CN101355149A - Method for processing anode material and battery with anode material processed by the method - Google Patents
Method for processing anode material and battery with anode material processed by the method Download PDFInfo
- Publication number
- CN101355149A CN101355149A CNA2007100752840A CN200710075284A CN101355149A CN 101355149 A CN101355149 A CN 101355149A CN A2007100752840 A CNA2007100752840 A CN A2007100752840A CN 200710075284 A CN200710075284 A CN 200710075284A CN 101355149 A CN101355149 A CN 101355149A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- carrying
- washing treatment
- carried out
- battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000012545 processing Methods 0.000 title claims description 17
- 239000010405 anode material Substances 0.000 title description 3
- 238000005406 washing Methods 0.000 claims abstract description 87
- 239000000463 material Substances 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 238000012986 modification Methods 0.000 claims description 25
- 230000004048 modification Effects 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000003672 processing method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 230000002776 aggregation Effects 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 238000005054 agglomeration Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 239000010406 cathode material Substances 0.000 abstract description 22
- 238000005253 cladding Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 10
- 238000004513 sizing Methods 0.000 description 10
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 description 9
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000011882 ultra-fine particle Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
Images
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for treating cathode materials, and is suitable for treating the cathode materials which are subjected to modifying treatment to improve the property of the materials. The method comprises the following processes: a. the cathode materials are subjected to washing treatment, washing media for washing and treating comprise a washing medium containing a surface active agent. The invention also discloses a battery for treating the cathode materials by the method, the cathode materials for the battery are subjected to modifying treatment, and washing treatment through the washing medium with the surface active agent, and the cathode materials after the washing treatment are separated from the washing medium. The method eliminates the glomeration among particles of the cathode materials, thereby improving the foil-cladding capability and the electric conductivity of the materials. When the materials treated by the method are used to manufacture positive plates, the bonding between the cathode materials and a current collector is better, and the cathode materials are distributed uniformly, thereby the battery of the invention has higher gram specific capacity to exert and higher cycle performance.
Description
Technical field
The present invention relates to a kind of processing method of cell positive material, especially the back positive electrode is handled in modification and handled the method for improving material property with further.
Background technology
Lithium ion battery is a kind of big capacity, high-power battery, and it is mainly used on the mini-plant, particularly mobile phone, laptop computer, portable power tool.Lithium ion battery is generally formed by battery cover board assembly, battery container, electrolyte and by the battery unit that positive and negative plate and diaphragm paper are wound into.Wherein be coated with positive active material on the positive plate, be coated with negative electrode active material on the negative plate.The performance of positive active material and negative electrode active material is most important to the quality of lithium ion battery.
In recent years, the research and development of lithium ion battery has obtained gratifying achievement, particularly the exploitation of the improvement of negative pole performance and electrolyte system has all obtained very big achievement, but the research of anode material for lithium-ion batteries seems and relatively lags behind, and has become the bottleneck that restriction lithium ion battery market and application are expanded.The positive electrode of dominate still is a cobalt acid lithium at present.The development and application progress of nickel-cobalt-manganese ternary material and nickelic binary material is swift and violent, but the price that several security incidents, metallic nickel successively take place because of the cobalt acid lithium ion battery that is used for notebook computer soars all the way, and has caused very big obstacle in the research of lithium ion battery applications invention all for nickel-cobalt-manganese ternary material and nickelic binary material.As a kind of cleaning green energy resource, lithium ion battery all has vast potential for future development in a lot of applications.Therefore, the development and application of the positive electrode of cheap, excellent performance becomes the current important topic that faces of lithium ion battery research staff.
At present, the iron with Nasicon structure is that the exploitation of phosphate cathode material has become the research focus, LiFePO4 (LiFePO wherein
4) be subjected to extensive concern.The theoretical capacity of LiFePO4 is up to 170mAh/g, the reversible capacity height, and structure is firm before and after discharging and recharging, and all has voltage platform stably.But because the restriction of self structure, the ion of this type of material and electronic conductivity are all relatively poor.It is that the electric conductivity of phosphate cathode material has obtained improvement to a certain degree that the researcher makes iron by preparation ultrafine particle, modified method such as surface coating etc.But, compare with the cobalt acid lithium that generally adopts now, after above-mentioned modification processing, iron is that tens times of increasing to cobalt acid lithium of the specific area of phosphate cathode material, tap density are then less than 1/2nd of cobalt acid lithium, and contain organic remains in the material, brought difficulty for the preparation of electrode slurry, the existence of organic remains has simultaneously also influenced material property, solves the important directions that the problems referred to above that cause because of the material modification processing become this type of investigation of materials.
