CN107845812A - Anode pole piece and preparation method thereof and secondary cell - Google Patents
Anode pole piece and preparation method thereof and secondary cell Download PDFInfo
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- CN107845812A CN107845812A CN201610827130.1A CN201610827130A CN107845812A CN 107845812 A CN107845812 A CN 107845812A CN 201610827130 A CN201610827130 A CN 201610827130A CN 107845812 A CN107845812 A CN 107845812A
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
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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
- H01M4/623—Binders being polymers fluorinated polymers
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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
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- 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
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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
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Abstract
The present invention provides a kind of anode pole piece and preparation method thereof and secondary cell.The anode pole piece includes plus plate current-collecting body and the positive pole diaphragm being arranged on plus plate current-collecting body.Positive pole diaphragm includes positive electrode active materials, binding agent and additive.The additive includes：Silicone compounds shown in formula 1 and/or formula 2；And crosslinking agent.The anode pole piece of the present invention has higher cohesive force, can be obviously improved the cycle performance and security performance of secondary cell.
Description
Technical field
The present invention relates to cell art, and in particular to a kind of anode pole piece and preparation method thereof and secondary cell.
Background technology
At present, with the fast development of secondary cell, especially lithium rechargeable battery, secondary cell energy density is improved
Turn into the important directions of secondary cell research with the security performances such as its impact resistance, drift bolt are improved.In order to improve energy density, mainly
Method has exploitation high-energy-density active material, reduces nonactive material using thinner collector, raising active material dosage
Expect (binding agent, conductive agent etc.) dosage.In order to improve the security performances such as the impact resistance of secondary cell, drift bolt, main method is to carry
The cementitiousness of high active material, conductive agent and collector.
Binding agent as the non-active material in pole piece thereof, be prepare important materials that pole piece must use it
One, its main function is to bond and keep active material, strengthen between active material and conductive agent, active material between each other with
And the electronics between active material, conductive agent and collector contacts, preferably stable pole piece structure.Improve active material dosage and
Consumption of binder is reduced, the stability of pole piece structure will necessarily reduce.Therefore, in order to ensure the stability of pole piece structure, develop
The binding agent of higher cohesive force turns into an important research direction.
At present, secondary cell field is generally used as positive electrode binder using polyvinylidene fluoride (PVDF).PVDF is mainly
Vinylidene fluoride homopolymer or vinylidene and the copolymer of other compounds.Compared with other positive electrode binders, PVDF is in electrification
Performance, heat endurance and chemical stability etc. is learned to have a clear superiority.
However, PVDF is as crystalline polymer, for crystallinity 50% or so, crystalline melt temperature is 150 DEG C~170 DEG C.
The temperature in use of usual secondary cell is less than 100 DEG C, therefore PVDF high-crystallinity causes its cohesive force between collector
It is poor, there is demoulding risk during long circulating, produce potential safety hazard.
In order to reduce PVDF crystallinity, improve its flexibility, improve its caking property, the method that researcher uses mainly has
VDF homopolymers are modified, VDF and second comonomer and Third monomer copolymerization, VDF homopolymers and another kind it is copolymer blended etc. and
Pole piece additive is directly applied in pole piece preparation process, to improve the performances such as the circulation of secondary cell, infiltration.
Japanese documentation JP1997-199112A is disclosed in anode pole piece preparation process disclosed in 31 days July in 1997
Middle addition aluminate coupling agent, the cycle performance of battery under high voltage can be improved.Japan disclosed in 31 days October in 2002 is specially
Sharp document JP2002-319405A, which discloses to add in pole piece preparation process, has epoxy, amino isoreactivity group and tool
There is the silane coupler of the wellability group such as methoxyl group, ethyoxyl, the wellability of anode pole piece and electrolyte can be improved.2007
Japanese documentation JP2007-242303A disclosed on September 20, is disclosed using containing at multi-functional silane coupler
Active material is managed, cycle performance of battery can be improved.Chinese patent literature CN1277236A is disclosed disclosed in 20 days December in 2000
The coupling agents such as γ-(methacryloxy) propyl trimethoxy silicane are added in pole piece preparation process and improve the viscous of pole piece
Tie power and electrolyte resistance performance.
