CN109265682A - A kind of fast charging and discharging positive electrode active materials and its preparation method and application - Google Patents
A kind of fast charging and discharging positive electrode active materials and its preparation method and application Download PDFInfo
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- CN109265682A CN109265682A CN201810895451.4A CN201810895451A CN109265682A CN 109265682 A CN109265682 A CN 109265682A CN 201810895451 A CN201810895451 A CN 201810895451A CN 109265682 A CN109265682 A CN 109265682A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/606—Polymers containing aromatic main chain polymers
- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
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- 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
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Abstract
The invention discloses a kind of fast charging and discharging positive electrode active materials, the characteristic that the acid imide small molecule of use makes it be difficult to dissolve with good electric conductivity and in most of common organic solvents in the pi-pi accumulation in phenyl ring plane is that one kind extremely has potential ion battery positive electrode；The present invention forms polymer by oxamides and tetracarboxylic acid dianhydride small molecule reaction, and the synthesis of polymer can be effectively reduced dissolubility in the electrolyte and improve cyclical stability；In addition, the stacking of intermolecular carbonyl forms new ion transmission channel, the efficiency of transmission of ion is greatly improved by introducing additional carbonyl between monomer, the cycle performance and high rate performance of prepared alkali metal-ion battery are thus increased substantially.The chemical structural formula of such imide polymer is as follows:
Description
Technical field
The invention belongs to alkali metal-ion battery electrode active material technical fields, and in particular to a kind of fast charging and discharging is just
Pole active material and preparation method thereof and the application in alkali metal-ion battery.
Background technique
As the energy such as petroleum are petered out, the exploitation and storage of new energy are increasingly becoming the focus of social concerns.Lithium from
Sub- battery has been widely used in various miniaturized electronic devices and electric vehicle by its excellent performance as energy storage devices.
However, the content of elemental lithium is limited in nature, with continual exploitation, price increasingly increases.With elemental lithium with
The sodium element of one main group not only has chemical property similar with elemental lithium with potassium element, and has remote super lithium in the earth's crust
Reserves, therefore sodium-ion battery and kalium ion battery equally have very important application prospect.Due to there is similar chemistry
Property and identical outermost electron number, a kind of alkali metal ions electricity that electrode material can be different applied to three kinds simultaneously
Pond.
There are three the parameter of characterization ion battery performance is main: specific capacity, cycle performance and high rate performance.Permitted existing
In more researchs, organic positive electrode of the specific capacity higher than 150mAh/g has been encountered with many times, but the cycle performance of these materials is general
It is not high, it will occur obviously to decay in the charge and discharge cycles less than 200 times, and in the current density of 1A/g or more
Under after tens of secondary charge and discharge cycles specific capacity be difficult to maintain 100mA h/g or more.Itself main reason is that these
Generally all less, less stable when participating in redox reaction in charge and discharge process is easily dissolved in electricity to the molecular weight of material
Xie Zhizhong.
Studies show that, acid imide small molecule with a conjugated structure has good because it is in intermolecular carry out pi-pi accumulation
Good electric conductivity and difficult dissolution characteristics in organic solvent, more simultaneous higher theoretical specific capacity is a kind of ideal alkali metal
Ion battery positive electrode active materials.As imide group isophthalic number of rings purpose increases, molecular conjugation degree is constantly reinforced, is led
Electric energy power and cyclical stability also enhance therewith, but its theoretical specific capacity can reduce with the increase of molecular weight.In addition, ion
The formation in channel has the diffusion conducive to ion in active material, and being finally embodied in reduces battery specific capacity at higher current densities
Decaying.Another method for effectively improving cycle performance and high rate performance be then the covalent organic network of construction inhibiting or even
It eliminates decomposition in the electrolyte and more efficiently ion diffusion admittance is provided, however this there is covalent organic network structure
The usual specific capacity of electrode material it is not high.For now, although generally believing that there are four carbonyls in tetracarboxylic acid acid imide molecule
Base active site, but excessive sodium ion insertion during real reaction will increase energy density in structure and cause structure broken
Bad, so generally at most can only stablize there are two carbonyl, reversible redox reaction, the utilization rate of active site is general
Lower than 50%.
