CN113410468A - Negative electrode binder and preparation method thereof, preparation method of negative electrode sheet and lithium ion battery - Google Patents
Negative electrode binder and preparation method thereof, preparation method of negative electrode sheet and lithium ion battery Download PDFInfo
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- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a negative electrode binder and a preparation method thereof, a preparation method of a negative electrode sheet and a lithium ion battery. The cathode binder is organic-inorganic composite emulsion with a core-shell structure, and comprises an organic core and an inorganic shell, wherein the inorganic shell is coated outside the organic core, the organic core is styrene-butadiene copolymer emulsion, the inorganic shell is a mixture of modified hydrous oxide sol and a small amount of organic matters, and the modified hydrous oxide sol is one or more of silica sol, aluminum sol, titanium sol and zirconium sol. The invention can improve the quick charge performance of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a negative electrode binder and a preparation method thereof, a preparation method of a negative electrode sheet and a lithium ion battery.
Background
With the popularization and application of digital products and electric vehicles, lithium ion batteries are rapidly developed. Nowadays, in order to meet the demand of future electromotion, especially the further development of the mobile phone and electric automobile industries, the performance improvement of the lithium ion battery also faces a huge challenge. At present, the market has higher and higher requirements for improving the energy density of the lithium ion battery, and the functional requirement for quick charging is more and more important.
The lithium ion battery is formed by winding or overlapping basic unit structures, wherein the basic unit structures are a positive electrode/a diaphragm/a negative electrode. The positive electrode and the negative electrode are places where electrochemical reaction occurs, and current generated by the electrochemical reaction is collected and led out through current collectors in the positive electrode and the negative electrode; the diaphragm is responsible for separating positive pole and negative pole, avoids positive negative pole to take place to contact and appears the short circuit.
The binder is an inactive component in the electrode plate of the lithium ion battery and is one of important materials for preparing the electrode plate of the lithium ion battery. The binder serves to connect the electrode active material, the conductive agent, and the electrode current collector with overall connectivity therebetween. In the process of charging and discharging, the binder effectively maintains the structural integrity of the electrode and ensures that the electrode material can repeatedly insert and remove lithium, so the binder is a crucial factor for the normal operation of the lithium ion battery and has an important effect on improving the cycle performance of the silicon-based negative electrode material. Common binders include PAA (polyacrylic acid), CMC/SBR (sodium carboxymethylcellulose/styrene butadiene rubber), sodium alginate, chitosan and the like, wherein the SBR-type binder is widely applied to carbon-based graphite and low-silicon/graphite composite negative electrode systems due to small addition amount in the system and strong binding force between the SBR-type binder and active substances and a current collector. However, the components of the SBR binder are low-polarity components, and have poor affinity with a strongly polar electrolyte, and a lithium ion battery using the SBR binder as a negative electrode binder has poor dynamic performance, and cannot achieve satisfactory rapid charging performance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: in order to solve the technical problem that the affinity of an SBR binder and an electrolyte is poor in the prior art, so that a lithium ion battery cannot achieve good quick charge performance, the invention provides a negative electrode binder, a preparation method of a negative plate and the lithium ion battery.
The technical scheme adopted by the invention for solving the technical problems is as follows: the negative electrode binder is organic-inorganic composite emulsion with a core-shell structure, and comprises an organic core and an inorganic shell, wherein the inorganic shell is coated outside the organic core, the organic core is styrene-butadiene copolymer emulsion, the inorganic shell is a mixture of modified hydrous oxide sol and a small amount of organic matters, and the modified hydrous oxide sol is one or more of silica sol, alumina sol, titanium sol and zirconium sol.
According to the cathode binder, the shell mainly comprising the modified hydrated oxide sol (inorganic matter) is combined with the core mainly comprising the butylbenzene copolymer emulsion (organic matter), so that the surface of the cathode binder has more polar groups, the affinity of the cathode binder and an electrolyte is better, and the cathode binder has strong liquid absorption capacity; the cathode binder disclosed by the invention has good conductivity, can bear more lithium ions, and is beneficial to the round-trip transmission of the lithium ions between the anode and the cathode, so that the lithium ion battery has better quick charge performance.
Furthermore, the particle size range of the negative electrode binder is 100-1000nm, the particle size distribution is that PDI is less than or equal to 0.5, and the viscosity range of the negative electrode binder is 10-1000 mPa.s.
