CN115084518A - Negative electrode binder and application thereof - Google Patents
Negative electrode binder and application thereof Download PDFInfo
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- CN115084518A CN115084518A CN202210559856.7A CN202210559856A CN115084518A CN 115084518 A CN115084518 A CN 115084518A CN 202210559856 A CN202210559856 A CN 202210559856A CN 115084518 A CN115084518 A CN 115084518A
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- 239000007773 negative electrode material Substances 0.000 claims abstract description 46
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Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a negative electrode binder and application thereof. The cathode binder comprises a binder matrix containing a group B and an organic additive dispersed in the binder, wherein the molecular general formula of the organic additive is RA x Wherein R is an organic group containing-S-S-, A is a group capable of forming a chemical bond with the group B, and x is a positive integer greater than or equal to 2. The negative electrode binder has high binding strength, stress buffering performance and self-repairing capacity, can effectively inhibit the volume expansion of a negative electrode active material, particularly a silicon-based negative electrode material, and relieves the stress of the negative electrode caused by the volume expansion, thereby inhibiting the occurrence of phenomena such as material pulverization, structural damage and the like of the negative electrode in application, prolonging the cycle service life of the negative electrode and the negative electrode material, and not consuming active lithium.The preparation method of the cathode binder has the advantages that the process conditions are easy to control, and the prepared cathode binder is stable in performance and high in efficiency.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a negative electrode binder and application thereof.
Background
With the enhancement of awareness of environmental protection and energy crisis, secondary batteries, such as lithium batteries, are becoming more popular as an environmentally friendly energy storage technology. Lithium batteries are widely used due to their high energy density, long cycle, and high stability. With the wide application of electronic products and the vigorous development of electric automobiles, the market of lithium batteries is increasingly wide, but higher requirements on the safety of the lithium batteries are provided.
Currently, the negative electrode materials of lithium batteries are mainly classified into carbon-based materials and non-carbon-based materials. Graphite is a lithium ion battery cathode material with the most widely commercialized and applied carbon materials, the actual specific capacity of the graphite is very close to the theoretical specific capacity limit of 372mAh/g, the graphite is difficult to further promote, and the graphite cannot meet the requirement of high energy density of a future power battery more and more. In the non-carbon materials, the theoretical specific capacity of the silicon-based negative electrode material can reach up to 4200mAh/g, which is about 10 times of that of the graphite negative electrode, and meanwhile, the silicon-based negative electrode material has a lower de-intercalation lithium potential, can avoid the phenomenon of lithium precipitation on the surface during charging, and has safety performance superior to that of the graphite negative electrode material. Therefore, silicon-based anode materials are considered as an alternative choice for current graphite anode materials. However, during the practical use of the silicon-based negative electrode material, a huge volume expansion effect exists when lithium is deintercalated, for example, the volume change of silicon can reach more than 300%. The internal stress generated by the severe volume change can cause the problems of crack pulverization and peeling of silicon-based negative electrode particles, damage of an electrode structure, continuous formation of a new SEI film at the crack and the like, and seriously influences the cycle life and the capacity exertion of the lithium ion battery.
The addition of a proper binder is one of effective ways for inhibiting the volume expansion of the silicon-based negative electrode material, but the existing binder has poor binding performance and buffering performance, and has no obvious effect on inhibiting the volume expansion of the silicon-based negative electrode and improving the electrochemical performance, particularly the cycle performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a negative electrode binder to solve the technical problem that the caking property and the buffering property of the conventional binder are not ideal.
The invention also aims to provide a negative electrode and a secondary battery, which aim to solve the technical problems that the existing negative electrode is not high in structural strength and low in peel strength, so that the cycle performance and other performances of the battery are not ideal.
In order to achieve the above object, according to a first aspect of the present application, there is provided an anode binder. The negative electrode binder comprises a binder matrix, wherein the binder matrix contains a group B, and also comprises an organic additive, the organic additive is dispersed in the binder matrix, and the molecular general formula of the organic additive is RA x Wherein RA is x Wherein R is an organic group containing-S-, A is a group capable of forming a covalent bond with the group B, and x is a positive integer of 2 or more.