The content of the invention
In view of problem present in background technology, it is an object of the invention to provide a kind of anode pole piece and preparation method thereof
And secondary cell, the anode pole piece have higher cohesive force, can be obviously improved the cycle performance and safety of secondary cell
Performance.
In order to achieve the above object, in one aspect of the invention, the invention provides a kind of anode pole piece, it includes positive pole
Collector and the positive pole diaphragm being arranged on plus plate current-collecting body.Positive pole diaphragm includes positive electrode active materials, binding agent and added
Add agent.The additive includes：Silicone compounds shown in formula 1 and/or formula 2；And crosslinking agent.In formula 1 and formula 2, X choosings
From methoxyl group (- O-CH3), ethyoxyl (- O-CH2CH3), methoxy ethoxy (- O-CH2CH2-O-CH3), (ethoxymethyl) epoxide (-
O-CH2-O-CH2CH3) in one kind；R1Selected from the alkyl that carbon number is 1~8, and R1Can by hydroxyl, carboxyl, cyano group, amino,
One or more of substitutions in epoxy radicals, carbonyl, NCO, double bond, acyloxy, ether, amide groups；R2Selected from carbon atom
Count the alkylidene for 1~6, and R2Can be by hydroxyl, carboxyl, cyano group, amino, epoxy radicals, carbonyl, NCO, double bond, acyl-oxygen
One or more of substitutions in base, ether, amide groups, disulfide bond, four sulfide linkages.
In another aspect of this invention, the invention provides a kind of preparation method of anode pole piece, for preparing the present invention
Anode pole piece described in one side, including step：Silicone compounds shown in formula 1 and/or formula 2 are added into Solvents N-methyl pyrrole
Stirred in pyrrolidone, add binding agent and positive electrode active materials afterwards, stir, be eventually adding crosslinking agent, stirred
Uniformly, anode sizing agent is obtained；Anode sizing agent is coated uniformly on plus plate current-collecting body, the preparation of anode pole piece is completed after drying,
Wherein, positive pole diaphragm is formed after anode sizing agent is dried.
In still another aspect of the invention, the invention provides a kind of secondary cell, it includes institute according to an aspect of the present invention
The anode pole piece stated.
Relative to prior art, beneficial effects of the present invention are：
The anode pole piece of the present invention has higher cohesive force, can be obviously improved the cycle performance and security of secondary cell
Energy.
The preparation method of the anode pole piece of the present invention is simple, cheap, suitable for scale industrial production.
Embodiment
The following detailed description of anode pole piece according to the present invention and preparation method thereof and secondary cell.
Illustrate anode pole piece according to a first aspect of the present invention first.
Anode pole piece according to a first aspect of the present invention includes plus plate current-collecting body and is arranged on plus plate current-collecting body just
Pole diaphragm.Positive pole diaphragm includes positive electrode active materials, binding agent and additive.The additive includes：Formula 1 and/or the institute of formula 2
The silicone compounds shown；And crosslinking agent.In formula 1 and formula 2, X is selected from methoxyl group (- O-CH3), ethyoxyl (- O-
CH2CH3), methoxy ethoxy (- O-CH2CH2-O-CH3), (ethoxymethyl) epoxide (- O-CH2-O-CH2CH3) in one kind；R1Choosing
From the alkyl that carbon number is 1~8, and R1Can be by hydroxyl, carboxyl, cyano group, amino, epoxy radicals, carbonyl, NCO, double
One or more of substitutions in key, acyloxy, ether, amide groups；R2Selected from the alkylidene that carbon number is 1~6, and R2Can quilt
Hydroxyl, carboxyl, cyano group, amino, epoxy radicals, carbonyl, NCO, double bond, acyloxy, ether, amide groups, disulfide bond, four
One or more of substitutions in sulfide linkage.
