CN103855360B - Lithium ion battery and cathode pole piece thereof and preparation method - Google Patents
Lithium ion battery and cathode pole piece thereof and preparation method Download PDFInfo
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- CN103855360B CN103855360B CN201410068771.4A CN201410068771A CN103855360B CN 103855360 B CN103855360 B CN 103855360B CN 201410068771 A CN201410068771 A CN 201410068771A CN 103855360 B CN103855360 B CN 103855360B
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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
- 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
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 provides a kind of lithium ion battery and cathode pole piece thereof and preparation method.The cathode pole piece of described lithium ion battery, including: negative current collector；Anode active material layer, containing cathode conductive agent, negative electrode binder and negative active core-shell material and be coated on negative current collector；Modified porous ion polymeric layer, is coated in anode active material layer surface.Wherein, the porous ion polymeric layer of described modification is polyimide modified porous ion polymeric layer.Described lithium ion battery includes the cathode pole piece of above-mentioned lithium ion battery.Present invention reduces the deformation rate of lithium ion battery, improve cycle performance and the overcharging resisting performance of lithium ion battery.
Description
Technical field
The present invention relates to field of batteries, particularly relate to a kind of lithium ion battery and cathode pole piece thereof and preparation side
Method.
Background technology
Lithium ion battery is because having higher energy density and advantages of environment protection, at portable electronic
Equipment and electric automobiles are widely used.
But, in use, battery core body there will be concavo-convex, wave to lithium ion battery or local is thick
The irreversible metabolies such as degree increase, when deforming serious, electronic mobile terminal equipment cannot accommodate lithium
Ion battery, may burst equipment, affects the normal use of equipment.Find through research, more than generation
The reason of problem mainly has three below aspect: (1), when winding battery core, does not has in pole piece and isolation
Between film, reserved unnecessary space, causes having bigger internal stress inside the battery core of winding；(2)
The lithium ion battery prepared is after discharge and recharge, and cathode pole piece, due to embedding lithium, causes its thickness obvious
Increase；(3) during the most coat activated material paste, due in active material slurry
The adhesion strength of the binding agent used is relatively big, can shrink after coating completes.
For problem above, current ameliorative way is poly-partially in anode active material layer surface-coated porous
Fluorothene (PVDF) layer, but the structure comparison of traditional porous Kynoar (PVDF) is loose,
Easily caving in, therefore, the problem on deformation of lithium ion battery is not the most well solved.
Summary of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of lithium ion battery and
Its cathode pole piece and preparation method, which reduce the deformation rate of lithium ion battery, improve lithium ion battery
Cycle performance and overcharging resisting performance.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of lithium-ion electric
The cathode pole piece in pond, comprising: negative current collector；Anode active material layer, containing cathode conductive agent,
Negative electrode binder and negative active core-shell material and be coated on negative current collector；Modified porous ion gathers
Compound layer, is coated in anode active material layer surface.Wherein, the porous ion polymeric layer of described modification
For polyimide modified porous ion polymeric layer.
In a second aspect of the present invention, the invention provides the preparation of the cathode pole piece of a kind of lithium ion battery
Method, including step: (1) is by negative active core-shell material, cathode conductive agent, negative electrode binder and bears
Pole dispersant is sufficiently mixed according to proper proportion and obtains negative active material slurry, by negative electrode active material slip
Material is coated on negative current collector, obtains anode active material layer after drying；(2) by porous ion
Polymer and polyimide monomers disperse in organic solvent, stir at normal temperatures, obtain composite mortar；
(3) composite mortar is coated in the surface of anode active material layer, after drying, under vacuo or protect
Protect and heat under gas shield and be incubated, so that polyimide monomers polymerization, after cooling, i.e. form polyimides
Modified porous ion polymeric layer, obtains 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, including: anode pole piece；
Cathode pole piece；Isolating membrane, is interval between anode pole piece and cathode pole piece；Electrolyte；And package foil.
Wherein, described cathode pole piece is the cathode pole piece of the lithium ion battery according to first aspect present invention.
Beneficial effects of the present invention is as follows:
The most traditional porous ion polymeric layer loosely organized, easily caves in, the porous ion of the present invention
Polymeric layer is through polyimide modified, and polyimide monomers at high temperature can occur polyreaction, polymerization
Porous ion polymeric layer, close to metal, can be played support and make by the intensity of the polyimides formed afterwards
With, the structure making porous ion polymeric layer is more stable.