Further, organic additive RA x Comprises at least one of 2-hydroxyethyl disulfide, 4 ' -diaminodiphenyl disulfide, 3 ' -dithiodipropionic acid, dithiodiglycolic acid, 4 ' -dithiodibutyric acid, 6 ' -dithiodinicotinic acid, 4 ' -dihydroxydiphenyl sulfide and bis (6-hydroxy-2-naphthalene) disulfide.
Further, the group B includes-COOH, and the group A includes-OH and-NH 2 At least one of (1).
Or further, the group B comprises-OH, -NH 2 And a group represented by a comprises-COOH.
Further, the binder matrix comprises at least one of polyacrylic acid, polyvinyl alcohol-polyacrylic acid graft copolymer, polyethylene glycol-polyacrylic acid block copolymer, carboxymethyl cellulose, guar gum, chitosan and polyacrylic acid copolymer.
Further, the mass ratio of the binder matrix to the organic additive is 100: 1-10: 1.
Furthermore, the mass ratio of the binder matrix to the organic additive is 70: 1-30: 1.
In a second aspect of the present application, a negative electrode is provided. The negative electrode comprises a current collector and a negative active layer combined on the surface of the current collector, wherein the negative active layer contains a binder and a negative active material, and the binder is a negative binder of the application.
Further, the negative active material includes a silicon-based negative electrode material.
Furthermore, the mass of the negative electrode binder accounts for 1-20% of the total mass of the negative electrode active layer.
In a third aspect of the present application, a secondary battery is provided. The secondary battery comprises a positive electrode, a negative electrode and a diaphragm stacked between the positive electrode and the negative electrode, wherein the negative electrode is the negative electrode of the secondary battery.
Compared with the prior art, the method has the following technical effects:
the binder matrix contained in the negative electrode binder endows the negative electrode binder with good binding performance and flexibility. The organic additive introduces active groups and reversible disulfide bonds shown in A, and can form covalent bonds with a binder matrix in the preparation process of the negative electrode to form a self-repairable three-dimensional cross-linked network structure. Therefore, the negative electrode binder has high binding strength, stress buffering performance and self-repairing capability through the synergistic effect between the contained binder matrix and the organic matter additive, can effectively inhibit the volume expansion of a negative electrode active material, particularly a silicon-based negative electrode material, and relieves the stress of the negative electrode caused by the volume expansion, thereby inhibiting the phenomena of material pulverization, structural damage and the like of the negative electrode in application and prolonging the cycle service life of the negative electrode and the negative electrode material. In addition, the negative electrode binder does not consume active lithium and does not influence the first effect of the battery.
This application negative pole contains this application negative pole binder, consequently, the negative pole binder can form three-dimensional network structure in the negative pole active layer, has effectively strengthened negative pole active layer structural stability to with the mass flow body between the bonding strength high, thereby make this application negative pole in charge-discharge cycle in-process structural strength with if electrochemical properties such as cyclicity can be high, and first effective high. And the negative active layer is effectively prevented from being pulverized, peeled and the like.
The negative pole of this application secondary battery is above-mentioned this application negative pole, and consequently, this application secondary battery cyclicity can be good, longe-lived, and electrochemical performance is stable, and is first effective high moreover.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, for example, a and/or B, may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the contextual objects are in an "or" relationship.
In the description of the present invention, "at least one" means one or more, and "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
It should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also refer to the proportional relationship of the weight of each component, and therefore, the proportional enlargement or reduction of the content of the related components according to the embodiments of the present invention is within the scope of the present disclosure. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In addition, unless the context clearly uses otherwise, an expression of a word in the singular is to be understood as including the plural of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
In a first aspect, embodiments of the present application provide an anode binder. The negative electrode binder of the embodiment of the application contains a binder matrix and an organic additive which are uniformly dispersed to form a mixture.
