CN109400852A - A kind of organic polymer and preparation method based on anthraquinone and the application as anode material for lithium-ion batteries - Google Patents
A kind of organic polymer and preparation method based on anthraquinone and the application as anode material for lithium-ion batteries Download PDFInfo
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
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- C08G2261/40—Polymerisation processes
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Abstract
The present invention relates to a kind of organic polymer based on anthraquinone and preparation method and as the application of anode material for lithium-ion batteries.Polymer is poly- [norbornene 2,3- dimethyl alcohol two (anthraquinone 2- carboxylic acid) ester];By 5- norbornene -2,3- dimethanol and 2- carboxyl anthraquinone under the catalytic action of 4-dimethylaminopyridine and 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, pure monomer is obtained;Monomer is dissolved in good solvent, and polymerization catalyst reaction is added and is terminated with vinyl ethyl ether;Obtain polymer;Convieniently synthesized, raw material is cheap and easy to get.The polymer electrode is applied to the positive electrode of lithium battery, and at higher multiplying power (1C), after 450 circle of circulation, capacity retention ratio is up to 96%, and stability significantly increases;Under the current density of 5C, specific capacity shows excellent high rate performance up to 145mAh/g.
Description
Technical field
It is the invention belongs to lithium ion battery organic electrode materials technical field, in particular to a kind of organic poly- based on anthraquinone
Close object and preparation method and the application as anode material for lithium-ion batteries.
Background technique
Lithium ion battery has been widely used for social life as a kind of highest energy storage device of present energy density
Every aspect living, the especially application in terms of portable electronic product.The presently used positive electrode of lithium ion battery is
Metal oxide or phosphide etc., such as LiCoO2、LiFePO4And nickel-cobalt-manganese ternary material etc..With electric car and intelligence
Can power grid etc. high speed development, seek high-energy density and cheap large-scale energy storage system be meet the market demand it is necessary it
Road.Precious metal chemical complex as positive electrode during the large-scale use of lithium battery, there is at high cost, to environmental pressure
Big and specific capacity is difficult to the shortcomings that further increasing.Organic electrode materials are due to elements groups such as C, H, O, N, S by rich content
At, have many advantages, such as mild low in cost, synthesis condition, structure-rich and it is adjustable, to throw aside rear effect on environment small, become current
The research hotspot of academia and industrial circle is expected to that current inorganic electrode material can be substituted, and especially becomes next-generation organic
The positive electrode of battery.
However, organic electrode materials, especially small molecule electrode material, it is however generally that, there are lacking for cyclical stability difference
Point, this is because acting on compared to ionic bond strong in metallic compound, weaker intermolecular force makes between small organic molecule
Bioactive molecule is dissolved more soluble in by electrolyte solvent.And polymer, especially heavy polymer, due to depositing for chain entanglement
Dissolubility can all substantially reduce, therefore, it is however generally that, the charge and discharge cycles stability of polymer electrode material can obtain very
It is big to improve.In addition, all there is asking for poorly conductive in current organic electrode materials, either small molecule compound or polymer
Topic, so that the high rate performance of organic electrode materials is not ideal enough, which has limited their practical applications in certain fields.Raising follows
Ring stability and high rate performance are the important directions of current organic electrode materials development.
Summary of the invention
The present invention is in view of the above problems and demand, design have synthesized a kind of heavy polymer based on anthraquinone.It should
Polymer monomer it is convieniently synthesized;Polymerization reaction is efficient, conversion ratio 100%.It, can by compound with the graphene of high conductivity
Prepare uniform polymer organic electrode.The organic electrode (polymer-graphite alkene is compound) that the present invention is prepared is used as lithium
The positive electrode of metal battery (half-cell) shows high stability and powerful electrochemical properties.