Summary of the invention
It is that phosphate cathode material is handled the method for improving material property with further to modification processing (by preparing modified methods such as ultrafine particle, surface coating) back iron that technical problem to be solved by this invention provides a kind of.
For solving the problems of the technologies described above, the invention provides a kind of positive electrode processing method, this method is applicable to be handled to improve material property the positive electrode after the modification processing, comprises following process:
A, positive electrode is carried out carrying out washing treatment with the positive electrode particle agglomeration of drawing up with washing medium.
Here said modification is handled and is meant that carrying out modification by modified methods such as preparation ultrafine particle, surface coatings handles.
According to the different designs of formula of size, in some cases, washing medium can be used as the part of slurry, and washing medium is not the part of slurry under other certain situation.When washing medium is not the part of slurry, after step a, need to carry out following process: b, positive electrode is separated with washing medium.
The preferred carrying out washing treatment temperature of step a is 20 ℃～80 ℃.
The preferred carrying out washing treatment time of step a is 5min-4hr.
As the improvement of the inventive method, the carrying out washing treatment process among the step a is carried out under stirring or ultrasound condition.Like this, can suppress the positive electrode particle agglomeration more effectively.
Washing medium among the step a is one or more the combination in surfactant, water, the organic solvent; Surfactant is one or more the combination in polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone and the dodecyl sodium sulfate; Organic reagent is one or more the combination in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, acetone, butanols and the butanol derivs thing.
Further improve as the inventive method, step b comprises positive electrode is carried out dried.Help the evaporation of washing medium like this.
The selected water of washing medium can be water, deionized water or industrial pure water.
The inventive method is applicable to be handled with the further material property that improves the positive electrode after the modification processing, also is applicable to the mixture of the different positive electrodes after the modification processing is handled, with the further performance of improving the positive electrode mixture.
Another technical problem to be solved by this invention provides the battery that the positive electrode after a kind of modification processing (by modified methods such as preparation ultrafine particle, surface coatings) adopts above-mentioned the inventive method to handle.
For solving this technical problem, the invention provides the battery that a kind of positive electrode adopts above-mentioned the inventive method to handle, this battery comprises the positive plate that is coated with positive electrode, the positive electrode of positive electrode for handling through modification; Positive electrode is handled the back through modification and with washing medium positive electrode is carried out carrying out washing treatment with the positive electrode particle agglomeration of drawing up.Here said modification is handled and is meant that carrying out modification by modified methods such as preparation ultrafine particle, surface coatings handles.
In the carrying out washing treatment process of being carried out after positive electrode being carried out the modification processing, preferred carrying out washing treatment temperature is 20 ℃～80 ℃.Temperature is low excessively, and the Brownian movement speed of material and solvent is low, and dispersion effect is undesirable; Temperature is too high, and then solvent molecule Brownian movement speed is far longer than Brownian movement four degree of material particle, easily cause the material particle aggregation, and temperature is too high, and the solvent evaporates loss is big, contaminated environment.
The time of positive electrode being carried out the carrying out washing treatment process that modification carried out after handling is preferably 5min-4hr.
As the improvement of battery of the present invention, the carrying out washing treatment process of being carried out after positive electrode being carried out the modification processing is carried out under stirring or ultrasound condition.Such clean result is better.
After positive electrode is carried out carrying out washing treatment, positive electrode is separated with washing medium.
It is one or more combination in surfactant, water, the organic solvent that positive electrode is carried out the used washing medium of carrying out washing treatment; Surfactant is one or more the combination in polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone and the dodecyl sodium sulfate; Organic reagent is one or more the combination in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, acetone, butanols and the butanol derivs thing.