The binder matrix contained in the negative electrode binder of the embodiments of the present application serves as a binder base component, and the negative electrode binder of the embodiments of the present application has good binding performance and flexibility. The binder matrix also contains active groups B which can react with the active groups contained in the organic additive to form chemical bonds. In an embodiment, the binder matrix may contain reactive groups B comprising-COOH, -OH, -NH 2 At least one of (1). The active groups B can effectively react with active groups contained in the organic additive to generate chemical bonds, such as covalent bonds, and can enhance the compatibility with the cathode active material, so that the bonding strength of the cathode active material is improved. In an embodiment, the binder matrix comprises at least one of polyacrylic acid, polyvinyl alcohol-polyacrylic acid graft copolymer, polyethylene glycol-polyacrylic acid block copolymer, carboxymethyl cellulose, guar gum, chitosan, and polyacrylic acid copolymer. The binder matrixes have strong binding property and excellent flexibility, have excellent compatibility with a negative electrode active material, particularly a silicon-based active material, and improve the binding strength of the negative electrode active material. The organic matter additive is rich in the group B, and can form stable chemical bonds with the organic matter additive, so that a self-repairable three-dimensional cross-linked network structure is formed in the negative electrode active layer. For example, polyacrylic acid is used as a binder matrix, which has good binding properties and flexibility, and whichAbundant carboxyl groups can form a hydrogen bond network between molecular chains; moreover, polyacrylic acid can be connected with an organic additive containing reversible disulfide bonds in a covalent bond mode to form a self-repairable three-dimensional cross-linked network structure.
The molecular general formula of the organic additive contained in the negative electrode binder in the embodiment of the application is RA x (ii) a Wherein R is an organic group containing-S-S-, A is a group capable of forming a chemical bond with the group B contained in the binder matrix; x is a positive integer greater than or equal to 2, specifically, x is greater than or equal to 2 and less than or equal to 12, and further, x is greater than or equal to 2 and less than or equal to 5, and x is greater than or equal to 5 and less than or equal to 12. Thus, the organic additive introduces an active group shown by A and a reversible disulfide bond (-S-S-), and can form a chemical bond with a binder matrix in the preparation process of the negative electrode to form a self-repairable three-dimensional cross-linked network structure, specifically, a chemical bond formed between the active group A and a group B contained in the binder matrix can form a covalent bond, so that a three-dimensional network structure is formed in the negative electrode active material; the reversible disulfide bond can play a role in synergism, endows the negative electrode binder in the embodiment of the application with high bonding strength, buffering performance and self-repairing capability, can effectively inhibit the volume expansion of a negative electrode active material, particularly a silicon-based negative electrode material, and relieves the stress of the negative electrode caused by the volume expansion, thereby inhibiting the phenomena of material powdering, structural damage and the like of the negative electrode in application and prolonging the cycle service life of the negative electrode and the negative electrode material. In addition, the negative electrode binder does not consume active lithium, so that the first effect of the battery is ensured.
In one embodiment, the reactive group A of the organic additive may be a group including-COOH, -OH, -NH 2 At least one of (a). The active groups A can effectively react with the active groups B contained in the binder matrix to generate chemical bonds, such as covalent bonds, and can enhance compatibility with the negative active material, so that the bonding strength of the negative active material is improved. Specifically, the polar active groups can generate hydrogen bonds with the surface of the negative active material, particularly silicon-based active material, so that the negative active material, particularly the silicon-based active material, is firmly bonded and coated, and the negative active material is improvedParticularly, the dispersibility of the silicon-based active material and the dispersion stability in the active layer restrict the movement and separation between the negative active material and other components such as a conductive agent during the cycle, and suppress the enormous volume expansion of the negative active material, particularly the silicon-based active material, during the charge and discharge. In one embodiment, the binder matrix includes groups B comprising-COOH and the organic additive includes groups A comprising-OH, -NH 2 At least one of; or, the group B comprises-OH, -NH 2 And a group represented by a comprises-COOH. At this time, covalent bonds are formed between the groups A and B, so that a rich network structure can be formed in the negative electrode active layer, the compatibility between the negative electrode binders is enhanced, and the mechanical strength of the negative electrode active layer is improved.