Technical scheme is as follows:
A kind of organic polymer based on anthraquinone: poly- [norbornene 2,3- dimethyl alcohol two (anthraquinone 2- carboxylic acid) ester];Its
It is characterized in that structural formula is as follows:
Wherein n=300-500;
Nucleus magnetic hydrogen spectrum characterization:1H NMR(CDCl3,298K)δ:8.89(d,2H),8.43(dd,2H),8.35(d,2H),
8.33-8.31(m,2H),8.28-8.26(m,2H),7.82(m,4H),6.33(s,2H),4.72-4.68(m,2H),4.48-
4.43(m,2H),2.94(s,2H),2.25(m,2H),1.70(d,2H),1.54(d,2H)ppm。
A kind of organic polymer preparation method based on anthraquinone of the invention;Include the following steps:
(1) monomer synthesizes: under an inert atmosphere, 5- norbornene -2,3- dimethanol and 2- carboxyl anthraquinone are in 4- diformazan ammonia
Under the catalytic action of yl pyridines and 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, the lower reaction in good solvent;
After the reaction was completed, it extracts, dries, filters, be concentrated, pillar layer separation obtains pure monomer;The wherein feeding quantity of above-mentioned four kinds of drugs
Molar ratio is followed successively by 1:2.2-3:0.15-0.3:2.5-4;
(2) Macroscopic single crystal: under an inert atmosphere, the monomer in step (1) being dissolved in good solvent, and catalyst is added
It is Grubbs third generation catalyst dichloro [bis- (2,4,6- the trimethylphenyl) -2- imidazolidine subunits of 1,3-] (benzal) bis- (3-
Bromopyridine) ruthenium;The molar ratio of monomer and catalyst is 300-500:1;Polymerization reaction is terminated with vinyl ethyl ether;Use poor solvent
Precipitating, washing, filtering, vacuum drying, obtain polymer I.
Reaction equation is as follows:
The inert atmosphere is high pure nitrogen or high-purity argon gas 99.999%.
Reaction temperature in the step 1) is 20~35 DEG C, the reaction time is 5~for 24 hours.
The good solvent used is methylene chloride or tetrahydrofuran;Poor solvent is methanol, n-hexane.
In the step 1) in extraction process, organic phase successively uses 1N dilute hydrochloric acid, saturated sodium bicarbonate, water, saturated common salt
Water is respectively washed twice;Organic phase anhydrous magnesium sulfate or anhydrous sodium sulfate are dry after extraction.
The filler of step 1) the center pillar used in chromatograph is neutral alumina, and the eluent used is petroleum ether: acetic acid
Ethyl ester volume ratio is 10:1.
Reaction temperature is 20~35 DEG C in the step 2), and the reaction time is 1~5h.
Application based on the organic polymer of anthraquinone as electrode material of the invention;Dry polymer I is dissolved in low
In boiling point solvent, stirring be completely dissolved after, be added conductive agent, ultrasonic agitation volatilize completely to solvent, then be added binder and
High boiling solvent, ground and mixed is uniform, and by slurries blade coating on aluminium foil, vacuum drying is rolled into round positive plate;Wherein it polymerize
Object, conductive agent, binder mass ratio be 45~60:45~30:10%.
The amount of taking of the low boiling point solvent (methylene chloride or tetrahydrofuran) is that 60-100mg polymer is molten with 5-10mL
Agent dissolution;Conductive agent is graphene, thickness: 0.55-3.74nm, diameter: 0.5-3 μm, the number of plies < 10;Binder be PVDF or
CMC;High boiling solvent used is N-Methyl pyrrolidone or water.
Reaction temperature in the step 1) is 20~35 DEG C, the reaction time is 5~for 24 hours.
Reaction temperature in the step 2) is 20~35 DEG C, and the reaction time is 1~5h.
Vacuum drying condition is dry 10h at 40 DEG C in the step 2).
To test the assembling condition of the button cell of electrode material in the present invention are as follows: battery assembly is in the hand for being full of argon gas
It is carried out in casing, wherein water, oxygen content are below 0.1ppm;Button cell model is CR2032, and cathode uses lithium metal piece, every
Film is the Celgard 2025 of polyolefins, and the electrolyte used is the 1,3- of the bis- trifluoromethanesulfonimide lithiums (LiTFSI) of 1M
In dioxolanes (DOL)/glycol dimethyl ether (DME) (1/1, v/v) solvent.
