CN103337632B - A kind of carbon nanometer paper load ferrous phosphate lithium ion positive pole and preparation method thereof - Google Patents
A kind of carbon nanometer paper load ferrous phosphate lithium ion positive pole and preparation method thereof Download PDFInfo
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- CN103337632B CN103337632B CN201310288466.1A CN201310288466A CN103337632B CN 103337632 B CN103337632 B CN 103337632B CN 201310288466 A CN201310288466 A CN 201310288466A CN 103337632 B CN103337632 B CN 103337632B
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- carbon nanometer
- nanometer paper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Abstract
The invention discloses a kind of carbon nanometer paper load ferrous phosphate lithium ion positive pole and preparation method thereof.Positive pole comprises: carbon nanometer paper is the loose porous network configuration of being assembled by a kind of or mixing in carbon nano-tube, carbon nano-fiber, porosity more than 50%; Ferrous phosphate uniform particles be attached to flexible, loose porous, conduct electricity on good carbon nanometer paper.Its preparation method comprises prepares dispersion liquid, load LiFePO 4, applying glue, drying course.The present invention adopts LiFePO
4on the carbon nanometer paper of the direct load of nano particle and Nanostructure Network, avoid LiFePO
4nano particle traditional slurry preparation in be difficult to scattering problem.Carbon nanometer paper is carbon Nanostructure Network simultaneously, namely serves as the effect of conductive filler, collector effect of charging again.
Description
Technical field
The present invention relates to a kind of lithium ion cell positive and preparation method thereof, particularly carbon nanometer paper load ferrous lithium phosphate cathode and preparation method thereof.
Background technology
As the lithium ion battery of new generation of green high-power rechargeable, advantages such as, energy density high with its open circuit voltage is large, long service life and be widely used in various miniature portable belt electronic equipment.The LiFePO 4 of olivine-type is because of its low price, low toxicity, excellent cycle life (being greater than 2000 times), good specific capacity (168mAh/g), smooth discharge platform and become the mainstay material of lithium ion cell positive.But it is low that LiFePO 4 exists conductivity, the problem that ion diffusion rates is slow, result in it when heavy-current discharge, specific capacity sharply declines.
The mode of current head it off is mainly, and the coated and gold doping of nanometer, carbon belongs to.2005, open magazine Electrochemical and Solid-State Letters reported Charles etc. and adopts nano-form to prepare LiFePO
4nanometer rods, and adopt carbon-coated nano rod, with 3C discharge and recharge, specific capacity be 165mAh/g almost close to theoretical value, fully electric at the super-large current of 65C, capability retention people still reaches 36%.2002, open magazine Electrochemical and Solid-State Letters reports Corce etc., Cu and Ag of 1% is mixed in LiFePO 4, because the metal mixed instead of the position of part Fe, create defect, improve diffusivity and the conductivity of lithium ion, specific capacity, than being doping, improves the specific capacity of 25mAh/g.
Nanometer LiFePO
4, can effectively shorten lithium ion diffusion length, effectively improve high rate performance, then in conjunction with carbon coated or carbon dope material, significantly can heighten electrode performance, but, as above 2005 report prepare LiFePO
4nanorod electrodes, complex process, is unsuitable for large-scale industrial production.But, if adopt traditional adhesive organic solvent that adds to be made into slurry coating, for nano material, there is again the problem of difficulties in dispersion.Therefore, at present, realize nanometer is all make micron particles or the micron ball of nanostructure.Such as, the John B. Goodenough etc. of JACS magazine ran in 2011 has prepared a kind of micron ball of 3-D nano, structure, has shown good circulation performance.Chinese patent CN 102509799 A also discloses a kind of LiFePO of the nanostructure containing conducting matrix grain
4micron ball.Journal of Power Sources magazine ran in 2009 adopts spray-on process to prepare the LiFePO of nano-porous structure
4micron ball.The micron particles of these nanostructures, preparation process is comparatively complicated, and finally traditional technique with slurry also will be adopted to prepare electrode.
Summary of the invention
The first object of the present invention is to provide a kind of carbon nanometer paper load ferrous phosphate lithium ion battery positive pole; Another object is the preparation method providing above-mentioned electrode.