In the examples, the organic additive includes at least one of 2-hydroxyethyl disulfide, 4 ' -diaminodiphenyl disulfide, 3 ' -dithiodipropionic acid, dithiodiglycolic acid, 4 ' -dithiodibutanoic acid, 6 ' -dithiodinicotinic acid, 4 ' -dihydroxydiphenyl sulfide, bis (6-hydroxy-2-naphthalene) disulfide, based on the kind of groups represented by R and a contained in the organic additive and the functions thereof. The organic additives are rich in reversible disulfide bonds (-S-S-) and active groups A, and can form chemical bonds with groups B contained in a binder matrix, specifically, covalent bonds can be formed, and a three-dimensional network structure is formed in a negative active material.
In an embodiment, a mass ratio of the binder matrix to the organic additive contained in the negative electrode binder of the embodiment of the present application may be 100:1 to 10: 1. The mass ratio of the binder matrix to the organic matter additive has an influence on the binding performance of the cathode binder, for example, when the mass ratio of the binder matrix to the organic matter additive is greater than 100:1, the cross-linked network density is too low, and the binding strength, the stress buffering capacity and the self-repairing capacity are poor; when the ratio is less than 10:1, the crosslinked network is easy to be too dense, the flexibility of the negative active layer is insufficient and the negative active layer becomes hard, and the volume shrinkage is severe, so that the negative active layer and the current collector are peeled. Further, the mass ratio of the binder matrix to the organic additive is 70: 1-30: 1. It can be understood that by optimizing the ratio of the two, the synergistic effect between the two can be improved, the stability of the three-dimensional network structure formed by the two can be enhanced, the adhesive strength between the negative electrode binder and the negative electrode active material, the current collector and the materials contained in the active layer can be enhanced, the movement and separation between the negative electrode active material and other components such as a conductive agent during the circulation process can be further limited, the huge volume expansion of the negative electrode active material such as a silicon-based active material during the charge and discharge process can be inhibited, the mechanical strength of the negative electrode active material can be enhanced, and the dispersion uniformity of the negative electrode active material in the negative electrode active layer and the stability during the circulation process can be improved. Meanwhile, the using amount of the cathode binder is reduced, so that the structural stability and the electrochemical performance stability of the cathode in the circulation process are effectively improved.
In addition, the negative electrode binder of the examples of the above text application can be prepared by a method comprising the following steps:
and mixing the binder matrix with the organic additive to obtain the cathode binder.
Wherein, the binder matrix is the binder matrix contained in the negative electrode binder of the embodiment of the application, such as the binder matrix containing the group B. The organic additive is also the organic additive contained in the negative electrode binder of the embodiment of the application, such as the organic additive containing-S-S-and having a molecular general formula RA x The organic additive of (1). For the sake of brevity, the binder matrix and the organic additive will not be described in detail herein.
In this way, the negative electrode binder in the embodiment of the application forms a mixture by directly mixing the binder matrix and the organic additive, so that the prepared negative electrode binder forms a chemical bond between the organic additive and the binder matrix in the negative electrode preparation process to form a self-repairable three-dimensional cross-linked network structure, has high binding strength, buffering performance and self-repairing capability, and does not consume active lithium. In addition, the preparation method of the negative electrode binder in the embodiment of the application has the advantages that the process conditions are easy to control, and the prepared negative electrode binder is stable in performance and high in efficiency.
In the embodiment, during or before the mixing treatment, the binder matrix and the organic additive are added according to the mass ratio of 100: 1-10: 1, and further 70: 1-30: 1. Thereby improving the synergistic effect between the binder matrix and the organic additive and improving the binding strength of the prepared cathode binder.
In a second aspect, embodiments of the present application also provide a negative electrode. The negative electrode of the embodiment of the application comprises a current collector and a negative active layer combined on the surface of the current collector.
Among them, the current collector may be a commonly used negative electrode current collector.
