to 100 nanometers.
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concretely comprise the following steps：By the activity prepared
Material Na2C6H2O4Powder is with acetylene black, binding agent Kynoar (PVDF) according to 70:20:10 mass ratio mixing, is added
Appropriate 1-METHYLPYRROLIDONE (NMP) solution, grinding forms slurry in the environment of air drying, and then slurry is uniformly applied
It is overlying in current collector aluminum foil, and is dried under infrared baking lamp, is cut into 8 × 8mm2Pole piece.Under vacuum in 100 DEG C of dryings
10 hours, glove box is transferred to immediately standby.Carried out in the glove box for being assemblied in Ar atmosphere of simulated battery, using metallic sodium as
To electrode, with NaClO4/ diethyl carbonate (EC:DEC) solution is assembled into CR2032 button cells as electrolyte.Use perseverance
Flow charge and discharge mode and carry out charge-discharge test, all tests are carried out under C/10 current densities, be when discharging by voltage
0.9V, charging is when voltage is 2V, and test result is shown in Fig. 7.The charge and discharge cycles of first week and second week are shown respectively in figure
Curve.It can be seen from Fig. 7 that its first all discharge capacity is up to 288mAh/g, first week coulombic efficiency is about 88.7%.
Embodiment 7
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
GND active material is prepared using aqueous solution method in the present embodiment, concretely comprised the following steps：Weigh chemistry meter
The sodium hydroxide of the HNQ and 105wt% of measuring ratio is dissolved in deionized water, is evaporated at 100 DEG C, then use ethanol
Ultrasonic cleaning is dried afterwards several times, and the reddish brown powder of gained is the active material NaC of the present invention10H6O3, its structural formula is as follows：
Its XRD spectrum is shown in Fig. 8 a, from XRD, and the crystallinity of the active material is good.Fig. 9 is the SEM figures of the material,
It can be seen that 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.Concretely comprise the following steps：By the activity prepared
Material Na2C6H2O4Powder is with Ketjen black (KB), polyfluortetraethylene of binding element (PTFE) according to 70:20:10 mass ratio mixing,
Sheet in uniform thickness is made, then suppresses in collector aluminium net, and is dried under infrared baking lamp, 8 × 8mm is cut into2Pole
Piece.Dried 10 hours under 100 DEG C of vacuum conditions, glove box is transferred to immediately standby.Simulated battery is assemblied in Ar atmosphere
Carried out in glove box, using metallic sodium as to electrode, with NaPF6/EC:DEC：Propene carbonate (PC) solution as electrolyte,
It is assembled into CR2032 button cells.Charge-discharge test is carried out using constant current charge-discharge pattern, all tests are close in C/10 electric currents
Degree is lower to be carried out, and test voltage scope is 1.5-3V, and test result is shown in Figure 10.First week and second week discharge and recharge are shown respectively in figure
Curve.It can be seen from Fig. 10 that its first all charging capacity is up to 151mAh/g, first week coulombic efficiency is about 99%.
Embodiment 8
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
The present embodiment uses aqueous solution method GND active material, and specific steps be the same as Example 7 is raw materials used to be
2,6- dihydroxy anthraquinones.Gained powder is polished standby, is the active material Na of the present invention2C14H6O4, its structural formula is such as
Under：
Its XRD spectrum is shown in Fig. 8 b.Figure 11 is the SEM figures of the material, it can be seen that particle size distribution it is main from
Several microns to more than ten microns, big particle is to be reunited with forming by small rod-shpaed particle.