The present invention first object is achieved in that described carbon nanometer paper is the loose porous network configuration of being assembled by a kind of or mixing in carbon nano-tube, carbon nano-fiber, porosity more than 50%; Ferrous phosphate uniform particles be attached to flexible, loose porous, conduct electricity on good carbon nanometer paper.
Described carbon nanometer paper can add a small amount of adhesive to increase its mechanical strength.
Described LiFePO 4 particle size is less than 500nm.
The present invention second object is achieved in that to comprise prepares dispersion liquid, load LiFePO 4, applying glue, dries, is specially:
A. LiFePO is prepared
4dispersion liquid;
B. load LiFePO
4nano particle, on carbon nanometer paper, adopts filter type load;
C. the LiFePO in load
4carbon nanometer paper on applying glue, to increase mechanical strength;
D. dry, carbon nanometer paper good for load is dried.
Described preparation method, can increase a baking step as required before C applying glue step.
Described preparation method, after C applying glue step, can increase calandering steps, to increase electrode density.
Described LiFePO
4dispersion liquid is LiFePO
4nano particle is dispersed in the aqueous solution, can add dispersant dispersed to increase it.
The load of described employing filter type, is be placed on planar filtration devices by carbon nanometer paper, serves as filter membrane, by LiFePO
4dispersion liquid is poured on carbon nanometer paper, filters; Described filter process can adopt vacuum filtration, to improve the rate of filtration.
Described Process of Applying Glue, adopts and sprays one of dipping glue and suction filtration coating glue two kinds of modes.
Described glue is the one in the PVA aqueous solution, the PEO aqueous solution, PVAc emulsion, SBR emulsion, PVDF solution, PDMS dilution.
beneficial effect
The present invention adopts LiFePO
4on the carbon nanometer paper of the direct load of nano particle and Nanostructure Network, avoid LiFePO
4nano particle traditional slurry preparation in be difficult to scattering problem.Carbon nanometer paper is carbon Nanostructure Network simultaneously, namely serves as the effect of conductive filler, collector effect of charging again.
Accompanying drawing explanation
Fig. 1 is carbon nanometer paper load ferrous phosphate lithium ion anode preparation method flow chart in the present invention;
In figure: 1-LiFePO
4dispersion liquid, 2-carbon nanometer paper, 3-glue.
Fig. 2 is the X ray diffracting spectrum of carbon nanometer paper load ferrous phosphate lithium ion positive pole in the present invention.
Fig. 3 is the SEM microphoto of carbon nanometer paper load ferrous phosphate lithium ion positive pole in the present invention.
Embodiment
Do further to explanation to the present invention at carbon nanometer paper load ferrous phosphate lithium ion positive pole and preparation method thereof below in conjunction with accompanying drawing and embodiment; but never in any form the present invention is limited; according to the teachings of the present invention done any change or replacement, all belong to protection scope of the present invention.
The present invention discloses a kind of carbon nanometer paper load ferrous phosphate lithium ion battery positive pole, and described carbon nanometer paper is the loose porous network configuration of being assembled by a kind of or mixing in carbon nano-tube, carbon nano-fiber, porosity more than 50%; Ferrous phosphate uniform particles be attached to flexible, loose porous, conduct electricity on good carbon nanometer paper.
Described carbon nanometer paper can add a small amount of adhesive to increase its mechanical strength.
Described LiFePO 4 particle size is less than 500nm.
The present invention also discloses a kind of preparation method of carbon nanometer paper load ferrous phosphate lithium ion positive pole, comprises and prepares dispersion liquid, load LiFePO 4, applying glue, dries, is specially:
A. LiFePO is prepared
4dispersion liquid 1;
B. load LiFePO
4nano particle, on carbon nanometer paper 2, adopts filter type load;
C. the LiFePO in load
4carbon nanometer paper on applying glue 3, to increase mechanical strength;
D. dry, carbon nanometer paper good for load is dried.
Described preparation method, can increase a baking step as required before C applying glue step.
Described preparation method, after C applying glue step, can increase calandering steps, to increase electrode density.
Described LiFePO
4dispersion liquid is LiFePO
4nano particle is dispersed in the aqueous solution, can add dispersant dispersed to increase it.