In anode pole piece described according to a first aspect of the present invention, silicone compounds have amphipathic, can improve
Wellability between positive electrode active materials, conductive agent and binding agent；On the other hand, the polar group (Si- in silicone compounds
The Si-OH formed after X hydrolysis) generation can be polymerize with the polar group of binding agent, positive electrode active materials, collection liquid surface,
Improve anode pole piece cohesive force.Crosslinking agent can make the active function groups in binding agent be cross-linked with each other to form spatial network knot simultaneously
Structure, the cohesive force of binding agent is further improved, prevent anode pole piece in long circulating process or fall, puncture, extrude etc. and to make extremely
Occur demoulding or short circuit under the conditions of, improve the cycle performance and security performance of secondary cell.
In anode pole piece described according to a first aspect of the present invention, the silicone compounds shown in formula 1 are selected from methyl three
Methoxy silane, MTES, octyltri-ethoxysilane, vinyl three (methoxyethoxy) silane, vinyl
Triethoxysilane, vinyltrimethoxy silane, γ-chloropropyltrimethoxy silane, γ-chloro propyl-triethoxysilicane
Alkane, γ-(methacryloxy) propyl trimethoxy silicane, chlorination (dimethylaminoethyl methacrylate base) propyl group front three
TMOS, γ-glycidyl ether oxygen propyl trimethoxy silicane, β-(3,4- 7-oxa-bicyclo[4.1.0s) ethyl trimethoxy silane,
N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy silicon
Double (β-the aminoethyl)-γ aminopropyltriethoxy silanes of alkane, N-N-, γ-isocyanates propyl-triethoxysilicane, γ-
(polyethylene amino) propyl trimethoxy silicane, maleimide base propyl-triethoxysilicane, maleic acid acid amides
One or more in base propyl-triethoxysilicane.Preferably, the silicone compounds shown in formula 1 are selected from γ-(metering system
Acyloxy) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, N- β-(aminoethyl)-γ-ammonia third
Base trimethoxy silane, gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N-N- double (β-aminoethyl)-
One or more in γ aminopropyltriethoxy silane, γ-isocyanates propyl-triethoxysilicane.
In anode pole piece described according to a first aspect of the present invention, silicone compounds shown in formula 2 be selected from two (γ-
Tri-ethoxy silylpropyl) tetrasulfide, double (triethoxy silicon substrate propyl group) disulphide, two (γ-trimethyoxysilane
Base propyl group) one or more in amine.
In anode pole piece described according to a first aspect of the present invention, silicone compounds shown in formula 1 and/or formula 2
Gross mass is the 0.01%~2.0% of the gross mass of the positive pole diaphragm.
In anode pole piece described according to a first aspect of the present invention, it is double that the crosslinking agent is selected from 2,5- dimethyl -2,5-
Double (the tert-butyl peroxide) -3- hexins of (tert-butyl peroxide) hexane, 2,5- dimethyl -2,5-, di-tert-butyl peroxide, mistake
BP, the peroxylauric acid tert-butyl ester, peroxide acetic acid butyl ester, peroxidating (2 ethyl hexanoic acid) tert-butyl ester, 2,5-
Dimethyl -2,5- double (benzoyl peroxide) hexane, 4,4 '-two (tert-butyl peroxide) n-butyl pentanoates, double (4- tert-butyl group rings
Hexyl) peroxy dicarbonate, tert-butylperoxyiso-propyl formic acid esters, TBHP, double (the tertiary fourths of peroxidating of 2,2-
Base) butane, 2,2- double (the tert-butyl peroxy cyclohexyl of 4,4- bis-) propane, α, α-bis- (tert-butyl peroxy bases) diisopropylbenzene (DIPB), peroxidating
Double (tert-butyl peroxide) hexamethylenes of diisopropylbenzene (DIPB), peroxidized t-butyl perbenzoate, 1,1-, 1,1- double (tert-butyl peroxides)-
3,3,5- trimethyl-cyclohexanes, diperoxy phthalic acid di tert butyl carbonate, t-butylcumylperoxide, 1,3- pairs-(uncle 2-
Butyl peroxy base isopropyl) benzene, the one or more in triallyl isocyanurate.