2. the loose structure of porous ion polymeric layer ensure that the migration of lithium ion in lithium ion battery
Unimpeded, thus ensure that the cycle performance of lithium ion battery.
3. after the electrolyte in lithium ion battery infiltrates cathode pole piece, owing to modified porous ion gathers
Compound layer contains the porous ion polymer with loose structure and the polyimides with supporting role,
Reduce the swelling set of lithium ion battery.
4. through polyimide modified porous ion polymeric layer be swollen in charge and discharge process of cathode pole piece
Swollen reserve cushion space, the problem on deformation of lithium ion battery can be obviously improved.
5. can form microcosmic on cathode pole piece surface through polyimide modified porous ion polymeric layer
Physical property intercepts, and reduces Li dendrite and pierces through isolating membrane, 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 the lithium ion battery of the present invention；
Fig. 2 is the SEM photograph of unmodified porous Kynoar (PVDF) layer in comparative example 2；
Fig. 3 is the SEM photograph of porous Kynoar (PVDF) layer modified in embodiment 1.
Detailed description of the invention
The following detailed description of the lithium ion battery according to the present invention and cathode pole piece thereof and preparation method and
Comparative example, embodiment and test result.
First the cathode pole piece of lithium ion battery according to a first aspect of the present invention is described.
The cathode pole piece of lithium ion battery according to a first aspect of the present invention, as it is shown in figure 1, include: negative
Pole collector；Anode active material layer, containing cathode conductive agent, negative electrode binder and negative electrode active
Material and being coated on negative current collector；Modified porous ion polymeric layer, is coated in negative electrode active material
Bed of material surface.The porous ion polymeric layer of described modification is polyimide modified porous ion polymer
Layer.
In the cathode pole piece of lithium ion battery according to a first aspect of the present invention, described negative active core-shell material
The thickness of layer can be 20 μm～100 μm.
In the cathode pole piece of lithium ion battery according to a first aspect of the present invention, the porous of described modification from
The thickness of sub-polymeric layer can be 1 μm～10 μm.
In the cathode pole piece of lithium ion battery according to a first aspect of the present invention, the porous of described modification from
The porous ion polymer of sub-polymeric layer can be Kynoar (PVDF), polyacrylic acid (PAA),
One or several in polyacrylate, polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP)
Kind.
In the cathode pole piece of lithium ion battery according to a first aspect of the present invention, the porous of described modification from
The porosity of the porous ion polymer of sub-polymeric layer can be 40%～65%.
In the cathode pole piece of lithium ion battery according to a first aspect of the present invention, described negative active core-shell material
It can be the one in native graphite, Delanium, silicon alloy, Si-C composite material and lithium titanate or several
Kind.
In the cathode pole piece of lithium ion battery according to a first aspect of the present invention, described cathode conductive agent can
For acetylene black, carbon fiber (VGCF), CNT (CNT) and conductive black (Super-P)
In one or more.
In the cathode pole piece of lithium ion battery according to a first aspect of the present invention, described negative electrode binder can
For butadiene-styrene rubber (SBR), polyacrylic acid, polyacrylate and sodium carboxymethyl cellulose (CMC)
In one or more.
Secondly the preparation method of the cathode pole piece of explanation lithium ion battery according to a second aspect of the present invention.
The preparation method of the cathode pole piece of lithium ion battery according to a second aspect of the present invention, including step:
(1) by negative active core-shell material, cathode conductive agent, negative electrode binder and negative pole dispersant according to suitably
Ratio is sufficiently mixed and obtains negative active material slurry, and negative active material slurry is coated in negative pole currect collecting
On body, obtain anode active material layer after drying；(2) by porous ion polymer and polyimides
Monomer dispersion in organic solvent, stirs at normal temperatures, obtains composite mortar；(3) by composite mortar
It is coated in the surface of anode active material layer, after drying, under vacuo or heats under protective gas protection
And be incubated, so that polyimide monomers polymerization, i.e. form polyimide modified porous ion after cooling and gather
Compound layer, obtains the cathode pole piece of lithium ion battery.
In the preparation method of the cathode pole piece of lithium ion battery according to a second aspect of the present invention, described negative
Pole dispersant can be polyvinylpyrrolidone (PVP), sodium carboxymethyl cellulose (CMC) and poly-second
One or more in enol (PVA).
In the preparation method of the cathode pole piece of lithium ion battery according to a second aspect of the present invention, described in have
Machine solvent can be in N-Methyl pyrrolidone (NMP), toluene, oxolane and dichloromethane
One or more.