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concretely comprise the following steps：By the activity prepared
Material Na2C14H6O4Powder is with carbon black Super P, binding agent PTFE according to 80:15:5 mass ratio mixing, is made thickness uniform
Sheet, then suppress in collector aluminium net, and dried under infrared baking lamp, be cut into 8 × 8mm2Pole piece.In vacuum condition
Under in 100 DEG C dry 10 hours, glove box is transferred to immediately standby.Simulated battery is assemblied in the glove box of Ar atmosphere
OK, using metallic sodium as to electrode, with NaPF6/ PC solution is assembled into CR2032 button cells as electrolyte.Use constant current
Charge and discharge mode carries out charge-discharge test, and all tests are carried out under C/10 current densities, and test voltage scope is 0.9-3V,
Test result is shown in Figure 12.It is respectively first week and second week charging and discharging curve shown in figure.It can be seen from Fig. 12 that its first week charging is held
Amount is up to 185mAh/g, and first week coulombic efficiency is about 81%.
Embodiment 9
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
The present embodiment uses foregoing spray drying process GND active material, concretely comprises the following steps：Weigh stoichiometric proportion
Anthraquinone-1-sulfonic acid and 101wt%~110wt% sodium hydroxide be dissolved in deionized water, add 10wt% aqueous dispersion
CNT.Mixed solution is spray-dried by ultrasonic mixing after 3 hours at 120 DEG C.Gained powder is under vacuo at 100 DEG C
Drying, is the active material NaC of the present invention14H7O5S, its structural formula is as follows：
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concretely comprise the following steps：By the activity prepared
Material NaC14H7O5S powder is with acetylene black (AB), binding agent PVDF according to 85:10:5 mass ratio mixing, adds appropriate NMP
Solution, grinding forms slurry in the environment of air drying, and then slurry is evenly applied in current collector aluminum foil, and infrared
Dry and dried under lamp, be cut into 8 × 8mm2Pole piece.Dried 10 hours under 100 DEG C of vacuum conditions, glove box is transferred to immediately standby
With.Carried out in the glove box for being assemblied in Ar atmosphere of simulated battery, using metallic sodium as to electrode, with NaClO4/EC:DMC is molten
Liquid is assembled into CR2032 button cells as electrolyte.Charge-discharge test is carried out using constant current charge-discharge pattern, all tests are equal
Carried out under C/10 current densities, be 1V when discharging by voltage, charging is when voltage is 3V, and test result is shown in Figure 13.Figure
In the charge and discharge cycles curve of first week and second week is shown respectively.It can be seen from Fig. 13 that its first all discharge capacity is up to 144mAh/
G, first week coulombic efficiency is about 82.3%.
Embodiment 10
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
Aqua-solution method synthetic active substance is used in the present embodiment, raw material is 2- hydroxy-anthraquiones, method be the same as Example 7.Institute
Obtain the active material NaC that reddish brown powder is the present invention14H7O3, its structural formula is as follows：
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concretely comprise the following steps：By the activity prepared
Material NaC14H7O3Powder is with acetylene black (AB), binding agent PTFE according to 80:10:10 mass ratio mixing, is made thickness uniform
Sheet, be then compressed on stainless (steel) wire, and under infrared baking lamp dry, be cut into 8 × 8mm2Pole piece.In 100 DEG C of vacuum
Under the conditions of dry 10 hours, glove box is transferred to immediately standby.Carried out in the glove box for being assemblied in Ar atmosphere of simulated battery, with
Metallic sodium is as to electrode, with NaClO4/ PC solution is assembled into CR2032 button cells as electrolyte.Use constant current charge and discharge
Power mode carries out charge-discharge test, and all tests are carried out under C/10 current densities, and test voltage scope is 1-3V, test knot
Fruit sees Figure 14.It can be seen from Fig. 14 that its first all discharge capacity is up to 189mAh/g, first week coulombic efficiency is about 88.7%.