In anode pole piece described according to a first aspect of the present invention, the quality of the crosslinking agent is the positive pole diaphragm
The 0.01%~0.05% of gross mass.
In anode pole piece described according to a first aspect of the present invention, the mass ratio of binding agent and positive electrode active materials can be
(1~3):(92~97.99).
In anode pole piece described according to a first aspect of the present invention, the binding agent is selected from polyvinylidene fluoride, inclined two
Viton copolymers, vinylidene-tetrafluoroethylene-propylene terpolymer, biasfluoroethylene-hexafluoropropylene-tetrafluoro
One or more in ethylene-dien terpolymer, vinylidene-chlorotrifluoroethylene.
In anode pole piece described according to a first aspect of the present invention, the positive pole diaphragm may also include conductive agent.It is described
Conductive agent is selected from acetylene black, Super-P, Super-S, 350G, carbon fiber, CNT, Ketjen black, KS-6, KS-15, SFG-
6th, the one or more in SFG-15.
In anode pole piece described according to a first aspect of the present invention, binding agent, conductive agent, the quality of positive electrode active materials
Than that can be (1~3):(1~3):(92~97.99).
Secondly the preparation method of the anode pole piece of explanation according to a second aspect of the present invention, for preparing first aspect present invention
Described anode pole piece, including step：Silicone compounds shown in formula 1 and/or formula 2 are added into solvent N-methyl pyrilidone
In stir, add binding agent and positive electrode active materials afterwards, stir, be eventually adding crosslinking agent, stir, obtain
To anode sizing agent；Anode sizing agent is coated uniformly on plus plate current-collecting body, the preparation of anode pole piece is completed after drying, wherein, just
Positive pole diaphragm is formed after the slurry drying of pole.
In the preparation method of anode pole piece described according to a second aspect of the present invention, binding agent and positive pole work are being added
During property material, conductive agent can also be added.
Illustrate secondary cell according to a third aspect of the present invention again, it include according to a first aspect of the present invention it is described just
Pole pole piece.
In secondary cell described according to a third aspect of the present invention, the secondary cell also includes cathode pole piece, isolation
Film and electrolyte.
In secondary cell described according to a third aspect of the present invention, the secondary cell is lithium rechargeable battery, sodium
Ion secondary battery or zinc ion secondary cell.
In secondary cell described according to a third aspect of the present invention, when the secondary cell is lithium rechargeable battery
When, the positive electrode active materials may be selected from LiFePO4 (LFP), cobalt acid lithium (LCO), nickel-cobalt-manganese ternary material (NCM), nickel cobalt aluminium
One or more in sour lithium material (NCA).
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.The situation that secondary cell is lithium rechargeable battery, but the present invention are only shown in embodiment
Not limited to this.
Comparative example 1
(1) preparation of anode pole piece
At 25 DEG C, binding agent polyvinylidene fluoride is added in 1-METHYLPYRROLIDONE, 1000r/min stirs；
Conductive agent Super-P and positive electrode active materials cobalt acid lithium are added afterwards, and 1000~2000r/min stirs, and obtains positive pole slurry
Material.Wherein, binding agent, conductive agent, the mass ratio of positive electrode active materials are 3:3:94.
Anode sizing agent is uniformly coated on two surfaces of plus plate current-collecting body aluminium foil (thickness is 14 μm), coating weight is
0.300g/1540.25mm2, in 130 DEG C of oven for drying, it is 20*100mm anode pole pieces that size is cut into after cold pressing, standby.
