CN105895921A - Preparation method of current collector for lithium-ion battery - Google Patents
Preparation method of current collector for lithium-ion battery Download PDFInfo
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- CN105895921A CN105895921A CN201610309467.3A CN201610309467A CN105895921A CN 105895921 A CN105895921 A CN 105895921A CN 201610309467 A CN201610309467 A CN 201610309467A CN 105895921 A CN105895921 A CN 105895921A
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- China
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- collector
- preparation
- ion battery
- lithium ion
- polyoxometallic acid
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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
- H01M4/64—Carriers or collectors
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/666—Composites in the form of mixed materials
-
- 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 preparation method of a current collector for a lithium-ion battery. The method comprises the following steps: adding an adhesive to a composite material of a conductive polymer-polyoxometallic acid lithium salt to form a current collector printing compound; and evenly stirring the current collector printing compound in a solvent to form slurry and printing the slurry on aluminum foil through a gravure printing machine to prepare a positive electrode current collector. In the charge and discharge processes, lithium ions can also be conducted in a three-dimensional skeleton of the polyoxometallic acid lithium salt when transmitted in a conductive polymer; the lithium ion transmission characteristic is improved; the electron transmission characteristic is also improved through the conductive polymer; and double requirements of the composite material on lithium ion transmission and electron transmission are met.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to the preparation method of the collector of a kind of lithium ion battery.
Background technology
Wretched insufficiency along with Global Oil resource, problem of environmental pollution increases the weight of day by day, increasing to the demand of extensive clean energy resource, but solar energy, the clean energy resourcies such as wind energy are in time, spatially skewness, it is necessary to utilize the seriality of large-scale energy storage system stability and supply of electric power to ensure electrical network.Lithium battery is as the conversion of one effective energy and energy storage device, having received publicity the most again since invention, the feature such as its running voltage is high, energy density is big, specific energy is high, specific power is big, electric discharge is steady, memory-less effect is widely used in various electronic product.Although lithium battery achieves very ten-strike in 3C Product, but it is still at an early stage in power application and energy storage field, the key factor restricting its development is composite, the positive electrode being currently mainly applied to power and energy storage field is LiFePO4, LiFePO4 has the advantage of heat stability and safety compared to other positive electrode, but owing to its internal crystal framework limits, electric conductivity is poor, it is impossible to meet the demand of high current charge-discharge.Mainstream technology in the market is by one layer of traditional material with carbon element of intaglio printing on aluminium foil, it is used for making up the deficiency of LiFePO4 self-conductive, the gravure process of conventional carbon material can have a certain degree of lifting to its electric conductivity, but the gravure process of the affluxion body in lithium ion batteries of traditional material with carbon element, can only promote for the requirement of electric transmission.
China Patent No. is 201510116174.9 to disclose the preparation method of a kind of lithium ion battery in 2015.8.5, initially with gravure application at netted Copper Foil/aluminum foil current collector surface-coated one layer composite Nano conductive liquid, again at its surface-coated anode and cathode slurry after Gan Zaoing, use cold-hot pressure rolling techniques that pole piece is carried out roll-in afterwards, use laser dicing technology that its pole piece is cut the most again, and finally prepare lithium ion battery.The method that above-mentioned patent is used is similar with the main flow gravure process of lithium battery circle, it is all to apply one layer of conductive materials on a current collector, to improve electrical conductivity, this kind of method can be used to make up the deficiency of positive electrode active material self-conductive, its electric conductivity there is a certain degree of lifting, but the transmission speed of electronics can only be improved, it is impossible to improve the transmission speed of lithium battery interior lithium ion, limited with polarization role to reducing the internal resistance of cell.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the invention provides the preparation method of the collector of a kind of lithium ion battery, plus plate current-collecting body prepared by the method, can also conduct in the three-dimensional framework of polyoxometallic acid lithium salts while in charge and discharge process, lithium ion transmits in conducting polymer, improve lithium ion transport properties, improve the transmission characteristic of electronics further through conducting polymer, meet composite to lithium ion transport and the double requirements of electric transmission.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is:
A kind of preparation method of the collector of lithium ion battery, it is characterized in that: in the composite of conducting polymer-polyoxometallic acid lithium salts, add bonding agent, become collector printing complex, described collector printing complex is stirred for slurry in a solvent, through intaglio press, described slurry is printed on aluminium foil, makes plus plate current-collecting body.
