CN103855360A - Lithium ion battery, negative electrode pole piece and preparation method of lithium ion battery - Google Patents
Lithium ion battery, negative electrode pole piece and preparation method of lithium ion battery Download PDFInfo
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- CN103855360A CN103855360A CN201410068771.4A CN201410068771A CN103855360A CN 103855360 A CN103855360 A CN 103855360A CN 201410068771 A CN201410068771 A CN 201410068771A CN 103855360 A CN103855360 A CN 103855360A
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- H01—ELECTRIC ELEMENTS
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- 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
- 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
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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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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention provides a lithium ion battery, a negative electrode pole piece and a preparation method of the lithium ion battery. The negative electrode pole piece of the lithium ion battery comprises a negative electrode current collector, a negative electrode active material layer and a modified porous ionic polymer layer, wherein the negative electrode active material layer comprises a negative electrode conductive agent, a negative electrode bonding agent and a negative electrode active material and is arranged on the negative electrode current collector in a coating manner, the modified porous ionic polymer layer is a modified polyimide porous ionic polymer layer and is arranged on the surface of the negative electrode active material layer in a coating manner. The lithium ion battery comprises the negative electrode pole piece. According to the invention, the deformation rate of the lithium ion battery is reduced and the cycling performance and overcharge resistance of the lithium ion battery are increased.
Description
Technical field
The present invention relates to field of batteries, relate in particular to a kind of lithium ion battery and cathode pole piece thereof and preparation method.
Background technology
Lithium ion battery, because having higher energy density and advantages of environment protection, is widely used at portable electric appts and electric automobiles.
But, lithium ion battery in use, the irreversible metaboly such as that battery core body there will be is concavo-convex, wave or local thickness's increase, in the time that distortion is serious, electronics mobile terminal device cannot hold lithium ion battery, may burst equipment, affects the normal use of equipment.Find through research, the reason that produces above problem mainly contains following three aspects: (1), in the time of coiling battery core, reserved unnecessary space between pole piece and barrier film, does not cause the battery core inside of winding to have larger internal stress; (2) lithium ion battery of preparing is through after discharging and recharging, and cathode pole piece, due to embedding lithium, causes its thickness obviously to increase; (3) on collector, be coated with in the process of active material slurry, because the adhesion strength of the binding agent using in active material slurry is larger, after coating completes, can shrink.
For above problem, current improvement method is at anode active material layer surface-coated porous Kynoar (PVDF) layer, but the structure of traditional porous Kynoar (PVDF) is more open, very easily cave in, therefore, the problem on deformation of lithium ion battery is not still well solved.
Summary of the invention
In view of the problem existing in background technology, the object of the present invention is to provide a kind of lithium ion battery and cathode pole piece thereof and preparation method, the deformation rate that it has reduced lithium ion battery, has improved cycle performance and the overcharging resisting performance of lithium ion battery.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of cathode pole piece of lithium ion battery, it comprises: negative current collector; Anode active material layer, contains cathode conductive agent, negative pole binding agent and negative active core-shell material and is coated on negative current collector; The porous ion polymeric layer of modification, is coated in anode active material layer surface.Wherein, the porous ion polymeric layer of described modification is polyimide modified porous ion polymeric layer.
In a second aspect of the present invention, the invention provides a kind of preparation method of cathode pole piece of lithium ion battery, comprise step: (1) is fully mixed to get negative active core-shell material slurry by negative active core-shell material, cathode conductive agent, negative pole binding agent and negative pole dispersant according to proper proportion, negative active core-shell material slurry is coated on negative current collector, obtains after drying anode active material layer; (2) porous ion polymer and polyimides monomer are dispersed in organic solvent, stir at normal temperatures, obtain composite mortar; (3) composite mortar is coated in to the surface of anode active material layer; after dry, under vacuum or under protective gas protection, heat and be incubated, so that polyimides monomer polymerization; after cooling, form polyimide modified porous ion polymeric layer, obtain the cathode pole piece of lithium ion battery.
In a third aspect of the present invention, the invention provides a kind of lithium ion battery, comprising: anode pole piece; Cathode pole piece; Barrier film, is interval between anode pole piece and cathode pole piece; Electrolyte; And package foil.Wherein, described cathode pole piece is according to the cathode pole piece of the lithium ion battery of first aspect present invention.
Beneficial effect of the present invention is as follows:
1. traditional porous ion polymeric layer is loosely organized, very easily cave in, porous ion polymeric layer of the present invention is through polyimide modified, polyimides monomer at high temperature can polymerization reaction take place, the intensity of the polyimides forming after polymerization approaches metal, can play a supporting role to porous ion polymeric layer, make the structure of porous ion polymeric layer more stable.