In the preparation method of the cathode pole piece of lithium ion battery according to a second aspect of the present invention, described poly-
The quality of dant monomer can be the 20%～30% of the quality of porous ion polymer.
In the preparation method of the cathode pole piece of lithium ion battery according to a second aspect of the present invention, described poly-
Dant monomer can be monomer A and the pre-composition of monomer B,
Wherein, it can be 60%～80% that monomer A accounts for the weight/mass percentage composition of polyimide monomers, monomer B
The weight/mass percentage composition accounting for polyimide monomers can be 20%～40%, and R is the alkyl of 1-8 carbon atom.
In the preparation method of the cathode pole piece of lithium ion battery according to a second aspect of the present invention, in step
(1) in, the temperature being dried can be 85 DEG C～120 DEG C, and the time being dried can be 4h～8h.
In the preparation method of the cathode pole piece of lithium ion battery according to a second aspect of the present invention, in step
(2), in, mixing time at normal temperatures can be 0.5h～2h.
In the preparation method of the cathode pole piece of lithium ion battery according to a second aspect of the present invention, in step
(3) in, the temperature being dried can be 100 DEG C～150 DEG C, and the time being dried can be 5min～30min.
In the preparation method of the cathode pole piece of lithium ion battery according to a second aspect of the present invention, in step
(3) in, vacuum under vacuo >-97Kpa.
In the preparation method of the cathode pole piece of lithium ion battery according to a second aspect of the present invention, in step
(3), in, protective gas can be argon or nitrogen.
In the preparation method of the cathode pole piece of lithium ion battery according to a second aspect of the present invention, in step
(3) in, the temperature of heating can be 300 DEG C～350 DEG C, and temperature retention time can be 15min～60min.
Lithium ion battery according to a third aspect of the present invention is described again.
Lithium ion battery according to a third aspect of the present invention, including: anode pole piece；Cathode pole piece；Isolation
Film, is interval between anode pole piece and cathode pole piece；Electrolyte；And package foil.Described cathode pole piece
Cathode pole piece for the lithium ion battery according to first aspect present invention.
In lithium ion battery according to a third aspect of the present invention, described package foil can be aluminum plastic film.
Next explanation is according to the lithium rechargeable battery of the present invention and cathode pole piece thereof and preparation method
Embodiment and comparative example.
Embodiment 1
The preparation of A cathode pole piece
(1) by negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and
Dispersant sodium carboxymethyl cellulose is sufficiently mixed according to mass ratio 96:1:2:1, obtains negative electrode active material slip
Material, is coated in negative active material slurry on the negative current collector Copper Foil of 12 μ m-thick, at 100 DEG C
Obtain, after being dried 5h, the anode active material layer that thickness is 90 μm.
(2) porous Kynoar (PVDF) that porosity is 41.2% is used N-methylpyrrole in advance
Alkanone (NMP) is dissolved, and wherein the quality of porous Kynoar (PVDF) accounts for solution gross mass
7%, it is subsequently adding the polyimide monomers accounting for this solution 1% mass parts, wherein polyimide monomers is single
The mass ratio of body A and the pre-composition of monomer B and monomer A and monomer B is 3:2, after stirring at normal temperature 1h,
Obtain composite mortar.
(3) composite mortar is coated in the surface of anode active material layer, at 120 DEG C, is dried 20min,
It is heated to 310 DEG C the most under nitrogen protection, and at 310 DEG C, is incubated 60min, make polyimide monomers
Monomer A be polymerized with monomer B, obtain after cooled cooling gathering inclined fluorine with polyimide modified porous
The cathode pole piece of ethylene (PVDF) layer.
The preparation of B anode pole piece
2.4g Kynoar (PVDF) is dissolved in 32g solvent N-methyl pyrilidone (NMP)
In prepare binder solution, then in gained solution add 145g positive electrode active materials LiCoO2 and
2.55g conductive agent Super-P, prepares positive electrode active materials slurry, by positive-active after stirring
Material paste is coated on the plus plate current-collecting body aluminium foil of 16 μ m-thick, drying, cold pressing after obtain thickness and be
The anode pole piece of 100 μm.
The preparation of C lithium ion battery
By the cathode pole piece of above-mentioned preparation, isolating membrane (polyethylene of 12 μ m-thick), anode pole piece in due order
Sequence winding makes battery core, with package foil aluminum plastic film by battery core closedtop and side seal, injects electrolyte (1mol/L
LiPF6, EC:DMC mass ratio is 1:1), stand 24h afterwards, then through operations such as chemical conversion, capacity
Prepare lithium ion battery.
