CN108615867A - A kind of organic macromolecule negative material and preparation method thereof for secondary cell - Google Patents
A kind of organic macromolecule negative material and preparation method thereof for secondary cell Download PDFInfo
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- CN108615867A CN108615867A CN201810420792.6A CN201810420792A CN108615867A CN 108615867 A CN108615867 A CN 108615867A CN 201810420792 A CN201810420792 A CN 201810420792A CN 108615867 A CN108615867 A CN 108615867A
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/362—Composites
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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
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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Abstract
The present invention discloses a kind of organic macromolecule negative material and preparation method thereof for secondary cell, the organic macromolecule negative material is the multi-layer compound structure of metal phthalocyanine tetrasulfonic acid four salt lamellas and the alternately stacked formation of graphene oxide layer, and the mass ratio of four salt lamella of the metal phthalocyanine tetrasulfonic acid and graphene oxide layer is (1~4):1, the thickness of the multi-layer compound structure is 2~20um.It uses four salt of metal phthalocyanine tetrasulfonic acid, using graphene oxide as template, using hydro-thermal sonic oscillation method one-step synthesis.The product can solve the problems, such as to be dissolved in electrolyte in electrochemical reaction process, at the same it is compound after greatly strengthen its electric conductivity；And it is excellent for secondary battery system energy-storage property, it is more than most of organic electrode materials.
Description
Technical field
The present invention relates to the negative material technical fields of secondary cell, and in particular to a kind of for the organic big of secondary cell
Molecule negative material and preparation method thereof.
Background technology
It is considered as before most having in electric vehicle and portable electronic device by the secondary cell of representative of lithium ion battery
The energy storage device on way has excellent energy-storage property and high energy density.Currently, most of secondary cells use inorganic material
As commercialized electrode material, such as LiCoO2And LiFePO4.However, resource exhaustion, environmental pollution are serious, it is allowed to hold
Continue or not can be recycled, the demand of growing energy market far can not be met.And since Williams et al. are 1969
Year for the first time use organic electrode materials since, due to its abundant natural resources, environmentally friendly and organic molecule diversity and
Cause the extensive concern of people.Organic battery material perhaps can become the inexpensive battery of next-generation Green Sustainable
Optimal selection.
Green (W Ai, W Zhou, Z Du, the et al. (2017) of the organic electrode materials reported at present such as reducing agent
TowardHigh Energy Organic Cathodes for Li-Ion Batteries:A Case Study of Vat
Dye/Graphene Composites Advanced Functional Materials 27.), organic nano hybrid (M
Lee,J Hong,H Kim,et al.(2014)Organic Nanohybrids for Fast and Sustainable
Energy Storage Adv.Mater.26:2558.), quinone derivative (T Nokami, T Matsuo, Y Inatomi, et
al.(2012)Polymer-Bound Pyrene-4,5,9,10-tetraone for Fast-Charge and-Discharge
Lithium-Ion Batteries with High Capacity Journal of the American
ChemicalSociety 134:19694.) etc..However organic battery material there are still some universal problems hinder it into
One step develops.First, organic electrode materials poor chemical stability, due to similar compatibility, they are easy to be dissolved in organic electricity
Xie Zhizhong causes capacity of the battery in prolonged electrochemical reaction process gradually to be decayed, it is made to be difficult to reach commercialized
It is required that；Second, in battery system, the poorly conductive of most organic materials, in electrochemical reaction system so that organic
The actual specific capacity of battery, which is unable to get, to be made full use of.
Invention content
For above-mentioned organic electrode materials poor chemical stability, battery capacity gradually decays, and poorly conductive make it is organic
The actual specific capacity of battery is unable to get the problem of making full use of, and the present invention provides a kind of organic macromolecule for secondary cell
Negative material and preparation method thereof.
The technical solution of first aspect provided by the invention is a kind of organic macromolecule negative material for secondary cell,
The organic macromolecule negative material is four salt lamella of metal phthalocyanine tetrasulfonic acid and the alternately stacked formation of graphene oxide layer
The mass ratio of multi-layer compound structure, four salt lamella of the metal phthalocyanine tetrasulfonic acid and graphene oxide layer is (1~4):1, institute
The thickness for stating multi-layer compound structure is 2~20um.
