CN103779569A - Lithium ion battery anode sheet and preparation method thereof - Google Patents
Lithium ion battery anode sheet and preparation method thereof Download PDFInfo
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- CN103779569A CN103779569A CN201210407324.8A CN201210407324A CN103779569A CN 103779569 A CN103779569 A CN 103779569A CN 201210407324 A CN201210407324 A CN 201210407324A CN 103779569 A CN103779569 A CN 103779569A
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a lithium ion battery anode sheet, which comprises a current collector, a conductive layer formed on the surface of the current collector, a diffusion layer formed on the surface of the conductive layer, and an active layer formed on the surface of the diffusion layer. The conductive layer materials include a conductive layer conductive agent and a conductive layer binder. The diffusion layer is composed of a diffusion layer anode active material, a diffusion layer conductive agent and a diffusion layer binder that are in a mass ratio of 15-78:20-80:2-5. The active layer comprises an active layer anode active material, an active layer conductive agent and an active layer binder that are in a mass ratio of 90-96:2-5:2-5. The lithium ion battery anode sheet provided by the invention can reduce the internal resistance of the lithium ion battery. The invention also provides a preparation method of the lithium ion battery anode sheet.
Description
Technical field
The present invention relates to a kind of based lithium-ion battery positive plate and preparation method thereof.
Background technology
Lithium ion battery is a kind of portable chemical power supply that current specific energy is the highest, and it has, and voltage is high, specific energy is large, discharging voltage balance, cryogenic property is good, security performance is excellent and the advantage such as storage and long working life.Along with the fast development of electronics and information industry, mobile communication, digital processor, portable computer are widely applied, the development of the development of space technology and the demand of defence equipment and electric automobile and exploitation to chemical power source particularly the demand of high-energy secondary battery increase rapidly, the research of lithium ion battery with application also more and more paid attention to.
The power-performance that improves lithium ion battery is the study hotspot that current lithium ion battery is applied.The wherein a kind of means that improve the power-performance of lithium ion battery are exactly to reduce the internal resistance of lithium ion battery.
Summary of the invention
Based on this, be necessary based lithium-ion battery positive plate providing a kind of internal resistance that reduces lithium ion battery and preparation method thereof.
A kind of based lithium-ion battery positive plate, comprise collector, be formed at described collection liquid surface conductive layer, be formed at the diffusion layer of described conductive layer surface and be formed at the active layer on described diffusion layer surface; The material of described conductive layer comprises conductive layer conductive agent and conductive layer binding agent; The material of described diffusion layer comprises diffusion layer positive electrode active materials, diffusion layer conductive agent and diffusion layer binding agent, and the mass ratio of described diffusion layer positive electrode active materials, described diffusion layer conductive agent and described diffusion layer binding agent is 15 ~ 78:20 ~ 80:2 ~ 5; The material of described active layer comprises active layer positive electrode active materials, active layer conductive agent and active layer binding agent, and the mass ratio of described active layer positive electrode active materials, described active layer conductive agent and described active layer binding agent is 90 ~ 96:2 ~ 5:2 ~ 5.
In an embodiment, described conductive layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black therein; Described conductive layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose; The mass ratio of described conductive layer conductive agent and described conductive layer binding agent is 92 ~ 95:5 ~ 8.
In an embodiment, described diffusion layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate therein; Described diffusion layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black; Described diffusion layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
In an embodiment, described active layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate therein; Described active layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black; Described active layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
In an embodiment, the thickness of described conductive layer is 3 μ m ~ 10 μ m therein; The thickness of described diffusion layer is 3 μ m ~ 20 μ m; The thickness of described active layer is 50 μ m ~ 300 μ m.