Further, the mass of the modified hydrous oxide sol in the inorganic shell accounts for 5-20% of the total mass of the anode binder. The inorganic shell mainly comprising the modified hydrated oxide sol can completely coat the surface of the organic core, or only coat part of the surface of the organic core, and a small amount of organic matters in the inorganic shell can ensure that the inorganic shell and the organic core have better interface compatibility.
A preparation method of the negative electrode binder comprises the following steps: s1: the monomer A consists of butadiene, styrene and functional monomers, and the mass ratio of the butadiene to the styrene is 1: 10-1: 1, the functional monomer accounts for 0-20% of the mass of the monomer A, the initiator with the amount of 0.01-1% of the mass of the monomer A, the emulsifier with the amount of 0.05-3.5% of the mass of the monomer A and the monomer A are added into deionized water together and stirred for free radical copolymerization reaction, the polymerization reaction temperature is 40-90 ℃, the polymerization reaction pressure is 0.3-1.2 MPa, and the polymerization reaction time is 2-12 hours, so that the butylbenzene copolymer emulsion is obtained, and the material for preparing the organic core is obtained. S2: reacting the hydrated oxide sol with a silane coupling agent, wherein the dosage of the silane coupling agent is 1-15% of the solid mass of the hydrated oxide sol, the reaction temperature is 40-80 ℃, and the reaction time is 4-12 hours, so as to obtain the modified hydrated oxide sol. S3: butadiene and styrene are used for forming a monomer B, and the mass ratio of the butadiene to the styrene is 1: 10-1: 2, adding an initiator in an amount of 0.01-1% by mass of the monomer B, an emulsifier in an amount of 0.05-3.5% by mass of the monomer B, the monomer B and the modified hydrated oxide sol into deionized water, and stirring to obtain a pre-emulsion C; and S4, adding the pre-emulsion C into the butylbenzene copolymerized emulsion obtained in the step S1, and continuously stirring and reacting for 2-12 hours at 40-90 ℃ to obtain an organic-inorganic composite emulsion with a core-shell structure, namely a cathode binder.
According to the preparation method of the cathode binder, the hydrated oxide sol is modified by using the silane coupling agent, and organic groups can be introduced on the surface of the hydrated oxide sol through covalent bonds, so that the hydrated oxide sol can be emulsified to obtain the modified hydrated oxide sol, the modified hydrated oxide sol has better compatibility with the monomer B, the emulsifier and the styrene-butadiene copolymer emulsion, and free independent nucleation cannot occur, so that the free radical copolymerization is coated on the styrene-butadiene copolymer emulsion to form the cathode binder with a core-shell structure.
Further, the ratio of the sum of the masses of the monomer a and the monomer B to the mass of the modified hydrous oxide sol was 19: 1-4: 1; the ratio of the mass of the modified hydrous oxide sol to the mass of the monomer B was 15: 1-5: 1.
further, the modified hydrous oxide sol is in a sodium type, and the particle size range of the modified hydrous oxide sol is 10-200 nm.
Further, the initiator is one or more of ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, azobisisobutyrimidazoline hydrochloride and azobisisopropylimidazoline hydrochloride.
Further, the functional monomer is acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and C-methacrylic acid8～C16One or more of alkyl esters.
Further, the emulsifier is one or more of alkyl sulfate, alkylphenol polyoxyethylene, disproportionated potassium rosinate and sorbitan fatty acid ester.
Further, the molecular formula of the silane coupling agent is Y- (CH)2)k-Si(OR)3Wherein k is more than or equal to 0 and less than or equal to 4, Y is one or more of vinyl, amino, epoxy, methacryloxy, mercapto and ureido, and R is one or more of chloro, methyl, ethyl and acetyl. Y is an organic functional group, the lipophilicity of the organic functional group Y is better, the acting force between the organic functional group Y and the monomer B, the emulsifier and the butylbenzene copolymerized emulsion is stronger, and the group OR can be combined with the monomer B, the emulsifier and the butylbenzene copolymerized emulsionThe hydroxyl groups on the surface of the modified hydrous oxide sol material are bonded. The hydrated oxide sol modified by the silane coupling agent can be coated on the surface of the organic core butylbenzene copolymer emulsion under the action of the monomer B and the emulsifier to form the cathode binder.