There are certain research and report about acid imide electrode material at present, such as: with tetramethyl acid imide (PTCDI) work
For positive electrode active materials sodium-ion battery (Deng, W., Shen, Y., Qian, J., Cao, Y., H. (2015) .A
perylene diimide crystal with high capacity and stable cyclability for na-ion
batteries.Acs Applied Materials&Interfaces,7(38),21095-9.DOI:10.1021/
Acsami.5b04325 after) carrying out 300 charge and discharge under the constant current density of 200mA/g, specific capacity is from about 120mAh/
G decays to 110mAh/g or so, retention rate 91.7%；Its specific capacity about 100mAh/g under 600mA/g current density.With
After tetracarboxylic dianhydride and hydrazine hydrate aggregate into polyimides, sodium-ion battery obtained by the active material (Banda, H.,
Damien,D.,Nagarajan,K.,Hariharan,M.,&Shaijumon,M.M.(2015).Polyimide based
all-organic sodium ion battery.Journal of Materials Chemistry A,3(19),10453-
10458.DOI:10.1039/C5TA02043C) under 100mA/g current density after 50 charge and discharge cycles specific capacity from
120mAh/g at the beginning decays to 100mAh/g or so, retention rate 83.3%；Under 800mA/g current density, fill for 50 times
Specific capacity decays to about 60mAh/g, retention rate 57.1% from initial 105mAh/g after discharge cycles.With triptycene and four
Polyimides synthesized by carboxylic acid dianhydride have covalent organic network structure (Schon, T.B., Tilley, A.J., Kynaston,
E.L.,&Seferos,D.S.(2017).Three-dimensional arylene diimide frameworks for
highly stable lithium-ion batteries.Acs Appl Mater Interfaces,9(18),15631-
15637.DOI:10.1021/acsami.7b02336), after carrying out 500 charge and discharge cycles under 100mA/g current density,
Specific capacity decays to 44mAh/g, retention rate 84.7% from 52mAh/g.
Summary of the invention
It is a primary object of the present invention in view of the deficienciess of the prior art, to existing tetramethyl with a conjugated structure
Acid imide Na-like ions battery anode active material optimizes, and provides prepared by a series of oxamides and tetracarboxylic dianhydride
Polymer can express excellent chemical property as sodium-ion battery positive electrode active materials；This series polymer is almost
There is the work more than the cyclical stability of above-mentioned acid imide active material and more than 60% under the premise of not increasing molecular weight
Property site utilization rate, is furthermore also able to maintain excellent specific capacity at higher current densities, meets fast charging and discharging application demand.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of fast charging and discharging positive electrode active materials, general structure are shown in Formulas I:
In formula, X is selected from H, F, Cl, Br or I；For dianhydride residue；N is the degree of polymerization, and value range is n >=2.
In above scheme, the dianhydride residue is one or more of following group:
A kind of preparation method of above-mentioned fast charging and discharging positive electrode active materials, includes the following steps:
Tetracarboxylic acid dianhydride derivative, oxamides, zinc acetate and organic solvent are uniformly mixed, heating is stirred to react,
Cool down, washs, dries to get final product；
The reaction route being related to is shown in Formula II:
In above scheme, the tetracarboxylic acid dianhydride derivative is selected from following compound:
In formula, X is selected from H, F, Cl, Br or I.
In above scheme, the organic solvent is selected from imidazoles, quinoline, N, one or more of N- diethylformamide.
In above scheme, the temperature that is stirred to react is 120~180 DEG C, and the time is 6~120h.
In above scheme, the molar ratio of the tetracarboxylic acid dianhydride derivative, oxamides and zinc acetate is 1:(0.8-1.2):
(0.8-1.2)。
Fast charging and discharging positive electrode active materials obtained by above scheme are applied to prepare alkali metal battery, it can be effectively improved
Specific capacity at higher current densities shows excellent chemical property.