A preparation method for based lithium-ion battery positive plate, comprises the following steps:
The surface-coated that is formed with the collector of conductive layer on surface is prepared diffusion layer, the material of described conductive layer comprises conductive layer conductive agent and conductive layer binding agent, the material of described diffusion layer comprises diffusion layer positive electrode active materials, diffusion layer conductive agent and diffusion layer binding agent, and the mass ratio of described diffusion layer positive electrode active materials, described diffusion layer conductive agent and described diffusion layer binding agent is 15 ~ 78:20 ~ 80:2 ~ 5; And
Surface-coated at described diffusion layer is prepared active layer, the material of described active layer comprises active layer positive electrode active materials, active layer conductive agent and active layer binding agent, and the mass ratio of described active layer positive electrode active materials, described active layer conductive agent and described active layer binding agent is 90 ~ 96:2 ~ 5:2 ~ 5.
Therein in an embodiment, described conductive layer is by applying preparation, specifically comprise the following steps: described conductive layer conductive agent and described conductive layer binding agent are added and in solvent, form conductive layer slurry, described conductive layer slurry is coated in and dryly after described collection liquid surface forms described conductive layer; Wherein, the mass ratio of described conductive layer conductive agent and described conductive layer binding agent is 92 ~ 95:5 ~ 8, and described conductive layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black; Described conductive layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
Therein in an embodiment, when the surface-coated that is formed with the collector of conductive layer on surface is prepared described diffusion layer, described diffusion layer positive electrode active materials, described diffusion layer conductive agent and described diffusion layer binding agent are added in solvent and form diffusion layer slurry, described diffusion layer slurry is coated in to the surface described diffusion layer of dry formation afterwards of described conductive layer; Described diffusion layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate; Described diffusion layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black; Described diffusion layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
Therein in an embodiment, in the time that the surface-coated of described diffusion layer is prepared described active layer, described active layer positive electrode active materials, described active layer conductive agent and described active layer binding agent are added in solvent and form active layer slurry, described active layer slurry is coated in to the surface described active layer of dry formation afterwards of described diffusion layer; Described active layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate; Described active layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super PLi conductive carbon black and acetylene carbon black; Described active layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
In an embodiment, the thickness of described conductive layer is 3 μ m ~ 10 μ m therein; The thickness of described diffusion layer is 3 μ m ~ 20 μ m; The thickness of described active layer is 50 μ m ~ 300 μ m.
Above-mentioned based lithium-ion battery positive plate and preparation method thereof, by diffusion layer being set between conductive layer and active layer, can improve the conductivity of based lithium-ion battery positive plate, reduces the internal resistance of the lithium ion battery that uses this based lithium-ion battery positive plate.
Accompanying drawing explanation
Fig. 1 is the structural representation of the based lithium-ion battery positive plate of an execution mode;
Fig. 2 is the preparation method's of the based lithium-ion battery positive plate of an execution mode flow chart.
Embodiment
Below in conjunction with the drawings and specific embodiments, based lithium-ion battery positive plate and preparation method thereof is further illustrated.
Refer to Fig. 1, the based lithium-ion battery positive plate 100 of an execution mode comprises collector 10, be formed at the conductive layer 30 on collector 10 surfaces, be formed at the diffusion layer 50 on conductive layer 30 surfaces and be formed at the active layer 70 on diffusion layer 50 surfaces.
In present embodiment, collector 10 is aluminium foil.Collector 10 is roughly sheet.Collector 10 has first surface 12 and the second surface 14 relative with first surface 12.
Preferably, the thickness of collector 10 is 6 μ m ~ 10 μ m.
Preferably, conductive layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black.
Preferably, conductive layer binding agent is selected from least one in Kynoar (PVDF), polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
Preferably, the mass ratio of conductive layer conductive agent and conductive layer binding agent is 92 ~ 95:5 ~ 8.
Preferably, the thickness of conductive layer 30 is 3 μ m ~ 10 μ m.It should be noted that, the thickness of two conductive layers 30 can be the same or different.
Preferably, diffusion layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate.
Preferably, diffusion layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black.