Embodiment 11
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
The present embodiment uses foregoing spray drying process GND active material, and specific steps be the same as Example 9 is raw materials used
For anthraquinone-2-sulfonic acid.Gained powder is polished standby, is the active material NaC of the present invention14H7O5S, its structural formula is such as
Under：
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concretely comprise the following steps：By the activity prepared
Material NaC14H7O5S powder is with graphene, binding agent PTFE according to 80:15:5 mass ratio mixing, is made in uniform thickness
Shape, is then suppressed in collector aluminium net, and is dried under infrared baking lamp, is cut into 8 × 8mm2Pole piece.In 100 DEG C of vacuum bars
Dried 10 hours under part, glove box is transferred to immediately standby.Carried out in the glove box for being assemblied in Ar atmosphere of simulated battery, with gold
Belong to sodium as to electrode, with NaPF6/EC：DEC solution is assembled into CR2032 button cells as electrolyte.Use constant current charge and discharge
Power mode carries out charge-discharge test, and all tests are carried out under C/10 current densities, and test voltage scope is 1-3V, test knot
Fruit is shown in Table 1.
Embodiment 12
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
Aqueous solution method synthetic active substance is used in the present embodiment, raw material is 1,2- dihydroxy anthraquinones, and method is with real
Apply example 6.Gained powder is the active material Na of the present invention2C14H6O4, its structural formula is as follows：
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concretely comprise the following steps：By the activity prepared
Material Na2C14H6O4Powder is with Ketjen black (KB), binding agent sodium alginate according to 60:30:10 mass ratio mixing, in normal temperature
Grinding forms slurry in environment, and then slurry is evenly applied on copper foil of affluxion body, and is dried under infrared baking lamp, is cut into 8
×8mm2Pole piece.Dried 10 hours under 100 DEG C of vacuum conditions, glove box is transferred to immediately standby.The assembling of simulated battery
Carry out, using metallic sodium as to electrode, using NaFSI/PC solution as electrolyte, be assembled into the glove box of Ar atmosphere
CR2032 button cells.Charge-discharge test is carried out using constant current charge-discharge pattern, all tests are entered under C/10 current densities
OK, test voltage scope is 0.9-3V, and test result is shown in Table 1.
Embodiment 13
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
Aqueous solution method synthetic active substance is used in the present embodiment, is concretely comprised the following steps：Stoichiometric proportion needed for weighing
Tetrahydroxy quinone and 105wt% sodium hydroxides be dissolved in deionized water.Add 5wt% aqueous dispersion CNT.Ultrasound
Mixed solution is spray-dried by mixing after 3 hours at 150 DEG C.Gained powder is under vacuo this hair in being dried at 100 DEG C
Bright active material Na4C6H2O4, its structural formula is as follows：
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concretely comprise the following steps：By the activity prepared
Material Na2C6H2O4Powder is with Ketjen black (KB), binding agent PTFE according to 80:10:10 mass ratio mixing, is made thickness uniform
Sheet, then suppress in collector aluminium net, and dried under infrared baking lamp, be cut into 8 × 8mm2Pole piece.In vacuum condition
Under in 100 DEG C dry 10 hours, glove box is transferred to immediately standby.Simulated battery is assemblied in the glove box of Ar atmosphere
OK, using metallic sodium as to electrode, with NaPF6/EC:DMC solution is assembled into CR2032 button cells as electrolyte.Use
Constant current charge-discharge pattern carries out charge-discharge test, and all tests are carried out under C/10 current densities, and test voltage scope is
0.8-3V, test result is shown in Table 1.
Embodiment 14
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
Aqueous solution method synthetic active substance is used in the present embodiment, raw material is 5,8- dihydroxy naphthoquinones, and method is with real
Apply example 13.Gained powder is the active material Na of the present invention2C10H4O4, its structural formula is as follows：
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concretely comprise the following steps：By the activity prepared
Material Na2C10H4O4Powder is with acetylene black, binding agent sodium carboxymethylcellulose (CMC) according to 75:15:10 mass ratio mixing,
Grinding forms slurry in the environment of normal temperature, and then slurry is evenly applied in current collector aluminum foil, and is dried under infrared baking lamp,
It is cut into 8 × 8mm2Pole piece.Dried 10 hours in 100 DEG C under vacuum, glove box is transferred to immediately standby.Simulated battery
The glove box for being assemblied in Ar atmosphere in carry out, using metallic sodium as to electrode, with NaClO4/EC:DMC:PC solution is used as electricity
Liquid is solved, CR2032 button cells are assembled into.Charge-discharge test is carried out using constant current charge-discharge pattern, all tests are in C/10 electricity
Carried out under current density, test voltage scope is 0.8-3V, test result is shown in Table 1.
