CN104993146A - Method for preparation of highly conductive slurry by doping fluorinated graphene - Google Patents
Method for preparation of highly conductive slurry by doping fluorinated graphene Download PDFInfo
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- CN104993146A CN104993146A CN201510287766.7A CN201510287766A CN104993146A CN 104993146 A CN104993146 A CN 104993146A CN 201510287766 A CN201510287766 A CN 201510287766A CN 104993146 A CN104993146 A CN 104993146A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Relating the field of highly conductive slurry preparation methods, the invention provides a method for preparation of a highly conductive slurry by doping fluorinated graphene, and solves the technical problems that existing mature conductive slurry has poor conductivity and has poor compatibility with an electrolyte solution. The method consists of the steps of: (1) weighing a conductive slurry, fluorinated graphene, a dispersing agent and deionized water according to a mass ratio of 100:5-15:3-5:700; (2) mixing the dispersing agent with half of the deionized water, performing vacuum pumping and conducting stirring for 1h; (3) adding the conductive slurry, and conducting vacuum stirring for 1.5h; (4) adding fluorinated graphene, conducting vacuum pumping and performing stirring for 2h; and (5) adding the remaining the deionized water, conducting vacuum pumping and performing stirring for 30min, measuring the viscosity and solid content of the prepared slurry to make the viscosity at 100-500mpa.s and the solid content at 3%-8%. By adding the fluorinated graphene, the conductivity and compatibility with electrolyte solution of the slurry are further enhanced, and the comprehensive performance of batteries can be improved significantly.
Description
Technical field
The present invention relates to a kind of compound method field of high-conductivity slurry, specifically a kind of preparation method preparing a kind of high-conductivity slurry on the basis of adult form electrocondution slurry.
Background technology
Research finds by reducing the internal resistance of cell, improve the conductive capability of conductive substrate material, greatly can improve the multiplying power discharging property of battery, and in high-multiplying power discharge situation, battery heat heats up steadily, less to battery cathode surface SEI membrane damage, improve the security performance of battery, simultaneously by improving matrix electron transmission, reducing battery polarization, improving the cycle performance of battery.We found through experiments, and basis material applies the high conductive material of 1u ~ 2u, and can reduce battery polarization internal resistance, security performance is improved, and its cycle performance also increases simultaneously, improves battery combination property.
Since strong K sea nurse (Andre K. Geim) of the peace moral of Univ Manchester UK etc. prepared grapheme material in 2004, pay attention to widely because the structure of its uniqueness and photoelectric property receive people.Graphene is called " nova " that material science and Condensed Matter Physics field are being risen, many novelties that it has and the character of uniqueness and potential application have just attracted many scientific workers.Single-layer graphene has large specific area, excellent conduction, heat conductivility and low thermal coefficient of expansion.As: 1. high strength, Young mole, (1,100 GPa), fracture strength: (125GPa); 2. high heat conductance, (5,000 W/mK); 3. high conductivity, carrier transport rate, (200,000 cm2/V*s); 4. high specific area, (calculated value: 2,630 m2/g).Especially its high connductivity character, the structural property of the nanoscale of large specific surface character and its monolayer two dimension, can be used as electrode material in ultracapacitor and lithium ion battery.In addition, fluorographite is as the active material of high-performance lithium ion battery, and oneself causes great interest and the attention of mechanism of new electrochemical power sources researchers, and has succeeded in developing corresponding high-energy battery.Fluorographite-lithium battery has following excellent performance: (1) voltage is high, energy density is high.(2) high, the voltage of utilance is steady etc.But the conductivity of fluorinated graphite material and stability low, thus limit its application as conductive agent.Fluorinated graphene, owing to having higher conductivity and having good compatibility with electrolyte, can be applicable in lithium ion battery and ultracapacitor.
Based on above reason, in conjunction with current also without any the report being used for electrocondution slurry about fluorinated graphene.We are by adding fluorinated graphene, and the basis of existing adult form electrocondution slurry is prepared the good and preparation method of the slurry that conductivity is higher of a kind of and compatibility of electrolyte.
Summary of the invention
The object of the invention is to solve existing adult form electrocondution slurry poor electric conductivity and the technical deficiency bad with compatibility of electrolyte, and propose a kind of method that doped with fluorine functionalized graphene prepares high-conductivity slurry.