Preferably, diffusion layer binding agent is selected from least one (PVDF) in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
Preferably, the thickness of diffusion layer 50 is 3 μ m ~ 20 μ m.It should be noted that, the thickness of two-layer diffusion layer 50 can be the same or different.
Preferably, active layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate.
Preferably, active layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black.
Preferably, active layer binding agent is selected from least one (PVDF) in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
Preferably, the thickness of active layer 70 is 50 μ m ~ 300 μ m.It should be noted that, the thickness of two active layers 70 can be the same or different.
It should be noted that, conductive layer conductive agent, diffusion layer conductive agent and active layer conductive agent can be the same or different; Diffusion layer positive electrode active materials and active layer positive electrode active materials can be the same or different.
Above-mentioned based lithium-ion battery positive plate 100, by diffusion layer 50 being set between conductive layer 30 and active layer 70, conductive layer 30 plays conduction electron, diffusion layer 50 plays conduction electron and energy storage simultaneously, and active layer 70 plays energy storage, diffusion layer 50 can play coordinative role between conductive layer 30 and active layer 70, can improve the conductivity of based lithium-ion battery positive plate 100, reduces the internal resistance of the lithium ion battery that uses this based lithium-ion battery positive plate 100.
Please refer to Fig. 2, the preparation method of the based lithium-ion battery positive plate 100 of an embodiment, it comprises the following steps:
Step S110, prepare conductive layer 30 in the coating of collector 10 surface.
In present embodiment, collector 10 is aluminium foil.Collector 10 is roughly sheet.Collector 10 has first surface 12 and the second surface 14 relative with first surface 12.
Preferably, the thickness of collector 10 is 6 μ m ~ 10 μ m.
Preferably, collector 10 carries out preliminary treatment before use, and preliminary treatment comprises: first clean with acetone, to remove its surperficial greasy dirt; The NaOH solution of again aluminium foil after cleaning being put into 0.5mol/L ~ 1mol/L soaks 30S, to remove the aluminum oxide film on it, then uses deionized water rinsing, in baking oven 60 ℃ dry 6 hours ~ 12 hours.
When conductive layer 30 is prepared in coating, conductive layer conductive agent and conductive layer binding agent are added and in solvent, form conductive layer slurry, conductive layer slurry is coated in to the dry conductive layers 30 that form behind collector 10 surfaces.In present embodiment, solvent is 1-METHYLPYRROLIDONE (NMP).
Preferably, conductive layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black.
Preferably, conductive layer binding agent is selected from least one in Kynoar (PVDF), polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
Preferably, the mass ratio of conductive layer conductive agent and conductive layer binding agent is 92 ~ 95:5 ~ 8.
Preferably, dry temperature is 80 ℃ ~ 100 ℃; The dry time is 6 hours ~ 12 hours.
Preferably, in conductive layer slurry, the mass concentration of solvent is 10% ~ 30%.
Preferably, the thickness of conductive layer 30 is 3 μ m ~ 10 μ m.
It should be noted that, step S110 can omit, and now can directly buy the collector that surface is formed with conductive layer and carry out subsequent step.
Step S120, prepare diffusion layer 50 in the surface coating of conductive layer 30.
When diffusion layer 50 is prepared in coating, diffusion layer positive electrode active materials, diffusion layer conductive agent and diffusion layer binding agent are added in solvent and form diffusion layer slurry, diffusion layer slurry is coated in to the surface dry diffusion layer 50 that forms afterwards of conductive layer 30.In present embodiment, solvent is 1-METHYLPYRROLIDONE (NMP).
Preferably, diffusion layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate.
Preferably, diffusion layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black.
Preferably, diffusion layer binding agent is selected from least one in Kynoar (PVDF), polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
Preferably, dry temperature is 80 ℃ ~ 100 ℃; The dry time is 6 hours ~ 12 hours.
Preferably, in diffusion layer slurry, the mass concentration of solvent is 10% ~ 30%.
Preferably, the thickness of diffusion layer 50 is 3 μ m ~ 20 μ m.