A method for preparing a negative electrode sheet using the negative electrode binder, comprising the steps of: t1: mixing a negative electrode active material, a conductive agent, a dispersing agent and a negative electrode binder to obtain a mixture M, and gradually adding the mixture M into deionized water for grinding to obtain uniformly mixed colloidal negative electrode slurry; t2: and after the solid content of the negative electrode slurry is adjusted to 50%, uniformly coating the negative electrode slurry on the surface of a current collector, and then drying and compacting to obtain the negative electrode piece.
According to the preparation method of the negative plate, because the surface of the negative binder is provided with a large number of polar groups (hydroxyl groups), in the baking process, moisture in the negative binder volatilizes, and the hydroxyl groups can be condensed to remove water molecules to form covalent bonds, so that hydrated oxides are formed to be adhered to the negative active material and the current collector, the negative active material and the negative active material can be adhered together, the negative active material and the current collector are adhered together, and then the negative plate is obtained through compaction treatment. The inner core in the negative electrode binder can bring better flexibility to the negative electrode plate, and is convenient to process; meanwhile, the specific surface area of the negative plate can be increased by using the negative adhesive, and the negative adhesive has good affinity with electrolyte, so that the negative plate has good electrolyte wettability and liquid retention property, and is beneficial to the shuttle of lithium ions between the positive and negative electrodes, and the lithium ion battery has good quick charge performance.
Further, the mass ratio of the negative electrode active material, the conductive agent, the dispersant and the negative electrode binder is m1：m2：m3：m4Wherein m is1Is 90 to 97 m20.1 to 2.0, m30.5 to 2.0, m40.5 to 3, and m1+m2+m3+m4=100。
Further, the negative active material is one or more of natural graphite, artificial graphite, hard carbon, soft carbon, mesophase microspheres, silicon material, silicon monoxide and silicon carbon; the conductive agent is one or more of graphite, carbon black, acetylene black, graphene and carbon nano tubes; the dispersing agent is one or more of sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, sodium polyacrylate and lithium polyacrylate. The dispersant is capable of dispersing solid particles in a liquid. The conductive agent in the negative electrode slurry needs to be uniformly distributed among the negative electrode active material particles, so that uniform conductive networks can be formed among the negative electrode active materials and between the negative electrode active materials and the current collector, the effect of collecting micro-current is achieved, the contact resistance is reduced, and the moving speed of electrons is improved.
A lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the negative plate comprises the negative binder. The lithium ion battery has good quick charging performance.
The cathode binder has the beneficial effects that the cathode binder has more polar groups on the surface through the combination of the inorganic shell mainly comprising the modified hydrous oxide sol (inorganic matter) and the butylbenzene copolymer emulsion (organic matter), so that the affinity of the cathode binder and the electrolyte is better; the cathode binder disclosed by the invention has good conductivity, so that the cathode binder has strong liquid absorption capacity, can bear more lithium ions, and is beneficial to the reciprocating transmission of the lithium ions between the anode and the cathode, and the lithium ion battery has better quick charge performance. According to the preparation method of the negative plate, because the surface of the negative binder is provided with a large number of polar groups (hydroxyl groups), in the baking process, moisture in the negative binder volatilizes, and the hydroxyl groups can be condensed to remove water molecules to form covalent bonds, so that hydrated oxides are formed to be adhered to the negative active material and the current collector, the negative active material and the negative active material can be adhered together, the negative active material and the current collector are adhered together, and then the negative plate is obtained through compaction treatment. The organic core in the negative electrode binder can bring better flexibility to the negative electrode plate, and is convenient to process; meanwhile, the specific surface area of the negative plate can be increased by using the negative adhesive, and the negative adhesive has good affinity with electrolyte, so that the negative plate has good electrolyte wettability and liquid retention property, and is beneficial to the shuttle of lithium ions between the positive and negative electrodes, and the lithium ion battery has good quick charge performance.
Drawings
The invention is further illustrated with reference to the following figures and examples.
Fig. 1 is a schematic view of the structure of the anode binder of the present invention.
Fig. 2 is a flow chart of a method of preparing the anode binder of the present invention.
Fig. 3 is a flowchart of a method for manufacturing a negative electrode sheet according to the present invention.
Fig. 4 is a schematic structural view of the negative electrode sheet of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to the accompanying drawings. These drawings are simplified schematic views illustrating only the basic structure of the present invention in a schematic manner, and thus show only the constitution related to the present invention.