(2) preparation of cathode pole piece
By negative active core-shell material Delanium, binding agent SBR emulsion, thickener sodium carboxymethylcellulose and conductive agent
Super-P in mass ratio 90:2:3:5 are mixed, and are made solvent using deionized water, are stirred through 1000~2000r/min,
Obtain cathode size.Cathode size is uniformly coated on two surfaces of negative current collector copper foil (thickness is 8 μm), coating
Weight is 0.150g/1540.25mm2, in 80 DEG C of oven for drying, it is 20*100mm cathode pole pieces that size is cut into after cold pressing, standby
With.
(3) preparation of lithium rechargeable battery
Conductive lug is welded on anode pole piece and cathode pole piece, and use thickness for 12 μm polypropylene barrier film every
Open, it is stacked to form naked battery core, then encapsulated with aluminum plastic film.Electrolyte uses the lithium hexafluorophosphate electrolyte solution containing 1M, and solvent is carbonic acid
Vinyl acetate, propene carbonate, dimethyl carbonate 1:1:The mixed solvent of 1 (volume ratio).Electrolyte is injected after encapsulation, obtains finished product
Lithium rechargeable battery.
Comparative example 2
Method according to comparative example 1 prepares lithium rechargeable battery, and difference is：
(1) preparation of anode pole piece
At 25 DEG C, silicone compounds MTMS is added in 1-METHYLPYRROLIDONE, 500r/min
Stir；Binding agent polyvinylidene fluoride is added afterwards, and 1000r/min stirs；Add conductive agent Super-P with just
Pole active material cobalt acid lithium, 1000~2000r/min stir, and obtain anode sizing agent.Wherein, silicone compounds, bonding
Agent, conductive agent, the mass ratio of positive electrode active materials are 0.1:2.9:3:94.
Embodiment 1
Method according to comparative example 1 prepares lithium rechargeable battery, and difference is：
(1) preparation of anode pole piece
At 25 DEG C, silicone compounds γ-glycidyl ether oxygen propyl trimethoxy silicane is added into N- methylpyrroles
In alkanone, 500r/min stirs；Binding agent polyvinylidene fluoride is added afterwards, and 1000r/min stirs；Add and lead
Electric agent Super-P and positive electrode active materials cobalt acid lithium, 1000~2000r/min stir, and are eventually adding crosslinking agent 1, and 3- is double-
(2- tert-butyl peroxy bases isopropyl) benzene, 300~1000r/min stir, and obtain anode sizing agent.Wherein, silicone compounds,
Binding agent, conductive agent, positive electrode active materials, the mass ratio of crosslinking agent are 0.1:2.85:3:94:0.05.
Embodiment 2
Method according to embodiment 1 prepares lithium rechargeable battery, and difference is：
(1) preparation of anode pole piece
Silicone compounds are N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane.
Crosslinking agent is triallyl isocyanurate.
Embodiment 3
Method according to embodiment 1 prepares lithium rechargeable battery, and difference is：
(1) preparation of anode pole piece
Silicone compounds are γ-aminopropyltrimethoxysilane.
Crosslinking agent is peroxidized t-butyl perbenzoate.
Embodiment 4
Method according to embodiment 1 prepares lithium rechargeable battery, and difference is：
(1) preparation of anode pole piece
Silicone compounds are γ-(methacryloxy) propyl trimethoxy silicane.
Crosslinking agent is triallyl isocyanurate.
Next the test process of explanation lithium rechargeable battery.
(1) the cohesive force test of anode pole piece
The one side of double faced adhesive tape is attached to the surface of anode pole piece, the another side of double faced adhesive tape is attached to the surface of stainless steel plate, uses
Roller compaction, double faced adhesive tape, anode pole piece and stainless steel plate is set to be bonded completely.Using high ferro puller system, by one end of stainless steel plate
The lower section fixture of high ferro puller system is fixed on, by 180 ° of bendings of anode pole piece, and end is bent and is fixed on the upper of high ferro puller system
Square fixture, then stretched with 50mm/min speed, displacement and active force in recording process, power during stress balance is
Peeling force, i.e. initial adhesive force between positive pole diaphragm and plus plate current-collecting body.