In order to solve technical problem proposed by the invention, the technical scheme of employing is: 1, a kind of doped with fluorine functionalized graphene prepares the method for high-conductivity slurry, it is characterized in that, comprises the following steps:
(1) weighing mass ratio is: 100:5 ~ 15:3 ~ 5: electrocondution slurry, fluorinated graphene, dispersant, the deionized water of 700;
(2) by dispersant with 1/2nd deionized water mix, pour in vacuum mixer, first with the 20 ± 3r/min that revolves round the sun, rotation 400 ± 20r/min low rate mixing is to dispersant complete wetting in deionized water, then-0.1mpa is evacuated to, by revolution 100 ± 5r/min, rotation 4000 ± 100r/min rapid stirring 1h;
(3) be added to by electrocondution slurry in the vacuum mixer of (2), first with the 20 ± 3r/min that revolves round the sun, rotation 400 ± 20r/min low rate mixing 1h, is then evacuated to-0.1mpa, by revolution 100 ± 5r/min, and rotation 4000 ± 100r/min rapid stirring 1.5h;
(4) be added to by fluorinated graphene in the vacuum mixer of (3), first with the 20 ± 3r/min that revolves round the sun, rotation 400 ± 20r/min low rate mixing 0.5h, is then evacuated to-0.1mpa, by revolution 100 ± 5r/min, and rotation 4000 ± 100r/min rapid stirring 2h;
(5) remaining deionized water is added in the vacuum mixer of (4), first with the 20 ± 3r/min that revolves round the sun, rotation 400 ± 20r/min low rate mixing 10min, then-0.1mpa is evacuated to, by revolution 80 ± 5r/min, rotation 2000 ± 100r/min rapid stirring 30min, measures and prepares slurry viscosity and solid content, make viscosity at 100 ~ 500mpa.s, solid content is 3% ~ 8%.
Described fluorinated graphene can oneself synthesize, and also can buy fluorinated graphene ready-made on the market.Comprise fluorinated graphene powder and take fluorinated graphene as the solution of major solute, or the mixture of fluorinated Graphene.If oneself synthesizes fluorinated graphene, can with reference to the preparation method at disclosed document or patent.Here a kind of method is wherein enumerated:
Graphite → graphene oxide → Graphene → fluorinated graphene
(1) graphite: purity 99.5%;
(2) graphene oxide: by improve Hummers legal system for graphene oxide;
(3) Graphene: obtain Graphene by liquid-phase reduction graphene oxide;
(4) fluorinated graphene: in (3) gained graphite rare by with F
2fluorinated graphene is obtained by reacting Deng fluorine-containing material.
Described electrocondution slurry selects its one or more the mixture of Henkel series, Japanese Showa SDX series, self-control electrocondution slurry.
Described dispersant select polyvinylpyrrolidone, sodium carboxymethylcellulose and other there is a kind of material of the polyacrylics of peptizaiton or the mixture of two or more material.
The present invention is compared with existing conventional conductive slurry preparation method, and the present invention has the following advantages: (1) improves electric conductivity, reduces coating layer thickness; (2) because fluorinated graphene and electrolyte have good compatibility, greatly strengthen the water retainability of pole piece; (3) because electrocondution slurry selects adult form electrocondution slurry, itself, containing certain bonding agent and dispersant, can play to a certain extent and be scattered in cementation; (4) agitating mode dispersion processing performance of the present invention is good; (5) technological process is short, simple to operate, energy consumption is low, security performance good, is easy to realize large-scale industrial and produces.
The present invention has the advantage of certain roughness in conjunction with graphite in electrocondution slurry, carbon black, the high connductivity of fluorinated graphene and the advantage good with compatibility of electrolyte are played, utilize the binder system in ripe electrocondution slurry system, avoid the step of complicated binding agent type selecting and mixing and dispersion, by dilution conventional conductive slurry, add a small amount of fluorinated graphene, ensureing that conductive coating has on the basis of certain roughness, improve electric conductivity, reduce coating layer thickness, simplify configuration flow.
Conductive agent in electrocondution slurry is generally nanoscale graphite or the carbon black of high connductivity.And the electric conductivity of fluorinated graphene is better than graphite or carbon black, therefore, sub-fraction fluorinated graphene can substitute manifold electrically conductive graphite and carbon black, strengthens conductivity, but also reduce consolidating in electrocondution slurry and contain, coating can be made towards thinner future development.Meanwhile, as the painting carbon aluminium foil of lithium battery collector, wish that there is certain roughness on surface, be beneficial to the contiguity between the particle of collector and positive active material and particle.Therefore, simple fluorinated graphene is as conductive agent, and surface is very smooth, and roughness is little, is unfavorable for the contiguity with positive active material.Therefore, the effective ways that conduction system that a kind of fluorinated graphene mixes with graphite is conductivity and the surperficial adhesion solved are developed.