2. the loose structure of porous ion polymeric layer can guarantee migration unimpeded of lithium ion in lithium ion battery, thereby has guaranteed the cycle performance of lithium ion battery.
3. after the electrolyte in lithium ion battery infiltrates cathode pole piece, because the porous ion polymeric layer of modification contains the porous ion polymer with loose structure and the polyimides with supporting role, reduced the swelling set of lithium ion battery.
4. be that cushion space has been reserved in the expansion of cathode pole piece in charge and discharge process through polyimide modified porous ion polymeric layer, can obviously improve the problem on deformation of lithium ion battery.
5. can form on cathode pole piece surface the physical property obstruct of microcosmic through polyimide modified porous ion polymeric layer, minimizing Li dendrite pierces through barrier film, improves the overcharging resisting performance of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the cross sectional representation of the cathode pole piece of lithium ion battery of the present invention;
Fig. 2 is the SEM photo of unmodified porous Kynoar (PVDF) layer in comparative example 2;
Fig. 3 is the SEM photo of porous Kynoar (PVDF) layer of modification in embodiment 1.
Embodiment
Describe in detail below according to lithium ion battery of the present invention and cathode pole piece and preparation method and comparative example, embodiment and test result.
First illustrate according to the cathode pole piece of the lithium ion battery of first aspect present invention.
According to the cathode pole piece of the lithium ion battery of first aspect present invention, as shown in Figure 1, comprising: negative current collector; Anode active material layer, contains cathode conductive agent, negative pole binding agent and negative active core-shell material and is coated on negative current collector; The porous ion polymeric layer of modification, is coated in anode active material layer surface.The porous ion polymeric layer of described modification is polyimide modified porous ion polymeric layer.
According in the cathode pole piece of the lithium ion battery of first aspect present invention, the thickness of described anode active material layer can be 20 μ m～100 μ m.
According in the cathode pole piece of the lithium ion battery of first aspect present invention, the thickness of the porous ion polymeric layer of described modification can be 1 μ m～10 μ m.
According in the cathode pole piece of the lithium ion battery of first aspect present invention, the porous ion polymer of the porous ion polymeric layer of described modification can be one or more in Kynoar (PVDF), polyacrylic acid (PAA), polyacrylate, polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP).
According in the cathode pole piece of the lithium ion battery of first aspect present invention, the porosity of the porous ion polymer of the porous ion polymeric layer of described modification can be 40%～65%.
According in the cathode pole piece of the lithium ion battery of first aspect present invention, described negative active core-shell material can be one or more in native graphite, Delanium, silicon alloy, Si-C composite material and lithium titanate.
According in the cathode pole piece of the lithium ion battery of first aspect present invention, described cathode conductive agent can be one or more in acetylene black, carbon fiber (VGCF), carbon nano-tube (CNT) and conductive black (Super-P).
According in the cathode pole piece of the lithium ion battery of first aspect present invention, described negative pole binding agent can be one or more in butadiene-styrene rubber (SBR), polyacrylic acid, polyacrylate and sodium carboxymethylcellulose (CMC).
Secondly explanation is according to the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention.
According to the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention, comprise step: (1) is fully mixed to get negative active core-shell material slurry by negative active core-shell material, cathode conductive agent, negative pole binding agent and negative pole dispersant according to proper proportion, negative active core-shell material slurry is coated on negative current collector, obtains after drying anode active material layer; (2) porous ion polymer and polyimides monomer are dispersed in organic solvent, stir at normal temperatures, obtain composite mortar; (3) composite mortar is coated in to the surface of anode active material layer; after dry, under vacuum or under protective gas protection, heat and be incubated, so that polyimides monomer polymerization; after cooling, form polyimide modified porous ion polymeric layer, obtain the cathode pole piece of lithium ion battery.
According in the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention, described negative pole dispersant can be one or more in polyvinylpyrrolidone (PVP), sodium carboxymethylcellulose (CMC) and polyvinyl alcohol (PVA).
According in the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention, described organic solvent can be one or more in 1-METHYLPYRROLIDONE (NMP), toluene, oxolane and carrene.
According in the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention, the quality of described polyimides monomer can be porous ion polymer quality 20%～30%.
According in the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention, described polyimides monomer can be the pre-composition of monomer A and monomers B,
Wherein, the quality percentage composition that monomer A accounts for polyimides monomer can be 60%～80%, and the quality percentage composition that monomers B accounts for polyimides monomer can be the alkyl that 20%～40%, R is 1-8 carbon atom.