The synthetic method of described slurry is:
(1) ratio of 1:4 is divided and is taken polyoxometallic acid lithium salts and aniline monomer in molar ratio, and polyoxometallic acid lithium salts and conducting polymer are configured to aqueous solution；
(2) polyoxometallic acid lithium salt solution is added dropwise in conducting polymer monomer solution, at room temperature reaction 1-24 hour, then with distilled water and ethanol cyclic washing precipitate, until filtrate is colourless, put the precipitate in 40-200 DEG C of vacuum drying oven and be dried 2-10 hour, obtain composite；
(3) composite is mixed into collector printing complex with bonding agent by the mass ratio of 19:1, collector is printed complex in solvent N-methyl pyrilidone, was stirred into described collector printing complex through 10-12 hour.
Described conducting polymer is one or more the mixture in polyaniline, polypyrrole, polythiophene.
Described polyoxometallic acid lithium salts includes Li3XY12O40, Li4XY12O40In one or more mixture；X refers in two kinds of elements of P, Si any one；Y refers in two kinds of elements of Mo, W any one.
The thickness of described aluminium foil is 12 microns.
Described bonding agent is Kynoar or politef.
The invention have the advantages that
1, the present invention adds bonding agent in the composite of conducting polymer-polyoxometallic acid lithium salts, become collector printing complex, described collector printing complex is stirred for slurry in a solvent, through intaglio press, described slurry is printed on aluminium foil, makes plus plate current-collecting body.The gravure process of the affluxion body in lithium ion batteries of traditional material with carbon element, can only promote for the requirement of electric transmission.The intaglio printing material that this patent is stated, in charge and discharge process, lithium ion can also conduct while transmitting in conducting polymer in the three-dimensional framework of polyoxometallic acid lithium salts, improve lithium ion transport properties, improve the transmission characteristic of electronics further through conducting polymer, meet composite to lithium ion transport and the double requirements of electric transmission.
2, the present invention uses this ratio that polyoxometallic acid lithium salts and aniline reaction can be made the most complete, and make both be uniformly distributed, the method being added dropwise over is used to can ensure that the reaction of polyoxometallic acid lithium salts fully, to be set in the response time 1-24 hour guarantee that both react complete, the vacuum drying temperature of 40-200 DEG C guarantees that the moisture in composite fully removes.
3, these three kinds of polymer monomers of one or more the mixture during the conducting polymer of the present invention is polyaniline, polypyrrole, polythiophene are conventional conducting polymer monomer, low cost, resource foot.
4, the polyoxometallic acid lithium salts of the present invention includes Li3XY12O40, Li4XY12O40In one or more mixture；X refers in two kinds of elements of P, Si any one；Y refers in two kinds of elements of Mo, W any one, and polyoxometallate series structure is the most stable, and resource foot, production cost is low.
Detailed description of the invention
Embodiment 1
Divide by the molar ratio of 1:4 and take Li3PMo12O40Polyoxometallic acid lithium salts and polyaniline monomer, not Pei Zhi polyoxometallic acid lithium salt solution and polyaniline solutions, the polyoxometallic acid lithium salts Li that will prepare3PMo12O40Solution is slowly added dropwise in polyaniline solutions, at room temperature reaction 1-24 hour, then with distilled water and ethanol cyclic washing precipitate, until filtrate is colourless, puts the precipitate in 40-200 DEG C of vacuum drying oven and is dried 2-10 hour, obtain composite.
Again by composite: Kynoar (PVDF)=19:1 is mixed into collector printing complex containing mass ratio admittedly, collector prints complex stirred through 10-12 hour in solvent N-methyl pyrilidone (NMP) form slurry, by intaglio press, slurry is printed on the aluminium foil of thickness 12um, after drying, as plus plate current-collecting body.
Plus plate current-collecting body is used for battery prepare, and carries out testing battery used and be:
Positive electrode forms: LiFePO4 content 91%, conductive carbon black content 5%, binding agent PVDF 4%.Positive electrode after uniform stirring 10-12 hour, is formed anode sizing agent, is coated in coating machine on the plus plate current-collecting body previously prepared, drying, pole piece thickness 139um after colding pressing in nmp solution according to the above ratio.
Negative material forms: active substance content of graphite 93%, conductive carbon black content 3%, binding agent PVDF4%.Negative material after uniform stirring 10-12 hour, is formed cathode size, is coated in 15um thickness copper foil current collector with coating machine, drying, pole piece thickness 100um after colding pressing in nmp solution according to the above ratio.
Barrier film is PP/PE/PP three-layer membrane, battery design capacity 20Ah.
Detection method:
By prepared battery full charge, with the internal resistance of AC internal Resistance tester detection battery.