Embodiment 15
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
Aqueous solution method synthetic active substance is used in the present embodiment, raw material is 1,4- dihydroxy anthraquinones, and method is with real
Apply example 7.Gained powder is the active material Na of the present invention2C14H6O4, its structural formula is as follows：
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concretely comprise the following steps：By the activity prepared
Material Na2C14H6O4Powder is with Super P, binding agent PVDF according to 50:40:10 mass ratio mixing, in the environment of air drying
Middle grinding forms slurry, and then slurry is evenly applied on copper foil of affluxion body, and is dried under infrared baking lamp, it is cut into 8 ×
8mm2Pole piece.Dried 10 hours under 100 DEG C of vacuum conditions, glove box is transferred to immediately standby.Simulated battery is assemblied in
Carried out in the glove box of Ar atmosphere, using metallic sodium as to electrode, with NaClO4/EC:DEC:PC solution is used as electrolyte, assembling
Into CR2032 button cells.Charge-discharge test is carried out using constant current charge-discharge pattern, all tests are under C/10 current densities
Carry out, test voltage scope is 0.9-3V, test result is shown in Table 1.
Embodiment 16
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
Aqueous solution method synthetic active substance is used in the present embodiment, raw material is 2,5- bis- chloro- 3,6- dihydroxy benzoquinones,
Method be the same as Example 7.Gained powder is the active material Na of the present invention2C6Cl2O4, its structural formula is as follows：
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concretely comprise the following steps：By the activity prepared
Material Na2C6Cl2O4Powder is with Ketjen black (KB), binding agent butadiene-styrene rubber (SBR) according to 80:10:10 mass ratio mixing, grinds
Mill forms uniform sizing material, and then slurry is evenly applied on copper foil of affluxion body, and is dried under infrared baking lamp, it is cut into 8 ×
8mm2Pole piece.Dried 10 hours under 100 DEG C of vacuum conditions, glove box is transferred to immediately standby.Simulated battery is assemblied in
Carried out in the glove box of Ar atmosphere, using metallic sodium as to electrode, with NaPF6/ PC solution is assembled into CR2032 as electrolyte
Button cell.Charge-discharge test is carried out using constant current charge-discharge pattern, all tests are carried out under C/10 current densities, tested
Voltage range is 0.9-3V, and test result is shown in Table 1.
Embodiment 17
The present embodiment is used for the preparation and its application for illustrating the GND active material of the present invention.
Aqueous solution method synthetic active substance is used in the present embodiment, raw material is 1,8- dihydroxy anthraquinones, and method is with real
Apply example 13.Gained powder is the active material Na of the present invention2C14H6O4, its structural formula is as follows：
Above-mentioned active material is prepared into sodium-ion battery as negative material.Concretely comprise the following steps：By the activity prepared
Material Na2C14H6O4Powder is with Super P, binding agent CMC according to 80:15:5 mass ratio mixing, grinds in the environment of normal temperature
Slurry is formed, then slurry is evenly applied on copper foil of affluxion body, and is dried under infrared baking lamp, 8 × 8mm is cut into2Pole
Piece.Dried 10 hours under 100 DEG C of vacuum conditions, glove box is transferred to immediately standby.Simulated battery is assemblied in Ar atmosphere
Carried out in glove box, using metallic sodium as to electrode, using NaFSI/PC solution as electrolyte, be assembled into CR2032 buttons electricity
Pond.Charge-discharge test is carried out using constant current charge-discharge pattern, all tests are carried out under C/10 current densities, test voltage model
Enclose for 0.9-3V, test result is shown in Table 1.
Table 1
As can be seen that the sodium ion secondary battery prepared in the above embodiment of the present invention using GND active material,
With higher operating voltage and first all coulombic efficiency, stable circulation, have a safety feature.