Further improve as battery of the present invention, positive electrode and washing medium separating process are comprised positive electrode is carried out dried.Help the evaporation of washing medium like this.
The inventive method has been eliminated modification and has been handled the intergranular reunion of back positive electrode, and the even distribution of positive electrode, conductive agent, binding agent when helping preparing burden can improve positive electrode monolithic conductive performance, helps the performance of positive electrode capacity; The colleague can remove the organic remains in the positive electrode, thereby has improved the foliation ability and the electric conductivity of material, obviously reduces the internal resistance that contacts between anodal material and collector, effectively improves cycle performance.Application when material positive plate that the inventive method is handled, cohering better between positive electrode and the collector, positive electrode is evenly distributed, thereby battery of the present invention has higher gram volume performance and cycle performance.
Description of drawings
Below by embodiment also in conjunction with the accompanying drawings, the present invention is described in further detail:
Fig. 1 is through the SEM of the lithium iron phosphate positive material of carrying out washing treatment figure among the embodiment 1;
Fig. 2 is without the SEM figure of the lithium iron phosphate positive material of carrying out washing treatment among the embodiment 1;
Fig. 3 is through the carrying out washing treatment positive electrode with without the voltage first-specific energy curve synoptic diagram of carrying out washing treatment positive electrode among the embodiment 2;
Fig. 4 is through the carrying out washing treatment positive electrode with without the cycle performance schematic diagram of carrying out washing treatment positive electrode among the embodiment 2;
Fig. 5 is through the carrying out washing treatment positive electrode with without the cycle performance schematic diagram of carrying out washing treatment positive electrode among the embodiment 3.
Embodiment
Below among each embodiment used positive electrode be and carried out modification and handle positive electrode afterwards by modified methods such as preparation ultrafine particle, surface coating.
At 20 ℃ down with the acetone soln carrying out washing treatment lithium iron phosphate positive material that contains surfactant (polyvinyl alcohol) 5 minutes, during washing with 200 rev/mins stirring, separate supernatant organic remains after the sedimentation and carry out Separation of Solid and Liquid, again with the positive electrode separated under 80 ℃ of conditions dry 4 hours.Through the SEM of the lithium iron phosphate positive material of carrying out washing treatment figure and respectively as depicted in figs. 1 and 2 without the SEM figure of the LiFePO4 of carrying out washing treatment.As seen from the figure, be the cluster shape, and after polyvinyl alcohol and acetone carrying out washing treatment without the lithium iron phosphate positive material of carrying out washing treatment, the dispersive property of material be improved significantly.
Ethanol is dissolved in deionized water, add polyvinylpyrrolidone as surfactant, with the derivative positive electrode of this solution carrying out washing treatment LiFePO4 and phosphoric acid vanadium lithium under 30 ℃ temperature 40 minutes, with 200 rev/mins stirring, separate supernatant organic remains after the sedimentation and carry out Separation of Solid and Liquid during washing.With the positive electrode separated under 100 ℃ of conditions dry 16 hours.
The derivative positive electrode of dried LiFePO4 and phosphoric acid vanadium lithium and Super P, PVDF, NMP etc. are made into the anode sizing agent that viscosity is 4000 ± 400mPas, press 285g/m
2Surface density be coated with, coated sheets is pressed 1.80g/cm after drying
3Compacted density be rolled into positive plate.Then graphite, conductive agent, CMC, SBR, industrial pure water etc. are mixed with the cathode size that viscosity is 3000 ± 300mPas, press 105g/m
2Surface density be coated with, coated sheets is pressed 1.55g/cm after drying
3Compacted density be rolled into negative plate.Again positive plate, negative plate, barrier film, aluminum hull, electrolyte etc. are assembled into 423048A type battery.To also be made into the anode sizing agent that viscosity is 4000 ± 400mPas (the derivative anode sizing agent of LiFePO4 that carrying out washing treatment is crossed in formula of size and this example and phosphoric acid vanadium lithium is identical) without the LiFePO4 of carrying out washing treatment and the derivative of phosphoric acid vanadium lithium, and make 423048A type battery by aforesaid technology and parameter in this example with Super P, PVDF, NMP etc.Battery is carried out the experiment of constant current charge and discharge cycle with 0.1C, and charging is by voltage 3.8V, and discharge is by voltage 2.0V, and the result is referring to Fig. 3 and Fig. 4.