Effect of the invention is described as follows:
The present invention relates to a kind of organic polymer based on anthraquinone and preparation method and as the application of electrode anode material.
The Macroscopic single crystal is easy, and raw material is cheap and easy to get, cost when this is by reduction final application;Polymer-graphite alkene combination electrode
Preparation procedure is simple, and the electrode obtained uniformity is good, facilitates the practical application of material.The polymer electrode is applied to lithium battery
Positive electrode, test result show: (1) polymer electrode material is at higher multiplying power (1C), after 450 circle of circulation, capacity
Conservation rate is up to 96%, and stability significantly increases;(2) under optimal conditions, for the electrode under the current density of 5C, specific capacity is reachable
145mAh/g (85% when for 0.1C), shows excellent high rate performance.Therefore, compared to traditional inorganic metal compound
Electrode material, the polymer electrode material is low in cost, preparation is simple, cycle performance and high rate performance are good, is expected to as under
The positive electrode of generation organic battery.
Detailed description of the invention
Fig. 1 is the monomer synthesized in embodiment 1;
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of the polymer I prepared in embodiment 4;
Fig. 3 (a) is the SEM photograph of pure graphene: (thickness: 0.55-3.74nm, diameter: 0.5-3 μm, the number of plies < 10);
Fig. 3 (b) be electrode slice prepared in embodiment 7 SEM photograph (polymer: graphene: PVDF=60:30:
10);
Fig. 3 (c) be electrode slice prepared in embodiment 8 SEM photograph (polymer: graphene: PVDF=45:45:
10);
Fig. 3 (d) be electrode slice prepared in embodiment 9 SEM photograph (polymer: graphene: CMC=45:45:
10);
Fig. 4 (a) is the high rate performance of electrode [multi-walled carbon nanotube: polymer: PVDF=45:45:10];
Fig. 4 (b) is the high rate performance and electrode [graphene: poly- of electrode [graphene: polymer: PVDF=45:45:10]
Close object: PVDF=30:60:10] high rate performance;
Fig. 5 is the high rate performance of the polymer electrode material under different binders;
Fig. 6 is the long circulating performance of polymer electrode (polymer: graphene: PVDF=45:45:10) at 1C;
Fig. 7 is the charging and discharging curve of polymer electrode (polymer: graphene: PVDF=45:45:10) at 1C.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Here it will be understood that after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modification to the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
The synthesis of embodiment 1- monomer
Take a 500mL branch mouth bottle, a built-in magneton;After drying, under nitrogen atmosphere, addition 2.24g (14.5mmol,
1.0eqv) 5- norbornene -2,3- dimethanol, 8g 2- carboxyl anthraquinone (32.0mmol, 2.2eqv), 0.264g (0.220mmol,
0.15eqv) 4-dimethylaminopyridine and 6.52g (36.3mmol, 2.5eqv) 1- (3- dimethylamino-propyl) -3- ethyl carbon two are sub-
400mL methylene chloride is added with syringe in amine hydrochlorate, and under magnetic agitation, 20 DEG C of reactions are for 24 hours.Organic phase successively uses the dilute salt of 1N
Acid, saturated sodium bicarbonate, water, saturated salt solution are respectively washed twice, and 300mL water phase is all used in extraction every time.Last organic phase is with anhydrous
Magnesium sulfate dry about half an hour, sand core funnel filtering, concentrated by rotary evaporation are added 100mL neutral alumina and fry sample.Use neutral alumina
Column is crossed, eluent is petroleum ether: ethyl acetate=10:1, it is final to obtain light yellow product 7.5g (yield 83.3%).Institute of the present invention
The structure of the monomer of synthesis is by liquid nucleus magnetic hydrogen spectrum, nuclear-magnetism carbon spectrum and mass spectral characteristi:1H NMR(CDCl3,298K)δ:8.89
(d,2H),8.43(dd,2H),8.35(d,2H),8.33-8.31(m,2H),8.28-8.26(m,2H),7.82(m,4H),6.33
(s,2H),4.72-4.68(m,2H),4.48-4.43(m,2H),2.94(s,2H),2.25(m,2H),1.70(d,2H),1.54
(d,2H)ppm;13C NMR(CDCl3,298K)δ:181.34,181.14,164.37,137.33,136.05,135.31,
133.79,133.66,133.63,133.56,133.49,132.49,128.16,127.05,66.57,45.52,43.09,
40.51ppm.MS(ESI),m/z calc.for[C39H26O8+Na]+calc.645.15;found 645.1525.Wherein, monomer
Nucleus magnetic hydrogen spectrum is listed in attached drawing 1.