Heretofore described four salt of metal phthalocyanine tetrasulfonic acid is a kind of phthalocyanine derivates, is used as organic macromolecule dyestuff
One of, there is special two-dimentional conjugated pi electron structure and higher photo and thermal stability.It is widely used in optical device, titanium dioxide
The fields such as electrochemical reduction, electrochemical sensor, the coloring agent of carbon.Four salt of discovery metal phthalocyanine tetrasulfonic acid of applicant's creativeness
Above-mentioned field is can not only be applied to, and can be used in secondary battery system, since four salt of metal phthalocyanine tetrasulfonic acid itself is
A kind of organic salt does not dissolve in organic solvent, solves it from the root cause and be dissolved in electrolyte in electrochemical reaction process
Problem；It is compounded to form multi-layer compound structure by itself and graphene oxide, can greatly be increased while not destroying original structure
Its strong electric conductivity, can be in contact with more active sites in electrochemical reaction, can make full use of its capacity, be used for
Secondary battery system, energy-storage property is excellent, is more than most of organic electrode materials.
The technical solution of second aspect provided by the invention is the above-mentioned organic macromolecule negative material for secondary cell
Preparation method, take four salt of metal phthalocyanine tetrasulfonic acid, using graphene oxide as template, using one step of hydro-thermal sonic oscillation method close
At four salt of metal phthalocyanine tetrasulfonic acid and graphene oxide compound to get the organic macromolecule negative material.
Preferably, four salt of hydro-thermal sonic oscillation method one-step synthesis metal phthalocyanine tetrasulfonic acid and graphene oxide compound
Specially：It takes four salt of metal phthalocyanine tetrasulfonic acid that deionized water dissolving is added and obtains four salting liquid of metal phthalocyanine tetrasulfonic acid completely, take
The mixed solution of second alcohol and water is added in graphene oxide, and sonic oscillation uniformly obtains graphene oxide liquid mixture, by metal phthalocyanine
Hydro-thermal is compound after mixing for four salting liquid of tetrasulfonic acid and graphene oxide liquid mixture, by being freeze-dried up to the metal
Four salt of phthalocyanine tetrasulfonic acid and graphene oxide compound.
Wherein, graphene oxide prepares to be formed by crystalline flake graphite freeze-drying.
Preferably, four salt of metal phthalocyanine tetrasulfonic acid is nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt, four sulphur of nickel (II) phthalocyanine
Any one in sour four sylvite.
Preferably, the mass ratio of four salt of metal phthalocyanine tetrasulfonic acid and the graphene oxide is (1~4):1.
Preferably, it is (1~8) that the mixed solution of the second alcohol and water, which is by volume ratio,：1 second alcohol and water is mixed to prepare.
Preferably, the temperature of the sonic oscillation is 20~50 DEG C, and the time is 0.3~0.5h.
Preferably, the compound temperature of the hydro-thermal be 120~250 DEG C, the time be 12~for 24 hours.
More preferably, the compound temperature of the hydro-thermal be 160~200 DEG C, the time be 12~for 24 hours.
Preferably, the incorporation time of four salting liquid of metal phthalocyanine tetrasulfonic acid and the graphene oxide liquid mixture is 4
~5h.
Preferably, the secondary cell is any one in lithium battery, sode cell, potassium battery.
Based on described above, compared with prior art, the present invention advantage is：(1) metal phthalocyanine tetrasulfonic acid four
Salt itself is a kind of organic salt, does not dissolve in organic solvent, solves it from the root cause and be dissolved in electrochemical reaction process
The problem of electrolyte；(2) with graphene oxide physics it is compound during not only without destroying original structure, and it is compound after
Its electric conductivity is greatly strengthened, can be in contact with more active sites in electrochemical reaction, can make full use of its capacity；
(3) four salt of metal phthalocyanine tetrasulfonic acid is proposed for secondary battery system for the first time, and energy-storage property is excellent, is more than most of organic
Electrode material.
Description of the drawings
Fig. 1 is the schematic arrangement of nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt in embodiment 1；
Fig. 2 is the XPS spectrum figure of the compound of nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt and graphene oxide in embodiment 1；
Fig. 3 is the SEM spectrum of the compound of nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt and graphene oxide in embodiment 1；
Fig. 4 is that nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt is close in different electric currents from the compound of graphene oxide in embodiment 1
Multiplying power collection of illustrative plates under degree.
Specific implementation mode
In order to make those skilled in the art more fully understand technical scheme of the present invention, with reference to specific embodiment pair
The present invention is described in further detail.