Curve A is the voltage first-mass-energy density discharge curve without the made battery of derivative positive electrode of the LiFePO4 of carrying out washing treatment and phosphoric acid vanadium lithium among Fig. 3, and curve B is through the voltage first-mass-energy density discharge curve of the made battery of derivative positive electrode of the LiFePO4 of ethanol, deionized water and polyvinylpyrrolidone carrying out washing treatment and phosphoric acid vanadium lithium in the present embodiment.As can be seen from Fig. 3, adopt the specific energy of the made battery of positive electrode of the inventive method processing to improve about 11% without the positive electrode of carrying out washing treatment.
Among Fig. 4 be in the present embodiment through the made battery of derivative positive electrode (curve C) of the LiFePO4 of ethanol, deionized water and polyvinylpyrrolidone carrying out washing treatment and phosphoric acid vanadium lithium with without the cycle performance of the made battery of derivative positive electrode (curve D) of the LiFePO4 of carrying out washing treatment and phosphoric acid vanadium lithium relatively, after visible material adopted the inventive method to handle, cycle performance was largely increased.
Normal propyl alcohol is dissolved in industrial pure water, add dodecyl sodium sulfate as surfactant, with this solution under 65 ℃ temperature, carrying out washing treatment manganate cathode material for lithium 2 hours, with 200 rev/mins stirring, separate supernatant organic remains after the sedimentation and carry out Separation of Solid and Liquid during washing.With the positive electrode separated under 120 ℃ of conditions dry 6 hours.Dried manganate cathode material for lithium and Super P, PVDF, NMP etc. are made into the anode sizing agent that viscosity is 4000mPas, press 320g/m
2Surface density be coated with, coated sheets is pressed 1.90g/cm after drying
3Compacted density be rolled into positive plate.To substitute the dry manganate cathode material for lithium that adopts the inventive method to handle in the present embodiment without the dry manganate cathode material for lithium of carrying out washing treatment, make positive plate according to above-mentioned formula of size, technical process and parameter.
Anodal material adheres to the firmness experiment with collector: 25 lattices that above-mentioned two kinds of positive plates divided into 2mm*2mm respectively with pocket knife, compress to attach to the 3M hinge then and draw on the good grid, hold one side of gummed paper and become 30 to spend angles with desktop, the gummed paper of tearing fast, few more as if the anode sizing agent that is torn with gummed paper and is bonded on the gummed paper, illustrate between anode sizing agent and collector to adhere to more firmly.Experimental result (seeing Table one) shows, the positive plate scribing zone of making without the LiMn2O4 of carrying out washing treatment take off that charge level is long-pending to be reached about 90%, to take off charge level long-pending be 39% and the positive plate that makes positive electrode in the use present embodiment after normal propyl alcohol, industrial pure water and dodecyl sodium sulfate carrying out washing treatment is drawn the lattice district, as seen, after the inventive method processing, anodal material can adhere to more firmly with collector.
Respectively will be without the dry manganate cathode material for lithium that adopts the inventive method to handle in the manganate cathode material for lithium of carrying out washing treatment and the present embodiment, be made into the anode sizing agent that viscosity is 4000 ± 400mPas according to the method among the embodiment 2 and Super P, PVDF, NMP etc., and make 423048A type battery by technology among the embodiment 2 and parameter.Battery is carried out the experiment of constant current charge and discharge cycle with 0.1C, and charging is by voltage 3.8V, and discharge is by voltage 2.0V, and the result is referring to Fig. 5.
Curve E is the voltage first-mass-energy density discharge curve without the made battery of manganate cathode material for lithium of carrying out washing treatment among Fig. 5, and curve F is the voltage first-mass-energy density discharge curve of the made battery of manganate cathode material for lithium that carrying out washing treatment is crossed in the present embodiment.As can be seen from Fig. 5, the specific energy of the made battery of positive electrode of process the inventive method processing is improved without the positive electrode of carrying out washing treatment.