The synthesis of embodiment 2- monomer
Take a 500mL branch mouth bottle, a built-in magneton.After drying, under argon atmosphere, addition 2.24g (14.5mmol,
1.0eqv) 5- norbornene -2,3- dimethanol, 9.1g 2- carboxyl anthraquinone (36.4mmol, 2.5eqv), 0.352g
(0.29mmol, 0.15eqv) 4-dimethylaminopyridine and 7.80g (43.5mmol, 2.5eqv) 1- (3- dimethylamino-propyl) -3-
400mL methylene chloride, the lower 30 DEG C of reactions 10h of magnetic agitation is added with syringe in ethyl-carbodiimide hydrochloride.Organic phase is successively
It is respectively washed twice with 1N dilute hydrochloric acid, saturated sodium bicarbonate, water, saturated salt solution, 300mL water phase is all used in extraction every time.It is last organic
Mutually with anhydrous magnesium sulfate dry about half an hour, sand core funnel filtering, concentrated by rotary evaporation, addition 100mL neutral alumina stir-fry sample.In
Property aluminium oxide cross column, eluent is petroleum ether: ethyl acetate=10:1, final light yellow product 7.6g (yield 84.4%).
The synthesis of embodiment 3- monomer
Take a 500mL branch mouth bottle, a built-in magneton.After drying, under nitrogen atmosphere, addition 2.24g (14.5mmol,
1.0eqv) 5- norbornene -2,3- dimethanol, 10.9 2- carboxyl anthraquinones (43.6mmol, 3.0eqv), 0.528g
(0.440mmol, 0.30eqv) 4-dimethylaminopyridine and 10.4g (58.1mmol, 4.0eqv) 1- (3- dimethylamino-propyl)-
400mL tetrahydrofuran is added with syringe in 3- ethyl-carbodiimide hydrochloride, and under magnetic agitation, 35 DEG C are reacted 5h overnight.It is organic
After being mutually spin-dried for, 400mL methylene chloride is added, is successively respectively washed twice with 1N dilute hydrochloric acid, saturated sodium bicarbonate, water, saturated salt solution,
300mL water phase is all used in extraction every time.Last organic phase is rotated dense with anhydrous magnesium sulfate dry about half an hour, sand core funnel filtering
Contracting is added 100mL neutral alumina and fries sample.Column is crossed with neutral alumina, eluent is petroleum ether: ethyl acetate=10:1, most
Obtain light yellow product 8.0g (yield 88.9%) eventually.
Embodiment 4- Macroscopic single crystal
A 250mL branch mouth bottle is taken, a built-in magneton bakes bottle three times on biexhaust pipe.After bottle is cooled to room temperature, nitrogen
Under atmosphere, 1g monomer is added, 150mL is added with syringe, stirring is to being completely dissolved monomer.Weigh the 4.5mg Grubbs third generation
Catalyst (dichloro [bis- (2,4,6- the trimethylphenyl) -2- imidazolidine subunits of 1,3-] (benzal) bis- (3- bromopyridine) rutheniums) in
The small ampere bottle of 5mL is added 1.6mL dichloromethane solvent, is completely dissolved catalyst.1mL green catalysis is taken out with syringe afterwards
Agent solution is injected into above-mentioned monomer solution (monomer/catalyst molar feed ratio is 500) immediately, and polymerization starts, and stirs at 20 DEG C
Mix 5h.Thin-layer chromatographic analysis, discovery monomer are aggregated completely.Vinyl ethyl ether is added and terminates reaction, continues to stir half an hour.
