CN103840169A - Preparation method for improving properties of positive aluminum-foil current collector with fluoboric acid - Google Patents
Preparation method for improving properties of positive aluminum-foil current collector with fluoboric acid Download PDFInfo
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- CN103840169A CN103840169A CN201410125066.3A CN201410125066A CN103840169A CN 103840169 A CN103840169 A CN 103840169A CN 201410125066 A CN201410125066 A CN 201410125066A CN 103840169 A CN103840169 A CN 103840169A
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- aluminium foil
- positive pole
- preparation
- sulfate
- current collector
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002253 acid Substances 0.000 title claims abstract description 8
- 239000011888 foil Substances 0.000 title abstract description 11
- 239000012530 fluid Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000005030 aluminium foil Substances 0.000 claims description 44
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 28
- 229910052708 sodium Inorganic materials 0.000 claims description 28
- 229910001416 lithium ion Inorganic materials 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000007605 air drying Methods 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 235000011132 calcium sulphate Nutrition 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 238000007739 conversion coating Methods 0.000 abstract 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- BVBRZOLXXOIMQG-UHFFFAOYSA-N fluoroborane Chemical compound FB BVBRZOLXXOIMQG-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- 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 a preparation method for improving properties of a positive aluminum-foil current collector with fluoboric acid. The preparation method is characterized by comprising the steps of treating an aluminum foil with a molybdate treating fluid within a temperature interval ranging from 35 DEG C to 78 DEG C for 1 to 30 minutes, rinsing thoroughly with water, and finally drying naturally or by virtue of hot air within a temperature interval ranging from 70 DEG C to 160 DEG C, and thereby obtaining the positive aluminum-foil current collector comprising a conversion coating. The positive aluminum-foil current collector comprising the conversion coating is applied to a battery or a super container, and has the advantages of good folding resistance, high adhesion to a positive material, low impedance, excellent charge and discharge performance and the like.
Description
Technical field
The invention belongs to technical field prepared by battery electrode, be specifically related to a kind of positive pole aluminium foil collector lithium battery, lithium ion battery, polymer battery and ultracapacitor, improve performance with fluoboric acid that can be used for.
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 lithium ion cell positive aluminum foil current collector, 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 processed to 1min～30 min with sodium fluoborate treatment fluid 35 ℃～78 ℃ temperature ranges, and then water is rinsed well, last natural drying or with the heated air drying of 70 ℃～160 ℃ of temperature ranges, makes the positive pole aluminium foil collector containing conversion film.
Described sodium fluoborate treatment fluid composed as follows: phosphoric acid 2 g/L～15g/L, sulfate 2 g/L～12g/L, sodium fluoborate 3 g/L～12g/L.
Described sulfate is sodium sulphate, potassium sulfate, calcium sulfate, zinc sulfate or magnesium sulfate.
In treatment fluid, phosphoric acid and aluminium surface react, and the porous aluminum phosphate of generation can react with sodium fluoborate and generate the porous skin covering of the surface that contains fluoro boron acid ion, and the surface property of aluminium is played a part to improvement.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 containing the positive pole aluminium foil collector of conversion film.
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 processed to 15min with sodium fluoborate treatment fluid at 68 ℃, and then water is rinsed well, finally natural drying, makes the positive pole aluminium foil collector containing conversion film.
Described sodium fluoborate treatment fluid composed as follows: phosphoric acid 5 g/L, zinc sulfate 6 g/L, sodium fluoborate 6 g/L.
Be designated as 180 ° containing returning back to original state after 180 ° of the positive pole aluminium foil collector doublings of conversion film, then roll over 180 °, be designated as 360 °, the rest may be inferred.Test shows, the positive pole aluminium foil collector containing conversion film of preparation 7306 ° of foldings continuously, can not fracture.3g polyvinylidene fluoride resin is dissolved in to 29ml dimethylacetylamide Making viscose.This viscose glue is coated on the aluminium foil containing conversion film, and the peel strength after 180 ℃ of heating 10min reaches 0.0773 N/mm
2above.Applying LiFePO4 sample containing on the aluminium foil of conversion film, while discharging and recharging under 2C multiplying power electric current, the discharge capacity of circulation is higher than 131mAh/g first.And on the aluminium foil through Modified Membrane processing, do not applying LiFePO4 sample, under same current, the discharge capacity of circulation can only reach 106mAh/g first.
Preparation 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 containing the positive pole aluminium foil collector of conversion film.
Embodiment 2
Aluminium foil is processed to 30 min with sodium fluoborate treatment fluid at 78 ℃, and then water is rinsed well, finally uses the heated air drying of 160 ℃, makes the positive pole aluminium foil collector containing conversion film.
Described sodium fluoborate treatment fluid composed as follows: phosphatase 11 5g/L, magnesium sulfate 12g/L, sodium fluoborate 12g/L.