As shown in fig. 1, a negative electrode binder is an organic-inorganic composite emulsion having a core-shell structure, which includes an organic core 1 and an inorganic shell 2, the inorganic shell 2 is coated outside the organic core 1, the organic core 1 is a styrene-butadiene copolymer emulsion, the inorganic shell 2 is a mixture of a modified hydrous oxide sol and a small amount of organic matter, and the modified hydrous oxide sol is one or more of silica sol, aluminum sol, titanium sol and zirconium sol. The modified hydrous oxide sol has the formula M (M)xOy)·nH2And O, wherein M is one or more of silicon, aluminum, titanium and zirconium metals, y/x is less than or equal to 2, M represents the content of metal oxides, and n represents the content of water.
The particle size range of the negative electrode binder is 100-1000nm, the particle size distribution is that PDI is less than or equal to 0.5, and the viscosity range of the negative electrode binder is 10-1000mPa. The mass of the modified hydrous oxide sol in the inorganic shell accounts for 5-20% of the total mass of the negative electrode binder. Therefore, the negative electrode binder can provide strong binding power to keep the structural integrity of the negative electrode plate and ensure the normal operation of the cycle charge and discharge of the lithium ion battery.
As shown in fig. 2, the method for preparing the anode binder includes the steps of:
s1, using butadiene, styrene and functional monomer to form monomer A, wherein the mass ratio of butadiene to styrene is 1: 10-1: the method comprises the following steps of 1, enabling a functional monomer to account for 0-20% of the mass of a monomer A, adding an initiator with the amount of 0.01-1% of the mass of the monomer A, an emulsifier with the amount of 0.05-3.5% of the mass of the monomer A and the monomer A into deionized water together, stirring, and carrying out free radical copolymerization reaction, wherein the polymerization reaction temperature is 40-90 ℃, the polymerization reaction pressure is 0.3-1.2 MPa, and the polymerization reaction time is 2-12 hours, so that a butylbenzene copolymerization emulsion is obtained, and the material for preparing the organic core is obtained.
S2: reacting the hydrated oxide sol with a silane coupling agent, wherein the dosage of the silane coupling agent is 1-15% of the solid mass of the hydrated oxide sol, the reaction temperature is 40-80 ℃, and the reaction time is 4-12 hours, so as to obtain the modified hydrated oxide sol.
S3: butadiene and styrene are used for forming a monomer B, and the mass ratio of the butadiene to the styrene is 1: 10-1: and 2, adding an initiator in an amount of 0.01-1% by mass of the monomer B, an emulsifier in an amount of 0.05-3.5% by mass of the monomer B, the monomer B and the modified hydrated oxide sol into deionized water, and stirring to obtain a pre-emulsion C.
S4: and (4) adding the pre-emulsion C into the styrene-butadiene copolymer emulsion obtained in the step S1, and continuously stirring and reacting for 2-12 hours at 40-90 ℃ to obtain the organic-inorganic composite emulsion with the core-shell structure, namely the cathode binder.
The ratio of the sum of the masses of the monomer a and the monomer B to the mass of the modified hydrous oxide sol is preferably 19: 1-4: 1, so that the organic component and the inorganic component in the negative electrode binder reach a proper state, the negative electrode binder has certain flexibility and is convenient to process, and meanwhile, the negative electrode binder can be soaked in more electrolyte. The ratio of the mass of the modified hydrous oxide sol to the mass of the monomer B is preferably 15: 1-5: 1, the monomer B with too much mass can reduce the content of inorganic matters in a shell layer, and cannot improve the wettability; the content of the monomer B is too low, the content of inorganic matters in a shell layer is too high, the interface compatibility is poor, and free inorganic sol which is not coated in a core layer easily exists.
The amount of the silane coupling agent is 1-15% of the solid mass of the hydrous oxide sol, so that the hydrous oxide sol can be pre-emulsified with the monomer B, and the shell is coated outside the core. The modified hydrated oxide sol is one or more of silica sol, aluminum sol, titanium sol and zirconium sol, and the modified hydrated oxide sol is sodium type with the particle size range of 10-200 nm. The molecular formula of the silane coupling agent is Y- (CH)2)k-Si(OR)3Wherein k is more than or equal to 0 and less than or equal to 4, Y is one or more of vinyl, amino, epoxy, methacryloxy, sulfydryl and carbamido, and R is one or more of chloro, methyl, ethyl and acetyl.