On biexhaust pipe, vacuum pumps about half solvent, remaining solution is added dropwise in 500mL petroleum ether.Canescence is obtained by filtration
Solid powder.10h is dried in vacuo at 40 DEG C.Weigh to obtain product 0.927g, yield 92.7%.GPC measures the molecular weight of opposite PS
It is 91500, molecular weight distribution 1.91.Wherein, the nucleus magnetic hydrogen spectrum of polymer is listed in attached drawing 2, and monomer reaction is complete, without residual
It stays.
Embodiment 5- Macroscopic single crystal
A 250mL branch mouth bottle is taken, a built-in magneton bakes bottle three times on biexhaust pipe.After bottle is cooled to room temperature, nitrogen
Under atmosphere, 1g monomer is added, 150mL is added with syringe, stirring is to being completely dissolved monomer.Weigh the 5.1mg Grubbs third generation
Catalyst is added 1.42mL dichloromethane solvent, is completely dissolved catalyst in the small ampere bottle of 5mL.1mL is taken out with syringe afterwards
Green catalyst solution is injected into above-mentioned monomer solution (monomer/catalyst molar feed ratio is 400) immediately, and polymerization starts,
3h is stirred at 30 DEG C.Thin-layer chromatographic analysis, discovery monomer are aggregated completely.Vinyl ethyl ether is added and terminates reaction, continues to stir
Mix half an hour.On biexhaust pipe, vacuum pumps about half solvent, remaining solution is added dropwise in 500mL petroleum ether.It filters
To pale solid powder.10h is dried in vacuo at 40 DEG C.Weigh to obtain product 0.915g, yield 91.5%.GPC measures opposite PS
Molecular weight be 74500, molecular weight distribution 1.73.
Embodiment 6- Macroscopic single crystal
A 250mL branch mouth bottle is taken, a built-in magneton bakes bottle three times on biexhaust pipe.After bottle is cooled to room temperature, argon gas
Under atmosphere, 1g monomer is added, 150mL is added with syringe, stirring is to being completely dissolved monomer.Weigh the 6.3mg Grubbs third generation
Catalyst is added 1.34mL dichloromethane solvent, is completely dissolved catalyst in the small ampere bottle of 5mL.1mL is taken out with syringe afterwards
Green catalyst solution is injected into above-mentioned monomer solution (monomer/catalyst molar feed ratio is 300) immediately, and polymerization starts,
1h is stirred at 35 DEG C.Thin-layer chromatographic analysis, discovery monomer are aggregated completely.Vinyl ethyl ether is added and terminates reaction, continues to stir
Mix half an hour.On biexhaust pipe, vacuum pumps about half solvent, remaining solution is added dropwise in 500mL petroleum ether.It filters
To pale solid powder.10h is dried in vacuo at 40 DEG C.Weigh to obtain product 0.91g, yield 91.0%.GPC measures opposite PS's
Molecular weight is 66300, molecular weight distribution 1.45.
Embodiment 7- polymer electrode prepares (polymer: graphene: PVDF=60:30:10)
It takes above-mentioned polymer 60mg to be dissolved in 5mL methylene chloride, to sufficiently dissolve, 30mg graphene (thickness: 0.55- is added
3.74nm, diameter: 0.5-3 μm, the number of plies < 10), ultrasound about half an hour, it is transferred in mortar, stirring to complete volatilization continues abundant
(hand mill) half an hour is ground, PVDF 10mg and few drops of NMP is added, continues grinding about half an hour, homogeneous slurry is scratched in aluminium
On foil, thickness control is 10 μm.After standing 5h, it is transferred in vacuum oven, is dried in vacuo 5h at 50 DEG C.It is rolled into directly with cut-off knife
Diameter is the electrode slice of 9mm, is dried in vacuo 7-9h at 80 DEG C again, it is spare to be then transferred to glove box.Its scanning electron microscope (SEM)
Attached drawing as shown in fig. 3b, compared to the SEM photograph (attached drawing 3a) of graphene, the polymer-graphite alkene combination electrode transparency
It is in a slight decrease, but can't see apparent polymer beads, illustrate that polymer is uniformly dispersed in graphene film, dispersibility is good
It is good.