According in the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention, in step (1), dry temperature can be 85 ℃～120 ℃, and the dry time can be 4h～8h.
According in the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention, in step (2), mixing time at normal temperatures can be 0.5h～2h.
According in the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention, in step (3), dry temperature can be 100 ℃～150 ℃, and the dry time can be 5min～30min.
According in the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention, in step (3), the vacuum degree >-97Kpa under vacuum.
According in the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention, in step (3), protective gas can be argon gas or nitrogen.
According in the preparation method of the cathode pole piece of the lithium ion battery of second aspect present invention, in step (3), the temperature of heating can be 300 ℃～350 ℃, and temperature retention time can be 15min～60min.
Lithium ion battery according to third aspect present invention is described again.
According to the lithium ion battery of third aspect present invention, comprising: anode pole piece; Cathode pole piece; Barrier film, is interval between anode pole piece and cathode pole piece; Electrolyte; And package foil.Described cathode pole piece is according to the cathode pole piece of the lithium ion battery of first aspect present invention.
According in the lithium ion battery of third aspect present invention, described package foil can be aluminum plastic film.
Next illustrate according to lithium rechargeable battery of the present invention and cathode pole piece and preparation method's embodiment and comparative example.
Embodiment 1
The preparation of A cathode pole piece
(1) negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and dispersant sodium carboxymethylcellulose are fully mixed according to mass ratio 96:1:2:1, obtain negative active core-shell material slurry, negative active core-shell material slurry is coated on the negative current collector Copper Foil that 12 μ m are thick, at 100 ℃, after dry 5h, obtains the anode active material layer that thickness is 90 μ m.
(2) the porous Kynoar that is 41.2% by porosity (PVDF) uses 1-METHYLPYRROLIDONE (NMP) to dissolve in advance, wherein the quality of porous Kynoar (PVDF) accounts for 7% of solution gross mass, then add the polyimides monomer that accounts for this solution 1% mass parts, wherein polyimides monomer is that the pre-composition of monomer A and monomers B and the mass ratio of monomer A and monomers B are 3:2, after stirring at normal temperature 1h, obtain composite mortar.
(3) composite mortar is coated in to the surface of anode active material layer; dry 20min at 120 ℃; under nitrogen protection, be heated to 310 ℃ afterwards; and be incubated 60min at 310 ℃; make monomer A and the monomers B polymerization of polyimides monomer, after cooling, obtain the cathode pole piece with polyimide modified porous Kynoar (PVDF) layer.
The preparation of B anode pole piece
2.4g Kynoar (PVDF) is dissolved in 32g solvent 1-METHYLPYRROLIDONE (NMP) and makes binder solution, then in gained solution, add 145g positive electrode active materials LiCoO2 and 2.55g conductive agent Super-P, after stirring, make positive electrode active materials slurry, positive electrode active materials slurry is coated on the plus plate current-collecting body aluminium foil that 16 μ m are thick, drying, obtains the anode pole piece that thickness is 100 μ m after colding pressing.
The preparation of C lithium ion battery
The cathode pole piece of above-mentioned preparation, barrier film (the thick polyethylene of 12 μ m), anode pole piece are reeled in order and made battery core, with package foil aluminum plastic film by battery core closedtop and side seal, inject electrolyte (1mol/LLiPF6, EC:DMC mass ratio is 1:1), the operations such as standing 24h, then process afterwards changes into, capacity make lithium ion battery.
Embodiment 2
The preparation of A cathode pole piece
(1) negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and dispersant sodium carboxymethylcellulose are fully mixed according to mass ratio 96:1:2:1, obtain negative active core-shell material slurry, negative active core-shell material slurry is coated on the negative current collector Copper Foil that 12 μ m are thick, at 100 ℃, after dry 5h, obtains the anode active material layer that thickness is 90 μ m.
(2) the porous Kynoar that is 52.2% by porosity (PVDF) uses 1-METHYLPYRROLIDONE (NMP) to dissolve in advance, wherein the quality of porous Kynoar (PVDF) accounts for 7% of solution gross mass, then add the polyimides monomer that accounts for this solution 2% mass parts, wherein polyimides monomer is that the pre-composition of monomer A and monomers B and the mass ratio of monomer A and monomers B are 7:3, after stirring at normal temperature 1h, obtain composite mortar.