In this example, the initiator is one or more of ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, azobisisobutyrimidazoline hydrochloride, and azobisisopropylimidazoline hydrochloride. The functional monomer is acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and C-methacrylic acid8～C16One or more of alkyl esters. The emulsifier is one or more of alkyl sulfate, alkylphenol polyoxyethylene, disproportionated potassium rosinate and sorbitan fatty acid ester.
As shown in fig. 3, a method for preparing a negative electrode sheet using the above negative electrode binder includes the steps of:
t1: mixing the negative electrode active material, the conductive agent, the dispersing agent and the negative electrode binder to obtain a mixture M, and gradually adding the mixture M into deionized water for grinding to obtain uniformly mixed negative electrode slurry. T2: after the solid content of the negative electrode slurry is adjusted to 50%, the negative electrode slurry is uniformly coated on the surface of the current collector, and then drying and compacting treatment are carried out to obtain the negative electrode piece.
The mass ratio of the negative electrode active material, the conductive agent, the dispersant, and the negative electrode binder is m1：m2：m3：m4Wherein m is1Is 90 to 97 m20.1 to 2.0, m30.5 to 2.0, m40.5 to 3, and m1+m2+m3+m4= 100. The negative active material is one or more of natural graphite, artificial graphite, hard carbon, soft carbon, mesophase microspheres, silicon material, silicon monoxide and silicon carbon; the conductive agent is one or more of graphite, carbon black, acetylene black, graphene and carbon nano tubes; the dispersant is one or more of sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, sodium polyacrylate and lithium polyacrylate.
A lithium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the negative plate comprises the negative binder. The positive active material in the positive plate can be one or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium-rich manganese-based materials, lithium nickel cobalt aluminate and lithium titanate.
Example 1
Preparing a negative electrode binder:
70 parts by mass of styrene, 29 parts by mass of butadiene, 1 part by mass of acrylic acid (functional monomer A), 100 parts by mass of deionized water, 1.5 parts by mass of disproportionated potassium rosinate (emulsifier) and 0.5 part by mass of ammonium persulfate (initiator) are added into a stainless steel high-pressure resistant reaction kettle U1 with stirring, after uniform stirring, free radical copolymerization reaction is carried out, the polymerization reaction temperature is 80 ℃, the polymerization reaction pressure is controlled to be less than or equal to 0.6MPa, the polymerization reaction time is 8 hours, and after 8 hours, the reaction is stopped by cooling to obtain butylbenzene copolymer emulsion, namely the material for preparing the organic core 1 is obtained.
10 parts by mass (calculated according to solid) of silica sol (the particle diameter is D50: 30 nm, the solid content is 20%) and 0.5 part by mass of gamma-glycidoxypropyltrimethoxysilane (KH 560, a silane coupling agent) are added into a stainless steel high-pressure resistant reaction kettle U2 with a stirrer, and after uniform stirring, the mixture reacts for 6 hours at 60 ℃ to obtain the modified silica sol.
1.4 parts by mass of styrene, 0.6 part by mass of butadiene, 0.03 part by mass of potassium disproportionated rosin acid (emulsifier), 0.01 part by mass of ammonium persulfate (initiator) and deionized water are continuously added into the reaction kettle U2, and the obtained modified silica sol is uniformly stirred at a high speed to obtain a pre-emulsion.
Stirring a reaction kettle U1, heating to 80 ℃, gradually adding the pre-emulsion obtained from the reaction kettle U2 into a reaction kettle U1 (styrene-butadiene copolymer emulsion exists in the reaction kettle U1), continuously stirring for 2 hours, cooling the reaction kettle U1 to stop reaction, and obtaining the organic-inorganic composite emulsion with the core-shell structure, namely the cathode binder.