Embodiment 8- polymer electrode prepares (polymer: graphene: PVDF=45:45:10)
It takes polymer 45mg to be dissolved in 5mL methylene chloride, to sufficiently dissolve, 45mg graphene (thickness: 0.55- is added
3.74nm, diameter: 0.5-3 μm, the number of plies < 10), ultrasound about half an hour, it is transferred in mortar, stirring is fully ground to complete volatilization
PVDF 10mg and few drops of NMP is added in (hand mill) half an hour, continues grinding about half an hour, homogeneous slurry is scratched in aluminium foil
On, thickness control is 10 μm.After standing 5h, it is transferred in vacuum oven, is dried in vacuo 5h at 50 DEG C.Diameter is rolled into cut-off knife
For the electrode slice of 9mm, 7-9h is dried in vacuo at 80 DEG C again, it is spare to be then transferred to glove box.Its scanning electron microscope (SEM) is attached
Figure is as shown in attached drawing 3c, without apparent polymer beads;Attached drawing 3b higher compared to polymer content, the stone of the electrode slice
Black alkene is more transparent, illustrates that electrode slice electric conductivity is stronger.
Embodiment 9- polymer electrode prepares (polymer: graphene: CMC=45:45:10)
It takes above-mentioned polymer 45mg to be dissolved in 5mL methylene chloride, to sufficiently dissolve, 45mg graphene (thickness: 0.55- is added
3.74nm, diameter: 0.5-3 μm, the number of plies < 10), ultrasound about half an hour, it is transferred in mortar, stirring to complete volatilization continues abundant
(hand mill) half an hour is ground, CMC 10mg and few drops of high purity waters are added, continues grinding about half an hour, homogeneous slurry blade coating is existed
On aluminium foil, thickness control is 10 μm.After standing 5h, it is transferred in vacuum oven, is dried in vacuo 5h at 50 DEG C.It is rolled into cut-off knife
Diameter is the electrode slice of 9mm, is dried in vacuo 7-9h at 80 DEG C again, it is spare to be then transferred to glove box.Its scanning electron microscope
(SEM) for attached drawing as shown in attached drawing 3d, the spectrogram is similar with Fig. 3 c of same polymer content.
Embodiment 10- battery assembly and test condition
Battery be assembled in water, oxygen content be below 0.1ppm, using high-purity argon gas to be implemented in the glove box of atmosphere.Electricity
Pond uses 2032 model button cell structures, and Celgard2500 is as diaphragm, and for metal lithium sheet as cathode, what is be prepared is poly-
Object electrode is closed as anode, electrolyte uses 1M LiTFSI in DOL:DME (v/v=1:1).Assemble being placed on for battery
Land 2001A battery test system carries out electrochemical property test, and test voltage window is 1.5-3.0V.Test condition is root
According to needing to have following three kinds of situations respectively: (1) different polymer electrodes, i.e., times under different conductive agents and different conductive agent ratios
Rate performance: 0.1C, 0.3C, 0.5C, 0.7C, 1.0C, 2.0C, 3.0C and 5C (1C=172.3mAg-1);(2) under different binders
High rate performance test;(3) at higher current density (1C), long circulating stability test.Fig. 3 to Fig. 5 gives accordingly
Test result.
