CN107845812A - Anode pole piece and preparation method thereof and secondary cell - Google Patents

Abstract

The invention provides a positive pole piece, a preparation method thereof and a secondary battery. The positive electrode sheet includes a positive electrode collector and a positive electrode membrane arranged on the positive electrode collector. The positive electrode membrane includes positive electrode active materials, binders and additives. The additive includes: a siloxane compound represented by Formula 1 and/or Formula 2; and a crosslinking agent. The positive electrode sheet of the invention has high cohesive force and can obviously improve the cycle performance and safety performance of the secondary battery.

Description

Positive electrode sheet, preparation method thereof, and secondary battery

technical field

The invention relates to the technical field of batteries, in particular to a positive pole piece, a preparation method thereof, and a secondary battery.

Background technique

At present, with the rapid development of secondary batteries, especially lithium-ion secondary batteries, increasing the energy density of secondary batteries and improving their safety performance such as impact resistance and nail penetration have become an important direction for secondary battery research. In order to increase energy density, the main methods are to develop high energy density active materials, use thinner current collectors, increase the amount of active materials and reduce the amount of inactive materials (binders, conductive agents, etc.). In order to improve the safety performance of secondary batteries such as impact resistance and nail penetration, the main method is to improve the bonding ability of active materials, conductive agents and current collectors.

As the inactive material in the pole piece of the secondary battery, the binder is one of the important materials that must be used in the preparation of the pole piece. Its main function is to bind and maintain the active material, and enhance the interaction between the active material and the conductive agent and the interaction between the active material. The electronic contact between the active material, the conductive agent and the current collector can better stabilize the pole piece structure. Increasing the amount of active material and reducing the amount of binder will inevitably reduce the stability of the pole piece structure. Therefore, in order to ensure the stability of the pole piece structure, it is an important research direction to develop a binder with higher cohesive force.

At present, polyvinylidene fluoride (PVDF) is generally used as the positive electrode binder in the secondary battery field. PVDF is mainly a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride and other compounds. Compared with other positive electrode binders, PVDF has obvious advantages in electrochemical performance, thermal stability and chemical stability.

However, as a crystalline polymer, PVDF has a crystallinity of about 50% and a crystalline melting temperature of 150°C to 170°C. Usually, the operating temperature of secondary batteries is lower than 100°C. Therefore, the high crystallinity of PVDF makes the adhesion between it and the current collector relatively poor, and there is a risk of film removal during the long cycle process, resulting in safety hazards.

In order to reduce the crystallinity of PVDF, improve its flexibility, and improve its cohesiveness, the methods used by researchers mainly include modification of VDF homopolymer, copolymerization of VDF with the second monomer and the third monomer, VDF homopolymer and Another copolymer blending, etc., and the direct application of pole piece additives in the process of pole piece preparation, to improve the performance of the secondary battery cycle, wetting and so on.

The Japanese patent document JP1997-199112A published on July 31, 1997 discloses that the cycle performance of the battery under high voltage can be improved by adding an aluminate coupling agent during the preparation of the positive electrode sheet. The Japanese patent document JP2002-319405A published on October 31, 2002 discloses adding reactive groups such as epoxy and amino groups and wetting groups such as methoxyl groups and ethoxyl groups during the preparation of pole pieces. The coupling agent can improve the wettability of the positive pole piece and the electrolyte. Japanese patent document JP2007-242303A published on September 20, 2007 discloses that active materials are treated with silane coupling agents containing multifunctional groups, which can improve battery cycle performance. The Chinese patent document CN1277236A published on December 20, 2000 disclosed that coupling agents such as gamma-(methacryloyloxy)propyltrimethoxysilane were added during the preparation of the pole piece to improve the adhesion and durability of the pole piece. Electrolyte performance.

Contents of the invention

In view of the problems existing in the background technology, the object of the present invention is to provide a positive pole piece and its preparation method and a secondary battery, the positive pole piece has a higher adhesive force, which can significantly improve the cycle performance of the secondary battery and safety performance.

