CN103872336B - Method for modifying positive aluminum foil current collector by utilizing phosphoric acid-fluorine-dichromate - Google Patents
Method for modifying positive aluminum foil current collector by utilizing phosphoric acid-fluorine-dichromate Download PDFInfo
- Publication number
- CN103872336B CN103872336B CN201410124972.1A CN201410124972A CN103872336B CN 103872336 B CN103872336 B CN 103872336B CN 201410124972 A CN201410124972 A CN 201410124972A CN 103872336 B CN103872336 B CN 103872336B
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- CN
- China
- Prior art keywords
- aluminium foil
- aluminum foil
- positive pole
- current collector
- phosphoric acid
- Prior art date
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Classifications
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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
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a method for modifying a positive aluminum foil current collector by utilizing phosphoric acid-fluorine-dichromate. The method is characterized by comprising the following steps of processing an aluminum foil for 1min to 30min by utilizing processing liquid at the temperature of 35 to 78 DEG C, washing the aluminum foil by utilizing the water, and finally naturally drying the aluminum foil or drying the aluminum foil by utilizing hot air at the temperature of 70 to 180 DEG C to obtain the modified positive aluminum foil current collector. When the prepared modified positive aluminum foil current collector is applied to a battery or a supercapacitor, the aluminum foil current collector has the advantages of good bending resistance, strong cohesive force with a positive material, small impedance, excellent charging-discharging performance and the like.
Description
Technical field
The invention belongs to battery electrode preparation technical field and in particular to one kind can be used for lithium battery, lithium ion battery,
Polymer battery and ultracapacitor, with the modified positive pole aluminium foil collector of phosphoric acid fluorine bichromate.
Technical background
Lithium ion battery have cell voltage height, energy density height, memory-less effect, have extended cycle life, self discharge low
Advantage, the performance of positive electrode plays a part decision to the performance of lithium ion battery.At present, lithium ion battery is mainly by organic
The parts such as electrolyte (polymer dielectric), barrier film, positive pole, negative pole, collector form.The liquid being used due to lithium ion battery
The conductive capability of organic electrolyte (or polymer dielectric) is weaker, and the large current density in order to realize lithium ion battery is electrical
Can, the positive electrode of lithium ion battery and negative material are typically all processed powdered, then by the powder of positive electrode or negative pole
Powder adhesive of material etc. bonds on a current collector, realizes the collection of electric current.Therefore, for lithium ion battery, collection
Contact impedance between the surface appearance of fluid, collector and positive electrode and negative material, collector table in charge and discharge process
Planar condition situation of change has a great impact to the performance of battery.For example, during charging, the positive pole aluminium foil collector of lithium ion battery
It is susceptible to be passivated and increases polarization of electrode, so that the charge-discharge performance of battery is decreased obviously；The positive pole aluminium foil of lithium ion battery
Bonding insecure and phenomenon that dry linting occurs, the impact charge-discharge performance of battery and the safety of battery between collector and positive electrode
Property.
When the powder of the positive electrode of lithium ion battery and aluminum foil current collector bond, adhesive segment is by by viscous aluminium foil, viscous
The part such as jelly and graphite agent forms.Each of which part all affects adhesive property.At present, enter to by bonding aluminium foil surface
The research that row is processed is less, main passes through graphene coated in advance in the aluminum foil current collector of lithium ion cell positive or carbon dust etc.
Improve the performance of aluminium foil, to realize following acting on.As suppressed battery polarization, reducing fuel factor, improve high rate performance, reduce electricity
Pond internal resistance is hence it is evident that reduce the dynamic internal resistance amplification of cyclic process；Improve battery with two side terminals, increase the cycle life of battery；Carry
High active substance and the adhesion of collector, reduce pole piece manufacturing cost；Protect collector not by electrolytic corrosion；Improve phosphoric acid
The high temperature of lithium iron battery and cryogenic property, improve the processing characteristics of LiFePO4, lithium titanate material.But, above-mentioned in advance in aluminium
On paper tinsel collector, the method such as graphene coated, carbon dust is for the limited use improving positive pole aluminium foil collector performance, and prepares work
Skill is complicated, high cost, improves lithium ion cell positive aluminum foil current collector for this present invention using the method for simple surface treatment
Surface property, reduce the impedance between lithium ion cell positive aluminum foil current collector and positive electrode, reduce the dry linting phenomenon of positive pole.
Content of the invention
For avoiding the deficiencies in the prior art, the present invention improves lithium ion cell positive using the method for simple surface treatment
The surface property of aluminum foil current collector, reduces impedance between lithium ion cell positive aluminum foil current collector and positive electrode, minimizing positive pole falls
Powder phenomenon, improve battery with two side terminals, so that the heavy-current discharge performance of sample is obviously improved.For realizing skill of the present invention
Art scheme is:
Aluminium foil treatment fluid is processed 1min～30 min in 35 DEG C～78 DEG C temperature ranges, is rinsed well with water, finally
Spontaneously dry or be dried with the hot-air of 70 DEG C～180 DEG C of temperature ranges, modification positive pole aluminium foil collector is obtained.