Embodiment 2
The preparation of A cathode pole piece
(1) by negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and
Dispersant sodium carboxymethyl cellulose is sufficiently mixed according to mass ratio 96:1:2:1, obtains negative electrode active material slip
Material, is coated in negative active material slurry on the negative current collector Copper Foil of 12 μ m-thick, at 100 DEG C
Obtain, after being dried 5h, the anode active material layer that thickness is 90 μm.
(2) porous Kynoar (PVDF) that porosity is 52.2% is used N-methylpyrrole in advance
Alkanone (NMP) is dissolved, and wherein the quality of porous Kynoar (PVDF) accounts for solution gross mass
7%, it is subsequently adding the polyimide monomers accounting for this solution 2% mass parts, wherein polyimide monomers is single
The mass ratio of body A and the pre-composition of monomer B and monomer A and monomer B is 7:3, after stirring at normal temperature 1h,
Obtain composite mortar.
(3) composite mortar is coated in the surface of anode active material layer, at 120 DEG C, is dried 20min,
It is heated to 310 DEG C the most under nitrogen protection, and at 310 DEG C, is incubated 60min, make polyimide monomers
Monomer A and monomer B polymerization, obtain after cooled cooling gathering inclined fluorine with polyimide modified porous
The cathode pole piece of ethylene (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) by negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and
Dispersant sodium carboxymethyl cellulose is sufficiently mixed according to mass ratio 96:1:2:1, obtains negative electrode active material slip
Material, is coated in negative active material slurry on the negative current collector Copper Foil of 12 μ m-thick, at 100 DEG C
Obtain, after being dried 5h, the anode active material layer that thickness is 90 μm.
(2) porous Kynoar (PVDF) that porosity is 41.2% is used N-methylpyrrole in advance
Alkanone (NMP) is dissolved, and wherein the quality of porous Kynoar (PVDF) accounts for solution gross mass
7%, it is subsequently adding the polyimide monomers accounting for this solution 3% mass parts, wherein polyimide monomers is single
The mass ratio of body A and the pre-composition of monomer B and monomer A and monomer B is 3:2, after stirring at normal temperature 1h,
Obtain composite mortar.
(3) composite mortar is coated in the surface of anode active material layer, at 120 DEG C, is dried 20min,
It is heated to 310 DEG C the most under nitrogen protection, and at 310 DEG C, is incubated 60min, make polyimide monomers
Monomer A and monomer B polymerization, obtain after cooled cooling gathering inclined fluorine with polyimide modified porous
The cathode pole piece of ethylene (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) by negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and
Dispersant sodium carboxymethyl cellulose is sufficiently mixed according to mass ratio 96:1:2:1, obtains negative electrode active material slip
Material, is coated in negative active material slurry on the negative current collector Copper Foil of 12 μ m-thick, at 100 DEG C
Obtain, after being dried 5h, the anode active material layer that thickness is 90 μm.
(2) porous Kynoar (PVDF) that porosity is 60.5% is used N-methylpyrrole in advance
Alkanone (NMP) is dissolved, and wherein the quality of porous Kynoar (PVDF) accounts for solution gross mass
7%, it is subsequently adding the polyimide monomers accounting for this solution 2% mass parts, wherein polyimide monomers is single
The mass ratio of body A and the pre-composition of monomer B and monomer A and monomer B is 7:3, after stirring at normal temperature 1h,
Obtain composite mortar.
(3) composite mortar is coated in the surface of anode active material layer, at 120 DEG C, is dried 20min,
It is heated to 310 DEG C the most under nitrogen protection, and at 310 DEG C, is incubated 60min, make polyimide monomers
Monomer A and monomer B polymerization, obtain after cooled cooling gathering inclined fluorine with polyimide modified porous
The cathode pole piece of ethylene (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) by negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and
Dispersant sodium carboxymethyl cellulose is sufficiently mixed according to mass ratio 96:1:2:1 and obtains negative electrode active material slip
Material, is coated in negative active material slurry on the negative current collector Copper Foil of 12 μ m-thick, at 110 DEG C
Obtain, after being dried 6h, the anode active material layer that thickness is 90 μm.
(2) microporous polyacrylate (PMMA) that porosity is 45.6% is used N-methyl pyrrole in advance
Pyrrolidone (NMP) dissolves, and wherein the quality of microporous polyacrylate (PMMA) accounts for solution gross mass
7%, be subsequently adding the polyimide monomers accounting for this solution 1% mass parts, wherein polyimide monomers is
The mass ratio of monomer A and the pre-composition of monomer B and monomer A and monomer B is 3:2, stirring at normal temperature 1h
After, obtain composite mortar.