Good Electolyte-absorptive performance must be had for lithium battery electrocondution slurry, because fluorinated graphene and electrolyte have higher compatibility, relative to the electrode slice not having fluorinated graphene, thus improve the water retainability of pole piece to a certain extent.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
Fig. 2 is high-conductivity slurry dispersion effect figure prepared by the present invention.
Fig. 3 is high-conductivity slurry prepared by the present invention makes battery loop test capability retention figure as coating material.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to these embodiments.
Embodiment 1:
Weigh electrocondution slurry 100g respectively, from buying fluorinated graphene 5g on the market, dispersant (pvp) 4g, deionized water 700 g, its total weight is 809g, and initial calculation solid content is 4.69% stand-by.Described electrocondution slurry select existing solid content be 29% Henkel series of conductive slurry, also can select the electrocondution slurry of Japanese Showa SDX series in implementation process, or Henkel series, Japanese Showa SDX series the mixture of its one or more electrocondution slurry.
That is to say electrocondution slurry: fluorinated graphene: dispersant: the score of deionized water quality is not: 100:5:4:700.
Whipping step is:
First, the dispersant (pvp) of 4g and the deionized water of 350g are poured in vacuum mixer and mixes, first with the 20 ± 3r/min that revolves round the sun, rotation 400 ± 20r/min low rate mixing is to dispersant complete wetting in deionized water, then-0.1mpa is evacuated to, by revolution 100 ± 5r/min, rotation 4000 ± 100r/min rapid stirring 1h.
Then, the electrocondution slurry of 100g is poured again in vacuum mixer, first with the 20 ± 3r/min that revolves round the sun during mixed process is same, rotation 400 ± 20r/min low rate mixing is to dispersant complete wetting in electrocondution slurry, then-0.1mpa is evacuated to, by revolution 100 ± 5r/min, rotation 4000 ± 100r/min rapid stirring 1h.Observing slurry scattering effect and vacuum degassing situation in time in whipping process, as there is dispersion situation not in place, then should adjust rate of dispersion and jitter time again, until slurry disperses completely.After completion of stirring as bubble carries out ventilation action to slurry more at most, eliminate slurry bubble.
Next, the fluorinated graphene of 5g is added in above-mentioned slurry, first with the 20 ± 3r/min that revolves round the sun, rotation 400 ± 20r/min low rate mixing 0.5h is to fluorinated graphene complete wetting, then-0.1mpa is evacuated to, by revolution 100 ± 5r/min, rotation 4000 ± 100r/min rapid stirring 2h.Same observation paste color after stirring completes, the situations such as mobile performance, and viscosity and the solid content of measuring slurry.
Finally, remaining 350g deionized water is added in above-mentioned slurry, is evacuated to-0.1mpa, by revolution 100 ± 5r/min, rotation 4000 ± 100r/min rapid stirring 0.5h.Carry out viscosity with solid containing adjusting, make viscosity at 100 ~ 500mpa.s, solid content is 3% ~ 8%.
High-conductivity slurry spraying technology even application the inventive method prepared is in the conventional aluminium foil two sides of 16u lithium battery, and dry measurement and make one side coating material thickness at 1u ~ 1.5u, coated on both sides material thickness is at 2u ~ 3u, and its dispersion effect as shown in Figure 2.
The lithium battery anode slurry that laboratory has been prepared, thickness is coated on respectively at 16u optical aluminum foil and scribble the thickness of high-conductivity slurry of the present invention on 16u aluminium foil by identical coating density, mate identical negative plate and other making used in battery materials, make battery and carry out contrast test, its cycle performance of battery test data curve chart as shown in Figure 3.
Present invention, avoiding complicated binding agent and underlying conductive agent type selecting process, by dilution adult form electrocondution slurry, original most of conductive agent is replaced with the fluorinated graphene doping of small part high connductivity, slurry configuration work simplification, the conductivity of slurry is high, internal resistance is little, even particle size distribution, be easy to coating, cost is low, and cost performance is high.