Substitute normal propyl alcohol, industrial pure water and dodecyl sodium sulfate as washing agent with industrial pure water, identical process conditions are carried out carrying out washing treatment to manganate cathode material for lithium in the employing present embodiment, be made into the anode sizing agent that viscosity is 4000 ± 400mPas according to the method among the embodiment 2 and Super P, PVDF, NMP etc., and make 423048A type battery by technology among the embodiment 2 and parameter.Battery is carried out the experiment of constant current charge and discharge cycle with 0.1C, and charging is by voltage 3.8V, and discharge is by voltage 2.0V, and voltage-mass-energy density discharge curve is the curve G among Fig. 5 first.As can be seen from Fig. 5, the specific energy of the made battery of positive electrode of process the inventive method processing is improved without the positive electrode of carrying out washing treatment.
At 20 ℃ down with the methanol aqueous solution carrying out washing treatment lithium iron phosphate positive material that contains surfactant (polyethylene glycol) 4 hours, during washing with 200 rev/mins stirring, separate supernatant organic remains after the sedimentation and carry out Separation of Solid and Liquid, again with the positive electrode separated under 150 ℃ of conditions dry 24 hours.
Embodiment 5
Identical with experimental procedure and the condition of embodiment 4, just, substitute lithium iron phosphate positive material with nickle cobalt lithium manganate with isopropanol water solution replacement methanol aqueous solution wherein.
Embodiment 6
Identical with experimental procedure and the condition of embodiment 4, just, substitute lithium iron phosphate positive material with LiMn2O4 with butanols aqueous solution replacement methanol aqueous solution wherein.
Embodiment 7
Identical with experimental procedure and the condition of embodiment 4, just with butanol derivs thing aqueous solution replacement methanol aqueous solution wherein.
Embodiment 8
Identical with experimental procedure and the condition of embodiment 4, just with the mixed aqueous solution replacement methanol aqueous solution wherein of methyl alcohol and ethanol, use the mixture replacing lithium iron phosphate positive material of LiMn2O4 and LiFePO4.
Embodiment 9
Identical with experimental procedure and the condition of embodiment 4, just with the mixed aqueous solution replacement methanol aqueous solution wherein of acetone and ethanol, use the mixture replacing lithium iron phosphate positive material of phosphoric acid vanadium lithium and LiFePO4.
With embodiment 4,5,6,7, the various positive electrodes that employing the inventive method of gained was handled in 8 and 9, carry out the positive pole material and adhere to the firmness experiment with collector, respectively according to the formula of size among the embodiment 3, technical process and parameter are made positive plate, above-mentioned various positive plates are divided into 25 lattices of 2mm*2mm respectively with pocket knife, compress to attach to the 3M hinge then and draw on the good grid, hold one side of gummed paper and become 30 to spend angles with desktop, the gummed paper of tearing fast, few more as if the anode sizing agent that is torn with gummed paper and is bonded on the gummed paper, illustrate between anode sizing agent and collector to adhere to more firmly.The charge level that takes off of measuring positive plate amasss, experimental result (seeing Table one) shows, the positive plate that the various positive electrodes that adopt the inventive method to handle make is drawn the lattice district and is taken off the long-pending 28%-40% of being of charge level, and in the prior art, amass more than 75% at the charge level that takes off that positive pole material and collector adhere in the firmness experiment without the positive electrode of carrying out washing treatment.As seen, after the inventive method processing, anodal material can adhere to more firmly with collector.
The anodal material of table one adheres to the firmness experimental result with collector
| |
3 | 4 | 5 | 6 | 7 | 8 | 9 |
| Take off the long-pending % of charge level | 39 | 37 | 43 | 28 | 41 | 34 | 31 |
By above embodiment as can be seen, adopt the inventive method that positive electrode is carried out carrying out washing treatment, can eliminate the intergranular reunion of positive electrode, and the organic remains in the removal positive electrode, improve the foliation ability and the electric conductivity of material, the lithium ion battery that makes has higher gram volume performance and cycle performance.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (14)
1, a kind of positive electrode processing method is characterized in that: this method is applicable to be handled to improve material property the positive electrode after the modification processing, comprises following process:
A, positive electrode is carried out carrying out washing treatment with the positive electrode particle agglomeration of drawing up with washing medium.