Step S130, prepare active layer 70 in diffusion layer 50 surface-coated.
When active layer 70 is prepared in coating, active layer positive electrode active materials, active layer conductive agent and active layer binding agent are added in solvent and form active layer slurry, active layer slurry is coated in to the surface dry active layer 70 that forms afterwards of diffusion layer 50.In present embodiment, solvent is 1-METHYLPYRROLIDONE (NMP).
Preferably, active layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate.
Preferably, active layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black.
Preferably, active layer binding agent is selected from least one in Kynoar (PVDF), polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
Preferably, dry temperature is 80 ℃ ~ 100 ℃; The dry time is 6 hours ~ 12 hours.
Preferably, in diffusion layer slurry, the mass concentration of solvent is 10% ~ 30%.
Preferably, the thickness of active layer 70 is 50 μ m ~ 300 μ m.
It should be noted that, conductive layer conductive agent, diffusion layer conductive agent and active layer conductive agent can be the same or different; Diffusion layer positive electrode active materials and active layer positive electrode active materials can be the same or different.
Above-mentioned based lithium-ion battery positive plate preparation method, technique is simple, the internal resistance that can effectively reduce lithium ion battery of the based lithium-ion battery positive plate of preparation.
Below in conjunction with specific embodiment, the preparation method of based lithium-ion battery positive plate provided by the invention is elaborated.
Embodiment 1
(1) preliminary treatment of aluminium foil: 6 μ m aluminium foils are first cleaned with acetone soln, to remove its surperficial greasy dirt.The NaOH solution of aluminium foil after cleaning being put into 0.5mol/L soaks, and the time is 30S, to remove the aluminum oxide film on it, then uses deionized water rinsing, 60 ℃ of dry 6h in baking oven.
(2) coating of conductive layer: according to mass percent, 92% Ketjen black, 8% Kynoar binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on an aluminium foil equably, coating thickness is that 3 μ m are thick, then puts it into baking oven, at 80 ℃ of dry 12h, and then adopt same operation coated with conductive layer at the another side of aluminium foil, wherein nmp solvent accounts for 10% of total slurry weight.
(3) coating of diffusion layer: according to mass percent, 15% LiFePO 4 of anode material, 80% conductive agent Ketjen black, 5% Kynoar binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on conductive layer equably, coating thickness is that 3 μ m are thick, then puts it into baking oven, at 80 ℃ of dry 12h, and then adopt same operation to apply diffusion layer at the another side of conductive layer, wherein nmp solvent accounts for 10% of total slurry weight.
(4) coating of active layer: according to mass percent, 90% iron phosphate serving as positive active material, 5% conductive agent Ketjen black, 5% Kynoar binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on diffusion layer equably, coating thickness is that 50 μ m are thick, then puts it into baking oven, at 80 ℃ of dry 12h, and then adopt same operation to apply active layer at the another side of diffusion layer, wherein nmp solvent accounts for 10% of total slurry weight.
Embodiment 2
(1) preliminary treatment of aluminium foil: 10 μ m aluminium foils are first cleaned with acetone soln, to remove its surperficial greasy dirt.The NaOH solution of aluminium foil after cleaning being put into 1mol/L soaks, and the time is 30S, to remove the aluminum oxide film on it, then uses deionized water rinsing, 60 ℃ of dry 12h in baking oven.
(2) coating of conductive layer: according to mass percent, 95% carbon nano-tube, 5% Kynoar binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on an aluminium foil equably, coating thickness is that 10 μ m are thick, then puts it into baking oven, at 100 ℃ of dry 6h, and then adopt same operation coated with conductive layer at the another side of aluminium foil, wherein nmp solvent accounts for 30% of total slurry weight.