Test result analysis is discussed below.Attached drawing 4a lists times using multi-walled carbon nanotube as the contrast sample of conductive agent
Rate performance, the high rate performance is very poor, and when current density is 0.6C, specific capacity is only the 25% of 0.1C.By attached drawing 4b it is found that
With graphene carry out it is solution combined after, using PVDF as binder, the high rate performance of material is greatly improved.Even if in electricity
When current density is 1C, capacity is not also decreased obviously, and is maintained at 160mAh/g or so;When current density is 2C, capacity is remained to
Keep about 145mAh/g or so, about 87.5% or so of initial capacity.Meanwhile discovery is tested, increase the content of graphene, i.e.,
It is increased to 60wt% from 45wt%, when current density is 3C, remains to the specific capacity for being kept close to 120mAh/g.Research hair
Existing, binder type also has an impact to the high rate performance of material.As shown in Fig. 5, when using hydroxymethyl cellulose as binder,
Under the current density of 5C, specific capacity is up to 145mAh/g.Last long circulating test shows (attached drawing 6), and the electrode material is in 1C
After lower 450 circle of circulation, capacity retention ratio 95%, stability is significantly increased;Moreover, can be seen that by the cyclic curve of attached drawing 7,
After 400 circles, without obvious polarization.
A kind of organic polymer and preparation method based on anthraquinone that the present invention is disclosed and proposed and as lithium ion battery
The application of positive electrode, those skilled in the art can be by using for reference present disclosure, and the appropriate links such as condition route that change are realized, to the greatest extent
Pipe method of the invention and technology of preparing are described by preferred embodiment, and related technical personnel can obviously not take off
Methods and techniques described herein route is modified or is reconfigured from the content of present invention, spirit and scope, Lai Shixian
Final technology of preparing.In particular, it should be pointed out that all similar replacements and change are for a person skilled in the art
It will be apparent that they are considered as being included in spirit of that invention, range and content.
Claims (10)
1. a kind of organic polymer based on anthraquinone, it is characterized in that polymer is poly- [norbornene 2, two (anthraquinone of 3- dimethyl alcohol
2- carboxylic acid) ester];Structural formula is as follows:
Wherein n=300-500.
2. polymer as described in claim 1, it is characterized in that poly- [norbornene 2,3- dimethyl alcohol two (anthraquinone 2- carboxylic acid)
Ester] nucleus magnetic hydrogen spectrum characterization:1HNMR(CDCl3,298K)δ:8.89(d,2H),8.43(dd,2H),8.35(d,2H),8.33-8.31
(m,2H),8.28-8.26(m,2H),7.82(m,4H),6.33(s,2H),4.72-4.68(m,2H),4.48-4.43(m,2H),
2.94(s,2H),2.25(m,2H),1.70(d,2H),1.54(d,2H)ppm。
3. a kind of organic polymer preparation method based on anthraquinone of claim 1;It is characterized in that including the following steps:
(1) monomer synthesizes: under an inert atmosphere, 5- norbornene -2,3- dimethanol and 2- carboxyl anthraquinone are in 4- dimethylamino pyrrole
Under pyridine and the catalytic action of 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, the lower reaction in good solvent;Reaction
After the completion, it extracts, dries, filters, be concentrated, pillar layer separation obtains pure monomer;Wherein 5- norbornene -2,3- dimethanol, 2-
The feeding quantity mole of carboxyl anthraquinone, 4-dimethylaminopyridine and 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride
Than for 1:2.2-3:0.15-0.3:2.5-4;
(2) Macroscopic single crystal: under an inert atmosphere, the monomer in step (1) being dissolved in good solvent, and Grubbs third is added
For catalyst dichloro [bis- (2,4,6- the trimethylphenyl) -2- imidazolidine subunits of 1,3-] (benzal) bis- (3- bromopyridine) rutheniums;It is single
The molar ratio of body and catalyst is 300-500:1;Polymerization reaction is terminated with vinyl ethyl ether;With poor solvent precipitating, washing, mistake
Filter, vacuum drying, obtain polymer I.
4. method as claimed in claim 3, it is characterized in that the reaction temperature in the step 1) is 20~35 DEG C, the reaction time
For 5~for 24 hours.
5. method as claimed in claim 3, it is characterized in that the good solvent used is methylene chloride or tetrahydrofuran;It is bad
Solvent is methanol or n-hexane.
