CN103887517A - Anode aluminum foil current collector processed through two-section process and molybdenum compounds - Google Patents

Anode aluminum foil current collector processed through two-section process and molybdenum compounds Download PDF

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Publication number
CN103887517A
CN103887517A CN201410125081.8A CN201410125081A CN103887517A CN 103887517 A CN103887517 A CN 103887517A CN 201410125081 A CN201410125081 A CN 201410125081A CN 103887517 A CN103887517 A CN 103887517A
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aluminium foil
molybdate
positive pole
molybdenum
compound treatment
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CN103887517B (en
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童庆松
粟雪
郑莹颍
李秀华
任媛媛
潘国涛
吕超
吴钦缘
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Fujian Normal University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/665Composites
    • H01M4/667Composites in the form of layers, e.g. coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/661Metal or alloys, e.g. alloy coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66Current collectors
    • H01G11/68Current collectors characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The invention relates to an anode aluminum foil current collector processed through a two-section process and molybdenum compounds. The anode aluminum foil current collector is characterized in that an aluminum foil is made into the anode aluminum foil current collector respectively by adopting an oil removing step and a conversion coating forming step, wherein the conversion coating forming step is realized as follows: processing the aluminum foil processed in the oil removing step within a temperature interval of 45-98 DEG C by using a molybdate conversion solution for 1-150 minutes, washing with water, and finally, naturally drying or drying with hot air within a temperature interval of 70-180 DEG C to obtain the anode aluminum foil current collector. The prepared anode aluminum foil current collector has the advantages of good folding endurance, strong adhesion force with an anode material, small impedance, excellent charging and discharging performance, and the like when being used in a battery or supercapacitor.