Embodiment 1
A kind of organic macromolecule negative material for secondary cell described in the present embodiment is metal phthalocyanine tetrasulfonic acid
The multi-layer compound structure of four salt lamellas and the alternately stacked formation of graphene oxide layer, thickness are 2~20um.Preparation method
Include the following steps：
Step 1：The 180m concentrated sulfuric acids and 20ml concentrated phosphoric acids are measured respectively, then weigh 1.5g crystalline flake graphites；
Step 2：Room-temperature water bath, the concentrated sulfuric acid, concentrated phosphoric acid and flake graphite are put into three-necked flask, and slowly mechanical
Then stirring divides 3~5 times and 6~10g potassium permanganate is added and control temperature is kept to be not higher than 50 DEG C, then by the mixture of generation
Mechanical agitation 12~24 hours between 40~55 DEG C, until blackish green liquid becomes the liquid of brown, finally by hydrogen peroxide
It is slowly added into mixing liquid, until color becomes glassy yellow from brown and not extra bubble generates；
Step 3：The yellow mercury oxide that will be obtained, it is neutral to be cleaned repeatedly with deionized water to pH, then is frozen into ice
Block is put into freeze drying box, finally obtains black oxidation graphene；
Step 4：It weighs 160mg nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt (TsNiPc, molecular structure are shown in Fig. 1) and is dissolved in 40ml
0.5h is stirred in deionized water solution to being completely dissolved；40mg graphene oxides are weighed again is dissolved in (ethyl alcohol in 30ml mixed solutions：
Water=2：1) the sonic oscillation 0.5h, and at 30 DEG C, two kinds of solution are uniformly mixed and stir 4h；
Step 5：Above-mentioned mixed solution is put into polytetrafluoroethyllining lining crystallizing kettle, high temperature hydro-thermal is for 24 hours at 180 DEG C；
Step 6：Above-mentioned mixed solution is put into refrigerator freezing into ice cube, is then placed into freeze drier until black
The ice cube of color becomes the powder of atropurpureus completely, obtains the compound of nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt and graphene oxide
(TsNiPc@GO), as the organic macromolecule negative material described in the present embodiment.
Above-mentioned organic macromolecule negative material is fabricated to lithium battery：
Step 7：By prepared organic macromolecule negative material and acetylene black and PVDF with 7：2：1 ratio uniform applies
It applies on copper foil, with 110 DEG C of Temperature Vacuum drying 12~for 24 hours, the electrode slice dried is cut into diameter with slitter
For the sequin of 14mm, and put it into oxygen and water content is below in 0.5ppm and glove box full of argon gas；
Step 8：Using the button cell mold of CR2032 models, using Celgard2500 as diaphragm, 1M LiPF6It is molten
In volume ratio be 1：1：1 EC：DEC：Electrolyte is used as in DMC mixed solutions, using metal lithium sheet as to electrode, in glove box
The inside assembles button cell.
XPS spectrum figure, the SEM of the compound of nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt and graphene oxide described in the present embodiment
Collection of illustrative plates and multiplying power collection of illustrative plates under different current densities are as shown in figs. 2 to 4.
The battery is tested after 100 circle of cycle by blue electric tester, in the case where current density is the size of 100mA/g,
Its reversible capacity has 460mAh/g.
Embodiment 2
A kind of organic macromolecule negative material for secondary cell described in the present embodiment is metal phthalocyanine tetrasulfonic acid
The multi-layer compound structure of four salt lamellas and the alternately stacked formation of graphene oxide layer, thickness 2-20um.Preparation method
Include the following steps：
Step 1~step 3, such as embodiment 1；
Step 4：Weigh four sylvite of 80mg nickel (II) phthalocyanine tetrasulfonic acid be dissolved in 40ml deionized water solutions stir 0.5h extremely
It is completely dissolved；40mg graphene oxides are weighed again is dissolved in (ethyl alcohol in 30ml mixed solutions：Water=1：1), and ultrasonic at 20 DEG C
0.5h is vibrated, two kinds of solution are uniformly mixed and stir 4h；
Step 5：Above-mentioned mixed solution is put into polytetrafluoroethylkettle kettle, high temperature hydro-thermal is for 24 hours at 120 DEG C；
Step 6：Above-mentioned mixed solution is put into refrigerator freezing into ice cube, is then placed into freeze drier until black
The ice cube of color becomes the powder of atropurpureus completely, obtains the compound of four sylvite and graphene oxide of nickel (II) phthalocyanine tetrasulfonic acid,
Organic macromolecule negative material as described in the present embodiment.