The composition of described treatment fluid is as follows: sodium dihydrogen phosphate 10 g/l～19g/l, sodium fluoride 2 g/l～10g/l,
Potassium bichromate 3 g/l～6g/l, concentrated hydrochloric acid 2 g/l～6g/l.
The concentration of described concentrated hydrochloric acid is in the range of the w.t.% of 36w.t.%～37.
In treatment fluid, hydrochloric acid is reacted with aluminium surface, and the aluminium chloride of generation can react generation porous with potassium bichromate
The skin covering of the surface of property.Enter in perforated membrane in the fluorine ion in treatment fluid, can be fixed in dry run, meanwhile, phosphoric acid
Ion also plays a part improvement to the surface property of aluminium simultaneously.The modified positive pole aluminium foil collector of preparation is as lithium ion battery
Plus plate current-collecting body when, have the advantages that the good cohesive force with positive electrode of folding resistance is strong, impedance is little, charge-discharge performance is excellent.
Specific embodiment
With reference to embodiment, the present invention is further detailed.Embodiment is only supplementing further to the present invention
And explanation, rather than the restriction to invention.
Embodiment 1
Aluminium foil treatment fluid is processed 5min at 51 DEG C, is rinsed well with water, finally spontaneously dry, modification positive pole aluminium is obtained
Paper tinsel collector.
The composition of described treatment fluid is as follows: sodium dihydrogen phosphate 15 g/l, sodium fluoride 6 g/l, potassium bichromate 5 g/l,
36 w.t.% hydrochloric acid 4 g/l.
It is designated as with returning back to original state after 180 ° modified of positive pole aluminium foil collector doubling of phosphoric acid fluorine bichromate
180 °, then roll over 180 ° and be designated as 360 °, the rest may be inferred.Test shows, 6300 ° of the continuous folding of the modified positive pole aluminium foil of preparation, will not fracture.
3g polyvinylidene fluoride resin is dissolved in 29ml dimethylacetylamide and prepares viscose glue.This viscose glue is coated in aluminum foil current collector, warp
Cross the peel strength after 180 DEG C of heating 10min and reach 0.0671 n/mm2More than.Phosphoric acid is coated on modified positive pole aluminium foil
Iron lithium sample, under 1c multiplying power electric current during discharge and recharge, the discharge capacity circulating first is higher than 140mah/g.And without modification
On the aluminium foil of film process, under same charging and discharging currents, the discharge capacity circulating first can only achieve coating LiFePO4 sample
115 mah/g.
Preparation modified positive pole aluminium foil collector as lithium ion battery plus plate current-collecting body when, have folding resistance good and
The advantages of cohesive force of positive electrode is strong, impedance is little, charge-discharge performance is excellent.
Embodiment 2
Aluminium foil treatment fluid is processed 30 min at 78 DEG C, then is rinsed well with water, finally done with 180 DEG C of hot-air
Dry, modification positive pole aluminium foil collector is obtained.
The composition of described treatment fluid is as follows: sodium dihydrogen phosphate 19g/l, sodium fluoride 10g/l, potassium bichromate 6g/l, and 37
W.t.% concentrated hydrochloric acid 6g/l.
Preparation modified positive pole aluminium foil collector as lithium ion battery plus plate current-collecting body when, have folding resistance good and
The advantages of cohesive force of positive electrode is strong, impedance is little, charge-discharge performance is excellent.
Embodiment 3
Aluminium foil treatment fluid is processed 1min at 35 DEG C, then is rinsed well with water, be finally dried with 70 DEG C of hot-airs, be obtained
Modified positive pole aluminium foil collector.
The composition of described treatment fluid is as follows: sodium dihydrogen phosphate 10 g/l, sodium fluoride 2 g/l, potassium bichromate 3 g/l, and 37
W.t.% concentrated hydrochloric acid 2 g/l.
Preparation modified positive pole aluminium foil collector as lithium ion battery plus plate current-collecting body when, have folding resistance good and
The advantages of cohesive force of positive electrode is strong, impedance is little, charge-discharge performance is excellent.
Embodiment 4
Aluminium foil treatment fluid is processed 1min at 78 DEG C, then is rinsed well with water, be finally dried with 100 DEG C of hot-air,
Modification positive pole aluminium foil collector is obtained.
The composition of described treatment fluid is as follows: sodium dihydrogen phosphate 10 g/l, sodium fluoride 10g/l, potassium bichromate 6g/l, 36
W.t.% concentrated hydrochloric acid 6g/l.