Anode pole piece is immersed in electrolyte (identical with the electrolyte in lithium rechargeable battery preparation process), is placed on
(relative humidity in dry environment<5%) soak at room temperature 24 hours, take out makes it be volatilized naturally in dry environment afterwards,
Treat that the organic solvent on anode pole piece surface is evaporated completely, the cohesive force tested between positive pole diaphragm and plus plate current-collecting body, method of testing
Ibid.
(2) the cycle performance test of lithium rechargeable battery
At 25 DEG C, the lithium rechargeable battery after encapsulation is with 0.1C constant-current charges to 4.2V, then constant-voltage charge is extremely
0.05mA, 5min is stood, afterwards with 0.1C constant-current discharges to 2.8V, be repeated 2 times said process, complete chemical conversion.
Afterwards by lithium rechargeable battery with 0.5C constant-current charges to 4.2V, then constant-voltage charge stands 5min to 0.05mA,
Afterwards with 0.5C constant-current discharges to 2.8V, this repeats 100 processes to circulate first.
The discharge capacity after capability retention (%)=100 time circulation after the circulation of lithium rechargeable battery 100 times/first
Discharge capacity after circulation.
(3) the extruding test of lithium rechargeable battery
Lithium rechargeable battery is completely filled by standard, then the maximum surface of lithium rechargeable battery is placed in parallel two
Between individual parallel plane, 17.2MPa, pressurize 1min, then release of pressure are gradually forced into, observes 1h.With it is not on fire, do not burn, not quick-fried
Fry for criterion, calculate the percent of pass of lithium rechargeable battery.
(4) the drift bolt test of lithium rechargeable battery
Lithium rechargeable battery is completely filled by standard, then by the maximum surface of lithium rechargeable battery parallel to testboard
Face is placed, and the stainless pin for being about 3mm with diameter is pierced through lithium rechargeable battery with 50mm/s speed completely, observes 1h.
With it is not on fire, do not burn, do not explode for criterion, calculate the percent of pass of lithium rechargeable battery.
The embodiment 1-4 of table 1 and comparative example 1-2 the performance test results
PVDF is only added it was found from the test result of table 1, in comparative example 1 as binding agent, the cohesive force of anode pole piece compared with
It is low, the cycle performance and security performance of lithium rechargeable battery can not be effectively improved.In comparative example 2, add on the basis of PVDF
Enter silicone compounds, the cohesive force of anode pole piece can be improved to a certain extent, improve the circulation of lithium rechargeable battery
Performance and security performance, this is due to silicone compounds molecule R-Si (OCH3)3In R and PVDF produce winding effect, silica
Si-OCH in hydride compounds3Functional group hydrolysis generation Si-OH, but the silicone compounds after general hydrolysis only have a Si-
OH bases functional group can react so as to improve cohesive force with the-OH functional groups of collection liquid surface, two other Si-OH base function
Group is in free state, therefore the improvement to the cohesive force of anode pole piece is limited.In embodiment 1-4 on the basis of PVDF, simultaneously
Silicone compounds and crosslinking agent are added, crosslinking agent is heated discharges free free radical in an oven, and the free radical that dissociates both can be with
It can also be crosslinked with PVDF crosslinkings with the Si-OH bases functional group of free state in silicone compounds, form tridimensional network, energy
The cohesive force of anode pole piece is further improved, and then greatly improves the cycle performance and security performance of lithium rechargeable battery.