Preparing a pole piece and a lithium ion battery:
97 parts by mass of NCM811 (with a gram volume of 191 mAh/g) active substance, 0.8 part by weight of conductive agent (SP) and 1.2 parts by weight of polyvinylidene fluoride are mixed to obtain a mixture P, N-methyl pyrrolidone (NMP) is gradually added into the mixture P for high-speed grinding to obtain anode slurry, the solid content of the anode slurry is adjusted to be 50%, then the anode slurry is evenly coated on an aluminum foil on two sides, after drying and compaction, an anode sheet is obtained, and the surface density of the anode sheet is set to be 330g/m2Compacted density of 3.5g/cm3。
Mixing 96 parts by mass of artificial graphite (with a gram volume of 350 mAh/g) active substance, 1.0 part by mass of conductive agent (SP), 1.2 parts by mass of CMC (sodium carboxymethylcellulose) and 1.8 parts by mass of negative pole binder to obtain a mixture M, gradually adding the mixture M into deionized water for high-speed grinding to obtain uniformly-mixed colloidal negative pole slurry, adjusting the solid content of the negative pole slurry to be 50%, uniformly coating the negative pole slurry on a copper foil on two sides, drying and compacting to obtain a negative pole piece, wherein the surface density of the negative pole piece is set to be 200 g/M2Compacted density 1.65 g/cm3。
And (3) carrying out vacuum drying on the obtained positive and negative pole pieces at the temperature of 100 +/-5 ℃ for 24 hours, and then cutting, laminating, packaging, injecting liquid, forming and fixing the volume to obtain the soft package battery. The diaphragm is a single-sided ceramic PE film (basal film 9 μm, Al)2O3Ceramic layer 3 μ M), the electrolyte was prepared by mixing 1.2M LiPF 6/Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) in a volume ratio of EC to Ethyl Methyl Carbonate (EMC) to diethyl carbonate (DEC): EMC: DEC = 45: 10: 45.
and finally, sequentially manufacturing the positive plate, the negative plate and the diaphragm into a battery cell, sealing the battery cell by using an aluminum type film or an aluminum shell, reserving a liquid injection port for injecting electrolyte, and preparing the lithium ion battery by processes of formation, capacity and the like.
Example 2: the difference from example 1 is that the added hydrous oxide sol is an aluminum sol.
Example 3: the difference from example 1 is that the hydrous oxide sol added was a titanium sol.
Example 4: the difference from example 1 is that the hydrous oxide sol added was a zirconium sol.
Example 5: except for example 1, 50 parts by mass of butadiene, 50 parts by mass of styrene and 0 part of a functional monomer were added.
Example 6: the difference from example 1 is that the silane coupling agent added is gamma-methacryloxypropyltrimethoxysilane.
Example 7: the difference from example 1 is that the silane coupling agent added is gamma-aminopropyltriethoxysilane.
Example 8: the difference from example 1 is that the silane coupling agent added is vinyltriethoxysilane.
Example 9: the difference from example 1 is that 20 parts by mass of silica sol was added.
Example 10: the difference from example 1 is that 20 parts by mass of butadiene, 60 parts by mass of styrene and 20 parts by mass of acrylonitrile (functional monomer) were added.
Comparative example 1: the difference from example 1 is that the anode binder used was ordinary SBR (JSR 104A, japan).
The specific surface area test of the negative electrode sheet, the conductivity test of the negative electrode binder and the performance test of the lithium ion battery are respectively carried out on the examples 1 to 10 and the comparative example 1.
And testing the specific surface area of the negative plate: and putting the prepared negative plate into a vacuum drying oven, and vacuum-baking for 24 hours at-0.1 MPa and 80 ℃. Then, the negative electrode sheet was taken out, and about 0.6g of the negative electrode sheet was cut by a blade and placed in a specific surface area tester (antopa QDS SI-MP), vacuum degassed at 80 ℃ for 5 hours, and then the porous specific surface area of the negative electrode sheet was tested by a nitrogen adsorption method. The larger the specific surface area is, the more the hole structures in the negative plate are, which is beneficial to the infiltration and liquid retention of the negative plate on the electrolyte.
And (3) testing the conductivity of the negative electrode binder: firstly, preparing a negative electrode binder into a compact adhesive film, and drying the adhesive film for 24 hours in vacuum at 100 ℃. Then, a 2032-type button cell is assembled into a blocking cell according to the sequence of the negative electrode shell, the steel sheet, the compact adhesive film, the steel sheet, the elastic sheet and the positive electrode shell, the conductivity of the adhesive film is tested at room temperature by adopting an alternating current impedance method, the frequency is set to be 0.1-105 Hz, and the amplitude is 5 Mv. The conductivity of the adhesive film is Be = L/(Rct A), A is the area of the adhesive film, L is the film thickness, and Rct is the AC impedance.