(3) composite mortar is coated in the surface of anode active material layer, at 120 DEG C, is dried 20min,
Under argon shield, it is heated to 310 DEG C afterwards, and at 310 DEG C, is incubated 60min, make the list of polyimides
Body A and monomer B polymerization, obtains with polyimide modified microporous polyacrylate after cooled cooling
(PMMA) cathode pole piece of 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) by negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and
Dispersant sodium carboxymethyl cellulose is sufficiently mixed according to mass ratio 96:1:2:1, obtains negative electrode active material slip
Material, is coated in negative active material slurry on the negative current collector Copper Foil of 12 μ m-thick, at 110 DEG C
Obtain, after being dried 6h, the anode active material layer that thickness is 90 μm.
(2) porous polyethylene alcohol (PVA) that porosity is 45.6% is used N-crassitude in advance
Ketone (NMP) dissolves, and wherein the quality of porous polyethylene alcohol (PVA) accounts for the 7% of solution gross mass,
Being subsequently adding the polyimide monomers accounting for this solution 1% mass parts, wherein polyimide monomers is monomer A
It is 3:2 with the pre-composition of monomer B and the mass ratio of monomer A and monomer B, after stirring at normal temperature 1h,
To composite mortar.
(3) composite mortar is coated in the surface of anode active material layer, at 120 DEG C, is dried 20min,
Under argon shield, it is heated to 310 DEG C afterwards, and at 310 DEG C, is incubated 60min, make polyimide monomers
Monomer A and monomer B polymerization, obtain with polyimide modified porous polyethylene after cooled cooling
The cathode pole piece of 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) by negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and
Dispersant sodium carboxymethyl cellulose is sufficiently mixed according to mass ratio 96:1:2:1, obtains negative electrode active material slip
Material, is coated in negative active material slurry on the negative current collector Copper Foil of 12 μ m-thick, at 110 DEG C
Obtain, after being dried 6h, the anode active material layer that thickness is 90 μm.
(2) porous polyethylene ketopyrrolidine (PVP) that porosity is 45.6% is used N-methyl in advance
Ketopyrrolidine (NMP) dissolves, and wherein to account for solution total for the quality of porous polyethylene ketopyrrolidine (PVP)
The 7% of quality, is subsequently adding the polyimide monomers accounting for this solution 1% mass parts, wherein polyimides list
Body be the mass ratio of monomer A and the pre-composition of monomer B and monomer A and monomer B be 3:2, stirring at normal temperature
After 1h, obtain composite mortar.
(3) composite mortar is coated in the surface of anode active material layer, at 120 DEG C, is dried 20min,
Under vacuum is for-90Kpa, it is heated to 310 DEG C afterwards, and at 310 DEG C, is incubated 60min, make polyamides
Monomer A and the monomer B polymerization of imide monomers, obtains after cooled cooling with polyimide modified many
The cathode pole piece of hole polyvinylpyrrolidone (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) by negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and
Dispersant sodium carboxymethyl cellulose is sufficiently mixed according to mass ratio 96:1:2:1 and obtains negative electrode active material slip
Material, is coated in negative active material slurry on the negative current collector Copper Foil of 12 μ m-thick, at 110 DEG C
Obtain, after being dried 6h, the anode active material layer that thickness is 90 μm.
(2) porous polypropylene acid (PAA) that porosity is 45.6% is used N-crassitude in advance
Ketone (NMP) dissolves, and wherein the quality of porous polypropylene acid (PAA) accounts for the 7% of solution gross mass,
Being subsequently adding the polyimide monomers accounting for this solution 1% mass parts, wherein polyimide monomers is monomer A
It is 3:2 with the pre-composition of monomer B and the mass ratio of monomer A and monomer B, after stirring at normal temperature 1h,
To composite mortar.
(3) composite mortar is coated in the surface of anode active material layer, at 120 DEG C, is dried 20min,
Under vacuum is for-90Kpa, it is heated to 310 DEG C afterwards, and at 310 DEG C, is incubated 60min, make polyamides
Monomer A and the monomer B polymerization of imines, obtains after cooled cooling gathering with polyimide modified porous
The cathode pole piece of acrylic 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) by negative active core-shell material native graphite, conductive agent conductive black, binding agent butadiene-styrene rubber and
Dispersant sodium carboxymethyl cellulose is sufficiently mixed according to mass ratio 96:1:2:1, obtains negative electrode active material slip
Material, is coated in negative active material slurry on the negative current collector Copper Foil of 12 μ m-thick, at 100 DEG C
Obtain, after being dried 5h, the anode active material layer that thickness is 90 μm.