Claims (10)
1. a kind of anode pole piece, including plus plate current-collecting body and the positive pole diaphragm that is arranged on plus plate current-collecting body, positive pole diaphragm bag
Include positive electrode active materials, binding agent and additive；
Characterized in that,
The additive includes：
Silicone compounds shown in formula 1 and/or formula 2；And
Crosslinking agent；
In formula 1 and formula 2,
The one kind of X in methoxyl group, ethyoxyl, methoxy ethoxy, (ethoxymethyl) epoxide；
R1Selected from the alkyl that carbon number is 1~8, and R1Can be by hydroxyl, carboxyl, cyano group, amino, epoxy radicals, carbonyl, isocyanic acid
One or more of substitutions in ester group, double bond, acyloxy, ether, amide groups；
R2Selected from the alkylidene that carbon number is 1~6, and R2Can be by hydroxyl, carboxyl, cyano group, amino, epoxy radicals, carbonyl, isocyanide
One or more of substitutions in perester radical, double bond, acyloxy, ether, amide groups, disulfide bond, four sulfide linkages.
2. anode pole piece according to claim 1, it is characterised in that
Silicone compounds shown in formula 1 are selected from MTMS, MTES, octyl group triethoxysilicane
Alkane, vinyl three (methoxyethoxy) silane, VTES, vinyltrimethoxy silane, γ-chloro propyl group
Trimethoxy silane, γ-chloropropyltriethoxandlane, γ-(methacryloxy) propyl trimethoxy silicane, chlorination
(dimethylaminoethyl methacrylate base) propyl trimethoxy silicane, γ-glycidyl ether oxygen propyl trimethoxy silicane, β-
(3,4- 7-oxa-bicyclo[4.1.0s) ethyl trimethoxy silane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyl
Double (β-the aminoethyl)-γ aminopropyltriethoxy silanes of triethoxysilane, γ-aminopropyltrimethoxysilane, N-N-,
γ-isocyanates propyl-triethoxysilicane, γ-(polyethylene amino) propyl trimethoxy silicane, maleimide
One or more in base propyl-triethoxysilicane, maleic acid amidopropyl triethoxysilane；
Silicone compounds shown in formula 2 are selected from two (γ-tri-ethoxy silylpropyl) tetrasulfides, double (triethoxysilicanes
Base propyl group) disulphide, the one or more in two (γ-trimethoxy-silylpropyl) amine.
3. anode pole piece according to claim 2, it is characterised in that
Silicone compounds shown in formula 1 are selected from γ-(methacryloxy) propyl trimethoxy silicane, N- β-(ammonia second
Base)-γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N-N- be double
One or more in (β-aminoethyl)-γ aminopropyltriethoxy silane, γ-isocyanates propyl-triethoxysilicane.
4. anode pole piece according to claim 1, it is characterised in that it is double that the crosslinking agent is selected from 2,5- dimethyl -2,5-
Double (the tert-butyl peroxide) -3- hexins of (tert-butyl peroxide) hexane, 2,5- dimethyl -2,5-, di-tert-butyl peroxide, mistake
BP, the peroxylauric acid tert-butyl ester, peroxide acetic acid butyl ester, peroxidating (2 ethyl hexanoic acid) tert-butyl ester, 2,5-
Dimethyl -2,5- double (benzoyl peroxide) hexane, 4,4 '-two (tert-butyl peroxide) n-butyl pentanoates, double (4- tert-butyl group rings
Hexyl) peroxy dicarbonate, tert-butylperoxyiso-propyl formic acid esters, TBHP, double (the tertiary fourths of peroxidating of 2,2-
Base) butane, 2,2- double (the tert-butyl peroxy cyclohexyl of 4,4- bis-) propane, α, α-bis- (tert-butyl peroxy bases) diisopropylbenzene (DIPB), peroxidating
Double (tert-butyl peroxide) hexamethylenes of diisopropylbenzene (DIPB), peroxidized t-butyl perbenzoate, 1,1-, 1,1- double (tert-butyl peroxides)-
3,3,5- trimethyl-cyclohexanes, diperoxy phthalic acid di tert butyl carbonate, t-butylcumylperoxide, 1,3- pairs-(uncle 2-
Butyl peroxy base isopropyl) benzene, the one or more in triallyl isocyanurate.