The negative electrode active layer may be a negative electrode active layer as contained in a conventional electrode, or a modified negative electrode active layer, which includes negative electrode active materials, a binder, a conductive agent, and other components, and may include other additives that are beneficial to the electrochemical performance of the negative electrode. In the present embodiment, the binder contained in the negative electrode active layer is the negative electrode binder of the embodiment of the above-mentioned application. Thus, in the negative active layer, the negative binder can form a three-dimensional network structure in the negative active layer, so that the movement and separation between the negative active material and other components such as a conductive agent can be effectively limited in the circulation process, the huge volume expansion in the charge and discharge process of the negative active material such as a silicon-based active material is inhibited, meanwhile, the components in the negative active layer such as the negative active material and the conductive agent can be uniformly dispersed, the structure of the negative active layer is stable, the bonding strength between the negative active layer and a current collector is high, the structural strength of the negative electrode in the charge and discharge circulation process is high, the electrochemical performance such as the circulation performance is also high, the first effect is high, and the adverse phenomena such as pulverization and stripping of the negative active layer are effectively avoided. In addition, since the anode binder has high binding strength as described above, its content in the anode is low, so that the anode conductivity is high. In the embodiment, the content of the negative electrode binder may be 1% to 20% by mass, more preferably 5% to 15%, 10% to 15%, 5% to 10% by mass, or the like, of the total mass of the negative electrode active layer.
Based on the excellent properties of the anode binder of the examples of the above-mentioned application as described above, the anode active material contained in the anode active layer may include a silicon-based anode material. Therefore, the negative electrode binder in the negative electrode active layer can be uniformly coated and combined on the surface of the silicon-based negative electrode material, so that the movement and separation between the silicon-based negative electrode material and other components such as a conductive agent in the circulation process are limited, and the huge volume expansion of the silicon-based active material in the charge-discharge process is inhibited, so that the structure of the silicon-based negative electrode active layer is stable before the silicon-based negative electrode active layer is obvious, the combination strength between the silicon-based negative electrode active layer and a current collector is high, and the structure and the electrochemical properties such as the circulation performance of the negative electrode in the charge-discharge circulation process are obviously improved.
In a third aspect, embodiments of the present application also provide a secondary battery. The secondary battery includes a positive electrode, a negative electrode, and a separator stacked between the positive electrode and the negative electrode, and of course, includes other components necessary for the secondary battery, such as an electrolyte or a solid electrolyte. The negative electrode is the negative electrode in the embodiment of the present application. Therefore, the secondary battery provided by the embodiment of the application has the advantages of good cycle performance, long service life, stable electrochemical performance and high first-order efficiency. In an embodiment, the negative active material contained in the negative active layer is a silicon-based negative material. Therefore, the secondary battery has high gram capacity, good cycle performance, long service life and stable electrochemical performance. In an embodiment, the secondary battery may be a lithium ion battery.
The negative electrode binder, the method for preparing the same, the lithium metal battery, and the like according to the embodiments of the present invention will be illustrated below by way of a plurality of specific examples.
Negative pole binder and preparation method embodiment thereof
Example A1
The present embodiment provides an anode binder. The negative electrode binder comprises the following components in a mass ratio of 100:1 and an organic additive dispersed in the binder matrix. Wherein the binder matrix is polyacrylic acid [ C ] 3 H 4 O 2 ] n (PAA) and the organic additive is 2-hydroxyethyl disulfide.
Example A2
The present embodiment provides an anode binder. The negative electrode binder comprises 50: 1 and an organic additive dispersed in the binder matrix. Wherein the binder matrix isPolyacrylic acid [ C ] 3 H 4 O 2 ] n (PAA) and the organic additive is 2-hydroxyethyl disulfide.
Example A3
The present embodiment provides an anode binder. The negative electrode binder comprises 30:1 and an organic additive dispersed in the binder matrix. Wherein the binder matrix is polyacrylic acid [ C ] 3 H 4 O 2 ] n (PAA) and the organic additive is 2-hydroxyethyl disulfide.
Example A4
The present embodiment provides an anode binder. The negative electrode binder comprises the following components in a mass ratio of 10:1 and an organic additive dispersed in the binder matrix. Wherein the binder matrix is polyacrylic acid [ C ] 3 H 4 O 2 ] n (PAA) and the organic additive is 2-hydroxyethyl disulfide.