Above-mentioned organic macromolecule negative material is fabricated to lithium battery, such as embodiment 1.
The battery is tested after 100 circle of cycle by blue electric tester, in the case where current density is the size of 100mA/g,
Its reversible capacity has 420mAh/g.
Embodiment 3
A kind of organic macromolecule negative material for secondary cell described in the present embodiment is metal phthalocyanine tetrasulfonic acid
The multi-layer compound structure of four salt lamellas and the alternately stacked formation of graphene oxide layer, thickness are 2~20um.Preparation method
Include the following steps：
Step 1~step 3, such as embodiment 1；
Step 4：Weigh 40mg nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt be dissolved in 40ml deionized water solutions stir 0.5h extremely
It is completely dissolved；40mg graphene oxides are weighed again is dissolved in (ethyl alcohol in 30ml mixed solutions：Water=8：1), and ultrasonic at 50 DEG C
0.3h is vibrated, two kinds of solution are uniformly mixed and stir 4h；
Step 5：Above-mentioned mixed solution is put into polytetrafluoroethyllining lining crystallizing kettle, the high temperature hydro-thermal 12h at 250 DEG C；
Step 6：Above-mentioned mixed solution is put into refrigerator freezing into ice cube, is then placed into freeze drier until black
The ice cube of color becomes the powder of atropurpureus completely, obtains the compound of nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt and graphene oxide,
Organic macromolecule negative material as described in the present embodiment.
Above-mentioned organic macromolecule negative material is fabricated to lithium battery, such as embodiment 1.
The battery is tested after 100 circle of cycle by blue electric tester, in the case where current density is the size of 100mA/g,
Its reversible capacity has 404mAh/g.
Comparative example 1
Organic electrode materials described in this comparative example, preparation method includes the following steps：
Step 1：Four sylvite of 70mg nickel (II) phthalocyanine tetrasulfonic acid is weighed, 20mg acetylene blacks and 10mgPVDF are uniformly mixed simultaneously
Coated on copper foil, with 110 DEG C of Temperature Vacuum drying 12~for 24 hours, the electrode slice dried is cut into directly with slitter
Diameter is the sequin of 14mm, and puts it into oxygen and water content is below in 0.5ppm and glove box full of argon gas；
Step 2：Using the button cell mold of CR2032 models, using Celgard2500 as diaphragm, 1M LiPF6It is molten
In volume ratio be 1：1：1 EC：DEC：Electrolyte is used as in DMC mixed solutions, using metal lithium sheet as to electrode, in glove box
The inside assembles button cell.
By testing the battery on blue electric tester after 100 circle of cycle, in the condition that current density is 100mA/g
Under, reversible capacity has 230mAh/g.
By 1~embodiment of embodiment 3 and comparative example 1 as it can be seen that organic macromolecule negative material system of the present invention
It is standby at lithium battery, reversible capacity reaches 450mAh/g or more, and energy-storage property is excellent, is more than most of organic electrode material
Material, while the lithium battery prepared with graphene oxide compound using four salt of metal phthalocyanine tetrasulfonic acid is relative to only using metal phthalocyanine
Lithium battery prepared by four salt of tetrasulfonic acid, reversible capacity greatly improve, and pass through four salt of metal phthalocyanine tetrasulfonic acid and graphene oxide
Its electric conductivity is greatly strengthened after compound, can be in contact with more active sites in electrochemical reaction, it can be fully sharp
With its capacity.
Embodiment 4
The present embodiment is identical as the first seven step of embodiment 1, and the organic macromolecule negative material of preparation gone out is fabricated to sodium
Battery, i.e., in step 8, using the button cell mold of CR2032 models, using glass fiber as diaphragm, 0.8M NaPF6
It is 1 to be dissolved in volume ratio：1 EC：Electrolyte is used as in DEC mixed solutions, using metallic sodium piece as to electrode, inside glove box
Assemble button cell.
By testing the battery on blue electric tester after 100 circle of cycle, in the condition that current density is 100mA/g
Under, reversible capacity has 203mAh/g.
Embodiment 5
The present embodiment is identical as the first seven step of embodiment 1, and the organic macromolecule negative material of preparation gone out is fabricated to potassium
Battery, i.e., in step 8, using the button cell mold of CR2032 models, using glass fiber as diaphragm, 0.8M KPF6
It is 1 to be dissolved in volume ratio：1 EC：Electrolyte is used as in DEC mixed solutions, using metallic potassium piece as to electrode, inside glove box
Assemble button cell.