Claims (5)
1. the method that fluorinated graphene prepares high-conductivity slurry is fluoridized in doping, it is characterized in that, comprises the following steps:
(1) weighing mass ratio is: 100:5 ~ 15:3 ~ 5: electrocondution slurry, fluorinated graphene, dispersant, the deionized water of 700;
(2) by dispersant with 1/2nd deionized water mix, pour in vacuum mixer, first with the 20 ± 3r/min that revolves round the sun, rotation 400 ± 20r/min low rate mixing is to dispersant complete wetting in deionized water, then-0.1mpa is evacuated to, by revolution 100 ± 5r/min, rotation 4000 ± 100r/min rapid stirring 1h;
(3) be added to by electrocondution slurry in the vacuum mixer of (2), first with the 20 ± 3r/min that revolves round the sun, rotation 400 ± 20r/min low rate mixing 1h, is then evacuated to-0.1mpa, by revolution 100 ± 5r/min, and rotation 4000 ± 100r/min rapid stirring 1.5h;
(4) be added to by fluorinated graphene in the vacuum mixer of (3), first with the 20 ± 3r/min that revolves round the sun, rotation 400 ± 20r/min low rate mixing 0.5h, is then evacuated to-0.1mpa, by revolution 100 ± 5r/min, and rotation 4000 ± 100r/min rapid stirring 2h;
(5) remaining deionized water is added in the vacuum mixer of (4), first with the 20 ± 3r/min that revolves round the sun, rotation 400 ± 20r/min low rate mixing 10min, then-0.1mpa is evacuated to, by revolution 80 ± 5r/min, rotation 2000 ± 100r/min rapid stirring 30min, measures and prepares slurry viscosity and solid content, make viscosity at 100 ~ 500mpa.s, solid content is 3% ~ 8%.
2. preparation method according to claim 1, it is characterized in that: described fluorinated graphene can oneself synthesize, also fluorinated graphene ready-made on the market can be bought, comprise fluorinated graphene powder and take fluorinated graphene as the solution of major solute, or the mixture of fluorinated Graphene.
3.
fluorinated grapheneits preparation method and technique can with reference to the preparation methods of the document published now or patent.
4. preparation method according to claim 1, is characterized in that: described electrocondution slurry selects its one or more the mixture of Henkel series, Japanese Showa SDX series, self-control electrocondution slurry.
5. preparation method according to claim 1, is characterized in that: described dispersant select polyvinylpyrrolidone, sodium carboxymethylcellulose and other there is a kind of material of the polyacrylics of peptizaiton or the mixture of two or more material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336486A (en) * | 2016-08-19 | 2017-01-18 | 雷海波 | Polymer conductive polymer and preparation method thereof |
| CN112599780A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院过程工程研究所 | Method for modifying surface of current collector of lithium slurry battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012083538A1 (en) * | 2010-12-22 | 2012-06-28 | 海洋王照明科技股份有限公司 | Electrode sheet and its preparation method and super capacitor and lithium ion battery |
| CN103181001A (en) * | 2010-12-30 | 2013-06-26 | 海洋王照明科技股份有限公司 | Conductive polymer materials and preparing method and uses thereof |
| CN103500812A (en) * | 2013-09-16 | 2014-01-08 | 杨海燕 | Method for preparing high-conductivity slurry from doped graphene |
| US20140030590A1 (en) * | 2012-07-25 | 2014-01-30 | Mingchao Wang | Solvent-free process based graphene electrode for energy storage devices |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012083538A1 (en) * | 2010-12-22 | 2012-06-28 | 海洋王照明科技股份有限公司 | Electrode sheet and its preparation method and super capacitor and lithium ion battery |
| CN103181001A (en) * | 2010-12-30 | 2013-06-26 | 海洋王照明科技股份有限公司 | Conductive polymer materials and preparing method and uses thereof |
| US20140030590A1 (en) * | 2012-07-25 | 2014-01-30 | Mingchao Wang | Solvent-free process based graphene electrode for energy storage devices |
| CN103500812A (en) * | 2013-09-16 | 2014-01-08 | 杨海燕 | Method for preparing high-conductivity slurry from doped graphene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336486A (en) * | 2016-08-19 | 2017-01-18 | 雷海波 | Polymer conductive polymer and preparation method thereof |
| CN112599780A (en) * | 2020-12-14 | 2021-04-02 | 中国科学院过程工程研究所 | Method for modifying surface of current collector of lithium slurry battery |
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Application publication date: 20151021 |