Description

The positive pole aluminium foil collector of the compound treatment of process two-stage method and molybdenum
Technical field
The invention belongs to technical field prepared by battery and ultracapacitor, be specifically related to a kind of lithium battery, lithium ion battery, polymer battery and ultracapacitor of can be used for, with the positive pole aluminium foil collector of the compound treatment of two-stage method and molybdenum.
Technical background
Lithium ion battery has that cell voltage is high, energy density is high, memory-less effect, have extended cycle life, the advantage such as self discharge is low, the performance of positive electrode plays a part decision to the performance of lithium ion battery.At present, lithium ion battery is mainly made up of parts such as organic electrolyte (polymer dielectric), barrier film, positive pole, negative pole, collectors.Due to lithium ion battery use liquid state organic electrolyte (or polymer dielectric) conductive capability a little less than, in order to realize the high rate during charging-discharging of lithium ion battery, the positive electrode of lithium ion battery and negative material are generally all processed into Powdered, again the powder of the powder of positive electrode or negative material is bonded on collector with adhesive etc., realizes the collection of electric current.Therefore,, for lithium ion battery, contact impedance, collector surface appearance situation of change in charge and discharge process between the surface appearance of collector, collector and positive electrode and negative material have a great impact the performance of battery.For example, when charging, easily there is passivation and increase polarization of electrode in the positive pole aluminium foil collector of lithium ion battery, the charge-discharge performance of battery is obviously declined; Bonding insecure and occur the phenomenon of dry linting between the positive pole aluminium foil collector of lithium ion battery and positive electrode, affect the fail safe of charge-discharge performance and the battery of battery.
When the powder of the positive electrode of lithium ion battery and aluminum foil current collector bonding, adhesive segment is by being formed by parts such as sticky aluminium foil, adhesive and graphite agent.Wherein every part all affects adhesive property.At present, the research that bonded aluminium foil surface is processed is less, mainly by the aluminum foil current collector of lithium ion cell positive in advance graphene coated or carbon dust etc. improve the performance of aluminium foil, to realize following effect.As, suppress battery polarization, reduce thermal effect, improve high rate performance, reduce the internal resistance of cell, obviously reduce the dynamic internal resistance amplification of cyclic process; Improve the consistency of battery, increase the cycle life of battery; Improve the adhesion of active material and collector, reduce pole piece manufacturing cost; Protection collector is not corroded by electrolyte; Improve high temperature and the cryogenic property of ferric phosphate lithium cell, improve the processing characteristics of LiFePO4, lithium titanate material.But, the methods such as above-mentioned graphene coated in aluminum foil current collector, carbon dust are in advance limited for the effect that improves positive pole aluminium foil collector performance, and complicated process of preparation, cost are high, the present invention adopts simple surface-treated method to improve the surface property of lithium ion cell positive aluminum foil current collector for this reason, reduces impedance between lithium ion cell positive aluminum foil current collector and positive electrode, reduces anodal dry linting phenomenon.
Summary of the invention
For avoiding the deficiencies in the prior art, the present invention adopts simple surface-treated method to improve the surface property of the positive pole aluminium foil collector of battery and ultracapacitor, reduce impedance between positive pole aluminium foil collector and positive electrode, reduce anodal dry linting phenomenon, improve the consistency of battery, the heavy-current discharge performance of sample is significantly improved.For realizing the technical scheme that object of the present invention adopts be:
Aluminium foil is formed to step by deoiling step and conversion film respectively and make the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.
Described deoiling step is that aluminium foil is placed in except oil solution, at 70 ℃, processes 1min, and metallic matrix is come out.The described composition except oil solution is: NaOH 20g/L, Na 3pO 412 H 2o 40g/L, Na 2cO 315g/L, Na 2siO 39 H 2o 8g/L, Octylphenol polyoxyethylene ether 3g/L.
It is to be placed in molybdate conversion fluid through the aluminium foil of deoiling step processing that described conversion film forms step, process 1min~150 min 45 ℃~98 ℃ temperature ranges, then water is rinsed well, last natural drying or with the heated air drying of 70 ℃~180 ℃ of temperature ranges, make the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.
Described molybdate conversion fluid composed as follows: molybdate 1 g/L~15 g/L, ammonium chloride 3 g/L~15 g/L, concentrated ammonia liquor 2 ml/L~15 ml/L.
The concentration of described concentrated ammonia liquor is within the scope of 25 w.t.%~28 w.t.%.
Described molybdate is sodium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate or ammonium molybdate.
When the positive pole aluminium foil collector of the compound treatment of process two-stage method and molybdenum uses in battery or ultracapacitor, there is the advantages such as folding resistance is good, strong with the cohesive force of positive electrode, impedance is little, charge-discharge performance is excellent.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed.Embodiment further supplements and explanation of the present invention, rather than to the restriction of inventing.
Embodiment 1
Aluminium foil is formed to step by deoiling step and conversion film respectively and make the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.Described deoiling step is that aluminium foil is placed in except oil solution, at 70 ℃, processes 1min, and metallic matrix is come out.The described composition except oil solution is: NaOH 20g/L, Na 3pO 412 H 2o 40g/L, Na 2cO 315g/L, Na 2siO 39 H 2o 8g/L, Octylphenol polyoxyethylene ether 3g/L.
It is to be placed in molybdate conversion fluid through the aluminium foil of deoiling step processing that described conversion film forms step, processes 10min at 68 ℃, and water is rinsed well, finally natural drying, makes the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.Described molybdate conversion fluid composed as follows: sodium molybdate 8 g/L, ammonium chloride 8 g/L, 25 wt.% concentrated ammonia liquor 5 ml/L.Be designated as 180 ° through returning back to original state after 180 ° of the positive pole aluminium foil collector doublings of the compound treatment of two-stage method and molybdenum, then roll over 180 ° and be designated as 360 °, the rest may be inferred.Test shows, through the positive pole aluminium foil collector of the compound treatment of two-stage method and molybdenum continuously 6200 ° of foldings can not fracture.3g polyvinylidene fluoride resin is dissolved in to 29ml dimethylacetylamide Making viscose.This viscose glue is coated on the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum, and the peel strength after 180 ℃ of heat treated 10min reaches 0.07623 N/mm 2above.When using aluminium foil with through the positive pole aluminium foil collector of the compound treatment of two-stage method and molybdenum during respectively as the collector of the ferrous lithium phosphate cathode of lithium ion battery; while discharging and recharging with 2C multiplying power electric current, the 1st cyclic discharge capacity of making plus plate current-collecting body take aluminium foil is as 97mAh/g; And the 1st cyclic discharge capacity take the positive pole aluminium foil collector of the compound treatment through two-stage method and molybdenum as plus plate current-collecting body is as 119mAh/g.