(3) composite mortar is coated in to the surface of anode active material layer; dry 20min at 120 ℃; under nitrogen protection, be heated to 310 ℃ afterwards; and be incubated 60min at 310 ℃; make monomer A and the monomers B polymerization of polyimides monomer, after cooling, obtain the cathode pole piece with polyimide modified porous Kynoar (PVDF) layer.
The preparation of B anode pole piece
With embodiment 1.
The preparation of C lithium ion battery
With embodiment 1.
Embodiment 3
The preparation of A cathode pole piece
(1) negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and dispersant sodium carboxymethylcellulose are fully mixed according to mass ratio 96:1:2:1, obtain negative active core-shell material slurry, negative active core-shell material slurry is coated on the negative current collector Copper Foil that 12 μ m are thick, at 100 ℃, after dry 5h, obtains the anode active material layer that thickness is 90 μ m.
(2) the porous Kynoar that is 41.2% by porosity (PVDF) uses 1-METHYLPYRROLIDONE (NMP) to dissolve in advance, wherein the quality of porous Kynoar (PVDF) accounts for 7% of solution gross mass, then add the polyimides monomer that accounts for this solution 3% mass parts, wherein polyimides monomer is that the pre-composition of monomer A and monomers B and the mass ratio of monomer A and monomers B are 3:2, after stirring at normal temperature 1h, obtain composite mortar.
(3) composite mortar is coated in to the surface of anode active material layer; dry 20min at 120 ℃; under nitrogen protection, be heated to 310 ℃ afterwards; and be incubated 60min at 310 ℃; make monomer A and the monomers B polymerization of polyimides monomer, after cooling, obtain the cathode pole piece with polyimide modified porous Kynoar (PVDF) layer.
The preparation of B anode pole piece
With embodiment 1.
The preparation of C lithium ion battery
With embodiment 1.
Embodiment 4
The preparation of A cathode pole piece
(1) negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and dispersant sodium carboxymethylcellulose are fully mixed according to mass ratio 96:1:2:1, obtain negative active core-shell material slurry, negative active core-shell material slurry is coated on the negative current collector Copper Foil that 12 μ m are thick, at 100 ℃, after dry 5h, obtains the anode active material layer that thickness is 90 μ m.
(2) the porous Kynoar that is 60.5% by porosity (PVDF) uses 1-METHYLPYRROLIDONE (NMP) to dissolve in advance, wherein the quality of porous Kynoar (PVDF) accounts for 7% of solution gross mass, then add the polyimides monomer that accounts for this solution 2% mass parts, wherein polyimides monomer is that the pre-composition of monomer A and monomers B and the mass ratio of monomer A and monomers B are 7:3, after stirring at normal temperature 1h, obtain composite mortar.
(3) composite mortar is coated in to the surface of anode active material layer; dry 20min at 120 ℃; under nitrogen protection, be heated to 310 ℃ afterwards; and be incubated 60min at 310 ℃; make monomer A and the monomers B polymerization of polyimides monomer, after cooling, obtain the cathode pole piece with polyimide modified porous Kynoar (PVDF) layer.
The preparation of B anode pole piece
With embodiment 1.
The preparation of C lithium ion battery
With embodiment 1.
Embodiment 5
The preparation of A cathode pole piece
(1) negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and dispersant sodium carboxymethylcellulose are fully mixed to get to negative active core-shell material slurry according to mass ratio 96:1:2:1, negative active core-shell material slurry is coated on the negative current collector Copper Foil that 12 μ m are thick, at 110 ℃, after dry 6h, obtains the anode active material layer that thickness is 90 μ m.
(2) microporous polyacrylate that is 45.6% by porosity (PMMA) uses 1-METHYLPYRROLIDONE (NMP) to dissolve in advance, wherein the quality of microporous polyacrylate (PMMA) accounts for 7% of solution gross mass, then add the polyimides monomer that accounts for this solution 1% mass parts, wherein polyimides monomer is that the pre-composition of monomer A and monomers B and the mass ratio of monomer A and monomers B are 3:2, after stirring at normal temperature 1h, obtain composite mortar.
(3) composite mortar is coated in to the surface of anode active material layer; dry 20min at 120 ℃; under argon shield, be heated to 310 ℃ afterwards; and be incubated 60min at 310 ℃; make monomer A and the monomers B polymerization of polyimides, after cooling, obtain the cathode pole piece with polyimide modified microporous polyacrylate (PMMA) layer.
The preparation of B anode pole piece
With embodiment 1.
The preparation of C lithium ion battery
With embodiment 1.