(2) porous Kynoar (PVDF) that porosity is 45.6% is used N-methylpyrrole in advance
Alkanone (NMP) is dissolved, and wherein the quality of porous Kynoar (PVDF) accounts for solution gross mass
7%, it is subsequently adding the polyimide monomers accounting for this solution 1% mass parts, wherein polyimide monomers is single
The mass ratio of body A and the pre-composition of monomer B and monomer A and monomer B is 4:1, after stirring at normal temperature 1h,
Obtain composite mortar.
(3) composite mortar is coated in the surface of anode active material layer, at 120 DEG C, is dried 20min,
It is heated to 310 DEG C the most under nitrogen protection, and at 310 DEG C, is incubated 60min, make polyimide monomers
Monomer A and monomer B polymerization, obtain after cooled cooling gathering inclined fluorine with polyimide modified porous
The cathode pole piece of ethylene (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 uncoated of anode active material layer surface
What material.
Comparative example 2
The preparation method of lithium ion battery is with embodiment 1, but anode active material layer surface-coated is porose
Gap rate is the unmodified porous Kynoar (PVDF) of 41.2%.
Test process and the test result of the 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, measure lithium ion when voltage is 4.35V by high metric respectively
The thickness P1 of thickness maximum position on battery main body, by the thickness near miking lithium ion cell polar ear
Degree is P2, the then deformation rate of lithium ion battery=(P1-P2)/P2.
Wherein, lithium ion battery charge step is: (1) stands 3min；(2) constant-current charge: charging
Electric current is 0.7C, and charge cutoff voltage is 4.35V；(3) constant-voltage charge: constant-voltage charge under 4.35V,
Cut-off current is 0.025C；(4) standing 3min, the thickness of test lithium ion battery, test temperature is
25℃。
(2) cycle performance of lithium ion battery test
Loop test flow process: (1) stands 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: discharge current is 1C, discharge cut-off voltage is 3.0V；(5) discharge and recharges
After completing, repeating step (1), enter next one circulation, test temperature is 25 DEG C.
(3) lithium ion battery over-charging test
Over-charging testing process: (1) chooses the lithium ion battery that voltage is 4.35V, before charging
60 DEG C stand 30min, make inside lithium ion cell consistent with external temperature；(2) with 4.35V at 60 DEG C
Constant-voltage charge, when the charging interval reaches 60h, 80h, 160h, records the electric current of correspondence respectively.
Table 1 provides embodiment 1-9 and the parameter of comparative example 1-2 and the performance test results.
(1) lithium ion battery deformation test result analysis
It can be seen that on anode active material layer surface from the contrast of embodiment 1-9 and comparative example 1-2
The lithium ion battery of the porous ion polymeric layer that coating is modified effectively improves its deformation, this be by
Provide cushion space in the modified expansion that porous ion polymeric layer is cathode pole piece, reduce pole piece
Expand the size of the internal stress of the inside lithium ion cell brought.
It is clear that unmodified many from the stereoscan photograph of embodiment 1 and comparative example 2
The loose structure of hole Kynoar (PVDF) layer there occurs cave in (Fig. 2) after discharge and recharge, it is impossible to
Ensure the stability of the structure of porous Kynoar (PVDF) layer, thus do not have buffering internal stress
Effect, the deformation rate causing lithium ion battery is bigger；And through polyimide modified porous polyvinylidene fluoride
Alkene (PVDF) layer (Fig. 3), owing to having the intensity support close to the polyimides of metal, structure comparison
Stable, the effect of buffering internal stress can be played, therefore the deformation rate of lithium ion battery is less.
It can be seen that the weight/mass percentage composition of polyimides is the highest from the contrast of embodiment 1-3, lithium from
The deformation rate of sub-battery is less.This is owing to the strength ratio of polyimides is relatively big and intensity close to metal,
The structure of porous Kynoar (PVDF) layer of whole modification is played a supporting role, the most permissible
Playing the effect of buffering internal stress, therefore the weight/mass percentage composition of polyimides is the highest, lithium ion battery
Deformation rate is less.
It can be seen that porous Kynoar (PVDF) from the contrast of embodiment 2 and embodiment 4
Porosity the highest, the deformation rate of lithium ion battery is less.This is due to porous Kynoar (PVDF)
Layer can be as cushion, and the expansion for negative active core-shell material provides a part of hole, slow down negative pole
Active material volumetric expansion during discharge and recharge removal lithium embedded and contraction.