Preparation modified positive pole aluminium foil collector as lithium ion battery plus plate current-collecting body when, have folding resistance good and
The advantages of cohesive force of positive electrode is strong, impedance is little, charge-discharge performance is excellent.
Embodiment 5
Aluminium foil treatment fluid is processed 30 min at 35 DEG C, then is rinsed well with water, be finally dried with 180 DEG C of hot-airs,
Modification positive pole aluminium foil collector is obtained.
The composition of described treatment fluid is as follows: sodium dihydrogen phosphate 19g/l, sodium fluoride 2 g/l, potassium bichromate 3 g/l, and 37
W.t.% concentrated hydrochloric acid 2 g/l.
Preparation modified positive pole aluminium foil collector as lithium ion battery plus plate current-collecting body when, have folding resistance good and
The advantages of cohesive force of positive electrode is strong, impedance is little, charge-discharge performance is excellent.
Embodiment 6
Aluminium foil treatment fluid is processed 25min at 73 DEG C, then is rinsed well with water, finally spontaneously dry, prepared modification is just
Pole aluminum foil current collector.
The composition of described treatment fluid is as follows: sodium dihydrogen phosphate 12 g/l, sodium fluoride 5 g/l, potassium bichromate 3 g/l, and 36
W.t.% concentrated hydrochloric acid 2 g/l.
Preparation modified positive pole aluminium foil collector as lithium ion battery plus plate current-collecting body when, have folding resistance good and
The advantages of cohesive force of positive electrode is strong, impedance is little, charge-discharge performance is excellent.
Embodiment 7
Aluminium foil treatment fluid is processed 1min at 35 DEG C, then is rinsed well with water, be finally dried with 70 DEG C of hot-airs, be obtained
Modified positive pole aluminium foil collector.
The composition of described treatment fluid is as follows: sodium dihydrogen phosphate 10 g/l, sodium fluoride 10g/l, potassium bichromate 3 g/l, and 36
W.t.% concentrated hydrochloric acid 3 g/l.
Preparation modification positive pole aluminium foil collector as lithium ion battery plus plate current-collecting body when, have folding resistance good,
The advantages of, impedance strong with the cohesive force of positive electrode is little, charge-discharge performance is excellent.
Claims (3)
1. with phosphoric acid fluorine bichromate modification positive pole aluminium foil collector method it is characterised in that: by aluminium foil treatment fluid
Process 1min～30 min in 35 DEG C～78 DEG C temperature ranges, then rinsed well with water, finally spontaneously dry or with 70 DEG C～
The hot-air of 180 DEG C of temperature ranges is dried, and modification positive pole aluminium foil collector is obtained；
The composition of described treatment fluid is as follows: sodium dihydrogen phosphate 10 g/l～19g/l, sodium fluoride 2 g/l～10g/l, weight chromium
Sour potassium 3 g/l～6g/l, concentrated hydrochloric acid 2 g/l～6g/l.
2. the method for use phosphoric acid fluorine bichromate modification positive pole aluminium foil collector according to claim 1, its feature
The concentration being described concentrated hydrochloric acid is in the range of 36wt%～37wt%.
3. the method for use phosphoric acid fluorine bichromate modification positive pole aluminium foil collector according to claim 1, its feature
It is that described positive pole aluminium foil collector is used for lithium ion battery, polymer battery or ultracapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410124972.1A CN103872336B (en) | 2014-03-31 | 2014-03-31 | Method for modifying positive aluminum foil current collector by utilizing phosphoric acid-fluorine-dichromate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410124972.1A CN103872336B (en) | 2014-03-31 | 2014-03-31 | Method for modifying positive aluminum foil current collector by utilizing phosphoric acid-fluorine-dichromate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103872336A CN103872336A (en) | 2014-06-18 |
| CN103872336B true CN103872336B (en) | 2017-01-18 |
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| CN201410124972.1A Expired - Fee Related CN103872336B (en) | 2014-03-31 | 2014-03-31 | Method for modifying positive aluminum foil current collector by utilizing phosphoric acid-fluorine-dichromate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108011082B (en) * | 2017-11-20 | 2020-02-11 | 萝北泰东德新材料科技有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN109346724A (en) * | 2018-10-24 | 2019-02-15 | 遵义源创生产力促进中心有限公司 | A kind of fluoboric acid improvement positive pole aluminium foil collector performance methodology |
| CN109390550A (en) * | 2018-10-24 | 2019-02-26 | 遵义源创生产力促进中心有限公司 | A kind of positive pole aluminium foil collector performance improvement method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| BE467610A (en) * | 1945-06-30 | |||
| CN103620839B (en) * | 2011-06-21 | 2017-08-18 | 海德鲁铝业钢材有限公司 | Collector foil that is chemically treated, being made up of aluminum or aluminum alloy |
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