Embodiment 6
The preparation of A cathode pole piece
(1) negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and dispersant sodium carboxymethylcellulose are fully mixed according to mass ratio 96:1:2:1, obtain negative active core-shell material slurry, negative active core-shell material slurry is coated on the negative current collector Copper Foil that 12 μ m are thick, at 110 ℃, after dry 6h, obtains the anode active material layer that thickness is 90 μ m.
(2) the porous polyethylene alcohol that is 45.6% by porosity (PVA) uses 1-METHYLPYRROLIDONE (NMP) to dissolve in advance, wherein the quality of porous polyethylene alcohol (PVA) accounts for 7% of solution gross mass, then add the polyimides monomer that accounts for this solution 1% mass parts, wherein polyimides monomer is that the pre-composition of monomer A and monomers B and the mass ratio of monomer A and monomers B are 3:2, after stirring at normal temperature 1h, obtain composite mortar.
(3) composite mortar is coated in to the surface of anode active material layer; dry 20min at 120 ℃; under argon shield, be heated to 310 ℃ afterwards; and be incubated 60min at 310 ℃; make monomer A and the monomers B polymerization of polyimides monomer, after cooling, obtain the cathode pole piece with polyimide modified porous polyethylene alcohol (PVA) layer.
The preparation of B anode pole piece
With embodiment 1.
The preparation of C lithium ion battery
With embodiment 1.
Embodiment 7
The preparation of A cathode pole piece
(1) negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and dispersant sodium carboxymethylcellulose are fully mixed according to mass ratio 96:1:2:1, obtain negative active core-shell material slurry, negative active core-shell material slurry is coated on the negative current collector Copper Foil that 12 μ m are thick, at 110 ℃, after dry 6h, obtains the anode active material layer that thickness is 90 μ m.
(2) the porous polyethylene pyrrolidones that is 45.6% by porosity (PVP) uses 1-METHYLPYRROLIDONE (NMP) to dissolve in advance, wherein the quality of porous polyethylene pyrrolidones (PVP) accounts for 7% of solution gross mass, then add the polyimides monomer that accounts for this solution 1% mass parts, wherein polyimides monomer is that the pre-composition of monomer A and monomers B and the mass ratio of monomer A and monomers B are 3:2, after stirring at normal temperature 1h, obtain composite mortar.
(3) composite mortar is coated in to the surface of anode active material layer, dry 20min at 120 ℃, be heated to 310 ℃ in vacuum degree under-90Kpa afterwards, and be incubated 60min at 310 ℃, make monomer A and the monomers B polymerization of polyimides monomer, after cooling, obtain the cathode pole piece with polyimide modified porous polyethylene pyrrolidones (PVP) layer.
The preparation of B anode pole piece
With embodiment 1.
The preparation of C lithium ion battery
With embodiment 1.
Embodiment 8
The preparation of A cathode pole piece
(1) negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and dispersant sodium carboxymethylcellulose are fully mixed to get to negative active core-shell material slurry according to mass ratio 96:1:2:1, negative active core-shell material slurry is coated on the negative current collector Copper Foil that 12 μ m are thick, at 110 ℃, after dry 6h, obtains the anode active material layer that thickness is 90 μ m.
(2) the porous polypropylene acid that is 45.6% by porosity (PAA) uses 1-METHYLPYRROLIDONE (NMP) to dissolve in advance, the quality of wherein porous polypropylene acid (PAA) accounts for 7% of solution gross mass, then add the polyimides monomer that accounts for this solution 1% mass parts, wherein polyimides monomer is that the pre-composition of monomer A and monomers B and the mass ratio of monomer A and monomers B are 3:2, after stirring at normal temperature 1h, obtain composite mortar.
(3) composite mortar is coated in to the surface of anode active material layer, dry 20min at 120 ℃, be heated to 310 ℃ in vacuum degree under-90Kpa afterwards, and be incubated 60min at 310 ℃, make monomer A and the monomers B polymerization of polyimides, after cooling, obtain the cathode pole piece with polyimide modified porous polypropylene acid (PAA) layer.
The preparation of B anode pole piece
With embodiment 1.
The preparation of C lithium ion battery
With embodiment 1.
Embodiment 9
The preparation of A cathode pole piece
(1) negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and dispersant sodium carboxymethylcellulose are fully mixed according to mass ratio 96:1:2:1, obtain negative active core-shell material slurry, negative active core-shell material slurry is coated on the negative current collector Copper Foil that 12 μ m are thick, at 100 ℃, after dry 5h, obtains the anode active material layer that thickness is 90 μ m.