The load of described employing filter type, is be placed on planar filtration devices by carbon nanometer paper, serves as filter membrane, by LiFePO
4dispersion liquid 1 is poured on carbon nanometer paper 2, filters; Described filter process can adopt vacuum filtration, to improve the rate of filtration.
Described Process of Applying Glue, adopts and sprays one of dipping glue and suction filtration coating glue two kinds of modes.
Described glue is the one in the PVA aqueous solution, PEO solution, PVAc emulsion, SBR emulsion, PVDF solution, PDMS dilution.
Fig. 2 is the X ray diffracting spectrum of carbon nanometer paper load ferrous phosphate lithium ion positive pole in the present invention, and can find out in figure, there is LiFePO at the peak of existing carbon again
4peak, prepare LiFePO in addition
4the impurity peaks of the Fe2 (PO5) do not reacted completely, illustrates LiFePO
4load is at LiFePO
4on.
Fig. 3 is the SEM microphoto of carbon nanometer paper load ferrous phosphate lithium ion positive pole in the present invention: the left side be the SEM photo that load capacity accounts for electrode quality 50%, can LiFePO be seen
4less, also have many spaces can be, right figure be the SEM photo that load capacity accounts for gross mass 90%, can see LiFePO
4carbon nanometer paper covers full completely, and load capacity is adjustable in a word.
Embodiment 1:
LiFePO will be fitted
4nanometer powder is added to the water, and makes dispersion liquid, adopts carbon nanometer paper to be placed in Suction filtration device, adds LiFePO
4dispersion liquid, carries out vacuum filtration, treats that liquid is taken out to the greatest extent, adds the appropriate PVA aqueous solution, again carry out suction filtration, and liquid is taken out to the greatest extent, takes out carbon nanometer paper, carries out roll-in, oven dry.
Embodiment 2:
LiFePO will be fitted
4nanometer powder is added to the water, and makes dispersion liquid, adopts carbon nanometer paper to be placed in Suction filtration device, adds LiFePO
4dispersion liquid, carries out vacuum filtration, treats that liquid is taken out to the greatest extent, takes out load LiFePO
4carbon nanometer paper, carbon nanometer paper sprays the PEO aqueous solution, carbon nanometer paper is fully infiltrated, finally carries out roll-in, oven dry.
Embodiment 3:
LiFePO will be fitted
4nanometer powder is added to the water, and makes dispersion liquid, adopts carbon nanometer paper to be placed in Suction filtration device, adds LiFePO
4dispersion liquid, carries out vacuum filtration, treats that liquid is taken out to the greatest extent, is taken out by carbon nanometer paper, immerse in PVAc emulsion, again, take out carbon nanometer paper, dry.
Embodiment 4:
LiFePO will be fitted
4nanometer powder is added to the water, and makes dispersion liquid, adopts carbon nanometer paper to be placed in Suction filtration device, adds LiFePO
4dispersion liquid, carries out vacuum filtration, treats that liquid is taken out to the greatest extent, is taken out by carbon nanometer paper, immerse in SBR emulsion, again, take out carbon nanometer paper, carry out roll-in, oven dry.
Embodiment 5:
LiFePO will be fitted
4nanometer powder is added to the water, and makes dispersion liquid, adopts carbon nanometer paper to be placed in Suction filtration device, adds LiFePO
4dispersion liquid, carries out vacuum filtration, treats that liquid is taken out to the greatest extent, dries carbon nanometer paper, add PVDF solution, again suction filtration in Suction filtration device, treats that liquid is taken out to the greatest extent, takes out carbon nanometer paper, carry out roll-in, oven dry.
Embodiment 6::
LiFePO will be fitted
4nanometer powder is added to the water, and makes dispersion liquid, adopts carbon nanometer paper to be placed in Suction filtration device, adds LiFePO
4dispersion liquid, carries out vacuum filtration, treats that liquid is taken out to the greatest extent, dries carbon nanometer paper, add PDMS dilution, again suction filtration in Suction filtration device, treats that liquid is taken out to the greatest extent, takes out carbon nanometer paper, carry out roll-in, oven dry.