Embodiment 2
Divide by the molar ratio of 1:3 and take phosphotungstic acid lithium Li3PW12O40Polyoxometallic acid lithium salts and polypyrrole monomer, not Pei Zhi polyoxometallic acid lithium salt solution and polypyrrole solution, the polyoxometallic acid lithium salts Li that will prepare3PW12O40Solution is slowly added dropwise in polypyrrole solution, at room temperature reaction 6-8 hour, then with distilled water and ethanol cyclic washing precipitate, until filtrate is colourless, puts the precipitate in 80 DEG C of vacuum drying ovens and is dried 6 hours, obtain composite.
Again by composite: politef=19:1 is mixed into collector printing complex containing mass ratio admittedly, collector is printed complex in solvent N-methyl pyrilidone (NMP) through 11 hours form slurry that stir, by intaglio press, slurry is printed on the aluminium foil of thickness 12um, after drying, as plus plate current-collecting body.
Plus plate current-collecting body is used for battery preparation and detection method with embodiment 1.
Embodiment 3
Divide by the molar ratio of 3:7 and take silicotungstate lithium Li4SiW12O40Polyoxometallic acid lithium salts and polypyrrole monomer, not Pei Zhi polyoxometallic acid lithium salt solution and polypyrrole solution, the polyoxometallic acid lithium salts Li that will prepare4SiW12O40Solution is slowly added dropwise in polypyrrole solution, at room temperature reaction 10 hours, then with distilled water and ethanol cyclic washing precipitate, until filtrate is colourless, puts the precipitate in 40 DEG C of vacuum drying ovens and is dried 10 hours, obtain composite.
Again by composite: politef=19:1 is mixed into collector printing complex containing mass ratio admittedly, collector is printed complex in solvent N-methyl pyrilidone (NMP) through 10 hours form slurry that stir, by intaglio press, slurry is printed on the aluminium foil of thickness 12um, after drying, as plus plate current-collecting body.
Plus plate current-collecting body is used for battery preparation and detection method with embodiment 1.
Embodiment 4
Divide by the molar ratio of 1:3 and take Li3PMo12O40Polyoxometallic acid lithium salts and polypyrrole monomer, not Pei Zhi polyoxometallic acid lithium salt solution and polypyrrole solution, the polyoxometallic acid lithium salts Li that will prepare3PMo12O40Solution is slowly added dropwise in polypyrrole solution, at room temperature reaction 24 hours, then with distilled water and ethanol cyclic washing precipitate, until filtrate is colourless, puts the precipitate in 200 DEG C of vacuum drying ovens and is dried 6 hours, obtain composite.
Again by composite: politef=19:1 is mixed into collector printing complex containing mass ratio admittedly, collector is printed complex in solvent N-methyl pyrilidone (NMP) through 12 hours form slurry that stir, by intaglio press, slurry is printed on the aluminium foil of thickness 12um, after drying, as plus plate current-collecting body.
Plus plate current-collecting body is used for battery preparation and detection method with embodiment 1.
Embodiment 5
Divide by the molar ratio of 3.5:6.5 and take Li3PW12O40Polyoxometallic acid lithium salts and polyaniline monomer, not Pei Zhi polyoxometallic acid lithium salt solution and polyaniline solutions, the polyoxometallic acid lithium salts Li that will prepare3PW12O40Solution is slowly added dropwise in polyaniline solutions, at room temperature reaction 12 hours, then with distilled water and ethanol cyclic washing precipitate, until filtrate is colourless, puts the precipitate in 100 DEG C of vacuum drying ovens and is dried 8 hours, obtain composite.
Again by composite: politef=19:1 is mixed into collector printing complex containing mass ratio admittedly, collector is printed complex in solvent N-methyl pyrilidone (NMP) through 12 hours form slurry that stir, by intaglio press, slurry is printed on the aluminium foil of thickness 12um, after drying, as plus plate current-collecting body.
Plus plate current-collecting body is used for battery preparation and detection method with embodiment 1.
Comparative example 1
Battery Making programme and method of testing are with embodiment 1, simply use material with carbon element as intaglio printing material, material with carbon element: the solid content ratio of Kynoar (PVDF)=19:1, solvent N-methyl pyrilidone (NMP) stirred through 12 hours, by intaglio press, slurry is printed on the aluminium foil of 12um, after drying, as plus plate current-collecting body.
Comparative example 2
Battery Making programme, with embodiment 1, simply uses H2O2Make oxidizing polymerization monomer and form electrode material.In this example, polymer monomer is pyrroles, H2O2Being 4.5:5.5 with the molar ratio of pyrroles, at room temperature reaction obtains electrode material in 7-10 hour.Battery making step is with embodiment 1
Gained battery is done AC internal Resistance test, the results detailed in Table:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | Comparative example 2 | |
| Internal resistance (milliohm) | 1.32 | 1.29 | 1.41 | 1.57 | 1.34 | 2.40 | 1.93 |
Use composite as can be seen from the above table prints the battery prepared by collector, its internal resistance and polarization are less than the collector battery using the printing of conventional carbon material, smaller than be provided without the battery of collector of printing, thus use that the plus plate current-collecting body of the present invention makes to reducing the internal resistance of cell and polarization has remarkable result.