Example A5
The present embodiment provides an anode binder. The negative electrode binder comprises 50: 1 and an organic additive dispersed in the binder matrix. Wherein the binder matrix is polyacrylic acid [ C ] 3 H 4 O 2 ] n (PAA) the organic additive is 4, 4' -diaminodiphenyl disulfide.
Example A6
The present embodiment provides an anode binder. The negative electrode binder comprises 50: 1 and an organic additive dispersed in the binder matrix. Wherein, the binder matrix is polyvinyl alcohol, and the organic additive is 3, 3' -dithiodipropionic acid.
Example A7
The present embodiment provides an anode binder. The negative electrode binder comprises 50: 1 and an organic additive dispersed in the binder matrix. Wherein the binder matrix is guar gum, and the organic additive is 3, 3' -dithiodipropionic acid.
Comparative example A1
This comparative example provides a binder that does not contain organic additives as compared to example a 2.
Comparative example A2
This comparative example provides a binder that does not contain organic additives as compared to example a 6.
Comparative example A3
This comparative example provides a binder that does not contain organic additives as compared to example a 7.
Second, lithium ion Battery embodiment
Examples B1 to B7 and comparative examples B1 to B3
Examples B1 to B7 and comparative examples B1 to B3 each provide a lithium ion battery. The lithium ion batteries of examples B1-B7 and comparative examples B1-B3 respectively include the following structures:
negative electrode: the negative electrode binders provided in examples a 1-a 7 and comparative examples a 1-A3 were respectively blended according to silicon-based negative electrodes (SiO): conductive agent (SP): and (3) a negative electrode binder: preparing negative electrode slurry according to the mass ratio of the deionized water of 80:10:10:100, coating the negative electrode slurry on copper foil to prepare a negative electrode sheet, baking the negative electrode sheet for 4 hours in a vacuum oven at 150 ℃ to prepare the negative electrode sheets of the lithium ion batteries in the embodiments B1 to B7 and the comparative examples B1 to B3;
and (3) positive electrode: according to LiFePO 4 : conductive agent SP: binder PVDF: the NMP mass ratio is 95:2: 3: preparing anode slurry according to the proportion of 100, coating the anode slurry and drying the anode slurry on an aluminum foil to prepare an anode plate, and baking the anode plate in a vacuum oven at the temperature of 100 ℃ to remove trace water. (ii) a
A diaphragm: a Polyethylene (PE) separator was used. (ii) a
Electrolyte solution: LiPF with electrolyte of 1mol/L 6 A solution, wherein a solvent consists of EC (ethylene carbonate) and DEC (diethyl carbonate) according to a volume ratio of 1: 1;
assembling: and the positive plate, the negative plate, the electrolyte and the diaphragm are assembled into the lithium ion soft package battery according to the assembly requirements of the lithium ion battery.
Correlation characteristic test
The negative electrode sheets used in the above examples B1 to B7 and comparative examples B1 to B3 were subjected to the following performance tests, respectively:
and (3) testing the peel strength: dividing the negative electrode into strips with the thickness of 20 mm-100 mm, adhering the pressure-sensitive 3M-VHB double-sided adhesive to the surface of the negative electrode piece, adhering the other surface of the negative electrode piece to a stainless steel plate, and rolling the negative electrode piece back and forth for 3 times by using a pressing wheel; pre-stripping the free end of the current collector and the negative material layer, turning the free end of the current collector by 180 degrees, respectively clamping the free end of the current collector and the stainless steel plate on an upper clamp and a lower clamp of a tensile testing machine, carrying out a stripping test at a speed of 300mm/min and an angle of 180 degrees, and reading an average value in a stable stripping stage to serve as a stripping strength value.