In order to achieve the above object, in one aspect of the present invention, the present invention provides a positive electrode sheet, which includes a positive electrode current collector and a positive electrode membrane disposed on the positive electrode current collector. The positive electrode membrane includes positive electrode active materials, binders and additives. The additive includes: a siloxane compound represented by Formula 1 and/or Formula 2; and a crosslinking agent. In Formula 1 and Formula 2, X is selected from methoxy (-O-CH ₃ ), ethoxy (-O-CH ₂ CH ₃ ), methoxyethoxy (-O-CH ₂ CH ₂ - O-CH ₃ ), one of ethoxymethoxy (-O-CH ₂ -O-CH ₂ CH ₃ ); R ₁ is selected from an alkyl group with 1 to 8 carbon atoms, and R ₁ can be Substituted by one or more of hydroxyl, carboxyl, cyano, amino, epoxy, carbonyl, isocyanate, double bond, acyloxy, ether, amide; R2 is selected from 1 to ₂ carbon atoms ₆ alkylene group, and R2 can be hydroxy, carboxyl, cyano, amino, epoxy, carbonyl, isocyanate, double bond, acyloxy, ether, amide, disulfide bond, tetrasulfide bond One or more substitutions.

In another aspect of the present invention, the present invention provides a method for preparing a positive electrode sheet, which is used to prepare the positive electrode sheet described in one aspect of the present invention. Add the oxane compound into the solvent N-methylpyrrolidone and stir evenly, then add the binder and the positive electrode active material, stir evenly, finally add the crosslinking agent, stir evenly, and obtain the positive electrode slurry; apply the positive electrode slurry evenly on the positive electrode On the current collector, the preparation of the positive electrode sheet is completed after drying, wherein the positive electrode membrane is formed after the positive electrode slurry is dried.

In yet another aspect of the present invention, the present invention provides a secondary battery, which includes the positive electrode sheet according to one aspect of the present invention.

Compared with the prior art, the beneficial effects of the present invention are:

The positive electrode sheet of the invention has high cohesive force and can obviously improve the cycle performance and safety performance of the secondary battery.

The preparation method of the positive electrode sheet of the present invention is simple and low in price, and is suitable for large-scale industrial production.

Detailed ways

The positive electrode sheet, its preparation method and secondary battery according to the present invention will be described in detail below.

First, the positive electrode sheet according to the first aspect of the present invention will be described.

The positive electrode sheet according to the first aspect of the present invention includes a positive electrode collector and a positive electrode membrane disposed on the positive electrode collector. The positive electrode membrane includes positive electrode active materials, binders and additives. The additive includes: a siloxane compound represented by Formula 1 and/or Formula 2; and a crosslinking agent. In Formula 1 and Formula 2, X is selected from methoxy (-O-CH ₃ ), ethoxy (-O-CH ₂ CH ₃ ), methoxyethoxy (-O-CH ₂ CH ₂ - O-CH ₃ ), one of ethoxymethoxy (-O-CH ₂ -O-CH ₂ CH ₃ ); R ₁ is selected from an alkyl group with 1 to 8 carbon atoms, and R ₁ can be Substituted by one or more of hydroxyl, carboxyl, cyano, amino, epoxy, carbonyl, isocyanate, double bond, acyloxy, ether, amide; R2 is selected from 1 to ₂ carbon atoms ₆ alkylene group, and R2 can be hydroxy, carboxyl, cyano, amino, epoxy, carbonyl, isocyanate, double bond, acyloxy, ether, amide, disulfide bond, tetrasulfide bond One or more substitutions.

In the positive electrode sheet according to the first aspect of the present invention, the siloxane compound has amphiphilicity, which can improve the wettability between the positive electrode active material, the conductive agent and the binder; on the other hand, the siloxane compound The polar group (Si-OH formed after Si-X hydrolysis) can be polymerized with binder, positive electrode active material, and polar group on the surface of the current collector to improve the adhesion of the positive electrode sheet. At the same time, the crosslinking agent can make the active functional groups in the binder crosslink each other to form a spatial network structure, further improve the cohesive force of the binder, and prevent the positive electrode sheet from being used in abnormal conditions such as long cycle or dropping, puncturing, and extrusion. It can improve the cycle performance and safety performance of the secondary battery.