The principle of the present invention are as follows:
The present invention is by forming polymer for oxamides and tetracarboxylic acid dianhydride small molecule reaction, and small point of the acid imide of use
It is molten that son in the pi-pi accumulation in phenyl ring plane is difficult to it with good electric conductivity and in most of common organic solvents
The characteristic of solution, and higher theoretical specific capacity is had both, and dissolubility in the electrolyte can be effectively reduced simultaneously in the synthesis of polymer
Improve cyclical stability；In addition, by introducing additional carbonyl between monomer, the stacking of intermolecular carbonyl forms new ion
Transmission channel, can increase substantially the efficiency of transmission of ion, and then increase substantially the circulation of prepared alkali metal-ion battery
Performance and high rate performance
Compared with prior art, the beneficial effects of the present invention are:
1) in the polymer that the present invention designs, be conducive to sodium by introducing two carbonyls in acid imide interdigit to form one
The ion channel of ion diffusion is to realize fast charging and discharging；
2) resulting polymers of the present invention can express more than existing acid imide under the premise of hardly increasing molecular weight
The active site utilization rate of 60% or more active material, has excellent chemical property and stable circulation performance, and applicability is wide；
3) polymer raw material of the present invention is from a wealth of sources, at low cost, and reaction condition is mild, product without optimization at
Reason, it is easily prepared；
4) preparation method of the present invention is simple, products collection efficiency is high, is suitble to promote and apply.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
A kind of fast charging and discharging positive electrode active materials, preparation method include the following steps:
Sequentially added into 100ml single-necked flask pyromellitic acid anhydride (873mg, 4mmol), oxamides (360.33mg,
4mmol), zinc acetate (807.257mg, 4.4mmol) and imidazoles (10g), stirring are warming up to 90 DEG C, after imidazoles sufficiently melts simultaneously
150 DEG C are continuously heating to, insulated and stirred is reacted for 24 hours；To stop heating after reaction, carried out after system cooled to room temperature
Washing dries filter cake, and washs filter cake with dimethyl sulfoxide, is dried in vacuo, obtains product 1.04g, yield 86%.
Embodiment 2
A kind of fast charging and discharging positive electrode active materials, preparation method include the following steps:
Sequentially added into 100ml single-necked flask naphthalenetetracarbacidic acidic dianhydride (1.07g, 4mmol), oxamides (324.297mg,
3.6mmol), zinc acetate (733.87mg, 4mmol) and imidazoles (10g), stirring are warming up to 90 DEG C, after imidazoles sufficiently melts simultaneously
150 DEG C are continuously heating to, insulated and stirred is reacted for 24 hours；To stop heating after reaction, carried out after system cooled to room temperature
Filter cake is dried in washing.Filter cake is washed with dimethyl sulfoxide, is dried in vacuo, final products obtained therefrom 1.12g, yield 79%.
Embodiment 3
A kind of fast charging and discharging positive electrode active materials, preparation method include the following steps:
It is sequentially added into 100ml single-necked flask tetracarboxylic acid dianhydride (1.57g, 4mmol), oxamides (360.33mg,
4mmol), zinc acetate (733.87mg, 4mmol) and imidazoles (10g), stirring are warming up to 90 DEG C, continue after imidazoles sufficiently melts
150 DEG C are warming up to, insulated and stirred for 24 hours, is heated to stop after reaction, is washed after system cooled to room temperature, is dried
Dry filter cake washs filter cake with dimethyl sulfoxide, vacuum drying, final products obtained therefrom 1.37g, yield 72%.
Embodiment 4
A kind of fast charging and discharging positive electrode active materials, preparation method include the following steps:
5,12- dichloro tetracarboxylic acid dianhydride (1.86g, 4mmol), oxamides are sequentially added into 100ml single-necked flask
(360.33mg, 4mmol), zinc acetate (733.87mg, 4mmol) and imidazoles (10g), stirring is warming up to 90 DEG C, abundant to imidazoles
After fusing and it is continuously heating to 150 DEG C, insulated and stirred for 24 hours, is heated to stop after reaction, after system cooled to room temperature
It is washed, dries filter cake, wash filter cake with dimethyl sulfoxide, be dried in vacuo, final products obtained therefrom 1.59g, yield 77%.
Application examples
The polymer respectively prepared by the embodiment of the present invention 1 or 3 is applied to preparation as positive electrode active materials with sodium metal
For the button-shaped half-cell to electrode, specific steps include:
Embodiment 1 or 3 resulting polymers powder, conductive additive carbon black and adhesive polytetrafluoroethylene (PTFE) are pressed into 7:2 respectively:
1 mass ratio is mixed into electrode paste, and paste is then rolled into the films of about 100 μ m-thicks, and finally electrode film is pressed in aluminium net makes
It uses Na simple substance as cathode, makees separator, 1.0mol using porous polypropylene (Celgard No.2400, Celgard, Inc.)