(2) the porous Kynoar that is 45.6% by porosity (PVDF) uses 1-METHYLPYRROLIDONE (NMP) to dissolve in advance, wherein the quality of porous Kynoar (PVDF) accounts for 7% of solution gross mass, then add the polyimides monomer that accounts for this solution 1% mass parts, wherein polyimides monomer is that the pre-composition of monomer A and monomers B and the mass ratio of monomer A and monomers B are 4:1, after stirring at normal temperature 1h, obtain composite mortar.
(3) composite mortar is coated in to the surface of anode active material layer; dry 20min at 120 ℃; under nitrogen protection, be heated to 310 ℃ afterwards; and be incubated 60min at 310 ℃; make monomer A and the monomers B polymerization of polyimides monomer, after cooling, obtain the cathode pole piece with polyimide modified porous Kynoar (PVDF) layer.
The preparation of B anode pole piece
With embodiment 1.
The preparation of C lithium ion battery
With embodiment 1.
Comparative example 1
The preparation method of lithium ion battery is with embodiment 1, but the uncoated any material in anode active material layer surface.
Comparative example 2
The preparation method of lithium ion battery is with embodiment 1, is 41.2% unmodified porous Kynoar (PVDF) but anode active material layer surface-coated has porosity.
Test process and the test result of lithium ion battery of the present invention are finally described.
(1) lithium ion battery deformation test
After lithium ion battery completely fills for the first time, the thickness P1 of thickness maximum position on lithium-ion electric tank main body while being 4.35V by height gage measuring voltage respectively, with near thickness miking lithium ion cell polar ear be P2, the deformation rate of lithium ion battery=(P1-P2)/P2.
Wherein, lithium ion cell charging step is: (1) leaves standstill 3min; (2) constant current charge: charging current is 0.7C, charge cutoff voltage is 4.35V; (3) constant voltage charge: constant voltage charge under 4.35V, cut-off current is 0.025C; (4) leave standstill 3min, the thickness of test lithium ion battery, probe temperature is 25 ℃.
(2) cycle performance of lithium ion battery test
Loop test flow process: (1) leaves standstill 3min; (2) constant current charge: charging current is 0.7C, charge cutoff voltage is 4.35V; (3) constant voltage charge: constant voltage charge under 4.35V, cut-off current is 0.025C; (4) constant-current discharge: discharging current is 1C, discharge cut-off voltage is 3.0V; (5) one discharged and recharged after, repeating step (1), enters next circulation, probe temperature is 25 ℃.
(3) lithium ion battery over-charging test
Over-charging testing process: (1) chooses the lithium ion battery that voltage is 4.35V, at 60 ℃ of standing 30min, makes inside lithium ion cell consistent with external temperature before charging; (2) at 60 ℃ with 4.35V constant voltage charge, in the time that the charging interval reaches 60h, 80h, 160h, record respectively corresponding electric current.
Table 1 provides parameter and the performance test results of embodiment 1-9 and comparative example 1-2.
(1) lithium ion battery deformation test result analysis
From the contrast of embodiment 1-9 and comparative example 1-2, can find out, lithium ion battery at the porous ion polymeric layer of anode active material layer surface-coated modification has effectively improved its deformation, this is because the expansion that the porous ion polymeric layer of modification is cathode pole piece provides cushion space, has reduced the expand size of internal stress of the inside lithium ion cell that brings of pole piece.
From the stereoscan photograph of embodiment 1 and comparative example 2, can see clearly, after discharging and recharging, there is cave in (Fig. 2) in the loose structure of unmodified porous Kynoar (PVDF) layer, can not guarantee the stability of the structure of porous Kynoar (PVDF) layer, thereby do not have the effect that cushions internal stress, cause the deformation rate of lithium ion battery larger; And through polyimide modified porous Kynoar (PVDF) layer (Fig. 3), owing to there being intensity to approach the support of the polyimides of metal, structure is more stable, can play the effect of buffering internal stress, therefore the deformation rate of lithium ion battery is less.
From the contrast of embodiment 1-3, can find out, the quality percentage composition of polyimides is higher, and the deformation rate of lithium ion battery is less.This is due to the intensity that the strength ratio of polyimides is large and approach metal, the structure of porous Kynoar (PVDF) layer to whole modification is played a supporting role, can play the effect of buffering internal stress simultaneously, therefore the quality percentage composition of polyimides is higher, and the deformation rate of lithium ion battery is less.