6. method as claimed in claim 3, it is characterized in that organic phase successively uses the dilute salt of 1N in the step 1) in extraction process
Acid, saturated sodium bicarbonate, water, saturated salt solution are respectively washed twice;Organic phase anhydrous magnesium sulfate or anhydrous sodium sulfate are dry after extraction
It is dry.
7. method as claimed in claim 3, it is characterized in that the filler of step 1) the center pillar used in chromatograph is neutral alumina
Aluminium, the eluent used is petroleum ether: ethyl acetate volume ratio 10:1.
8. method as claimed in claim 3, it is characterized in that reaction temperature is 20~35 DEG C in the step 2), the reaction time is
1~5h.
9. the preparation method based on the organic polymer of anthraquinone as electrode material of claim 1;It is characterized in that by dry
Polymer I is dissolved in low boiling point solvent, after stirring is completely dissolved, conductive agent is added, ultrasonic agitation is volatilized completely to solvent, then
Binder and high boiling solvent is added, ground and mixed is uniform, and by slurries blade coating on aluminium foil, vacuum drying is being rolled into circle just
Pole piece;Wherein polymer, conductive agent, binder mass ratio be 45~60:45~30:10.
10. method as claimed in claim 9 is taken it is characterized in that low boiling point solvent is methylene chloride or tetrahydrofuran solvent
Amount is that 60-100mg polymer 5-10mL solvent dissolves;Conductive agent is graphene, thickness: 0.55-3.74nm, diameter: 0.5-3
μm, the number of plies < 10;Binder is PVDF or CMC;High boiling solvent used is N-Methyl pyrrolidone or water.
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CN110606936A (en) * | 2019-09-23 | 2019-12-24 | 天津大学 | Poly [ norbornene 1, 4-dimethyl dinaphthoquinone ] and preparation method and application thereof |
CN111211327A (en) * | 2020-01-10 | 2020-05-29 | 天津大学 | Compound for lithium ion battery anode material and preparation method and application thereof |
CN112480424A (en) * | 2020-12-07 | 2021-03-12 | 华南师范大学 | Application of anthraquinone-2, 3-dicarboxylic acid calcium coordination polymer as lithium ion battery anode material |
FR3107614A1 (en) * | 2020-02-21 | 2021-08-27 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Process for preparing a particulate composite material for an organic electrode |
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CN108461752A (en) * | 2018-03-12 | 2018-08-28 | 华南师范大学 | A kind of side chain carries triphen amine polymer and the preparation and application of conjugated carbonyl compound |
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CN107312114A (en) * | 2016-04-27 | 2017-11-03 | 北京理工大学 | A kind of azide polymer with polynorbornene backbone structure and preparation method thereof |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110606936A (en) * | 2019-09-23 | 2019-12-24 | 天津大学 | Poly [ norbornene 1, 4-dimethyl dinaphthoquinone ] and preparation method and application thereof |
CN110606936B (en) * | 2019-09-23 | 2022-03-15 | 天津大学 | Poly [ norbornene 1, 4-dimethyl dinaphthoquinone ] and preparation method and application thereof |
CN111211327A (en) * | 2020-01-10 | 2020-05-29 | 天津大学 | Compound for lithium ion battery anode material and preparation method and application thereof |
CN111211327B (en) * | 2020-01-10 | 2022-10-25 | 天津大学 | Compound for lithium ion battery anode material and preparation method and application thereof |
FR3107614A1 (en) * | 2020-02-21 | 2021-08-27 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Process for preparing a particulate composite material for an organic electrode |
CN112480424A (en) * | 2020-12-07 | 2021-03-12 | 华南师范大学 | Application of anthraquinone-2, 3-dicarboxylic acid calcium coordination polymer as lithium ion battery anode material |
CN112480424B (en) * | 2020-12-07 | 2022-08-19 | 华南师范大学 | Application of anthraquinone-2, 3-dicarboxylic acid calcium coordination polymer as lithium ion battery anode material |
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