And (3) testing the performance of the lithium ion battery: (1) battery internal resistance: when the battery core is charged to 50% SOC (SOC means charge state), the internal resistance of the battery is detected by a 1kHz voltage internal resistance tester. The higher the internal resistance, the worse the double charge performance. (2) Multiplying power charging: discharging the battery cell to 3.0V at a constant current of 0.2C at 25 +/-5 ℃, standing for 10 min, and then charging to 4.35V at a constant current of 2C; then changing constant voltage charging until the charging current is less than or equal to 0.02C; the capacity of the constant-current charging stage is C1, and the capacity of the constant-voltage charging stage is C2, so that the constant-current charging ratio is C1/(C1+ C2). The higher the constant current charge ratio, the better the quick charge performance.
Examples 1-10 and comparative example 1 the test data obtained using the test methods described above are shown in table one.
According to the table one, the following can be obtained:
the specific surface areas of the negative electrode sheets of examples 1 to 10 were all larger than that of the negative electrode sheet of comparative example 1, as compared with comparative example 1. The internal resistance of the cells of examples 1-10 was less than that of comparative example 1. The negative electrode binders of examples 1 to 10 all had higher electrical conductivities than the negative electrode binder of comparative example 1. The lithium ion batteries of examples 1 to 10 have higher constant current charge ratios than the lithium ion battery of comparative example 1, the constant current charge ratio can be increased by at least 17.5%, and the lithium ion battery has better quick charge performance.
In summary, the negative electrode binder of the present invention is an organic-inorganic composite emulsion having a core-shell structure, the inorganic shell 2 mainly containing an inorganic substance is coated on the surface of the organic core 1, and the surface of the inorganic shell 2 has a large number of polar groups (hydroxyl groups), such that the negative electrode binder has a better affinity with a strongly polar electrolyte, and the liquid absorption capability of the negative electrode binder can be improved. During the baking process of the negative plate, moisture in the negative binder volatilizes, hydroxyl groups can be condensed to remove water molecules to form covalent bonds, so that hydrated oxides are formed, the hydrated oxides can be adhered to the surfaces of the negative active material and the current collector, and the negative active material and the current collector are adhered together. The organic core 1 can provide good flexibility for the negative plate, and is convenient to process; the inorganic shell 2 enables the negative plate to have a larger specific surface area, and the conductivity of the negative electrode binder is higher. The large specific surface area can enable more electrolyte to be soaked, the high conductivity can improve the liquid absorption capacity of the negative electrode binder, the negative electrode binder can bear more lithium ion number, and the transmission of lithium ions is facilitated. Compared with the common SBR adhesive, the negative electrode adhesive has better affinity with a strong-polarity electrolyte and higher conductivity, and the negative electrode sheet has larger specific surface area, so that the negative electrode sheet has better electrolyte wettability and liquid retention, and is more favorable for the transmission of a lithium ion battery between a positive electrode and a negative electrode, and the lithium ion battery has good rapid charging performance.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the contents of the specification, and must be determined by the scope of the claims.
Claims (14)
1. The negative electrode binder is characterized in that the negative electrode binder is organic-inorganic composite emulsion with a core-shell structure, and comprises an organic core and an inorganic shell, wherein the inorganic shell is coated outside the organic core, the organic core is styrene-butadiene copolymer emulsion, the inorganic shell is a mixture of modified hydrated oxide sol and a small amount of organic matters, and the modified hydrated oxide sol is one or more of silica sol, aluminum sol, titanium sol and zirconium sol.
2. The negative electrode binder as claimed in claim 1, wherein the negative electrode binder has a particle size in the range of 100-1000nm, a particle size distribution of PDI ≤ 0.5, and a viscosity in the range of 10-1000 mpa-s.
3. The negative electrode binder according to claim 1, wherein the mass of the modified hydrous oxide sol in the inorganic casing accounts for 5% to 20% of the total mass of the negative electrode binder.