It can be seen that the monomer A of polyimide monomers and list from the contrast of embodiment 1 and embodiment 9
The mass ratio of body B is the highest, and the deformation rate of lithium ion battery is less.This is owing to being compared to monomer B,
Monomer A closed loop degree of strand after being polymerized is higher, and molecular chain movement performance is worse, therefore
The intensity of porous Kynoar (PVDF) layer formed is higher, and structural stability is more preferable, and monomer B
The structural stability of porous Kynoar (PVDF) layer formed is poor, and therefore deformation rate is than monomer A
Greatly.
(2) cycle performance of lithium ion battery test result analysis
From the contrast of embodiment 1-9 and comparative example 1-2 it can be seen that the modified porous of the present invention from
It is obvious that the cycle performance of lithium ion battery is improved effect by sub-polymeric layer, especially through 800 circulations
After lithium ion battery can also keep higher discharge capacity.Main reason is that: on the one hand, modified
Porous ion polymeric layer can absorb a certain amount of electrolyte, is consumed when electrolyte in cyclic process
Time, modified porous ion polymeric layer can discharge electrolyte, it is ensured that the superiority of circulation；Another
Aspect, modified porous ion polymeric layer significantly reduces cathode pole piece and takes off the generation of lithium situation, keeps
The structural stability of cathode pole piece.
It can be seen that the content of polyimides is the highest from the contrast of embodiment 1-3, lithium ion battery warp
Cross the discharge capacity after repeatedly circulation the highest.This causes due to interface stability, polyimide content
The highest, the interface that porous ion polymeric layer is formed is the most stable, and stable porous ion polymeric layer is living
Property material confine in a fixing space, maintain stability during discharge and recharge, promote that electrochemistry is anti-
Answer the formation of middle SEI film and stablize, further increasing the cycle performance of lithium ion battery.
It can be seen that porous Kynoar (PVDF) from the contrast of embodiment 2 and embodiment 4
Porosity the highest, lithium ion battery through repeatedly circulation after discharge capacity the highest.This is due to porous
Kynoar (PVDF) layer is that the deintercalation of lithium ion provides passage smoothly, on the other hand, poly-
Vinylidene (PVDF) itself can have rush with swelling a part of electrolyte, the equally deintercalation to lithium ion
Enter effect.
It can be seen that the monomer A of polyimide monomers and list from the contrast of embodiment 1 and embodiment 9
The mass ratio of body B is the highest, and lithium ion battery discharge capacity after repeatedly circulation is the highest.This be due to
Being compared to monomer B, the monomer A closed loop degree of strand after being polymerized higher, strand is transported
Dynamic performance is worse, and the intensity of porous Kynoar (PVDF) layer therefore formed is higher, and structure is steady
Qualitative more preferably, stable porous Kynoar (PVDF) layer active material confine one fix
Space in, maintain stability during discharge and recharge, promote the formation of SEI film in electrochemical reaction and steady
Fixed, further increase 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 it can be seen that in comparative example 1 and comparative example 2
After to lithium ion battery charging 160h, the charging current of lithium ion battery has been increased to bigger numerical value,
And the charging current of the lithium ion battery in embodiment 1-9 remains at a relatively low level, this is described
The modified porous ion polymeric layer of invention has had the biggest changing to the overcharging resisting performance of lithium ion battery
Kind, therefore the lithium ion battery of the present invention can be applied to high-tension occasion.Main reason is that: change
Property porous ion polymeric layer can cathode pole piece surface formed microcosmic physical property intercept so that every
Will not be penetrated by Li dendrite from film.
It can be seen that the content of polyimides is the highest from the contrast of embodiment 1-3, lithium ion battery warp
Charging current after long-time charging is the least, and overcharging resisting performance is the best.This is owing to interface stability causes
, polyimide content is the highest, and the interface that porous ion polymeric layer is formed is the most stable, can be formed good
Good physical barrier so that isolating membrane will not be penetrated by Li dendrite.
It can be seen that porous Kynoar (PVDF) from the contrast of embodiment 2 and embodiment 4
Porosity the highest, lithium ion battery charging current after long-time charging is the least, and overcharging resisting performance is more
Good.This is owing to the porosity of porous Kynoar (PVDF) is the highest, porous ion polymeric layer
Structural stability the best, physical barrier effect is the most obvious.