During as the plus plate current-collecting body of lithium ion battery, there is the advantages such as folding resistance is good, strong with the cohesive force of positive electrode, impedance is little, charge-discharge performance is excellent through the positive pole aluminium foil collector of the compound treatment of two-stage method and molybdenum.
Embodiment 2
Aluminium foil is formed to step by deoiling step and conversion film respectively and make the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.Described deoiling step is that aluminium foil is placed in except oil solution, at 70 ℃, processes 1min, and metallic matrix is come out.The described composition except oil solution is: NaOH 20g/L, Na 3pO 412 H 2o 40g/L, Na 2cO 315g/L, Na 2siO 39 H 2o 8g/L, Octylphenol polyoxyethylene ether 3g/L.
It is to be placed in molybdate conversion fluid through the aluminium foil of deoiling step processing that described conversion film forms step, processes 150 min at 98 ℃, and water is rinsed well, then natural drying, makes the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.
Described molybdate conversion fluid composed as follows: sodium molybdate 15 g/L, ammonium chloride 15 g/L, 28 w.t.% concentrated ammonia liquor 15 ml/L.
During as the plus plate current-collecting body of lithium ion battery, there is the advantages such as folding resistance is good, strong with the cohesive force of positive electrode, impedance is little, charge-discharge performance is excellent through the positive pole aluminium foil collector of the compound treatment of two-stage method and molybdenum.
Embodiment 3
Aluminium foil is formed to step by deoiling step and conversion film respectively and make the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.Described deoiling step is that aluminium foil is placed in except oil solution, at 70 ℃, processes 1min, and metallic matrix is come out.The described composition except oil solution is: NaOH 20g/L, Na 3pO 412 H 2o 40g/L, Na 2cO 315g/L, Na 2siO 39 H 2o 8g/L, Octylphenol polyoxyethylene ether 3g/L.
It is to be placed in molybdate conversion fluid through the aluminium foil of deoiling step processing that described conversion film forms step, process 1min at 45 ℃, water is rinsed well, then uses the heated air drying of 100 ℃, makes the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.
Described molybdate conversion fluid composed as follows: potassium molybdate 1 g/L, ammonium chloride 3 g/L, 26 w.t.% concentrated ammonia liquor 2 ml/L.
During as the plus plate current-collecting body of lithium ion battery, there is the advantages such as folding resistance is good, strong with the cohesive force of positive electrode, impedance is little, charge-discharge performance is excellent through the positive pole aluminium foil collector of the compound treatment of two-stage method and molybdenum.
Embodiment 4
Aluminium foil is formed to step by deoiling step and conversion film respectively and make the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.Described deoiling step is that aluminium foil is placed in except oil solution, at 70 ℃, processes 1min, and metallic matrix is come out.The described composition except oil solution is: NaOH 20g/L, Na 3pO 412 H 2o 40g/L, Na 2cO 315g/L, Na 2siO 39 H 2o 8g/L, Octylphenol polyoxyethylene ether 3g/L.
It is to be placed in molybdate conversion fluid through the aluminium foil of deoiling step processing that described conversion film forms step, process 100min at 98 ℃, water is rinsed well, then uses the heated air drying of 180 ℃, makes the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.
Described molybdate conversion fluid composed as follows: calcium molybdate 5 g/L, ammonium chloride 5 g/L, 25 w.t.% concentrated ammonia liquor 10 ml/L.
During as the plus plate current-collecting body of lithium ion battery, there is the advantages such as folding resistance is good, strong with the cohesive force of positive electrode, impedance is little, charge-discharge performance is excellent through the positive pole aluminium foil collector of the compound treatment of two-stage method and molybdenum.
Embodiment 5
Aluminium foil is formed to step by deoiling step and conversion film respectively and make the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.Described deoiling step is that aluminium foil is placed in except oil solution, at 70 ℃, processes 1min, and metallic matrix is come out.The described composition except oil solution is: NaOH 20g/L, Na 3pO 412 H 2o 40g/L, Na 2cO 315g/L, Na 2siO 39 H 2o 8g/L, Octylphenol polyoxyethylene ether 3g/L.
It is to be placed in molybdate conversion fluid through the aluminium foil of deoiling step processing that described conversion film forms step, process 1min at 98 ℃, water is rinsed well, then uses the heated air drying of 70 ℃, makes the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.
Described molybdate conversion fluid composed as follows: sodium molybdate 10 g/L, ammonium chloride 3 g/L, 28 w.t.% concentrated ammonia liquor 15 ml/L.
During as the plus plate current-collecting body of lithium ion battery, there is the advantages such as folding resistance is good, strong with the cohesive force of positive electrode, impedance is little, charge-discharge performance is excellent through the positive pole aluminium foil collector of the compound treatment of two-stage method and molybdenum.
Embodiment 6
Aluminium foil is formed to step by deoiling step and conversion film respectively and make the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.Described deoiling step is that aluminium foil is placed in except oil solution, in 70 ℃ of processing 1min, metallic matrix is come out.The described composition except oil solution is: NaOH 20g/L, Na 3pO 412 H 2o 40g/L, Na 2cO 315g/L, Na 2siO 39 H 2o 8g/L, Octylphenol polyoxyethylene ether 3g/L.
It is to be placed in molybdate conversion fluid through the aluminium foil of deoiling step processing that described conversion film forms step, process 150 min at 55 ℃, water is rinsed well, then uses the heated air drying of 170 ℃, makes the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.
Described molybdate conversion fluid composed as follows: magnesium molybdate 1 g/L, ammonium chloride 15 g/L, 27 w.t.% concentrated ammonia liquor 15 ml/L.
During as the plus plate current-collecting body of lithium ion battery, there is the advantages such as folding resistance is good, strong with the cohesive force of positive electrode, impedance is little, charge-discharge performance is excellent through the positive pole aluminium foil collector of the compound treatment of two-stage method and molybdenum.
Embodiment 7
Aluminium foil is formed to step by deoiling step and conversion film respectively and make the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.Described deoiling step is that aluminium foil is placed in except oil solution, in 70 ℃ of processing 1min, metallic matrix is come out.The described composition except oil solution is: NaOH 20g/L, Na 3pO 412 H 2o 40g/L, Na 2cO 315g/L, Na 2siO 39 H 2o 8g/L, Octylphenol polyoxyethylene ether 3g/L.
It is to be placed in molybdate conversion fluid through the aluminium foil of deoiling step processing that described conversion film forms step, process 1min at 45 ℃, water is rinsed well, then uses the heated air drying of 70 ℃, makes the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum.
Described molybdate conversion fluid composed as follows: ammonium molybdate 15 g/L, ammonium chloride 3 g/L, 25 w.t.% concentrated ammonia liquor 2 ml/L.
During as the plus plate current-collecting body of lithium ion battery, there is the advantages such as folding resistance is good, strong with the cohesive force of positive electrode, impedance is little, charge-discharge performance is excellent through the positive pole aluminium foil collector of the compound treatment of two-stage method and molybdenum.