The lithium ion batteries assembled from the above examples B1 to B7 and comparative examples B1 to B3 were respectively subjected to the following performance tests:
0.1C cycle performance test: the battery is placed at 25 ℃, and the battery is subjected to charge-discharge circulation by using 0.1C current in a charge-discharge pressure interval of 3.0-4.4V, and the initial capacity is recorded as Q 0 Capacity of Q circulating to 50 turns 1 The capacity retention at 50 cycles at 0.1C cycle was calculated from the following equation:
capacity retention (%) Q at 50 cycles at 0.1C cycle 1 /Q 0 X 100%. 0.5C cycle performance test: the charging and discharging current is 0.5C, and other operations are the same as the 0.1C cycle performance test.
The test results are shown in table 1 below:
TABLE 1
As can be seen from Table 1, the peel strength of examples B1 to B7 was 0.33N/cm or more, and the peel strength of comparative examples B1 to B3 containing no-S-was 0.25N/cm or less, indicating that the negative electrode binder containing a crosslinked network structure provided by the present invention had a higher peel strength; comparing the capacity retention rate of 50 cycles of the cycle of the negative electrode binder in the embodiments B1 to B7, the capacity retention rate of 50 cycles of the cycle of 0.1C (more than 92%) provided by the invention is obviously superior to that of the comparative example (less than 86%), and when the multiplying power is increased to 0.5C, the difference of the capacity retention rate is further widened, because the negative electrode binder provided by the invention can form a cross-linked network structure containing reversible-S-S-bonds, has high binding strength, buffering performance and self-repairing capability, can effectively inhibit the volume expansion of a silicon-based negative electrode material, and alleviate the stress of the negative electrode caused by the volume expansion, thereby inhibiting the phenomena of material pulverization, structural damage and the like of the negative electrode in application, and prolonging the cycle service life of the negative electrode and the negative electrode material.
The above examples only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent application shall be subject to the appended claims.
Claims (10)
1. The negative electrode binder comprises a binder matrix and is characterized in that the binder matrix contains a group B, and also comprises an organic additive, wherein the organic additive is dispersed in the binder matrix, and the molecular general formula of the organic additive is RA x Wherein R is an organic group containing-S-S-, A is a group capable of forming a covalent bond with the group B, and x is a positive integer greater than or equal to 2.
2. The negative electrode binder as claimed in claim 1, wherein: the group B comprises-COOH, and the group A comprises-OH and-NH 2 At least one of; or
The group B comprises-OH, -NH 2 And said A group comprises-COOH.
3. According toThe negative electrode binder as claimed in claim 2, wherein: the RA x Comprises at least one of 2-hydroxyethyl disulfide, 4 ' -diaminodiphenyl disulfide, 3 ' -dithiodipropionic acid, dithiodiglycolic acid, 4 ' -dithiodibutyric acid, 6 ' -dithiodinicotinic acid, 4 ' -dihydroxydiphenyl sulfide and bis (6-hydroxy-2-naphthalene) disulfide.
4. The negative electrode binder as claimed in any one of claims 1 to 3, wherein: the binder matrix comprises at least one of polyacrylic acid, polyvinyl alcohol, a polyvinyl alcohol-polyacrylic acid graft copolymer, a polyethylene glycol-polyacrylic acid block copolymer, carboxymethyl cellulose, guar gum, chitosan and a multi-component acrylic acid copolymer.
5. The negative electrode binder as claimed in any one of claims 1 to 3, wherein: the mass ratio of the binder matrix to the organic additive is 100: 1-10: 1.
6. The negative electrode binder as claimed in claim 5, wherein: the mass ratio of the binder matrix to the organic additive is 70: 1-30: 1.
7. A negative electrode comprising a current collector and a negative active layer bonded to a surface of the current collector, characterized in that: the negative electrode active layer contains a binder and a negative electrode active material, and the binder is the negative electrode binder described in any one of claims 1 to 6.
8. The negative electrode of claim 7, wherein: the negative active material includes a silicon-based negative electrode material.
9. The negative electrode of claim 8, wherein: the mass of the negative electrode binder accounts for 1-20% of the total mass of the negative electrode active layer.
10. A secondary battery, characterized in that: including positive pole, negative pole and fold and locate diaphragm between positive pole and the negative pole, its characterized in that: the negative electrode is the negative electrode according to any one of claims 7 to 9.
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