It can be seen that the monomer A of polyimide monomers and list from the contrast of embodiment 1 and embodiment 9
The mass ratio of body B is the highest, and lithium ion battery charging current after long-time charging is the least, overcharge resistance performance
Can be the best.This is that monomer A is the closed loop journey of strand after being polymerized owing to being compared to monomer B
Du Genggao, molecular chain movement performance is worse, porous Kynoar (PVDF) layer therefore formed
Intensity is higher, and structural stability is more preferable, can form good physical barrier so that isolating membrane will not be by
Li dendrite penetrates.
In sum, the lithium ion battery with polyimide modified porous ion polymeric layer of the present invention
Deformation rate can effectively reduce, cycle performance and overcharging resisting performance are improved simultaneously.And polyimides changes
In the porous ion polymeric layer of property, the content of polyimides is the highest, monomer A and list in polyimide monomers
The mass ratio of body B is the highest, the porosity of porous ion polymer is the highest, and the deformation rate of lithium ion battery is more
Low, cycle performance and overcharging resisting performance are the best.
Claims (10)
1. a cathode pole piece for lithium ion battery, including:
Negative current collector；
Anode active material layer, containing cathode conductive agent, negative electrode binder and negative active core-shell material and
It is coated on negative current collector；
Modified porous ion polymeric layer, 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.
The cathode pole piece of lithium ion battery the most according to claim 1, it is characterised in that
The thickness of described anode active material layer is 20 μm～100 μm；
The thickness of the porous ion polymeric layer of described modification is 1 μm～10 μm.
The cathode pole piece of lithium ion battery the most according to claim 1, it is characterised in that described in change
The porous ion polymer of the porous ion polymeric layer of property is Kynoar (PVDF), polypropylene
Acid (PAA), polyacrylate, polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP)
In one or more.
The cathode pole piece of lithium ion battery the most according to claim 3, it is characterised in that described in change
The porosity of the porous ion polymer of the porous ion polymeric layer of property is 40%～65%.
The cathode pole piece of lithium ion battery the most according to claim 1, it is characterised in that
Described negative active core-shell material be native graphite, Delanium, silicon alloy, Si-C composite material and
One or more in lithium titanate；
Described cathode conductive agent be acetylene black, carbon fiber (VGCF), CNT (CNT) and
One or more in conductive black (Super-P)；
Described negative electrode binder is butadiene-styrene rubber (SBR), polyacrylic acid, polyacrylate and carboxylic first
One or more in base sodium cellulosate (CMC).
6. a preparation method for the cathode pole piece of lithium ion battery, for preparation according to claim 1-5
According to any one of the cathode pole piece of lithium ion battery, including step:
(1) by negative active core-shell material, cathode conductive agent, negative electrode binder and negative pole dispersant according to
Proper proportion is sufficiently mixed and obtains negative active material slurry, and negative active material slurry is coated in negative pole
On collector, obtain anode active material layer after drying；
(2) porous ion polymer and polyimide monomers are disperseed in organic solvent, at normal temperatures
Stirring, obtains composite mortar；
(3) composite mortar is coated in the surface of anode active material layer, after drying, under vacuo or
Heat under the protection of person's protective gas and be incubated, so that polyimide monomers polymerization, after cooling, i.e. forming polyamides
Imine modified porous ion polymeric layer, obtains the cathode pole piece of lithium ion battery.
The preparation method of the cathode pole piece of lithium ion battery the most according to claim 6, its feature exists
In,
Described negative pole dispersant is polyvinylpyrrolidone (PVP), sodium carboxymethyl cellulose (CMC)
And one or more in polyvinyl alcohol (PVA)；
Described organic solvent is N-Methyl pyrrolidone (NMP), toluene, oxolane and dichloro
One or more in methane.
The preparation method of the cathode pole piece of lithium ion battery the most according to claim 7, its feature exists
In, the quality of described polyimide monomers is the 20%～30% of the quality of porous ion polymer.
The preparation method of the cathode pole piece of lithium ion battery the most according to claim 7, its feature exists
In, described polyimide monomers is monomer A and the pre-composition of monomer B,
Wherein, it is 60%～80% that monomer A accounts for the weight/mass percentage composition of polyimide monomers, and monomer B accounts for
The weight/mass percentage composition of polyimide monomers is 20%～40%, and R is the alkyl of 1-8 carbon atom.
10. a lithium ion battery, including:
Anode pole piece；
Cathode pole piece；
Isolating membrane, 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 lithium ion battery according to any one of claim 1-5
Cathode pole piece.
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