Claims (9)
1. a carbon nanometer paper load ferrous phosphate lithium ion battery positive pole, is specially: described carbon nanometer paper is the loose porous network configuration of being assembled by a kind of or mixing in carbon nano-tube, carbon nano-fiber, porosity more than 50%; Ferrous phosphate uniform particles be attached to flexible, loose porous, conduct electricity on good carbon nanometer paper; Its preparation method, comprises and prepares dispersion liquid, load LiFePO 4, applying glue, dries, is specially:
A. LiFePO4 dispersion liquid is prepared;
B. load LiFePO4 nano particle is on carbon nanometer paper, adopts filter type load, is be placed on planar filtration devices by carbon nanometer paper, serves as filter membrane, be poured on carbon nanometer paper by LiFePO4 dispersion liquid, filter;
C. the applying glue on the carbon nanometer paper of LiFePO4 in load, to increase mechanical strength;
D. dry, carbon nanometer paper good for load is dried.
2. carbon nanometer paper load ferrous phosphate lithium ion battery positive pole according to claim 1, is characterized in that: described carbon nanometer paper adds adhesive to increase its mechanical strength.
3. carbon nanometer paper load ferrous phosphate lithium ion battery positive pole according to claim 1, is characterized in that: described LiFePO 4 particle size is less than 500nm.
4. carbon nanometer paper load ferrous phosphate lithium ion battery positive pole according to claim 1, is characterized in that: described preparation method, before C applying glue step, increase a baking step.
5. carbon nanometer paper load ferrous phosphate lithium ion battery positive pole according to claim 1, is characterized in that: described preparation method, after C applying glue step, increases calandering steps, to increase electrode density.
6. carbon nanometer paper load ferrous phosphate lithium ion battery positive pole according to claim 1, is characterized in that: described LiFePO4 dispersion liquid is that LiFePO4 nano particle is dispersed in the aqueous solution, adds dispersant dispersed to increase it.
7. carbon nanometer paper load ferrous phosphate lithium ion battery positive pole according to claim 1, is characterized in that: described filter process adopts vacuum filtration, to improve the rate of filtration.
8. carbon nanometer paper load ferrous phosphate lithium ion battery positive pole according to claim 1, is characterized in that: described Process of Applying Glue, adopts and sprays one of dipping glue and suction filtration coating glue two kinds of modes.
9. carbon nanometer paper load ferrous phosphate lithium ion battery positive pole described according to Claim 8, it is characterized in that: described glue, is the one in the PVA aqueous solution, the PEO aqueous solution, PVAc emulsion, SBR emulsion, PVDF solution, PDMS dilution.
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| CN104241601A (en) * | 2014-07-02 | 2014-12-24 | 宁波艾特米克锂电科技有限公司 | Preparation method of metal-current-collector-free lithium battery or super-capacitor electrode |
| CN109742327A (en) * | 2018-12-29 | 2019-05-10 | 西安鸿钧睿泽新材料科技有限公司 | Preparation method of self-supporting flexible lithium ion battery carbon cloth loaded LiFePO4 positive electrode material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509799A (en) * | 2011-11-02 | 2012-06-20 | 江苏力泰锂能科技有限公司 | Anode material with lithium ferrous phosphate being embedded in stereoscopic reticular electric conductor and preparation method thereof |
| CN102593436A (en) * | 2012-02-27 | 2012-07-18 | 清华大学 | Self-supporting flexible carbon nano-tube paper composite electrode material for lithium ion battery |
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| WO2012051280A2 (en) * | 2010-10-12 | 2012-04-19 | The Research Foundation Of State University Of New York | Composite electrodes, methods of making, and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102509799A (en) * | 2011-11-02 | 2012-06-20 | 江苏力泰锂能科技有限公司 | Anode material with lithium ferrous phosphate being embedded in stereoscopic reticular electric conductor and preparation method thereof |
| CN102593436A (en) * | 2012-02-27 | 2012-07-18 | 清华大学 | Self-supporting flexible carbon nano-tube paper composite electrode material for lithium ion battery |
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Address after: 650091 Yunnan city of Kunming province high tech Zone Haiyuan A Road No. 1520 Building 2 floor, No. 215 Patentee after: KUNMING NATAI TECHNOLOGY CO., LTD. Address before: 650091 Yunnan city of Kunming province high tech Zone Haiyuan A Road No. 1520 Building 2 floor, No. 215 Patentee before: Kunming Natai Energy Technology Co., Ltd. |