L-1NaPF6In ethylene carbonate (EC), the mixed solvent (EC/DEC/ of diethyl carbonate (DEC) and propylene carbonate (PC)
PC, volume ratio 45:45:10) in mixing be used as electrolyte.
Button cell is prepared by above step and its ratio of 1000 cyclic charging and discharging tests is carried out under constant current density
Capacity the results are shown in Table 1 and table 2.
The sodium-ion battery specific capacity that table 1 is prepared using 1 products therefrom of embodiment as positive electrode active materials
The sodium-ion battery specific capacity that table 2 is prepared using 3 products therefrom of embodiment as positive electrode active materials
As can be seen from Table 2, using resulting polymers of the present invention as sodium-ion battery positive electrode active materials, have up to
The specific capacity of 145.8mAh/g, and remain to keep 132.5mA h/g after 1000 circulations at high current density (1A/g)
Specific capacity (retention rate up to 91.8%), illustrate it in fast charging and discharging process (the charge and discharge cycles of completion in 16 minutes) still
It can work normally, be a kind of very with the sodium-ion battery positive electrode active materials of application potential.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection scope of the invention.
Claims (8)
1. a kind of fast charging and discharging positive electrode active materials, general structure are shown in Formulas I:
In formula, X is selected from H, F, Cl, Br or I；For dianhydride residue；N is the degree of polymerization, and value range is n >=2.
2. fast charging and discharging positive electrode active materials according to claim 1, which is characterized in that the dianhydride residue is following
One or more of group:
3. the preparation method of fast charging and discharging positive electrode active materials as claimed in claim 1 or 2, which is characterized in that including walking as follows
It is rapid: tetracarboxylic acid dianhydride derivative, oxamides, zinc acetate and organic solvent to be uniformly mixed, heating is stirred to react, and is carried out cold
But, wash, is dry to get final product.
4. preparation method according to claim 3, which is characterized in that the tetracarboxylic acid dianhydride derivative is selected from following chemical combination
One or more of object:
In formula, X is selected from H, F, Cl, Br or I.
5. preparation method according to claim 3, which is characterized in that the organic solvent is selected from imidazoles, quinoline, N, N- bis-
One or more of ethyl-formamide.
6. preparation method according to claim 3, which is characterized in that the temperature that is stirred to react is 120~180 DEG C, when
Between be 6~120h.
7. preparation method according to claim 3, which is characterized in that the tetracarboxylic acid dianhydride derivative, oxamides and vinegar
The molar ratio of sour zinc is 1:(0.8-1.2): (0.8-1.2).
8. fast charging and discharging positive-active obtained by any one of claim 1-2 or any one of claim 3-7 preparation method
Application of the material in alkali metal battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112072062A (en) * | 2020-09-04 | 2020-12-11 | 西北工业大学 | Multi-carbonyl aza-condensed ring material for proton battery and preparation method of electrode thereof |
| CN112694613A (en) * | 2020-12-25 | 2021-04-23 | 武汉工程大学 | Polyimide material, preparation method thereof and application thereof in alkali metal ion battery |
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| US3903046A (en) * | 1972-02-24 | 1975-09-02 | Ciba Geigy Corp | Process for the production of shapeable polymers containing N-silyl groups |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3903046A (en) * | 1972-02-24 | 1975-09-02 | Ciba Geigy Corp | Process for the production of shapeable polymers containing N-silyl groups |
| CN107286157A (en) * | 2017-06-06 | 2017-10-24 | 武汉工程大学 | Yi Zhong perylene diimides class compounds and preparation method thereof, application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112072062A (en) * | 2020-09-04 | 2020-12-11 | 西北工业大学 | Multi-carbonyl aza-condensed ring material for proton battery and preparation method of electrode thereof |
| CN112072062B (en) * | 2020-09-04 | 2023-04-11 | 西北工业大学 | Multi-carbonyl aza-condensed ring material for proton battery and preparation method of electrode thereof |
| CN112694613A (en) * | 2020-12-25 | 2021-04-23 | 武汉工程大学 | Polyimide material, preparation method thereof and application thereof in alkali metal ion battery |
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