From the contrast of embodiment 2 and embodiment 4, can find out, the porosity of porous Kynoar (PVDF) is higher, and the deformation rate of lithium ion battery is less.This is because porous Kynoar (PVDF) layer can be used as resilient coating, for the expansion of negative active core-shell material provides a part of hole, has slowed down negative active core-shell material in the volumetric expansion and the contraction that discharge and recharge in removal lithium embedded process.
From the contrast of embodiment 1 and embodiment 9, can find out, the monomer A of polyimides monomer and the mass ratio of monomers B are higher, and the deformation rate of lithium ion battery is less.This is owing to being compared to monomers B, the closed loop degree of monomer A strand after there is polymerization is higher, molecular chain movement performance is poorer, the intensity of porous Kynoar (PVDF) layer therefore forming is higher, structural stability is better, and the structural stability of the porous Kynoar (PVDF) that monomers B forms layer is poor, therefore deformation rate is larger than monomer A.
(2) cycle performance of lithium ion battery test result analysis
From the contrast of embodiment 1-9 and comparative example 1-2, can find out, the porous ion polymeric layer of modification of the present invention improves successful to the cycle performance of lithium ion battery, and especially the lithium ion battery after 800 circulations can also keep higher discharge capacity.Main cause is: on the one hand, the porous ion polymeric layer of modification can absorb a certain amount of electrolyte, and in cyclic process, in the time that electrolyte is consumed, the porous ion polymeric layer of modification can discharge electrolyte, guarantees the superiority of circulation; On the other hand, the porous ion polymeric layer of modification has significantly reduced the generation of the de-lithium situation of cathode pole piece, has kept the structural stability of cathode pole piece.
From the contrast of embodiment 1-3, can find out, the content of polyimides is higher, and the discharge capacity of lithium ion battery after repeatedly circulating is higher.This is because interface stability causes, polyimides content is higher, the interface that porous ion polymeric layer forms is more stable, stable porous ion polymeric layer is confined active material in a fixing space, stability while having kept discharging and recharging, promote the formation of SEI film in electrochemical reaction and stablize, further having improved the cycle performance of lithium ion battery.
From the contrast of embodiment 2 and embodiment 4, can find out, the porosity of porous Kynoar (PVDF) is higher, and the discharge capacity of lithium ion battery after repeatedly circulating is higher.This is because porous Kynoar (PVDF) layer provides passage smoothly for the deintercalation of lithium ion, and on the other hand, Kynoar (PVDF) itself can swelling a part of electrolyte, equally the deintercalation of lithium ion is had to facilitation.
From the contrast of embodiment 1 and embodiment 9, can find out, the monomer A of polyimides monomer and the mass ratio of monomers B are higher, and the discharge capacity of lithium ion battery after repeatedly circulating is higher.This is owing to being compared to monomers B, the closed loop degree of monomer A strand after there is polymerization is higher, molecular chain movement performance is poorer, the intensity of porous Kynoar (PVDF) layer therefore forming is higher, structural stability is better, and stable porous Kynoar (PVDF) layer is confined active material in a fixing space, the stability while having kept discharging and recharging, promote the formation of SEI film in electrochemical reaction and stablize, further having improved the cycle performance of lithium ion battery.
(3) lithium ion battery over-charging test result analysis
From the contrast of embodiment 1-9 and comparative example 1-2, can find out, in comparative example 1 and comparative example 2 after to lithium ion cell charging 160h, the charging current of lithium ion battery has been elevated to larger numerical value, and the charging current of lithium ion battery in embodiment 1-9 still remains on a lower level, the porous ion polymeric layer that modification of the present invention is described has had very large improvement to the overcharging resisting performance of lithium ion battery, and therefore lithium ion battery of the present invention can be applied to high-tension occasion.Main cause is: the physical property that the porous ion polymeric layer of modification can form on cathode pole piece surface microcosmic intercepts, and barrier film can not penetrated by Li dendrite.
From the contrast of embodiment 1-3, can find out, the content of polyimides is higher, and the charging current of lithium ion battery after long-time charging is less, and overcharging resisting performance is better.This is because interface stability causes, and polyimides content is higher, and the interface that porous ion polymeric layer forms is more stable, can form good physical barrier, and barrier film can not penetrated by Li dendrite.
From the contrast of embodiment 2 and embodiment 4, can find out, the porosity of porous Kynoar (PVDF) is higher, and the charging current of lithium ion battery after long-time charging is less, and overcharging resisting performance is better.This is that the structural stability of porous ion polymeric layer is better because the porosity of porous Kynoar (PVDF) is higher, and physical barrier effect is more obvious.