In the positive electrode sheet according to the first aspect of the present invention, the siloxane compound represented by formula 1 is selected from methyltrimethoxysilane, methyltriethoxysilane, octyltriethoxysilane, ethylene Tris(methoxyethoxy)silane, Vinyltriethoxysilane, Vinyltrimethoxysilane, γ-Chloropropyltrimethoxysilane, γ-Chloropropyltriethoxysilane, γ -(methacryloyloxy)propyltrimethoxysilane, (dimethylaminoethylmethacrylate)propyltrimethoxysilane chloride, γ-glycidyloxypropyltrimethoxysilane, β -(3,4-epoxycyclohexane)ethyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-Aminopropyltrimethoxysilane, N-N-bis(β-aminoethyl)-γ-aminopropyltriethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-(polyethylene One or more of amino)propyltrimethoxysilane, maleimidopropyltriethoxysilane, and maleimidopropyltriethoxysilane. Preferably, the siloxane compound represented by formula 1 is selected from γ-(methacryloyloxy)propyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, N-β-(ammonia Ethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-N-bis(β-aminoethyl)-γ-aminopropyl One or more of propyl triethoxysilane, γ-isocyanate propyl triethoxysilane.

In the positive electrode sheet according to the first aspect of the present invention, the siloxane compound represented by formula 2 is selected from bis(γ-triethoxysilylpropyl)tetrasulfide, bis(triethoxysilane One or more of disulfide, bis(γ-trimethoxysilylpropyl)amine.

In the positive electrode sheet according to the first aspect of the present invention, the total mass of the siloxane compound represented by formula 1 and/or formula 2 is 0.01%-2.0% of the total mass of the positive electrode film.

In the positive electrode sheet according to the first aspect of the present invention, the crosslinking agent is selected from 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-di Methyl-2,5-bis(tert-butylperoxy)-3-hexyne, di-tert-butyl peroxide, benzoyl peroxide, tert-butyl peroxylaurate, tert-butyl peroxyacetate, (2-Ethylhexanoate) tert-butyl peroxide, 2,5-Dimethyl-2,5-bis(benzoyl peroxide)hexane, 4,4'-bis(tert-butyl peroxide) n-butyl valerate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, tert-butylperoxyisopropyl carbamate, tert-butyl hydroperoxide, 2,2-bis(tert-butylperoxy ) butane, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl) propane, α,α-bis(tert-butylperoxy) dicumyl, dicumyl peroxide, peroxide tert-butyl benzoate, 1,1-bis(tert-butyl peroxide)cyclohexane, 1,1-bis(tert-butyl peroxide)-3,3,5-trimethylcyclohexane, diperoxide One or more of di-tert-butyl phthalate, tert-butyl cumene peroxide, 1,3-bis-(2-tert-butylperoxyisopropyl)benzene, and triallyl isocyanurate kind.

In the positive electrode sheet according to the first aspect of the present invention, the mass of the crosslinking agent is 0.01%-0.05% of the total mass of the positive electrode film.

In the positive electrode sheet according to the first aspect of the present invention, the mass ratio of the binder to the positive electrode active material may be (1-3):(92-97.99).

In the positive electrode sheet according to the first aspect of the present invention, the binder is selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-propylene ternary One or more of copolymers, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymers, and vinylidene fluoride-chlorotrifluoroethylene copolymers.

In the positive electrode sheet according to the first aspect of the present invention, the positive electrode film may further include a conductive agent. The conductive agent is selected from one or more of acetylene black, Super-P, Super-S, 350G, carbon fiber, carbon nanotube, Ketjen black, KS-6, KS-15, SFG-6, SFG-15 kind.

In the positive electrode sheet according to the first aspect of the present invention, the mass ratio of the binder, the conductive agent, and the positive electrode active material may be (1-3):(1-3):(92-97.99).

Next, the preparation method of the positive electrode sheet according to the second aspect of the present invention is described, which is used to prepare the positive electrode sheet described in the first aspect of the present invention, including the steps of: adding the siloxane compound shown in formula 1 and/or formula 2 Stir evenly in the solvent N-methylpyrrolidone, then add the binder and the positive electrode active material, stir evenly, finally add the crosslinking agent, stir evenly, and obtain the positive electrode slurry; evenly coat the positive electrode slurry on the positive electrode current collector, After drying, the preparation of the positive pole piece is completed, wherein the positive pole membrane is formed after the positive pole slurry is dried.

In the method for preparing the positive electrode sheet according to the second aspect of the present invention, when adding the binder and the positive electrode active material, a conductive agent may also be added.

The secondary battery according to the third aspect of the present invention is described again, which includes the positive electrode sheet according to the first aspect of the present invention.

In the secondary battery according to the third aspect of the present invention, the secondary battery further includes a negative electrode sheet, a separator, and an electrolyte.

In the secondary battery according to the third aspect of the present invention, the secondary battery is a lithium ion secondary battery, a sodium ion secondary battery or a zinc ion secondary battery.