4. A method for preparing the negative electrode binder as claimed in any one of claims 1 to 3, comprising the steps of:
s1, using butadiene, styrene and functional monomer to form monomer A, wherein the mass ratio of butadiene to styrene is 1: 10-1: 1, the functional monomer accounts for 0-20% of the mass of the monomer A, an initiator with the amount of 0.01-1% of the mass of the monomer A, an emulsifier with the amount of 0.05-3.5% of the mass of the monomer A and the monomer A are added into deionized water together and stirred for free radical copolymerization reaction, the polymerization reaction temperature is 40-90 ℃, the polymerization reaction pressure is 0.3-1.2 MPa, and the polymerization reaction time is 2-12 hours, so that a butylbenzene copolymer emulsion is obtained, namely the material for preparing the organic core is obtained;
s2: reacting the hydrated oxide sol with a silane coupling agent, wherein the dosage of the silane coupling agent is 1-15% of the solid mass of the hydrated oxide sol, the reaction temperature is 40-80 ℃, and the reaction time is 4-12 hours, so as to obtain modified hydrated oxide sol;
s3: butadiene and styrene are used for forming a monomer B, and the mass ratio of the butadiene to the styrene is 1: 10-1: 2, adding an initiator in an amount of 0.01-1% by mass of the monomer B, an emulsifier in an amount of 0.05-3.5% by mass of the monomer B, the monomer B and the modified hydrated oxide sol into deionized water, and stirring to obtain a pre-emulsion C;
s4: and (3) adding the pre-emulsion C into the styrene-butadiene copolymer emulsion obtained in the step S1, and continuously stirring and reacting for 2-12 hours at 40-90 ℃ to obtain the organic-inorganic composite emulsion with the core-shell structure, namely the cathode binder.
5. The method for producing the anode binder according to claim 4, characterized in that: the ratio of the sum of the masses of the monomers A and B to the mass of the modified hydrous oxide sol is 19: 1-4: 1; the ratio of the mass of the modified hydrous oxide sol to the mass of the monomer B was 15: 1-5: 1.
6. the method for preparing the negative electrode binder according to claim 4, wherein the modified hydrous oxide sol is in a sodium type and has a particle size in a range of 10 to 200 nm.
7. The method for producing the negative electrode binder according to claim 4, wherein the initiator is one or more of ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, azobisisobutyrimidazoline hydrochloride, and azobisdiisopropylimidazoline hydrochloride.
8. The method of claim 4, wherein the functional monomer is acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylonitrile, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and C-ethyl methacrylate8～C16One or more of alkyl esters.
9. The method for preparing the negative electrode binder according to claim 4, wherein the emulsifier is one or more of alkyl sulfate, alkylphenol ethoxylate, disproportionated rosin potassium, and sorbitan fatty acid ester.
10. The method of preparing the negative electrode binder of claim 4, wherein the silane coupling agent has a formula of Y- (CH)2)k-Si(OR)3Wherein k is more than or equal to 0 and less than or equal to 4, Y is one or more of vinyl, amino, epoxy, methacryloxy, sulfydryl and carbamido, and R is one or more of chloro, methyl, ethyl and acetyl.
11. A method for producing a negative electrode sheet using the negative electrode binder according to claim 1, comprising the steps of:
t1: mixing a negative electrode active material, a conductive agent, a dispersing agent and a negative electrode binder to obtain a mixture M, and gradually adding the mixture M into deionized water for grinding to obtain uniformly mixed negative electrode slurry;
t2: and after the solid content of the negative electrode slurry is adjusted to 50%, uniformly coating the negative electrode slurry on the surface of a current collector, and then drying and compacting to obtain the negative electrode piece.
12. The method of manufacturing a negative electrode sheet according to claim 11, wherein the mass ratio of the negative electrode active material, the conductive agent, the dispersant, and the negative electrode binder is m1：m2：m3：m4Wherein m is1Is 90 to 97 m20.1 to 2.0, m30.5 to 2.0, m40.5 to 3, and m1+m2+m3+m4=100。
13. The method of manufacturing a negative electrode sheet according to claim 11, wherein the negative electrode active material is one or more of natural graphite, artificial graphite, hard carbon, soft carbon, mesogenic microspheres, silicon material, silica, and silicon carbon; the conductive agent is one or more of graphite, carbon black, acetylene black, graphene and carbon nano tubes; the dispersing agent is one or more of sodium carboxymethyl cellulose, lithium carboxymethyl cellulose, sodium polyacrylate and lithium polyacrylate.
14. A lithium ion battery comprising a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte, wherein the negative electrode sheet comprises the negative electrode binder according to any one of claims 1 to 3.
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