2, positive electrode processing method according to claim 1 is characterized in that: carry out following process: b after step a, positive electrode is separated with washing medium.
3, positive electrode processing method according to claim 1 and 2 is characterized in that: described step a carries out at 20 ℃～80 ℃.
4, according to any one described positive electrode processing method in the claim 3, it is characterized in that: the carrying out washing treatment time of described step a is 5min-4hr.
5, positive electrode processing method according to claim 4 is characterized in that: the carrying out washing treatment process among the step a is carried out under stirring or ultrasound condition.
6, positive electrode processing method according to claim 5 is characterized in that: the described washing medium among the step a is one or more the combination in surfactant, water, the organic solvent; Described surfactant is one or more the combination in polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone and the dodecyl sodium sulfate; Described organic reagent is one or more the combination in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, acetone, butanols and the butanol derivs thing.
7, positive electrode processing method according to claim 6 is characterized in that: step b comprises the withering process of positive electrode.
8, positive electrode adopts the battery that the described method of claim 1 is handled, and this battery comprises the positive plate that is coated with positive electrode, and described positive electrode is the positive electrode after handling through modification; It is characterized in that: described positive electrode is handled the back through modification and with washing medium positive electrode is carried out carrying out washing treatment with the positive electrode particle agglomeration of drawing up.
9, battery according to claim 8 is characterized in that: described positive electrode separates with described washing medium after having carried out carrying out washing treatment.
10, according to Claim 8 or 9 described batteries, it is characterized in that: in described positive electrode being carried out the carrying out washing treatment process that modification carried out after handling, the temperature of carrying out washing treatment is 20 ℃～80 ℃.
11, battery according to claim 10 is characterized in that: the time of described positive electrode being carried out the carrying out washing treatment process that modification carried out after handling is 5min-4hr.
12, battery according to claim 11 is characterized in that: the carrying out washing treatment process of being carried out after described positive electrode being carried out the modification processing is carried out under stirring or ultrasound condition.
13, according to any one described battery in the claim 12, it is characterized in that: described washing medium is one or more the combination in surfactant, water, the organic solvent; Described surfactant is one or more the combination in polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone and the dodecyl sodium sulfate; Described organic reagent is one or more the combination in methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, acetone, butanols and the butanol derivs thing.
14, battery according to claim 13 is characterized in that: described positive electrode and washing medium separating process comprise dried.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100752840A CN101355149A (en) | 2007-07-24 | 2007-07-24 | Method for processing anode material and battery with anode material processed by the method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100752840A CN101355149A (en) | 2007-07-24 | 2007-07-24 | Method for processing anode material and battery with anode material processed by the method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101355149A true CN101355149A (en) | 2009-01-28 |
Family
ID=40307826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100752840A Pending CN101355149A (en) | 2007-07-24 | 2007-07-24 | Method for processing anode material and battery with anode material processed by the method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101355149A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101908621A (en) * | 2010-07-14 | 2010-12-08 | 白洁明 | Method for modifying anode active material of lithium ion battery |
| CN104971938A (en) * | 2015-07-03 | 2015-10-14 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron based-humus composite material and application thereof in soil heavy metal pollution control |
| CN110034274A (en) * | 2018-01-11 | 2019-07-19 | 宁波纳微新能源科技有限公司 | Modified tertiary cathode material, preparation method and lithium ion battery |