The positive pole aluminium foil collector containing conversion film of preparation, as the plus plate current-collecting body of lithium ion battery, has the advantages such as folding resistance is good, strong with positive electrode cohesive force, impedance is little, charge-discharge performance is excellent.
Embodiment 3
Aluminium foil is processed to 1min with sodium fluoborate treatment fluid at 35 ℃, and then water is rinsed well, finally uses the heated air drying of 70 ℃, makes the positive pole aluminium foil collector containing conversion film.
Described sodium fluoborate treatment fluid composed as follows: phosphoric acid 2 g/L, sodium sulphate 2 g/L, sodium fluoborate 3 g/L.
Preparation 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 containing the positive pole aluminium foil collector of conversion film.
Embodiment 4
Aluminium foil is processed to 1min with sodium fluoborate treatment fluid at 78 ℃, and then water is rinsed well, finally uses the heated air drying of 100 ℃, makes the positive pole aluminium foil collector containing conversion film.
Described sodium fluoborate treatment fluid composed as follows: phosphoric acid 2 g/L, zinc sulfate 12g/L, sodium fluoborate 12g/L.
Preparation 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 containing the positive pole aluminium foil collector of conversion film.
Embodiment 5
Aluminium foil is processed to 30 min with sodium fluoborate treatment fluid at 35 ℃, and then water is rinsed well, finally uses the heated air drying of 138 ℃, makes the positive pole aluminium foil collector containing conversion film.
Described sodium fluoborate treatment fluid composed as follows: phosphatase 11 5g/L, zinc sulfate 2 g/L, sodium fluoborate 3 g/L.
Preparation 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 containing the positive pole aluminium foil collector of conversion film.
Embodiment 6
Aluminium foil is processed to 7min with sodium fluoborate treatment fluid at 66 ℃, and then water is rinsed well, finally uses 80 ℃ of heated air dryings, makes the positive pole aluminium foil collector containing conversion film.
Described sodium fluoborate treatment fluid composed as follows: phosphoric acid 5 g/L, potassium sulfate 7 g/L, sodium fluoborate 5 g/L.
Preparation 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 containing the positive pole aluminium foil collector of conversion film.
Embodiment 7
Aluminium foil is processed to 2min with sodium fluoborate treatment fluid at 35 ℃, and then water is rinsed well, finally uses the heated air drying of 77 ℃, makes the positive pole aluminium foil collector containing conversion film.
Described sodium fluoborate treatment fluid composed as follows: phosphoric acid 2 g/L, calcium sulfate 10 g/L, sodium fluoborate 7 g/L.
Preparation 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 containing the positive pole aluminium foil collector of conversion film.
Claims (3)
1. improve the preparation method of positive pole aluminium foil collector performance with fluoboric acid; it is characterized in that: aluminium foil sodium fluoborate treatment fluid is processed to 1min～30 min 35 ℃～78 ℃ temperature ranges; water is rinsed well; last natural drying or with the heated air drying of 70 ℃～160 ℃ of temperature ranges, make the positive pole aluminium foil collector containing conversion film;
Described sodium fluoborate treatment fluid composed as follows: phosphoric acid 2 g/L～15g/L, sulfate 2 g/L～12g/L, sodium fluoborate 3 g/L～12g/L.
2. the preparation method who improves positive pole aluminium foil collector performance with fluoboric acid according to claim 1, is characterized in that described sulfate is sodium sulphate, potassium sulfate, calcium sulfate, zinc sulfate or magnesium sulfate.
3. the preparation method who improves positive pole aluminium foil collector performance with fluoboric acid according to claim 1, is characterized in that the described positive pole aluminium foil collector containing conversion film is for lithium battery, lithium ion battery, polymer battery or ultracapacitor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410125066.3A CN103840169B (en) | 2014-03-31 | 2014-03-31 | The preparation method of positive pole aluminium foil collector performance is improved with fluoboric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410125066.3A CN103840169B (en) | 2014-03-31 | 2014-03-31 | The preparation method of positive pole aluminium foil collector performance is improved with fluoboric acid |
Publications (2)
| Publication Number | Publication Date |
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| CN103840169A true CN103840169A (en) | 2014-06-04 |
| CN103840169B CN103840169B (en) | 2016-10-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201410125066.3A Expired - Fee Related CN103840169B (en) | 2014-03-31 | 2014-03-31 | The preparation method of positive pole aluminium foil collector performance is improved with fluoboric acid |
Country Status (1)
| Country | Link |
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| CN (1) | CN103840169B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634227A (en) * | 2017-08-21 | 2018-01-26 | 清华大学 | Aluminium collector and preparation method thereof, and lithium secondary battery 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 |
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2014
- 2014-03-31 CN CN201410125066.3A patent/CN103840169B/en not_active Expired - Fee Related
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| 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 |
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| Publication number | Publication date |
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| CN103840169B (en) | 2016-10-05 |
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