From the contrast of embodiment 1 and embodiment 9, can find out, the monomer A of polyimides monomer and the mass ratio of monomers B are higher, and the charging current of lithium ion battery after long-time charging is less, and overcharging resisting performance is better.This is owing to being compared to monomers B, the closed loop degree of monomer A strand after there is polymerization is higher, molecular chain movement performance is poorer, the intensity of porous Kynoar (PVDF) layer therefore forming is higher, structural stability is better, can form good physical barrier, barrier film can not penetrated by Li dendrite.
In sum, the deformation rate of the lithium ion battery with polyimide modified porous ion polymeric layer of the present invention can effectively reduce, and cycle performance and overcharging resisting performance are improved simultaneously.And in polyimide modified porous ion polymeric layer, in higher, the polyimides monomer of the content of polyimides, the mass ratio porosity higher, porous ion polymer of monomer A and monomers B is higher, the deformation rate of lithium ion battery is lower, and cycle performance and overcharging resisting performance are better.
Claims (10)
1. a cathode pole piece for lithium ion battery, comprising:
Negative current collector;
Anode active material layer, contains cathode conductive agent, negative pole binding agent and negative active core-shell material and is coated on negative current collector;
The porous ion polymeric layer of modification, is coated in anode active material layer surface;
It is characterized in that, the porous ion polymeric layer of described modification is polyimide modified porous ion polymeric layer.
2. the cathode pole piece of lithium ion battery according to claim 1, is characterized in that,
The thickness of described anode active material layer is 20 μ m～100 μ m;
The thickness of the porous ion polymeric layer of described modification is 1 μ m～10 μ m.
3. the cathode pole piece of lithium ion battery according to claim 1, it is characterized in that, the porous ion polymer of the porous ion polymeric layer of described modification is one or more in Kynoar (PVDF), polyacrylic acid (PAA), polyacrylate, polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP).
4. the cathode pole piece of lithium ion battery according to claim 3, is characterized in that, the porosity of the porous ion polymer of the porous ion polymeric layer of described modification is 40%～65%.
5. the cathode pole piece of lithium ion battery according to claim 1, is characterized in that,
Described negative active core-shell material is one or more in native graphite, Delanium, silicon alloy, Si-C composite material and lithium titanate;
Described cathode conductive agent is one or more in acetylene black, carbon fiber (VGCF), carbon nano-tube (CNT) and conductive black (Super-P);
Described negative pole binding agent is one or more in butadiene-styrene rubber (SBR), polyacrylic acid, polyacrylate and sodium carboxymethylcellulose (CMC).
6. a preparation method for the cathode pole piece of lithium ion battery, for the preparation of according to the cathode pole piece of the lithium ion battery described in any one in claim 1-5, comprises step:
(1) negative active core-shell material, cathode conductive agent, negative pole binding agent and negative pole dispersant are fully mixed to get to negative active core-shell material slurry according to proper proportion, negative active core-shell material slurry is coated on negative current collector, obtains after drying anode active material layer;
(2) porous ion polymer and polyimides monomer are dispersed in organic solvent, stir at normal temperatures, obtain composite mortar;
(3) composite mortar is coated in to the surface of anode active material layer; after dry, under vacuum or under protective gas protection, heat and be incubated, so that polyimides monomer polymerization; after cooling, form polyimide modified porous ion polymeric layer, obtain the cathode pole piece of lithium ion battery.
7. the preparation method of the cathode pole piece of lithium ion battery according to claim 6, is characterized in that,
Described negative pole dispersant is one or more in polyvinylpyrrolidone (PVP), sodium carboxymethylcellulose (CMC) and polyvinyl alcohol (PVA);
Described organic solvent is one or more in 1-METHYLPYRROLIDONE (NMP), toluene, oxolane and carrene.
8. the preparation method of the cathode pole piece of lithium ion battery according to claim 7, is characterized in that, the quality of described polyimides monomer be porous ion polymer quality 20%～30%.
9. the preparation method of the cathode pole piece of lithium ion battery according to claim 7, is characterized in that, described polyimides monomer is the pre-composition of monomer A and monomers B,
Wherein, the quality percentage composition that monomer A accounts for polyimides monomer is 60%～80%, and the quality percentage composition that monomers B accounts for polyimides monomer is that 20%～40%, R is the alkyl of 1-8 carbon atom.
10. a lithium ion battery, comprising:
Anode pole piece;
Cathode pole piece;
Barrier film, is interval between anode pole piece and cathode pole piece;
Electrolyte; And
Package foil;
It is characterized in that, described cathode pole piece is the cathode pole piece of the lithium ion battery described in any one in claim 1-5.
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