(3) coating of diffusion layer: according to mass percent, 78% positive pole material of lithium cobalt acid, 20% conductive agent carbon nano-tube, 2% Kynoar binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on conductive layer equably, coating thickness is that 10 μ m are thick, then puts it into baking oven, at 100 ℃ of dry 6h, and then adopt same operation to apply diffusion layer at the another side of conductive layer, wherein nmp solvent accounts for 30% of total slurry weight.
(4) coating of active layer: according to mass percent, 96% positive electrode active materials cobalt acid lithium, 2% conductive agent carbon nano-tube, 2% polyvinyl alcohol adhesive are added in nmp solvent, stir and be configured to slurry, slurry is coated on diffusion layer equably, coating thickness is that 300 μ m are thick, then puts it into baking oven, at 100 ℃ of dry 6h, and then adopt same operation to apply active layer at the another side of diffusion layer, wherein nmp solvent accounts for 30% of total slurry weight.
Embodiment 3
(1) preliminary treatment of aluminium foil: 8 μ m aluminium foils are first cleaned with acetone soln, to remove its surperficial greasy dirt.The NaOH solution of aluminium foil after cleaning being put into 0.7mol/L soaks, and the time is 30S, to remove the aluminum oxide film on it, then uses deionized water rinsing, 60 ℃ of dry 8h in baking oven.
(2) coating of conductive layer: according to mass percent, 93% conduction charcoal fiber, 7% Kynoar binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on an aluminium foil equably, coating thickness is that 5 μ m are thick, then puts it into baking oven, at 90 ℃ of dry 8h, and then adopt same operation coated with conductive layer at the another side of aluminium foil, wherein nmp solvent accounts for 20% of total slurry weight.
(3) coating of diffusion layer: according to mass percent, 50% positive-material lithium manganate, 47% conductive agent conduction charcoal fiber, 3% polytetrafluoroethylene binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on conductive layer equably, coating thickness is that 5 μ m are thick, then puts it into baking oven, at 90 ℃ of dry 8h, and then adopt same operation to apply diffusion layer at the another side of conductive layer, wherein nmp solvent accounts for 25% of total slurry weight.
(4) coating of active layer: according to mass percent, 92% positive electrode active materials LiMn2O4,4% conductive agent conduction charcoal fiber, 4% polytetrafluoroethylene binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on diffusion layer equably, coating thickness is that 150 μ m are thick, then puts it into baking oven, at 90 ℃ of dry 8h, and then adopt same operation to apply active layer at the another side of diffusion layer, wherein nmp solvent accounts for 20% of total slurry weight.
Embodiment 4
(1) preliminary treatment of aluminium foil: 9 μ m aluminium foils are first cleaned with acetone soln, to remove its surperficial greasy dirt.The NaOH solution of aluminium foil after cleaning being put into 0.8mol/L soaks, and the time is 30S, to remove the aluminum oxide film on it, then uses deionized water rinsing, 60 ℃ of dry 10h in baking oven.
(2) coating of conductive layer: according to mass percent, 94%Super P Li conductive carbon black, 6% sodium carboxymethylcellulose binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on an aluminium foil equably, coating thickness is that 8 μ m are thick, then puts it into baking oven, at 95 ℃ of dry 10h, and then adopt same operation coated with conductive layer at the another side of aluminium foil, wherein nmp solvent accounts for 25% of total slurry weight.
(3) coating of diffusion layer: according to mass percent, 30% anode material nickel cobalt manganic acid lithium, 66% conductive agent Super P Li conductive carbon black, 4% sodium carboxymethylcellulose binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on conductive layer equably, coating thickness is that 8 μ m are thick, then puts it into baking oven, at 85 ℃ of dry 10h, and then adopt same operation to apply diffusion layer at the another side of conductive layer, wherein nmp solvent accounts for 30% of total slurry weight.
(4) coating of active layer: according to mass percent, 94% positive electrode active materials nickle cobalt lithium manganate, 3% conductive agent Super P Li conductive carbon black, 3% sodium carboxymethylcellulose binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on diffusion layer equably, coating thickness is that 200 μ m are thick, then put it into baking oven, at 85 ℃ of dry 10h, and then adopt same operation to apply active layer at the another side of diffusion layer, wherein nmp solvent accounts for 25% of total slurry weight.