The sodium ion secondary battery prepared using the method that provides of the present invention, can be used for solar power generation, wind-power electricity generation,
The extensive energy storage devices such as intelligent grid peak regulation, distribution power station, back-up source or communication base station.
Although it should be noted that present invention has been a certain degree of description, it will be apparent that, do not departing from the present invention's
Under conditions of spirit and scope, the appropriate change of each condition can be carried out.It can be understood as that the invention is not restricted to the embodiment party
Case, and it is attributed to the scope of claim, it includes the equivalent substitution of each factor.
Above-described embodiment, has been carried out further to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail, should be understood that the embodiment that the foregoing is only the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution and improvements done etc. all should be included
Within protection scope of the present invention.
Claims (12)
1. a kind of GND active material based on quinones structure, it is characterised in that the GND active material includes
Using quinones structure as the quinones in electrochemical redox reaction site；
Wherein, the quinones is included in benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative
Any one；The benzoquinones sodium salt derivative, anthraquinone sodium salt derivative or naphthoquinones sodium salt derivative respectively have following group-
ONa、-SO3At least one of Na.
2. GND active material according to claim 1, it is characterised in that the structure of the benzoquinones sodium salt derivative
As shown in logical formula (I)：
Wherein, group R1、R2、R3、R4In at least one group be-ONa ,-SO3One kind in Na, remaining group include-
ONa、-SO3Na、-COONa、-H、-CH3、-NH2、-OCH3,-Cl, the one or more in-Br or-F.
3. GND active material according to claim 1, it is characterised in that the structure of the anthraquinone sodium salt derivative
As shown in formula (II)：
Wherein, group R1、R2、R3、R4、R5、R6、R7、R8In at least one group be-ONa ,-SO3One kind in Na, its complementary basis
Group includes-ONa ,-SO3Na、-COONa、-H、-CH3、-NH2、-OCH3,-Cl, the one or more in-Br or-F.
4. GND active material according to claim 1, it is characterised in that the structure of the naphthoquinones sodium salt derivative
As shown in formula (III)：
Wherein, group R1、R2、R3、R4、R5、R6In at least one group be-ONa ,-SO3One kind in Na, remaining group bag
Include-ONa ,-SO3Na、-COONa、-H、-CH3、-NH2、-OCH3,-Cl, the one or more in-Br or-F.
5. a kind of preparation of GND active material based on quinones structure as described in the above-mentioned any claims of claim 1-4
Method, it is characterised in that methods described is aqua-solution method, including：
By required stoichiometry 101wt%~110wt% sodium hydroxide and the quinones of required stoichiometry in proportion
It is dissolved in deionized water, forms mixed solution；Wherein, the quinones is specially hydroxyl quinones, carboxylic acid quinones
One kind in compound or sulfonic acid quinones；
The mixed solution is evaporated in 100 DEG C of air atmosphere；
EtOH Sonicate cleaning is removed after excessive sodium hydrate, and drying, grinding obtains powder；
The powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtains the GND and live
Property material.
6. a kind of preparation of GND active material based on quinones structure as described in the above-mentioned any claims of claim 1-4
Method, it is characterised in that methods described is spray drying process, including：
By required stoichiometry 101wt%~110wt% sodium hydroxide and the quinones of required stoichiometry in proportion
It is dissolved in deionized water, forms mixed solution；Wherein, the quinones is specially hydroxyl quinones, carboxylic acid quinones
One kind in compound or sulfonic acid quinones；
The mixed solution is spray-dried；
EtOH Sonicate cleaning is removed after excessive sodium hydrate, and drying, grinding obtains powder；
The powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtains the GND and live
Property material.
7. preparation method according to claim 6, it is characterised in that described that the mixed solution is subjected to spray drying tool
Body is：
1wt%~10wt% aqueous dispersion CNT or graphene are added in the mixed solution, ultrasound is mixed for 3~5 hours
It is spray-dried after closing uniformly.