5. anode pole piece according to claim 1, it is characterised in that
The gross mass of silicone compounds shown in formula 1 and/or formula 2 for the positive pole diaphragm gross mass 0.01%~
2.0%；
The quality of the crosslinking agent is the 0.01%~0.05% of the gross mass of the positive pole diaphragm.
6. anode pole piece according to claim 1, it is characterised in that the binding agent is selected from polyvinylidene fluoride, inclined two
Viton copolymers, vinylidene-tetrafluoroethylene-propylene terpolymer, biasfluoroethylene-hexafluoropropylene-tetrafluoro
The one or more of ethylene-dien terpolymer, vinylidene-chlorotrifluoroethylene.
7. anode pole piece according to claim 1, it is characterised in that the positive pole diaphragm also includes conductive agent, described to lead
Electric agent be selected from acetylene black, Super-P, Super-S, 350G, carbon fiber, CNT, Ketjen black, KS-6, KS-15, SFG-6,
One or more in SFG-15.
8. anode pole piece according to claim 7, it is characterised in that binding agent, conductive agent, the quality of positive electrode active materials
Than for (1~3):(1~3):(92~97.99).
A kind of 9. preparation method of anode pole piece, for preparing the anode pole piece any one of claim 1-8, including step
Suddenly：
Silicone compounds shown in formula 1 and/or formula 2 are added in solvent N-methyl pyrilidone and stirred, are added afterwards
Binding agent and positive electrode active materials, stir, and are eventually adding crosslinking agent, stir, and obtain anode sizing agent；
Anode sizing agent is coated uniformly on plus plate current-collecting body, the preparation of anode pole piece is completed after drying, wherein, anode sizing agent is done
Positive pole diaphragm is formed after dry.
10. a kind of secondary cell, it is characterised in that including the anode pole piece according to any one of claim 1-8.
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| CN201610827130.1A CN107845812A (en) | 2016-09-18 | 2016-09-18 | Anode pole piece and preparation method thereof and secondary cell |
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| CN113224284A (en) * | 2021-04-26 | 2021-08-06 | 东莞市创明电池技术有限公司 | Lithium ion battery cathode and preparation method thereof, and lithium ion battery |
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| CN114551804B (en) * | 2020-11-24 | 2023-08-04 | 深圳市研一新材料有限责任公司 | Composition for forming film layer of positive electrode plate, preparation method of positive electrode plate and secondary battery |
| CN114551804A (en) * | 2020-11-24 | 2022-05-27 | 深圳市研一新材料有限责任公司 | Composition for forming positive pole piece film, positive pole piece and preparation method thereof, and secondary battery |
| CN114824258A (en) * | 2021-01-27 | 2022-07-29 | 恒大新能源技术(深圳)有限公司 | Electrode binder and preparation method thereof, battery pole piece and secondary battery |
| CN113224284A (en) * | 2021-04-26 | 2021-08-06 | 东莞市创明电池技术有限公司 | Lithium ion battery cathode and preparation method thereof, and lithium ion battery |
| CN115377371A (en) * | 2021-05-20 | 2022-11-22 | 恒大新能源技术(深圳)有限公司 | Silicon-carbon composite material, negative plate, preparation method of negative plate and lithium ion battery |
| CN113571710B (en) * | 2021-07-22 | 2022-05-31 | 中南大学 | A kind of copper current collector for lithium metal battery and its surface modification method and application |
| CN113571710A (en) * | 2021-07-22 | 2021-10-29 | 中南大学 | A kind of copper current collector for lithium metal battery and its surface modification method and application |
| US20230096965A1 (en) * | 2021-09-01 | 2023-03-30 | Enevate Corporation | Silicate and organosilicon containing additives for silicon-based li ion batteries |
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