Embodiment 5
(1) coating of diffusion layer: according to mass percent, 30% LiFePO 4 of anode material, 65% conductive agent Ketjen black, 5% Kynoar binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated in equably and is applied on aluminium foil, coating thickness is that 5 μ m are thick, then puts it into baking oven, at 90 ℃ of dry 10h, and then adopt same operation to apply diffusion layer at the another side that applies aluminium foil, wherein nmp solvent accounts for 25% of total slurry weight.Apply the conductive layer that aluminium foil comprises collector and is coated in collector two sides.
(2) coating of active layer: according to mass percent, 94% iron phosphate serving as positive active material, 3% conductive agent Ketjen black, 3% Kynoar binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on diffusion layer equably, coating thickness is that 150 μ m are thick, then puts it into baking oven, at 100 ℃ of dry 12h, and then adopt same operation to apply active layer at the another side of diffusion layer, wherein nmp solvent accounts for 25% of total slurry weight.
Comparative example
(1) preliminary treatment of aluminium foil: 6 μ m aluminium foils are first cleaned with acetone soln, to remove its surperficial greasy dirt.The NaOH solution of aluminium foil after cleaning being put into 0.5mol/L soaks, and the time is 30S, to remove the aluminum oxide film on it, then uses deionized water rinsing, 60 ℃ of dry 6h in baking oven.
(2) coating of conductive layer: according to mass percent, 92% Ketjen black, 8% Kynoar binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on an aluminium foil equably, coating thickness is that 3 μ m are thick, then puts it into baking oven, at 80 ℃ of dry 12h, and then adopt same operation coated with conductive layer at the another side of aluminium foil, wherein nmp solvent accounts for 10% of total slurry weight.
(3) coating of active layer: according to mass percent, 90% iron phosphate serving as positive active material, 5% conductive agent Ketjen black, 5% Kynoar binding agent are added in nmp solvent, stir and be configured to slurry, slurry is coated on conductive layer equably, coating thickness is that 50 μ m are thick, then puts it into baking oven, at 80 ℃ of dry 12h, and then adopt same operation to apply active layer at the another side of conductive layer, wherein nmp solvent accounts for 10% of total slurry weight.
Take graphite as negative pole, electrolyte is dissolved in propene carbonate (PC) by LiPF6 and dimethyl carbonate (DMC) forms, wherein the concentration of LiPF6 is 1mol/L, based lithium-ion battery positive plate prepared by embodiment 1 ~ 5 and comparative example is as the positive pole of lithium ion battery, lithium ion battery assembles to leave standstill and after 24 hours, at room temperature adopts battery Inner Resistance Tester in Virtual Instrument test internal resistance, the results are shown in following table.
As can be seen from the above table, by diffusion layer is set, the based lithium-ion battery positive plate of embodiment 1 ~ 5 preparation can effectively reduce the internal resistance of lithium ion battery.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a based lithium-ion battery positive plate, is characterized in that, comprise collector, be formed at described collection liquid surface conductive layer, be formed at the diffusion layer of described conductive layer surface and be formed at the active layer on described diffusion layer surface; The material of described conductive layer comprises conductive layer conductive agent and conductive layer binding agent; The material of described diffusion layer comprises diffusion layer positive electrode active materials, diffusion layer conductive agent and diffusion layer binding agent, and the mass ratio of described diffusion layer positive electrode active materials, described diffusion layer conductive agent and described diffusion layer binding agent is 15 ~ 78:20 ~ 80:2 ~ 5; The material of described active layer comprises active layer positive electrode active materials, active layer conductive agent and active layer binding agent, and the mass ratio of described active layer positive electrode active materials, described active layer conductive agent and described active layer binding agent is 90 ~ 96:2 ~ 5:2 ~ 5.