Claims (4)

1. the positive pole aluminium foil collector of the compound treatment of process two-stage method and molybdenum, is characterized in that: aluminium foil is formed to step by deoiling step and conversion film respectively and make the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum;
Described deoiling step is that aluminium foil is placed in except oil solution, in 70 ℃ of processing 1min, metallic matrix is come out; The described composition except oil solution is: NaOH 20g/L, Na 3pO 412 H 2o 40g/L, Na 2cO 315g/L, Na 2siO 39 H 2o 8g/L, Octylphenol polyoxyethylene ether 3g/L;
It is to be placed in molybdate conversion fluid through the aluminium foil of deoiling step processing that described conversion film forms step, process 1min~150 min 45 ℃~98 ℃ temperature ranges, then water is rinsed well, last natural drying or with the heated air drying of 70 ℃~180 ℃ of temperature ranges, make the positive pole aluminium foil collector through the compound treatment of two-stage method and molybdenum;
Described molybdate conversion fluid composed as follows: molybdate 1 g/L~15 g/L, ammonium chloride 3 g/L~15 g/L, concentrated ammonia liquor 2 ml/L~15 ml/L.
2. the positive pole aluminium foil collector of the compound treatment through two-stage method and molybdenum according to claim 1, is characterized in that described molybdate is sodium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate or ammonium molybdate.
3. the positive pole aluminium foil collector of the compound treatment through two-stage method and molybdenum according to claim 1, is characterized in that the concentration of described concentrated ammonia liquor is within the scope of 25 w.t.%~28 w.t.%.
4. the positive pole aluminium foil collector of the compound treatment through two-stage method and molybdenum according to claim 1, is characterized in that the positive pole aluminium foil collector of the described compound treatment through two-stage method and molybdenum is for lithium battery, lithium ion battery, polymer battery or ultracapacitor.
CN201410125081.8A 2014-03-31 2014-03-31 With the positive pole aluminium foil collector of two-stage method and the compound treatment of molybdenum Active CN103887517B (en)

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CN108039449A (en) * 2017-12-07 2018-05-15 福建荣华科技有限公司 The preparation method and lithium ion battery of lithium ion battery

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CN108039449A (en) * 2017-12-07 2018-05-15 福建荣华科技有限公司 The preparation method and lithium ion battery of lithium ion battery
CN108039449B (en) * 2017-12-07 2020-02-11 福建荣华科技有限公司 Preparation method of lithium ion battery and lithium ion battery

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