Claims (6)
1. the preparation method of the collector of a lithium ion battery, it is characterized in that: in the composite of conducting polymer-polyoxometallic acid lithium salts, add bonding agent, become collector printing complex, described collector printing complex is stirred for slurry in a solvent, through intaglio press, described slurry is printed on aluminium foil, makes plus plate current-collecting body.
The preparation method of the collector of lithium ion battery the most according to claim 1, it is characterised in that: the synthetic method of described composite is:
(1) ratio of 1:4 is divided and is taken polyoxometallic acid lithium salts and aniline monomer in molar ratio, and polyoxometallic acid lithium salts and conducting polymer are configured to aqueous solution；
(2) polyoxometallic acid lithium salt solution is added dropwise in conducting polymer monomer solution, at room temperature reaction 1-24 hour, then with distilled water and ethanol cyclic washing precipitate, until filtrate is colourless, put the precipitate in 40-200 DEG C of vacuum drying oven and be dried 2-10 hour, obtain composite；
(3) composite is mixed into collector printing complex with bonding agent by the mass ratio of 19:1, collector is printed complex in solvent N-methyl pyrilidone, was stirred into described collector printing complex through 10-12 hour.
The preparation method of the collector of lithium ion battery the most according to claim 1 and 2, it is characterised in that: described conducting polymer is one or more the mixture in polyaniline, polypyrrole, polythiophene.
The preparation method of the collector of lithium ion battery the most according to claim 1 and 2, it is characterised in that: described polyoxometallic acid lithium salts includes Li3XY12O40, Li4XY12O40In one or more mixture；X refers in two kinds of elements of P, Si any one；Y refers in two kinds of elements of Mo, W any one.
The preparation method of the collector of lithium ion battery the most according to claim 1 and 2, it is characterised in that: the thickness of described aluminium foil is 12 microns.
The preparation method of the collector of lithium ion battery the most according to claim 1 and 2, it is characterised in that: described bonding agent is Kynoar or politef.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107142507A (en) * | 2017-05-03 | 2017-09-08 | 中国东方电气集团有限公司 | A kind of preparation method of lithium ion battery collector |
| WO2019110947A1 (en) * | 2017-12-08 | 2019-06-13 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Current collector and current collector-electrode assembly for an accumulator operating according to the principle of ion insertion and deinsertion |
| WO2023098120A1 (en) * | 2021-12-02 | 2023-06-08 | Guangdong Haozhi Technology Co. Limited | Modified current collector for secondary battery |
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| US20070231700A1 (en) * | 2006-03-30 | 2007-10-04 | Kozo Watanabe | Non-aqueous electrolyte secondary battery and method of manufacturing the same |
| CN103131267A (en) * | 2011-11-24 | 2013-06-05 | 珠海银通新能源有限公司 | Lithium ion battery current collector precoating and preparation method thereof |
| CN103956499A (en) * | 2014-04-15 | 2014-07-30 | 洛阳月星新能源科技有限公司 | Preparation method of safety coating for positive current collector in lithium ion battery |
| CN104051734A (en) * | 2014-06-16 | 2014-09-17 | 中国东方电气集团有限公司 | Electrode material for polyoxometallate carbon nanotube lithium ion battery and preparation method of electrode material |
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2016
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| CN1186349A (en) * | 1996-12-26 | 1998-07-01 | 中国科学院长春应用化学研究所 | Preparation of material for anode of solid lithium battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107142507A (en) * | 2017-05-03 | 2017-09-08 | 中国东方电气集团有限公司 | A kind of preparation method of lithium ion battery collector |
| CN107142507B (en) * | 2017-05-03 | 2019-01-01 | 中国东方电气集团有限公司 | A kind of preparation method of lithium ion battery collector |
| WO2019110947A1 (en) * | 2017-12-08 | 2019-06-13 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Current collector and current collector-electrode assembly for an accumulator operating according to the principle of ion insertion and deinsertion |
| FR3074967A1 (en) * | 2017-12-08 | 2019-06-14 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | CURRENT COLLECTOR AND CURRENT-ELECTRODE COLLECTOR ASSEMBLY FOR ACCUMULATOR OPERATING ACCORDING TO THE PRINCIPLE OF INSERTION AND IONIC INSULATION |
| WO2023098120A1 (en) * | 2021-12-02 | 2023-06-08 | Guangdong Haozhi Technology Co. Limited | Modified current collector for secondary battery |
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