In the secondary battery according to the third aspect of the present invention, when the secondary battery is a lithium ion secondary battery, the positive electrode active material can be selected from lithium iron phosphate (LFP), lithium cobaltate (LCO) , nickel-cobalt-manganese ternary material (NCM), nickel-cobalt-lithium aluminate material (NCA) or one or more.

Below in conjunction with embodiment, further elaborate the present application. It should be understood that these examples are only used to illustrate the present application and are not intended to limit the scope of the present application. In the embodiment, only the case where the secondary battery is a lithium ion secondary battery is shown, but the present invention is not limited thereto.

Comparative example 1

(1) Preparation of positive pole piece

At 25°C, add the binder polyvinylidene fluoride into N-methylpyrrolidone, and stir at 1000r/min; then add the conductive agent Super-P and the positive electrode active material lithium cobaltate, and stir at 1000-2000r/min , to obtain positive electrode slurry. Wherein, the mass ratio of the binder, the conductive agent, and the positive electrode active material is 3:3:94.

The positive electrode slurry was uniformly coated on both surfaces of the positive electrode current collector aluminum foil (thickness 14 μm), the coating weight was 0.300g/1540.25mm ² , dried in an oven at 130°C, and cut into a size of 20 *100mm positive pole piece, spare.

(2) Preparation of negative pole piece

Mix the negative active material artificial graphite, the binder SBR emulsion, the thickener sodium carboxymethylcellulose and the conductive agent Super-P according to the mass ratio of 90:2:3:5, use deionized water as the solvent, and pass through 1000 Stir at ~2000r/min to obtain negative electrode slurry. The negative electrode slurry is evenly coated on both surfaces of the negative electrode current collector copper foil (thickness 8μm), the coating weight is 0.150g/1540.25mm ² , dried in an oven at 80°C, and cut to size after cold pressing It is a 20*100mm negative pole piece for spare.

(3) Preparation of lithium-ion secondary battery

Weld conductive lugs on the positive pole piece and the negative pole piece, and separate them with a polypropylene separator film with a thickness of 12 μm, stack them to form bare cells, and then package them with aluminum-plastic film. The electrolyte is a lithium hexafluorophosphate electrolyte containing 1M, and the solvent is a mixed solvent of ethylene carbonate, propylene carbonate, and dimethyl carbonate at a volume ratio of 1:1:1. After packaging, electrolyte solution is injected to obtain a finished lithium-ion secondary battery.

Comparative example 2

Lithium-ion secondary batteries were prepared according to the method of Comparative Example 1, the difference being:

(1) Preparation of positive pole piece

At 25°C, add the siloxane compound methyltrimethoxysilane into N-methylpyrrolidone and stir at 500r/min; then add the binder polyvinylidene fluoride and stir at 1000r/min; then add conductive The agent Super-P and the positive electrode active material lithium cobaltate are stirred evenly at 1000-2000 r/min to obtain the positive electrode slurry. Wherein, the mass ratio of the siloxane compound, the binder, the conductive agent, and the positive electrode active material is 0.1:2.9:3:94.

Example 1

Lithium-ion secondary batteries were prepared according to the method of Comparative Example 1, the difference being:

(1) Preparation of positive pole piece

At 25°C, add the siloxane compound γ-glycidyl etheroxypropyl trimethoxysilane into N-methylpyrrolidone, stir evenly at 500r/min; then add the binder polyvinylidene fluoride, 1000r/min Stir evenly; then add the conductive agent Super-P and the positive electrode active material lithium cobaltate, stir evenly at 1000-2000r/min, and finally add the crosslinking agent 1,3-bis-(2-tert-butylperoxyisopropyl)benzene , 300-1000r/min stirring evenly to obtain positive electrode slurry. Wherein, the mass ratio of the siloxane compound, the binder, the conductive agent, the positive electrode active material, and the crosslinking agent is 0.1:2.85:3:94:0.05.

Example 2

Lithium-ion secondary batteries were prepared according to the method of Example 1, the difference being:

(1) Preparation of positive pole piece

The silicone compound is N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.

The crosslinking agent is triallyl isocyanurate.

Example 3

Lithium-ion secondary batteries were prepared according to the method of Example 1, the difference being:

(1) Preparation of positive pole piece

The silicone compound is γ-aminopropyltrimethoxysilane.

The crosslinking agent is tert-butyl peroxybenzoate.