2. based lithium-ion battery positive plate according to claim 1, is characterized in that, described conductive layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black; Described conductive layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose; The mass ratio of described conductive layer conductive agent and described conductive layer binding agent is 92 ~ 95:5 ~ 8.
3. based lithium-ion battery positive plate according to claim 1, is characterized in that, described diffusion layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate; Described diffusion layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black; Described diffusion layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
4. based lithium-ion battery positive plate according to claim 1, is characterized in that, described active layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate; Described active layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black; Described active layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
5. based lithium-ion battery positive plate according to claim 1, is characterized in that, the thickness of described conductive layer is 3 μ m ~ 10 μ m; The thickness of described diffusion layer is 3 μ m ~ 20 μ m; The thickness of described active layer is 50 μ m ~ 300 μ m.
6. a preparation method for based lithium-ion battery positive plate, is characterized in that, comprises the following steps:
The surface-coated that is formed with the collector of conductive layer on surface is prepared diffusion layer, the material of described conductive layer comprises conductive layer conductive agent and conductive layer binding agent, the material of described diffusion layer comprises diffusion layer positive electrode active materials, diffusion layer conductive agent and diffusion layer binding agent, and the mass ratio of described diffusion layer positive electrode active materials, described diffusion layer conductive agent and described diffusion layer binding agent is 15 ~ 78:20 ~ 80:2 ~ 5; And
Surface-coated at described diffusion layer is prepared active layer, the material of described active layer comprises active layer positive electrode active materials, active layer conductive agent and active layer binding agent, and the mass ratio of described active layer positive electrode active materials, described active layer conductive agent and described active layer binding agent is 90 ~ 96:2 ~ 5:2 ~ 5.
7. the preparation method of based lithium-ion battery positive plate according to claim 6, it is characterized in that, described conductive layer is by applying preparation, specifically comprise the following steps: described conductive layer conductive agent and described conductive layer binding agent are added and in solvent, form conductive layer slurry, described conductive layer slurry is coated in and dryly after described collection liquid surface forms described conductive layer; Wherein, the mass ratio of described conductive layer conductive agent and described conductive layer binding agent is 92 ~ 95:5 ~ 8, and described conductive layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, SuperP Li conductive carbon black and acetylene carbon black; Described conductive layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
8. the preparation method of based lithium-ion battery positive plate according to claim 6, it is characterized in that: when the surface-coated that is formed with the collector of conductive layer on surface is prepared described diffusion layer, described diffusion layer positive electrode active materials, described diffusion layer conductive agent and described diffusion layer binding agent are added in solvent and form diffusion layer slurry, described diffusion layer slurry is coated in to the surface described diffusion layer of dry formation afterwards of described conductive layer; Described diffusion layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate; Described diffusion layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black; Described diffusion layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
9. the preparation method of based lithium-ion battery positive plate according to claim 6, it is characterized in that: in the time that the surface-coated of described diffusion layer is prepared described active layer, described active layer positive electrode active materials, described active layer conductive agent and described active layer binding agent are added in solvent and form active layer slurry, described active layer slurry is coated in to the surface described active layer of dry formation afterwards of described diffusion layer; Described active layer positive electrode active materials is selected from least one in LiFePO4, cobalt acid lithium, LiMn2O4 and nickle cobalt lithium manganate; Described active layer conductive agent is selected from least one in Ketjen black, carbon nano-tube, conduction charcoal fiber, Super P Li conductive carbon black and acetylene carbon black; Described active layer binding agent is selected from least one in Kynoar, polyvinyl alcohol, polytetrafluoroethylene and sodium carboxymethylcellulose.
10. the preparation method of based lithium-ion battery positive plate according to claim 6, is characterized in that: the thickness of described conductive layer is 3 μ m ~ 10 μ m; The thickness of described diffusion layer is 3 μ m ~ 20 μ m; The thickness of described active layer is 50 μ m ~ 300 μ m.
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