By testing the battery on blue electric tester after 100 circle of cycle, in the condition that current density is 100mA/g
Under, reversible capacity has 107mAh/g.
By 4~embodiment of embodiment, 5 data as it can be seen that organic macromolecule negative material of the present invention can also be prepared
Sode cell and potassium battery, the sode cell prepared and potassium battery, reversible capacity relative to conventional sode cell and potassium battery significantly
It is promoted.
It the above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair
The limitation of the present invention, protection scope of the present invention should be subject to claim limited range.For the art
For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change
Protection scope of the present invention is also should be regarded as into retouching.
Claims (10)
1. a kind of organic macromolecule negative material for secondary cell, it is characterised in that：The organic macromolecule negative material
For the multi-layer compound structure of metal phthalocyanine tetrasulfonic acid four salt lamellas and the alternately stacked formation of graphene oxide layer, the metal phthalein
Four salt lamella of cyanines tetrasulfonic acid and the mass ratio of graphene oxide layer are (1~4):1, the thickness of the multi-layer compound structure is 2
~20um.
2. the preparation method described in a kind of claim 1 for the organic macromolecule negative material of secondary cell, it is characterised in that：
Four salt of metal phthalocyanine tetrasulfonic acid is taken, using graphene oxide as template, using hydro-thermal sonic oscillation method one-step synthesis metal phthalocyanine
Four salt of tetrasulfonic acid is with graphene oxide compound to get the organic macromolecule negative material.
3. the preparation method of the organic macromolecule negative material according to claim 2 for secondary cell, feature exist
In：Four salt of hydro-thermal sonic oscillation method one-step synthesis metal phthalocyanine tetrasulfonic acid is specially with graphene oxide compound：Take gold
Belong to four salt addition deionized water dissolving of phthalocyanine tetrasulfonic acid and obtain four salting liquid of metal phthalocyanine tetrasulfonic acid completely, graphene oxide is taken to add
Enter the mixed solution of second alcohol and water, sonic oscillation uniformly obtains graphene oxide liquid mixture, and four salt of metal phthalocyanine tetrasulfonic acid is molten
Hydro-thermal is compound after mixing for liquid and graphene oxide liquid mixture, by being freeze-dried up to the metal phthalocyanine tetrasulfonic acid four
Salt and graphene oxide compound.
4. the preparation method of the organic macromolecule negative material according to claim 3 for secondary cell, feature exist
In：Four salt of metal phthalocyanine tetrasulfonic acid is in nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt, four sylvite of nickel (II) phthalocyanine tetrasulfonic acid
Any one.
5. the preparation method of the organic macromolecule negative material according to claim 3 for secondary cell, feature exist
In：The mass ratio of four salt of metal phthalocyanine tetrasulfonic acid and the graphene oxide is (1~4):1.
6. the preparation method of the organic macromolecule negative material according to claim 3 for secondary cell, feature exist
In：It is (1~8) that the mixed solution of the second alcohol and water, which is by volume ratio,：1 second alcohol and water is mixed to prepare.
7. the preparation method of the organic macromolecule negative material according to claim 3 for secondary cell, feature exist
In：The temperature of the sonic oscillation is 20~-50 DEG C, and the time is 0.3~0.5h.
8. the preparation method of the organic macromolecule negative material according to claim 3 for secondary cell, feature exist
In：The compound temperature of the hydro-thermal be 120~250 DEG C, the time be 12~for 24 hours.
9. the preparation method of the organic macromolecule negative material according to claim 3 for secondary cell, feature exist
In：The incorporation time of four salting liquid of metal phthalocyanine tetrasulfonic acid and the graphene oxide liquid mixture is 4~5h.
10. the preparation method of the organic macromolecule negative material according to claim 3 for secondary cell, feature exist
In：The secondary cell is any one in lithium battery, sode cell, potassium battery.
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| CN110148750A (en) * | 2019-04-08 | 2019-08-20 | 东莞天予天正新能源科技有限公司 | A kind of cathode material of lithium ion battery and preparation method thereof |
| CN111446428A (en) * | 2020-03-23 | 2020-07-24 | 珠海冠宇电池股份有限公司 | Lithium negative electrode material and application thereof |
| CN111446428B (en) * | 2020-03-23 | 2021-04-20 | 珠海冠宇电池股份有限公司 | Lithium negative electrode material and application thereof |
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