Example 4

Lithium-ion secondary batteries were prepared according to the method of Example 1, the difference being:

(1) Preparation of positive pole piece

The silicone compound was γ-(methacryloxy)propyltrimethoxysilane.

The crosslinking agent is triallyl isocyanurate.

Next, a test procedure of the lithium ion secondary battery will be described.

(1) Adhesion test of the positive pole piece

Stick one side of the double-sided tape on the surface of the positive pole piece, stick the other side of the double-sided tape on the surface of the stainless steel plate, and compact it with a pressure roller so that the double-sided tape, the positive pole piece and the stainless steel plate are completely bonded. Using a high-speed rail tensile machine, fix one end of the stainless steel plate to the lower fixture of the high-speed rail tensile machine, bend the positive pole piece 180°, and fix the bent end to the upper fixture of the high-speed rail tensile machine, and then pull at a speed of 50mm/min Stretching, the displacement and force during the recording process, the force at the balance of the force is the peeling force, that is, the initial bonding force between the positive electrode diaphragm and the positive electrode current collector.

Soak the positive electrode sheet in the electrolyte (the same as the electrolyte in the lithium-ion secondary battery preparation process), place it in a dry environment (relative humidity<5%) and soak it at room temperature for 24 hours, then take it out and let it dry Naturally volatilize in the environment. After the organic solvent on the surface of the positive electrode plate has evaporated, test the adhesion between the positive electrode diaphragm and the positive electrode current collector. The test method is the same as above.

(2) Cycle performance test of lithium-ion secondary battery

At 25°C, the packaged lithium-ion secondary battery is charged to 4.2V at a constant current of 0.1C, then charged at a constant voltage to 0.05mA, left to stand for 5min, and then discharged to 2.8V at a constant current of 0.1C, repeating the above two times The process is completed.

Then charge the lithium-ion secondary battery with a constant current of 0.5C to 4.2V, then charge it with a constant voltage to 0.05mA, let it stand for 5 minutes, and then discharge it with a constant current of 0.5C to 2.8V. This is the first cycle, and the process is repeated 100 times .

Capacity retention rate (%) of the lithium-ion secondary battery after 100 cycles=discharge capacity after 100 cycles/discharge capacity after the first cycle.

(3) Squeeze test of lithium-ion secondary battery

Fully charge the lithium-ion secondary battery according to the standard, then place the largest surface of the lithium-ion secondary battery in parallel between two parallel planes, gradually pressurize to 17.2MPa, keep the pressure for 1min, release the pressure, and observe for 1h. The pass rate of lithium-ion secondary batteries is calculated by taking no fire, no combustion, and no explosion as the judging criteria.

(4) Nail penetration test of lithium-ion secondary battery

Fully charge the lithium-ion secondary battery according to the standard, then place the largest surface of the lithium-ion secondary battery parallel to the test table, and use a stainless steel needle with a diameter of about 3mm to completely pierce the lithium-ion secondary battery at a speed of 50mm/s , observe for 1h. The pass rate of lithium-ion secondary batteries is calculated by taking no fire, no combustion, and no explosion as the judging criteria.

The performance test result of table 1 embodiment 1-4 and comparative example 1-2

From the test results in Table 1, it can be seen that only PVDF was added as a binder in Comparative Example 1, and the binding force of the positive electrode sheet was low, which could not effectively improve the cycle performance and safety performance of the lithium-ion secondary battery. In Comparative Example 2, adding siloxane compounds on the basis of PVDF can improve the adhesion of the positive electrode sheet to a certain extent, and improve the cycle performance and safety performance of lithium-ion secondary batteries. This is because the siloxane compounds The R in the molecule R-Si(OCH ₃ ) ₃ has an intertwining effect with PVDF, and the Si-OCH ₃ functional group in the siloxane compound is hydrolyzed to generate Si-OH, but generally the hydrolyzed siloxane compound has only one Si-OH group The functional group can react with the -OH functional group on the surface of the current collector to improve the binding force, and the other two Si-OH functional groups are in a free state, so the improvement of the binding force of the positive electrode sheet is limited. In Example 1-4, on the basis of PVDF, siloxane compound and cross-linking agent are added at the same time, and the cross-linking agent releases free radicals when heated in an oven. Free radicals can be cross-linked with PVDF or with silicone The free Si-OH group functional groups in the alkane compound are cross-linked to form a three-dimensional network structure, which can further improve the adhesion of the positive electrode sheet, thereby greatly improving the cycle performance and safety performance of the lithium-ion secondary 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.