8. a kind of preparation of GND active material based on quinones structure as described in the above-mentioned any claims of claim 1-4
Method, it is characterised in that methods described is organic solvent method, including：
Required stoichiometry 101wt%~110wt% sodium hydroxide ultrasound is dissolved in ethanol solution, the first solution is obtained；
The quinones of required stoichiometry is dissolved in organic solvent in proportion, the second solution is obtained；Wherein, the quinones
Compound is specially one kind in hydroxyl quinones, carboxylic acid quinones or sulfonic acid quinones；It is described organic molten
Agent includes dimethyl sulfoxide (DMSO) or dimethylformamide；
At room temperature, first solution is added in second solution with certain speed, and carries out magnetic agitation simultaneously, generated
Sediment；
The sediment is separated using centrifugal process；
The sediment isolated is carried out after EtOH Sonicate cleaning, drying obtains powder at 50 DEG C；
The powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtains the GND and live
Property material.
9. a kind of preparation of GND active material based on quinones structure as described in the above-mentioned any claims of claim 1-4
Method, it is characterised in that methods described is Ethanol Method, including：
Required stoichiometry 101wt%~110wt% sodium hydroxide ultrasound is dissolved in ethanol solution, the first solution is obtained；
The quinones of stoichiometry needed for being added in first solution；Wherein, the quinones is specially hydroxyl
One kind in base quinones, carboxylic acid quinones or sulfonic acid quinones；
After stirring 24 hours at room temperature, sediment is isolated using centrifugal process and dried；
The sediment isolated is ground and obtains powder；
The powder is placed in vacuum drying oven, 100 DEG C dry 8 hours, are ground again afterwards, obtains the GND and live
Property material.
10. a kind of cathode pole piece of sodium ion secondary battery, it is characterised in that the cathode pole piece includes：
Collector, the conductive additive being coated on the collector and binding agent and such as any power of above-mentioned claim 1-4
The GND active material based on quinones structure described in.
11. a kind of sodium ion secondary battery of the cathode pole piece including described in the claims 10.
12. a kind of purposes of sodium ion secondary battery as described in above-mentioned claim 11, it is characterised in that the sodium ion two
Primary cell is used for the big rule of solar power generation, wind-power electricity generation, intelligent grid peak regulation, distribution power station, back-up source or communication base station
Mould energy storage device.
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| CN106450324A (en) * | 2016-11-03 | 2017-02-22 | 华南师范大学 | Tetrahydroxy p-benzoquinone tetrasodium salt and preparation method and application thereof |
| CN106910895B (en) * | 2017-04-06 | 2020-02-21 | 广东工业大学 | Organic electrode material and preparation method and application thereof |
| CN107204465B (en) * | 2017-05-23 | 2019-09-24 | 广东工业大学 | A kind of preparation method of high molecular material and a kind of lithium ion battery |
| CN107579217A (en) * | 2017-08-21 | 2018-01-12 | 华南师范大学 | A kind of anthraquinone dihydroxy sodium salt graphene complex and preparation and application |
| CN107768670A (en) * | 2017-10-23 | 2018-03-06 | 东莞理工学院 | Positive electrode and preparation method and application, the preparation method of positive pole |
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| CN109467079B (en) * | 2018-11-19 | 2020-11-24 | 华南理工大学 | Organic functionalized graphene material and preparation method and application thereof |
| CN111312526A (en) * | 2019-11-11 | 2020-06-19 | 中国科学院福建物质结构研究所 | Battery-super capacitor hybrid energy storage device and preparation method thereof |
| CN111952586A (en) * | 2020-07-10 | 2020-11-17 | 西安理工大学 | High first-cycle coulombic efficiency potassium ion battery organic carbonyl negative electrode material and preparation method thereof |
| CN114204020A (en) * | 2021-11-29 | 2022-03-18 | 华中科技大学 | Organic electrode material universal for alkali metal ion battery and application thereof |
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