| CN111032575A (en) * | 2018-03-09 | 2020-04-17 | 株式会社Lg化学 | Positive electrode active material, method for preparing same, positive electrode comprising same, and secondary battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1773754A (en) * | 2005-11-04 | 2006-05-17 | 南开大学 | Ferrolithium phosphate and its compound metal phosphide electrode material and producing method thereof |
-
2007
- 2007-07-24 CN CNA2007100752840A patent/CN101355149A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1773754A (en) * | 2005-11-04 | 2006-05-17 | 南开大学 | Ferrolithium phosphate and its compound metal phosphide electrode material and producing method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101908621A (en) * | 2010-07-14 | 2010-12-08 | 白洁明 | Method for modifying anode active material of lithium ion battery |
| CN101908621B (en) * | 2010-07-14 | 2013-03-27 | 白洁明 | Method for modifying anode active material of lithium ion battery |
| CN104971938A (en) * | 2015-07-03 | 2015-10-14 | 广东省生态环境与土壤研究所（广东省土壤科学博物馆） | Iron based-humus composite material and application thereof in soil heavy metal pollution control |
| CN110034274A (en) * | 2018-01-11 | 2019-07-19 | 宁波纳微新能源科技有限公司 | Modified tertiary cathode material, preparation method and lithium ion battery |
| CN111032575A (en) * | 2018-03-09 | 2020-04-17 | 株式会社Lg化学 | Positive electrode active material, method for preparing same, positive electrode comprising same, and secondary battery |
| CN111032575B (en) * | 2018-03-09 | 2022-05-27 | 株式会社Lg化学 | Positive electrode active material, method for preparing same, positive electrode comprising same, and secondary battery |
| US11482702B2 (en) | 2018-03-09 | 2022-10-25 | Lg Chem, Ltd. | Positive electrode active material, preparation method thereof, positive electrode including same and secondary battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20190288279A1 (en) | Lithium ion battery and negative electrode material thereof | |
| CN102104140A (en) | Power battery electrode and manufacturing method thereof | |
| CN110993891A (en) | Silicon-containing negative plate, preparation method thereof and lithium ion battery | |
| CN102522524A (en) | Anode plate of lithium ion battery and its preparation method | |
| CN108400292B (en) | Preparation method and application of bismuth elementary substance nanosheet composite electrode | |
| CN103259002A (en) | Lithium ion battery and electrode plate thereof | |
| CN105406081A (en) | Preparation method for lithium ion battery positive electrode slurry | |
| CN108899528B (en) | Lithium ion battery negative electrode material P + TiO2+ CNT preparation method | |
| CN111933892B (en) | Negative plate, preparation method thereof and lithium ion secondary battery comprising negative plate | |
| CN105742695A (en) | Lithium-ion battery and preparation method thereof | |
| CN112768840A (en) | Multifunctional diaphragm of lithium-sulfur battery and preparation method thereof | |
| CN113851609A (en) | Silicon-based negative electrode plate, preparation method thereof and all-solid-state lithium ion battery | |
| CN108878893A (en) | A kind of fast charge negative electrode of lithium ion battery modified collector and preparation method thereof | |
| CN102723462A (en) | Manufacture method of anode of lithium ion secondary battery | |
| CN101355149A (en) | Method for processing anode material and battery with anode material processed by the method | |
| CN105513827A (en) | (LMO-NCM-AC)/(LTO-AC) hybrid battery capacitor electrode material and electrode sheets | |
| CN109244531A (en) | A kind of high purity copper matrix graphite alkene composite lithium ion cell and preparation method thereof | |
| CN108155027B (en) | A kind of method of the pre- embedding lithium of lithium ion super capacitor cathode | |
| CN107256963A (en) | Negative material and preparation method, negative pole and the full battery of lithium ion and preparation method | |
| WO2023134234A1 (en) | Positive electrode composite material, preparation method therefor, positive electrode, and lithium ion secondary battery | |
| Livshits et al. | Development of a bipolar Li/composite polymer electrolyte/pyrite battery for electric vehicles | |
| CN114079038B (en) | High-sulfur-load lithium-sulfur battery positive electrode and preparation method thereof | |
| CN212571048U (en) | Lithium ion battery | |
| CN114267823A (en) | Negative plate and lithium ion battery containing same | |
| CN107086294B (en) | Preparation method of nano silicon-based material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1126897 Country of ref document: HK |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: SoBright Technology (Wuhan) Co., Ltd. Assignor: Shenzhen Bak Battery Co., Ltd. Contract record no.: 2012440020151 Denomination of invention: Method for processing anode material and battery with anode material processed by the method License type: Exclusive License Open date: 20090128 Record date: 20120618 |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20090128 |
|
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1126897 Country of ref document: HK |